KR101981655B1 - Separator for electrochemical device, method for manufacturing the same, and electrochemical device comprising the same - Google Patents

Abstract

A separator for an electrochemical device, a method for manufacturing the same, and an electrochemical device including the same, comprising: a first porous nonwoven fabric including a plurality of first polymer fibers, and pores between a plurality of first polymer fibers in the first porous nonwoven fabric A separator for an electrochemical device, a manufacturing method thereof, and an electrochemical device including the same may be provided, including a first sheet including surface-functionalized inorganic nanoparticles filled therein.

Description

Separators for electrochemical devices, methods for manufacturing the same, and electrochemical devices including the same {SEPARATOR FOR ELECTROCHEMICAL DEVICE, METHOD FOR MANUFACTURING THE SAME, AND ELECTROCHEMICAL DEVICE COMPRISING THE SAME}

The present invention relates to a separator for an electrochemical device, a manufacturing method thereof, and an electrochemical device including the same.

Recently, as the importance of energy storage and conversion technologies such as electric vehicles and energy storage systems (ESS) increases, interest in various types of batteries is increasing. Among them, lithium secondary batteries have attracted much attention.

One of the important components that influence the characteristics of a battery in a lithium secondary battery is a separator that impregnates an electrolyte and functions as a passage for lithium ions.

The properties required for such a separator should not cause chemical stability and deterioration at the interface between the electrolyte and the electrode in the charge / discharge region of the battery, and have a porosity and pore size that can ensure the smooth movement of lithium ions in the electrolyte. Is required. In addition, the separator should have good wettability of the electrolyte and maintain electrolyte content. Wetting is very important for improving productivity in the electrolyte injection process, and sustained electrolyte content affects battery life.

In addition, the separator must have thermal stability. When the separator passes the softening temperature of the separator due to the temperature increase inside the battery, the separator contracts and heat shrinkage at a high temperature is less likely to occur.

Further, further research is required to improve the electrical characteristics of the electrochemical device through its own configuration of the separator.

In addition, Mn ^{2 +} , in the cathode material during charge and discharge of lithium secondary batteries Ni ^{2 +,} Co ^{2 +} After elution the like are moved to the cathode through the separator, may be reduced to the metallic form on the cathode surface, which can result in a significant decrease in cell capacity. Thus, research to prevent the movement of the eluted metal ions to the cathode is needed.

In one embodiment of the present invention, the smooth movement of the metal ions, which are the basis of the electrochemical device, exhibits excellent electrical conductivity, and can improve the electrical properties of the electrochemical device. After moving to the negative electrode, it is to provide a separator for an electrochemical device that can improve the battery characteristics by inhibiting the movement of the metal ions reduced in the negative electrode to reduce the battery characteristics to the negative electrode.

Another embodiment of the present invention is to provide a method for manufacturing a separator for an electrochemical device of the excellent characteristics as described above through a simple process.

Another embodiment of the present invention, to provide an electrochemical device comprising the separator for the electrochemical device.

In one embodiment of the present invention, a surface-functionalized inorganic material filled in pores between a first porous nonwoven fabric comprising a plurality of first polymer fibers and a plurality of first polymer fibers in the first porous nonwoven fabric Provided is a separator for an electrochemical device comprising a first sheet comprising nanoparticles.

Pores located between the surface-functionalized inorganic nanoparticles filled in the first sheet, and pores located between the surface-functionalized inorganic nanoparticles and the plurality of first polymer fibers It may be to include more.

Pores located between the surface-functionalized inorganic nanoparticles filled in the first sheet, and pores located between the surface-functionalized inorganic nanoparticles and the plurality of first polymer fibers The average diameter of may be 1um or more and 100um or less.

The porosity of the first sheet may be 10 vol% or more and 95 vol% or less with respect to 100 vol% of the total volume of the first sheet.

The first sheet may have a thickness of 1 μm or more and 100 μm or less.

The surface functional groups of the surface-functionalized inorganic nanoparticles include a thiol group (-SH), a pyridine group (-RC ₅ H ₄ N), an amine group (-NH ₃ ), and a cyano group (-CN) , Sulfide group (-R ₂ S), trifluorination popularity (-PF ₃ ), or a combination thereof.

The average particle diameter of the surface-functionalized inorganic nanoparticles,

0.001um or more may be 1um or less.

The first polymer fiber may be a mixture of polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN).

The mixing ratio (PVP: PAN) of the polyvinylpyrrolidone (PVP) and polyacrylonitrile (polyacrylonitrile, PAN) may be represented by 20:80 or more and 80:20 or less by weight.

The average diameter of the first polymer fibers may be 0.001um or more and 100um or less.

The content ratio of the first porous nonwoven fabric of the first sheet and the surface-functionalized inorganic nanoparticles (first porous nonwoven fabric: the surface functionalized inorganic nanoparticles) is based on the weight. , 1: 1 or 1: 5 or less.

The separator may be further included; a second sheet disposed on the first sheet and including a conductive material.

The second sheet may further include a second porous nonwoven fabric including a plurality of second polymer fibers, and the conductive material may be filled in pores in the second porous nonwoven fabric.

The conductive material may be located on a surface of a plurality of second polymer fibers in the second porous nonwoven fabric.

The conductive material positioned on the surfaces of the plurality of second polymer fibers in the second porous nonwoven fabric may be positioned to surround the surfaces of the second polymer fibers.

The average diameter of pores in the second sheet may be 0.001um or more and 10um or less.

The porosity in the second sheet may be 5 vol% or more and 95 vol% or less with respect to 100 vol% of the total volume of the second sheet.

The second sheet may have a thickness of 1 μm or more and 20 μm or less.

The second polymer fiber may be polyetherimide (PEI).

The average diameter of the second polymer fiber may be 0.01um or more and 100um or less.

The conductive material may include carbon nanotubes, silver nanowires, nickel nanowires, gold nanowires, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene ( poly (3,4-ethylenedioxithiophene)), polyaniline, polyaniline, derivatives thereof, or mixtures thereof.

Another embodiment of the present invention, a first spinning step of simultaneously spinning a first solution comprising a first polymer, and a second solution containing surface-functionalized inorganic nanoparticles; The resultant of the first spinning step is pressed to form a surface functional group filled with pores between a first porous nonwoven fabric including a plurality of first polymer fibers and a plurality of first polymer fibers in the first porous nonwoven fabric. Provided is a method for producing a separator for an electrochemical device, comprising a first pressing step, to obtain a first sheet comprising functionalized inorganic nanoparticles.

The first spinning step may be performed through double electrospinning, double electrosprays, double sprays, and combinations thereof.

The content of the first polymer in the first solution may be 5 wt% or more and 30 wt% or less with respect to 100 wt% of the first solution total amount.

The solvent in the first solution may be dimethylformamide (N, N-dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof. .

The content of the surface-functionalized inorganic nanoparticles in the second solution may be 1 wt% or more and 50 wt% or less with respect to 100 wt% of the total amount of the second solution.

The solvent in the second solution is deionized water, isopropylalcohol, butanol, ethanol, hexanol, acetone, dimethylformamide (N, N-dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof.

In the first spinning step, the spinning speed of the first solution may be 1 μl / min or more and 10 μl / min.

In the first spinning step, the spinning speed of the second solution may be 30 μl / min or more and 80 μl / min.

The manufacturing method includes a second spinning step of spinning a fourth solution containing a conductive material on the first sheet obtained in the first pressing step; And a second pressing step of pressing the resultant of the second spinning step to form a second sheet including a conductive material on the first sheet.

The second spinning step is to simultaneously spin the third solution containing the second polymer, and the fourth solution containing the conductive material on the first sheet obtained in the first pressing step, the second pressing step Is filled in the pores between the plurality of second polymer fibers in the porous non-woven fabric, and the second porous non-woven fabric is located on the first sheet, by pressing the result of the second spinning step It may be to form a second sheet comprising a conductive material.

The second pressing step may include: compressing the resultant of the second spinning step, the porous nonwoven fabric disposed on the first sheet and including a plurality of second polymer fibers, and the plurality of second polymers in the second porous nonwoven fabric. It may be to form a second sheet comprising a conductive material located in the fiber.

In the second pressing step, the conductive material may be positioned to surround the surfaces of the plurality of second polymer fibers.

The second spinning step may be performed through double electrospinning, double electrospray, double spray, and combinations thereof.

The content of the second polymer in the third solution may be 5 wt% or more and 30 wt% or less with respect to 100 wt% of the third solution.

The third solution solvent may be dimethylformamide (N, N-dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof.

The content of the conductive material in the fourth solution may be 0.01 wt% or more and 30 wt% or less with respect to 100 wt% of the fourth solution.

The fourth solution solvent, deionized water, isopropyl alcohol (iso-propylalcohol), butanol (buthalol), ethanol (ethanol), hexanol, acetone (Acatone), dimethylformamide (N, N -dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof.

In the second spinning step, the spinning speed of the third solution may be 1 μl / min or more and 10 μl / min or less.

In the second spinning step, the spinning speed of the fourth solution may be 30 μl / min or more and 80 μl / min or less.

Yet another embodiment of the present invention provides an electrochemical device including the separator for an electrochemical device according to the embodiment of the present invention.

In one embodiment of the present invention, the smooth movement of the metal ions, which are the basis of the electrochemical device, exhibits excellent electrical conductivity, and can improve the electrical properties of the electrochemical device. After moving to the negative electrode, it provides a separator for an electrochemical device that can improve the battery characteristics by inhibiting the movement of the metal ions reduced in the negative electrode to reduce the battery characteristics to the negative electrode.

Another embodiment of the present invention provides a method of manufacturing a separator for an electrochemical device having such excellent characteristics through a simple process.

Another embodiment of the present invention provides an electrochemical device including the separator for the electrochemical device.

1 is a schematic diagram showing a separator for an electrochemical device and a method of manufacturing the same according to an embodiment of the present invention.
2 is a visual observation photograph and a scanning electron microscope (Scanning Electron Microscope, SEM) photograph of the separator for an electrochemical device prepared in one embodiment of the present invention.
3 is a discharge capacity measurement data of a secondary battery including a separator for an electrochemical device manufactured in one embodiment of the present invention.
4 is a discharge capacity measurement data of a secondary battery including a separator for an electrochemical device manufactured in one embodiment of the present invention.
FIG. 5 is life characteristic measurement data of a secondary battery including a separator for an electrochemical device manufactured in one embodiment of the present invention. FIG.
6 is a high temperature life characteristic measurement data of a secondary battery including a separator for an electrochemical device manufactured in an embodiment of the present invention.
7 is a scanning electron microscope (Scanning Electron Microscope, SEM) photograph of the positive electrode surface of the secondary battery after measuring the high temperature life characteristics of the secondary battery including a separator for an electrochemical device manufactured in an embodiment of the present invention.
FIG. 8 is measurement data of metal ion concentration on the surface of a negative electrode after measurement of high temperature life characteristics of a secondary battery including a separator for an electrochemical device manufactured in an embodiment of the present invention.
FIG. 9 is data obtained by measuring high temperature life characteristics after employing the separator for an electrochemical device manufactured in one embodiment of the present invention in a secondary battery including a lithium manganese nickel composite oxide (LMNO positive electrode) positive electrode active material.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless otherwise defined, all terms used in the present specification (including technical and scientific terms) may be used as meanings that can be commonly understood by those skilled in the art. When any part of the specification is to "include" any component, this means that it may further include other components, except to exclude other components unless otherwise stated. In addition, singular forms also include the plural unless specifically stated otherwise in the text.

In one embodiment of the present invention, a surface-functionalized inorganic material filled in pores between a first porous nonwoven fabric comprising a plurality of first polymer fibers and a plurality of first polymer fibers in the first porous nonwoven fabric Provided is a separator for an electrochemical device comprising a first sheet comprising nanoparticles.

The inorganic nanoparticles may be filled with a three-dimensional dense filling structure (super lattice) in the pores of the interconnected porous network between the first polymer fibers.

The separator for an electrochemical device may include pores positioned between surface-functionalized inorganic nanoparticles filled in the first sheet, and the surface-functionalized inorganic nanoparticles and the plurality of surface-functionalized inorganic nanoparticles. It further comprises pores located between the first polymer fibers, which comprise a uniform pore structure.

Thus, a channel through which ions can move through such a uniform pore structure is formed, and thus ion conductivity can be given. In addition, surface-functionalized inorganic nanoparticles filled in the pores between the first polymer fibers trap nickel ions, manganese ions, cobalt ions, etc. eluted from the anode of the electrochemical device, and these are trapped on the surface of the cathode. Reduced to solve the problem of lowering the electrical properties of the electrochemical device.

Pores located between the surface-functionalized inorganic nanoparticles filled in the first sheet, and uniformity located between the surface-functionalized inorganic nanoparticles and the plurality of first polymer fibers In one pore structure, the average diameter of the pores may be 0.001um or more and 10um or less, and the porosity of the entire first sheet may be 10% by volume or more and 95% by volume or less with respect to 100% by volume of the first sheet. .

The average diameter of the pores is a pore of a size suitable for movement of ions such as lithium, has a higher porosity than porous polymer membranes such as polyethylene (PE) separation membrane as described above, further improves the ion conductivity, It can contribute to the improvement of the electrical properties of the electrochemical device.

In addition, when the porosity is in the above range, it is possible to easily absorb the electrolyte and at the same time contribute to improve the performance of the electrochemical device applied by appropriately adjusting the mobility of the ions.

The surface functional group of the surface functionalized inorganic nanoparticles may be any functional group containing a non-covalent electron pair capable of coordinating with and trapping cations such as manganese ions, and is not particularly limited.

For example, thiol group (-SH), pyridine group (-RC ₅ H ₄ N), amine group (-NH ₃ ), cyano group (-CN), sulfide group (-R ₂ S), trifluorinated popularity A functional group such as (-PF ₃ ), or a combination thereof may be introduced to the surface of the inorganic nanoparticle.

In addition, the inorganic nanoparticles may be silica (SiO ₂ ), titania (TiO ₂ ), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), or the like, but is not limited thereto.

The average particle diameter of the inorganic nanoparticles may be 0.001um or more and 1um. When in the above range, the inorganic nanoparticles may be uniformly filled in the pores between the first polymer fibers in the first porous nonwoven fabric, it is possible to form a uniform pore structure in the first sheet. In addition, in the method of manufacturing by the dual electrospinning method described later, the dispersibility of the inorganic nanoparticles in the solution containing the inorganic nanoparticles can be maximized.

In addition, in terms of the content of the constituents in the first sheet, the content ratio of the first porous nonwoven fabric and the surface-functionalized inorganic nanoparticles of the first sheet (first porous nonwoven fabric: surface functionalized) (surface-functionalized) inorganic nanoparticles) may be 1: 1 to 1: 5 by weight. Within this range, the overall structure of the above-described first sheet can be achieved.

The first polymer fiber may be a heat resistant polymer, and for example, polyethylene terephthalate (PET), polyimide, poly amide, poly sulfonate, polyvinyl Polydenylidene fluoride (PVdF), polyacrylonitrile (PAN), polyethylene (PE), polypropylene (PP), polyisoprene, polyetherimide ( polyetherimide (PEI), polyethylene oxide (PEO), polypropylene oxide (PPO), polyvinyl pyrrolidone (PVP), polyacrylic acid (polyacrylate), polyvinyl alcohol, Polystyrene (PS), polymethyl methacrylate (poly (methylmetacrylate)), polyacrylamide (polyacrylamide), derivatives thereof, and mixtures thereof may be used. However, the present invention is not limited thereto. In addition, the weight average molecular weight (M _w ) of the first polymer fiber may be from more than 100000g / mol 2000000g / mol.

More specifically, nickel eluted from the anode Polymer fibers having a property of trapping ions, manganese ions, cobalt ions and the like can be used. For example, polymer fibers incorporating polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) may be used. Polyvinylpyrrolidone (PVP) is nickel On the other hand, while trapping ions, manganese ions, cobalt ions, etc. shows a somewhat unstable behavior in the organic electrolyte. Herein, a polyacrylonitrile (PAN) that is stable in an organic electrolyte may be mixed to have a property of being able to capture nickel ions, manganese ions, and cobalt ions while being stable in the organic electrolyte. In this case, the mixing ratio of the two polymer fibers may be 20:80 or more and 80:20 or less (PVP: PAN) by weight. However, the present invention is not limited thereto.

The average diameter of the first polymer fibers may be 0.001um or more and 100um or less. More specifically, the thickness may be 0.1 μm or more and 10 μm or less. The pores formed between the fibers within the average diameter range of the first polymer fiber is easy to fill the inorganic nanoparticles, it is possible to manufacture a membrane (first sheet) having a uniform pore structure. Through this, absorption of the electrolyte and movement of the ions in the separator may be smooth.

In addition, in the case of the separator for an electrochemical device comprising only the first sheet, the thickness may be 1um or more and 100um or less, specifically 5um or more and 30um or less. When the thickness is in the above range, the energy density of the electrochemical device to be applied can be excellent.

The separator for an electrochemical device according to the embodiment of the present invention may further include a second sheet including a conductive material positioned on the first sheet.

The conductive material may be an electronic conductive material, and by including a second sheet having excellent electronic conductivity on the first sheet, it is possible to improve the electrical properties of the electrochemical device. Specifically, an electron conduction network is established between the conductive materials in the second sheet to impart electron conductivity in the thickness direction of the electrode in contact with the second sheet, thereby improving output characteristics of the electrode and discharging characteristics of the electrochemical device. Electrical characteristics such as lifespan characteristics can be improved.

More specifically, the separator for an electrochemical device according to an embodiment of the present invention, a second porous nonwoven fabric positioned on the first sheet, including a plurality of second polymer fibers, and a plurality of second porous nonwoven fabric It may further include; a second sheet including a conductive material filled in the pores between the second polymer fibers.

This is to form a three-dimensional filling structure (super lattice) by filling a conductive material in the pores between the plurality of second polymer fibers forming a three-dimensional irregular and continuously connected aggregate. Thus, the electron conduction network between the conductive materials can be formed more uniformly, and thus the aforementioned improvement in electrical characteristics can be further maximized.

More specifically, the second sheet may include a conductive material on the surfaces of the plurality of second polymer fibers in the second porous nonwoven fabric. More specifically, the conductive material may be positioned to surround the surface of the second polymer fiber. Thus, the pore structure between the plurality of second polymer fibers in the porous nonwoven fabric can be maintained, thereby ensuring ion conductivity. Furthermore, an electron conduction network is established between the uniform conductive materials on the surface of the second polymer fiber, and the electron conduction in the thickness direction of the electrode in contact with the second sheet can be imparted, thereby improving the output characteristics of the electrode, and the electrochemical device. Electrical characteristics such as discharge characteristics, lifetime characteristics, etc. can be improved.

In this case, the thickness of the first sheet may be 1 µm or more and 100 µm or less, specifically 5 µm or more and 30 µm or less, and the thickness of the second sheet may be 1 µm or more and 20 µm or less, specifically 1 µm or more and 10 µm or less, more specifically. It may be 1um or more and 5um or less. As such, the second sheet may be formed to have a thickness relatively thinner than that of the first sheet, and as a result, the above-described thickness direction electron conductivity may be imparted to the electrode without decreasing the ion conductivity.

The porosity in the second sheet may be 5 vol% or more and 95 vol% or less with respect to 100 vol% of the total volume of the second sheet. When the porosity is in the above range, the electrolyte can be easily absorbed and the mobility of ions can be adjusted appropriately, contributing to the improvement of the performance of the electrochemical device.

However, when the volume exceeds 95% by volume, the distance between the conductive materials may be far from each other, thereby forming an electron conducting network. On the other hand, when less than 5% by volume, the porosity is too small may cause a problem that the ion conductivity of the three-dimensional structure current collector is lowered.

In addition, the average diameter of the pores in the second sheet may be 0.001um or more and 10um or less. If the pores in the second sheet is too small, a problem may occur that the ionic conductivity is lowered. If the pores in the second sheet is too large, it may cause a problem that the electron conductivity is not sufficiently provided.

An average diameter of the plurality of second polymer fibers in the second sheet may be 0.01 μm or more and 100 μm or less. Thus, the second sheet may have a uniform pore structure, so that the absorption of the electrolyte and the movement of the ions in the electrode may be smooth. However, if it exceeds 100 ㎛ it is difficult to form the appropriate pore size and porosity while forming a thin thickness. On the other hand, if it is less than 0.01um likewise may form a problem that it is difficult to obtain the desired pore size and porosity while forming the appropriate thickness. In this case, the above effects can be maximized.

The average particle diameter of the conductive material may be 0.001um or more and 10um or less. Conductive materials having an average diameter in this range can contribute to controlling the porosity in the second sheet in the aforementioned range. In addition, in the manufacturing method to be described later, by improving the dispersibility of the colloidal solution containing the conductive material, and minimize the occurrence of problems in the double electrospinning method, the pores of the second sheet finally obtained can be made uniform have.

However, if it exceeds 10 ㎛ may cause a problem that the dispersibility of the colloidal solution is not properly maintained, if less than 0.001 ㎛ may cause a problem that is difficult to handle because the size of the particles is too small, as described above It defines the average diameter of the conductive material.

On the other hand, a detailed description of each material included in the second sheet is as follows.

The plurality of second polymer fibers may be non-uniformly formed so as to form the porous nonwoven fabric, but is not particularly limited. When the polymers constituting the plurality of second polymer fibers are heat resistant polymers, it is advantageous to secure thermal stability of the separator. .

For example, polyethylene terephthalate (PET), polyimide, polyamide, poly sulfonate, polyvinylidene fluoride (PVdF), Polyacrylonitrile (PAN), polyethylene (PE), polypropylene (PP), polyetherimide (PEI), polyethylene oxide (PEO), polyvinylpyrrolidone (polyvinyl pyrrolidone, PVP), polyacrylate, polyvinyl alcohol, agarose, nylon 6 (nylon 6), polypyrrole, poly (3,4-ethylenedioxythiophene) (poly (3,4-ethylenedioxithiophene)), polyaniline, derivatives thereof, and mixtures thereof. In addition, the weight average molecular weight (M _w ) of the second polymer fiber may be 100000g / mol or more and 2000000g / mol or less.

More specifically, it may be a polymer fiber including an aromatic functional group. For example, polyetherimide (PEI) is possible. In this case, additional π-π interaction between the directional functional group and the conductive material in the polymer fiber enables the conductive material to be uniformly positioned on the fiber surface. Thus, a uniform pore structure between the polymer fibers can be maintained, the ion conductivity can be maintained.

The conductive material is not particularly limited as long as it is a material capable of forming an electron conducting network.

For example, carbon nanotubes, silver nanowires, nickel nanowires, gold nanowires, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene (poly (3,4-ethylenedioxithiophene)), polyaniline, polyaniline, derivatives thereof, or mixtures thereof, and more specifically, carbon nanotubes.

Another embodiment of the present invention, a first spinning step of simultaneously spinning a first solution comprising a first polymer, and a second solution containing surface-functionalized inorganic nanoparticles; The resultant of the first spinning step is pressed to form a surface functional group filled with pores between a first porous nonwoven fabric including a plurality of first polymer fibers and a plurality of first polymer fibers in the first porous nonwoven fabric. Provided is a method for producing a separator for an electrochemical device, comprising a first pressing step, to obtain a first sheet comprising functionalized inorganic nanoparticles.

This is an electrochemical device having excellent characteristics as described above by a simple process of simultaneously spraying two solutions, a first solution containing the first polymer and a second solution containing the surface functionalized inorganic nanoparticles. It is a method for producing a separation membrane for. The second solution is in the form of a colloidal solution in which surface functionalized inorganic nanoparticles are dispersed in a solvent.

Specifically, by simultaneously spinning the first solution and the second solution, an interconnected porous network is formed by a plurality of first polymer fibers serving as a support, and the surface functionalized inorganic nanoparticles are formed. By filling the three-dimensional dense filling structure can be formed.

The first spinning step may be performed through double electrospinning, double electrosprays, double sprays, and combinations thereof.

The content of the first polymer in the first solution may be one of 5 wt% or more and 30 wt% or less with respect to 100 wt% of the first solution, and the solvent in the first solution may include dimethylformamide (N, N -dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof. However, what is necessary is just a solvent which can dissolve the employ | adopted 1st polymer, and the kind of solvent is not limited to this. When the content of the first polymer is within the above range, it is possible to maintain an appropriate viscosity during double electrospinning, and to form a stable polymer porous nonwoven fabric by controlling the diameter and physical properties of the formed fiber.

In the second solution, the content of surface-functionalized inorganic nanoparticles may be 1% by weight or more and 50% by weight or less with respect to 100% by weight of the total amount of the second solution. The solvent is deionized water, isopropyl alcohol, isopropyl alcohol, buthalol, ethanol, hexanol, acetone, dimethylformamide, N-N-dimethylformamide, Dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof. However, the solvent may be any solvent capable of dispersing the surface functionalized inorganic nanoparticles, and the type of solvent is not limited thereto. When the content of the surface functionalized inorganic nanoparticles is within the above range, by appropriately adjusting the concentration of the second solution including the same, by applying a double electrospinning method can effectively form a composite structure with the polymeric porous nonwoven fabric.

In the first spinning step, the spinning speed of the first solution may be 1μl / min or more and 10μl / min or less, and the spinning speed of the second solution may be 30μl / min or more and 80μl / min or less. When the first solution spinning speed is not satisfied, the first solution may not be evenly spun and beads may be formed. In addition, when the range of the second solution spinning speed is not satisfied, the second solution may not be uniformly radiated and may fall into a large droplet state.

The first pressing step; In this case, the pressing may be a pressing method suitable for producing a separator, and is not limited to a specific method. For example, it may be performed by roll pressing.

Specific types of materials in the first sheet are the same as described above, and thus will be omitted.

According to another embodiment of the present invention, a method of manufacturing a separator for an electrochemical device includes: a second spinning step of spinning a fourth solution including a conductive material on a first sheet obtained in the first pressing step; And a second pressing step of pressing the resultant of the second spinning step to form a second sheet including a conductive material on the first sheet.

The conductive material may be an electronic conductive material, and by including a second sheet having excellent electronic conductivity on the first sheet, it is possible to improve the electrical properties of the electrochemical device. Specifically, an electron conduction network is established between the conductive materials in the second sheet to impart electron conductivity in the thickness direction of the electrode in contact with the second sheet, thereby improving output characteristics of the electrode and discharging characteristics of the electrochemical device. Electrical characteristics such as lifespan characteristics can be improved.

Specifically, the second spinning step is to simultaneously spin the third solution containing the second polymer, and the fourth solution containing the conductive material on the first sheet obtained in the first pressing step, 2, the pressing step may include: compressing the resultant of the second spinning step, positioned on the first sheet, between the porous nonwoven fabric including the plurality of second polymer fibers, and the plurality of second polymer fibers in the second porous nonwoven fabric. It may be to form a second sheet including a conductive material filled in the pores.

This is to form a three-dimensional super lattice by filling a conductive material in the pores between a plurality of second polymer fibers forming a three-dimensional irregular and continuously connected aggregate. Thus, the electron conduction network between the conductive materials can be formed more uniformly, and thus the aforementioned improvement in electrical characteristics can be further maximized.

More specifically, the second pressing step, the compression of the resultant of the second spinning step, is located on the first sheet, a porous nonwoven fabric comprising a plurality of second polymer fibers, and a plurality of in the second porous nonwoven fabric It may be to form a second sheet comprising a conductive material located on the surface of the second polymer fiber of.

Further, more specifically, in the second pressing step, the conductive material may be formed to be positioned to surround the plurality of second polymer fiber surfaces. Thus, the pore structure between the plurality of second polymer fibers in the porous nonwoven fabric can be maintained, thereby ensuring ion conductivity. Furthermore, an electron conduction network is established between the uniform conductive materials on the surface of the second polymer fiber, and the electron conduction in the thickness direction of the electrode in contact with the second sheet can be imparted, thereby improving the output characteristics of the electrode, and the electrochemical device. Electrical characteristics such as discharge characteristics, lifetime characteristics, etc. can be improved.

1 is a schematic diagram of a method for producing a separator for an electrochemical device and a prepared membrane according to an embodiment of the present invention through a two-stage double electrospinning.

This corresponds to a method of manufacturing a separator having excellent properties as described above by a simple process of simultaneously spraying a third solution containing a second polymer and a fourth solution containing a conductive material on the first sheet. do. The fourth solution is in the form of a colloidal solution in which the conductive material is dispersed on the solvent.

Specifically, by simultaneously spinning the fourth solution containing the conductive material with the third solution containing the second polymer on the first sheet, the interconnected porous network by a plurality of second polymer fibers (interconnected porous network) At the same time to form a second sheet of the conductive material is filled in the pores between the plurality of second polymer. More specifically, the conductive material may be formed to surround the surface of the second polymer.

Simultaneously spinning a third solution comprising a second polymer and a fourth solution comprising a conductive material on the first sheet; double electrospinning, double electrospray, double Spray, and combinations thereof.

The content of the second polymer in the third solution may be 5 wt% or more and 30 wt% or less with respect to 100 wt% of the total amount of the third solution, and the solvent of the third solution may be methyl formamide (N, N− dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof. However, what is necessary is just a solvent which can melt | dissolve the employ | adopted polymer, and does not limit the kind of solvent to this.

If the content of the second polymer in the third solution exceeds 30% by weight, the spinning of the third solution is not smooth, in particular, the problem that the spinning is difficult to harden at the end of the nozzle that the third solution is spinning May occur. On the contrary, if it is less than 5% by weight, a problem may occur in which the third solution is not evenly spun and beads are formed.

The content of the conductive material in the fourth solution may be 0.01 wt% or more and 30 wt% or less with respect to 100 wt% of the fourth solution, and the solvent of the fourth solution may be deionized water or isopropyl alcohol ( iso-propylalcohol, buthalol, ethanol, hexanol, acetone, dimethylformamide (N, N-dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pi It may be a rolledon (N, N-Methylpyrrolidone), or a mixture thereof. However, the solvent may be any solvent capable of dispersing the conductive material, and the type of solvent is not limited thereto.

When the content of the conductive material in the fourth solution is more than 30% by weight, the conductive material in the fourth solution is difficult to be evenly dispersed. When the content of the conductive material is less than 0.01% by weight, the content of the conductive material is too small to form an electron conducting network. Problems may arise.

In addition, in the spinning step; the spinning speed of the third solution may be 1μl / min or more 10μl / min or less, the spinning speed of the fourth solution may be more than 30μl / min 80μl / min or less. When the third solution spinning rate is not satisfied, a problem may occur in that the third solution is not evenly spun and beads are formed. In addition, when the range of the fourth solution spinning speed is not satisfied, the fourth solution may not be uniformly spun and may fall into a large drop state.

Specific types of materials in the second sheet are the same as described above, and thus will be omitted.

In the second pressing step, the pressing may be a pressing method suitable for producing a separator, and is not limited to a specific method. For example, it may be performed by roll pressing.

Yet another embodiment of the present invention provides an electrochemical device including a separator for an electrochemical device according to the embodiment of the present invention.

For example, the electrochemical device may include a lithium secondary battery, a supercapacitor, 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 may be any one selected from the group containing.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.

Preparation Example: Preparation of Raw Material Solution

Preparation of First Solution Polyvinylpyrrolidone (PVP, weight average molecular weight: 150000 g / mol, Aldrich) and polyacrylonitrile (polyacrylonitrile, PAN, weight average molecular weight: 1300000 g / mol, Aldrich) N, N-dimethylacetamide, DMF) was dissolved for 12 hours at 70 ℃ to prepare a first solution.

The weight ratio of polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) in the first solution is 1: 1, and that of polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) in the first solution is The total amount was made 20 weight% with respect to 100 weight% of 1st total amounts of solutions.

Preparation of Second Solution First, as surface functionalized inorganic nanoparticles, precursor of SH-SiO ₂ is (3-mercapdopropyl) triethoxysilane ((3-mercaptopropyl) triethoxysilane.MPTMS, Aldrich). It synthesize | combined by the sol-gel method.

Subsequently, the synthesized SH-SiO ₂ was added to a solvent in which acetone and n-butanol were mixed at a volume ratio of 7: 3 to be dispersed, thereby preparing a second solution in the form of a colloidal solution.

The content of SH-SiO ₂ in the second solution was 5% by weight relative to 100% by weight of the total amount of the second solution.

Preparation of the third solution Polyetherimide (polyetherimide, PEI, product name: Ultem 1000) was added to dimethylacetamide (N, N-dimethylactamide, DMA) and N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone , NMP) was dissolved in a solvent in a 1: 1 weight ratio to prepare a third solution.

The content of polyether amide (PEI) in the third solution was 25% by weight based on 100% by weight of the total amount of the third solution.

Preparation of Fourth Solution Carbon nanotubes (conductive carbon nanotubes, Nanocyl), which can maintain a uniform spraying state, are mixed in a solvent in which deionized water and isopropyl alcohol are mixed at a 9: 1 weight ratio. Was dissolved to prepare a fourth solution in the form of a colloid.

The content of the carbon nanotubes in the fourth solution was 0.5% by weight based on 100% by weight of the total amount of the fourth solution.

Example 1 Preparation of Separation Membranes for Electrochemical Devices

After injecting the first solution and the second solution into the electrospinning apparatus (purchased: nano NC), the injection rate of the first solution is 3.5μl / min, the injection rate of the second solution is 50μl / min , 285 minutes at the same time (double electrospinning), and then roll-pressing (purchased: Gibae ANT Co., Ltd.) to prepare a separator (hereinafter referred to as 'first sheet') The thickness of the first sheet As can be seen in Figure 2b was about 25um.

Example 2 Preparation of Separation Membranes for Electrochemical Devices

Using the same electrospinning apparatus, on the first sheet, the third solution and the fourth solution were simultaneously spun (double electrospinning) at a spraying rate of 5 μl / min and 65 μl / min, respectively, followed by roll pressing Thus, a separator in which a second sheet having a thickness of about 3 μm was formed on the first sheet having a thickness of about 25 μm was obtained. (FIG. 2B).

Example 3 Fabrication of a Lithium Secondary Battery

A pouch type lithium secondary battery using the separator obtained in Example 1 was prepared.

As the positive electrode, a positive electrode mixture slurry was coated on the surface of an aluminum (Al) current collector and roll rolled to prepare a positive electrode having a loading of the active material of about 7 mg / cm ² . The positive electrode mixture slurry is a positive electrode active material 92% by weight of Li-rich layered cathode active material 4.9Li ₂ MnO ₃ 0.51LiNi _0.37 Co _0.24 Mn _0.39 O ₂ % Was added to the solvent N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, NMP) to prepare a slurry form.

Li metal was used as the cathode.

The electrolyte was dissolved in an organic solvent (EC: DMC = about 1: 1 (v: v)) so that the concentration of LiPF ₆ was about 1 M to prepare a non-aqueous electrolyte.

The separator obtained in Example 1 was disposed between the positive electrode and the negative electrode, and the electrolyte was injected to prepare a pouch type secondary battery.

Example 4 Fabrication of a Lithium Secondary Battery

A pouch type secondary battery was manufactured in the same manner as in Example 3, except that the separator obtained in Example 2 was used.

Example 5 Fabrication of a Lithium Secondary Battery

A slurry of positive electrode active material, LiNi _{0 . 5} Mn _{1 .} 85 wt% of ₅ O ₄ positive electrode active material, 7.5 wt% of carbon black as the conductive material, and 7.5 wt% of polyvinylidene fluoride (PVdF) as the binder, N-Methyl-2-pyrrolidone (N-Methyl) A pouch type secondary battery was prepared in the same manner as in Example 4, except that 2-pyrrolidone (NMP) was used to prepare a slurry.

Comparative Example 1

Using a polyethylene (PE) separator, a pouch type secondary battery was manufactured in the same manner as in Example 2.

Comparative Example 2

Using a polyethylene (PE) separator, a pouch type secondary battery was manufactured in the same manner as in Example 5.

Experimental Example  1: Visual and scanning electron microscope (Scanning Electron Microscope, SEM Photographic observation

For the separator prepared in Example 2, visual observation and SEM photograph (device name: S-4800, manufacturer: Hitachi) were observed, and the results are shown in FIG. 2.

2A is an SEM image corresponding to the first sheet of Example 2, and an average particle diameter of about 1 μm to 100 μm between the polymer fibers (PAN / PVP nanofiber) in the porous nonwoven fabric having an average diameter of about 1.5 μm. It can be seen that the large pores of are completely filled with inorganic nanoparticles (SH-silica) surface functionalized with a thiol group (-SH) having an average particle diameter of about 1 um. In addition, it can be seen that uniform pores having an average diameter of about 100 nm are formed between the filled inorganic nanoparticles or between the inorganic nanoparticles and the polymer fibers in the porous nonwoven fabric. In addition, the porosity in the first sheet was about 55%.

2C is an SEM image corresponding to the second sheet of Example 2, where carbon nanotubes are uniformly wrapped along polymer fibers (PEI nanofiber) in a porous nonwoven fabric having an average diameter of about 1 μm. This is due to the interaction between the polymer fibers (PEI) and the carbon nanotubes, it can be seen that the uniform pore structure of the average diameter of the second sheet in the range of about 0.001um or more and 10um or less. In addition, the porosity in the second sheet was about 75%.

2b is a photograph observing the appearance photograph and the cross section of the separator of Example 2. Since the separator of Example 2 is composed of two layers of the first sheet and the second sheet, the separator has a different color from front to back, and has very flexible physical properties. In the cross section, the large pores present in the porous nonwoven fabric of the first sheet were completely filled by the inorganic nanoparticles, and it can be seen that a uniform pore structure was formed by the introduced inorganic nanoparticles. Since the second sheet has a thinner thickness than the first sheet, the second sheet exhibits excellent electrical conductivity without disturbing ion conduction, thereby improving electrical characteristics of the electrochemical device.

In Example 2 manufactured using the dual electrospinning technique and roll pressing, since the polymer fibers and the inorganic nanoparticles in the porous nonwoven fabric are hybridized to form a separator, the inorganic nanoparticles do not detach even after the membrane is folded and pinned. It can be seen that one pore structure is maintained. In addition, it can be confirmed that the first sheet and the second sheet do not detach. (Fig. 2 d and e)

Experimental Example 2 Evaluation of Battery Characteristics

(1) discharge capacity measurement

For the pouch type secondary batteries of Comparative Examples 1, 3, and 4, the charging current rate was maintained at 0.2C, and the discharge behavior was shown in FIG. 3 when the discharge current rate was 5.0C. In addition, the results of observing the discharge capacity while increasing the discharge current rate from 0.2C to 10C are shown in FIG.

As the discharge current rate increases, the pouch-type secondary batteries of Examples 3 and 4 show a higher discharge capacity than Comparative Example 1. This is because the separators of Examples 1 and 2 included in the pouch-type secondary batteries of Examples 3 and 4, respectively, have higher porosity and uniform pore structure than the polyethylene (PE) separator included in Comparative Example 1. . In addition, the pouch type secondary battery of Example 4 exhibits the highest discharge capacity because the second sheet into which the separator of Example 2 included in Example 4 is introduced has excellent electron and ion conductivity.

(2) life characteristics

The results of observing the discharge capacity results after 150 cycles with the charge and discharge current rates of 1.0C for the pouch-type secondary batteries of Comparative Examples 1, 3, and 4 were shown in FIG. 5.

The pouch type secondary battery of Example 4 shows the highest discharge capacity after 150 cycles. This is because of the high porosity and uniform pore structure of the first sheet of the separator of Example 2 included in the secondary battery of Example 4, and the synergistic effect of excellent electrical conductivity by the second sheet.

(3) high temperature life characteristics

For the pouch type secondary batteries of Comparative Examples 1 and 4, the discharge capacity results after 50 cycles at a high temperature (60 ° C.) were shown in FIG. 6 with the charge and discharge current rates as 1.0C.

The pouch type secondary battery of Example 4 exhibits high temperature life characteristics superior to the secondary battery of Comparative Example 1. This is due to the polymer fibers (PAN / PVP nanofiber) and inorganic nanoparticles (SH-silica) in the functional porous nonwoven fabric of Example 2 separator included in Example 4.

Improved high temperature lifespan by capturing metal ions such as Mn ions, which are eluted at the anode and passed through the separator to the cathode, and then reduced at the cathode through functional porous nonwoven fabric and surface functionalized inorganic nanoparticles. I was.

Specifically, PVP capable of catching metal ions such as Mn ions may be mixed with PAN to ensure stability in the electrolyte and at the same time to capture metal ions. In addition, the surface functionalized inorganic nanoparticles can capture the metal ions through coordination bonds with the metal ions of the non-covalent electron pair of the thiol group (-SH) on the surface.

After observing the high temperature life characteristics shown in Figure 6, the SEM photograph (device name: S-4800, manufacturer: Hitachi) of the surface of the positive electrode was observed, the results are shown in Figure 7 below.

While the anode surface included in Comparative Example 1 was heavily contaminated by by-products, the anode surface included in Example 4 was observed to be relatively clean.

In addition, after observing the high temperature life characteristics shown in Figure 6, the amount of metal ions moved to the cathode was analyzed by ICP-MS (ELAN DRC-II, Perkin Elmer), the results are shown in Figure 8 below.

In the negative electrode included in Example 4 it can be seen that the amount of metal ions less than the negative electrode included in Comparative Example 1. This is because the membrane of Example 2 included in Example 4 captured metal ions such as Mn ²⁺ eluted from the anode through the functional porous nonwoven fabric and the surface functionalized inorganic nanoparticles.

(4) Application to LMNO anode

With respect to the pouch type secondary batteries of Comparative Examples 2 and 5, the discharge capacity results after 100 cycles at a high temperature (55 ° C) were shown in FIG.

The pouch type secondary battery of Example 5 exhibits high temperature life characteristics superior to the secondary battery of Comparative Example 2. This is because of the functional porous nonwoven fabric (PAN / PVP nanofiber) and surface functionalized inorganic nanoparticles (SH-silica) of Example 2 separator included in Example 5. After eluting from the positive electrode and moving to the negative electrode through the separator, the metal ions are reduced at the negative electrode to capture the battery ions through the functional porous non-woven fabric and inorganic nanoparticles to improve the high temperature life characteristics. Through this, it is possible to confirm the versatility of the separator of Example 2.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (41)

Surface functionalization filled with a first porous nonwoven fabric comprising a plurality of first polymer fibers, having a interconnected pore structure between the plurality of first polymer fibers, and pores between the plurality of first polymer fibers in the first porous nonwoven fabric A first sheet comprising surface-functionalized inorganic nanoparticles,
The surface functional groups of the surface-functionalized inorganic nanoparticles include a thiol group (-SH), a pyridine group (-RC ₅ H ₄ N), an amine group (-NH ₃ ), and a cyano group (-CN) , Sulfide group (-R ₂ S), trifluorination popularity (-PF ₃ ), or a combination thereof,
The first polymer fiber is one containing polyvinylpyrrolidone (PVP),
The surface functional group of the surface-functionalized inorganic nanoparticles, and the first polymer fiber adsorb the metal cations eluted at the anode of the electrochemical device,
Separators for Electrochemical Devices. In claim 1,
Pores located between the surface-functionalized inorganic nanoparticles filled in the first sheet, and pores located between the surface-functionalized inorganic nanoparticles and the plurality of first polymer fibers To further include,
Separators for Electrochemical Devices. In claim 2,
Pores located between the surface-functionalized inorganic nanoparticles filled in the first sheet, and pores located between the surface-functionalized inorganic nanoparticles and the plurality of first polymer fibers The average diameter of
1um or more and less than 100um,
Separators for Electrochemical Devices. In claim 2,
The porosity of the first sheet is,
For 100% by volume of the total volume of the first sheet,
10 volume% or more and 95 volume% or less,
Separators for Electrochemical Devices. In claim 1,
The thickness of the first sheet,
1um or more and less than 100um,
Separators for Electrochemical Devices. delete In claim 1,
The average particle diameter of the surface-functionalized inorganic nanoparticles,
What is 0.001um or more and 1um or less,
Separators for Electrochemical Devices. In claim 1,
The first polymer fiber is a mixture of polyvinylpyrrolidone (PVP) and polyacrylonitrile (polyacrylonitrile, PAN),
Separators for Electrochemical Devices. In claim 8,
The mixing ratio (PVP: PAN) of the polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) is
It is represented by 20:80 or more and 80:20 or less by weight,
Separators for Electrochemical Devices. In claim 1,
The average diameter of the first polymer fiber,
What is 0.001um or more and 100um or less,
Separators for Electrochemical Devices. In claim 1,
The content ratio (first porous nonwoven fabric: surface-functionalized inorganic nanoparticles) of the first porous nonwoven fabric and the surface-functionalized inorganic nanoparticles of the first sheet is based on weight. to,
It is 1: 1 or more and 1: 5 or less,
Separators for Electrochemical Devices. In claim 1,
Further comprising; a second sheet positioned on the first sheet, the second sheet comprising an electronic conductive material,
Separators for Electrochemical Devices. In claim 12,
The second sheet further includes a second porous nonwoven fabric including a plurality of second polymer fibers,
Wherein the electronic conductive material is a form filled in the pores in the second porous nonwoven fabric,
Separators for Electrochemical Devices. In claim 13,
The electron conductive material is located on the surface of the plurality of second polymer fibers in the second porous nonwoven fabric,
Separators for Electrochemical Devices. The method of claim 14,
The electronic conductive material located on the surface of the plurality of second polymer fibers in the second porous nonwoven fabric,
It is located in the form surrounding the surface of the second polymer fiber,
Separators for Electrochemical Devices. The method of claim 15,
The average diameter of the pores in the second sheet is,
What is 0.001um or more and 10um or less,
Separators for Electrochemical Devices. The method of claim 15,
The porosity in the second sheet is,
For 100% by volume of the total volume of the second sheet,
5 vol% or more and less than 95 vol%,
Separators for Electrochemical Devices. The method of claim 15,
The thickness of the second sheet is,
1um or more and 20um or less,
Separators for Electrochemical Devices. The method of claim 15,
The second polymer fiber,
Polyetherimide (PEI),
Separators for Electrochemical Devices. The method of claim 15,
The average diameter of the second polymer fiber,
It is 0.01um or more and 100um or less,
Separators for Electrochemical Devices. In claim 12,
The electron conductive material,
Carbon nanotubes, silver nanowires, nickel nanowires, gold nanowires, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene (poly (3,4) -ethylenedioxithiophene)), polyaniline (polyaniline), derivatives thereof, or mixtures thereof,
Separators for Electrochemical Devices. A first spinning step of simultaneously spinning a first solution comprising a first polymer, and a second solution comprising surface-functionalized inorganic nanoparticles;
Compressing the result of the first spinning step, the surface functionalization is filled in the pores of the first porous nonwoven fabric comprising a plurality of first polymer fibers, and interconnected structure between the plurality of first polymer fibers in the first porous nonwoven fabric A first compression step of obtaining a first sheet comprising surface-functionalized inorganic nanoparticles;
The surface functional groups of the surface-functionalized inorganic nanoparticles include a thiol group (-SH), a pyridine group (-RC ₅ H ₄ N), an amine group (-NH ₃ ), and a cyano group (-CN) , Sulfide group (-R ₂ S), trifluorination popularity (-PF ₃ ), or a combination thereof,
The first polymer fiber includes polyvinylpyrrolidone (PVP),
The surface functional group of the surface-functionalized inorganic nanoparticles, and the first polymer fiber adsorb the metal cations eluted at the anode of the electrochemical device,
Method of manufacturing a separator for an electrochemical device. The method of claim 22,
The first spinning step,
Is performed through double electrospinning, double electrosprays, double sprays, and combinations thereof,
Method of manufacturing a separator for an electrochemical device. The method of claim 22,
The content of the first polymer in the first solution,
5 wt% or more and 30 wt% or less of the total amount of the first solution,
Method of manufacturing a separator for an electrochemical device. The method of claim 22,
The solvent in the first solution,
Dimethylformamide (N, N-dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof,
Method of manufacturing a separator for an electrochemical device. The method of claim 22,
In the second solution, the content of surface-functionalized inorganic nanoparticles is
With respect to 100% by weight of the total amount of the second solution,
It is 1 weight% or more and 50 weight% or less,
Method of manufacturing a separator for an electrochemical device. The method of claim 22,
The solvent in the second solution,
Deionized water, isopropylalcohol, buthalol, ethanol, hexanol, acetone, dimethylformamide (N, N-dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof,
Method of manufacturing a separator for an electrochemical device. The method of claim 22,
In the first spinning step,
The spinning speed of the first solution is
1 μl / min or more and 10 μl / min,
Method of manufacturing a separator for an electrochemical device. The method of claim 22,
In the first spinning step,
The spinning speed of the second solution is
What is 30μl / min or more and 80μl / min,
Method of manufacturing a separator for an electrochemical device. The method of claim 22,
A second spinning step of spinning a fourth solution containing an electronic conductive material on the first sheet obtained in the first pressing step; And
And a second pressing step of pressing the resultant of the second spinning step to form a second sheet including an electronic conductive material on the first sheet.
Method of manufacturing a separator for an electrochemical device. The method of claim 30,
The second spinning step,
On the first sheet obtained in the first pressing step, the third solution containing the second polymer, and the fourth solution containing the electronic conductive material are spun at the same time,
The second pressing step;
Compressing the resultant of the second spinning step, the second porous nonwoven fabric disposed on the first sheet and including a plurality of second polymer fibers, and pores between a plurality of second polymer fibers in the second second porous nonwoven fabric. To form a second sheet comprising a filled electron conductive material,
Method of manufacturing a separator for an electrochemical device. The method of claim 31,
The second pressing step;
Compressing the resultant of the second spinning step, the second porous nonwoven fabric disposed on the first sheet, the second porous nonwoven fabric including a plurality of second polymer fibers, and the plurality of second polymer fibers in the second porous nonwoven fabric Forming a second sheet comprising an electronically conductive material,
Method of manufacturing a separator for an electrochemical device. The method of claim 32,
In the second pressing step;
Wherein the electronic conductive material is located in a form surrounding the surface of the plurality of second polymer fibers,
Method of manufacturing a separator for an electrochemical device. The method of claim 33,
The second spinning step,
Is performed through double electrospinning, double electrosprays, double sprays, and combinations thereof,
Method of manufacturing a separator for an electrochemical device. The method of claim 33,
The content of the second polymer in the third solution,
To 100% by weight of the total amount of the third solution,
5 wt% or more and 30 wt% or less,
Method of manufacturing a separator for an electrochemical device. The method of claim 33,
The solvent in the third solution,
Dimethylformamide (N, N-dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof,
Method of manufacturing a separator for an electrochemical device. The method of claim 33,
The content of the electron conductive material in the fourth solution is,
With respect to 100% by weight of the total amount of the fourth solution,
It is 0.01 weight% or more and 30 weight% or less,
Method of manufacturing a separator for an electrochemical device. The method of claim 33,
The solvent in the fourth solution,
Deionized water, isopropylalcohol, buthalol, ethanol, hexanol, acetone, dimethylformamide (N, N-dimethylformamide), dimethylacetamide (N, N-dimethylacetamide), methyl pyrrolidone (N, N-Methylpyrrolidone), or a mixture thereof,
Method of manufacturing a separator for an electrochemical device. The method of claim 33,
In the second spinning step,
The spinning speed of the third solution is
1 μl / min or more and 10 μl / min or less,
Method of manufacturing a separator for an electrochemical device. The method of claim 33,
In the second spinning step,
The spinning speed of the fourth solution is
What is 30μl / min or more and 80μl / min or less,
Method of manufacturing a separator for an electrochemical device. Claim 1 to 5, and comprising a separator for any one of the electrochemical device of any one of claims 7 to 21,
Electrochemical devices.

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