KR102161347B1 - Nanoporous transition metal alloy and manufacturing the same - Google Patents

Abstract

The present invention relates to a nanoporous transition metal alloy ribbon and a method of manufacturing the same, and more particularly, a specific transition metal that is phase separated by a rapid solidification method as an alloy raw material is selected, and the electrochemical properties of the transition metal selected as the alloy raw material are selected. The present invention relates to a nanoporous transition metal alloy ribbon manufactured by selectively removing only a specific transition metal using the difference in phosphorus corrosion tendency and a method of manufacturing the same.

Description

Nanoporous transition metal alloy and manufacturing method thereof {Nanoporous transition metal alloy and manufacturing the same}

The present invention relates to a super capacitor electrode, and more particularly, to a nanoporous transition metal alloy useful as a material for a super capacitor electrode, and a method of manufacturing the same.

Recently, as devices such as smart phones, notebook computers, electric vehicles, and wearable devices have been developed, interest in highly efficient energy storage devices is increasing. As an example, super capacitors are in the spotlight in the field of energy storage devices due to their high output and high durability. However, a super capacitor has a disadvantage in that it has a lower energy density than a lithium ion battery.

Recently, a supercapacitor using nickel hydroxide (Ni(OH)2) capable of realizing a high energy density has been studied. The stacked nanostructured nickel hydroxide has the advantage of having a large space for storing ions due to the wide interlayer spacing between the lattice, but nickel hydroxide has the disadvantage of frequent charge traps under conditions such as high current density because of low conductivity. have. Accordingly, it is difficult to apply the nickel hydroxide supercapacitor to various fields requiring high performance.

In addition, nanoporous gold (NPG) electrodes have also been studied as current collectors of super capacitors. For example, electrodes such as MnO2/NPG and SnO2/NPG have been developed to use the NPG as a current collector of a super capacitor, but the electric capacity is not high or cannot be maintained under various conditions such as high current density and long time use. there is a problem. This is because the metal oxide/NPG electrode is in the form of a metal/semiconductor contact, so it is not ideal for high electric capacity, and active materials fill the pores of the NPG current collector, reducing the amount of stored charge and reducing the amount of the electrolyte through the pores in the NPG network. It is believed that this is because it interferes with ion transport.

Accordingly, as a result of research by the present inventors, the present invention was completed by developing a novel high-entropy alloy ribbon that can replace the conventional electrode material for a super capacitor.

Korean Patent Registration No. 10-1540357

The technical problem to be solved by the present invention is to provide a nanoporous transition metal alloy for a super capacitor having a high energy density.

In addition, another technical problem to be solved by the present invention is to provide a method of manufacturing a nanoporous transition metal alloy for a super capacitor having the above-described advantages.

In addition, another technical problem to be solved by the present invention is to provide an electrode containing a nanoporous transition metal alloy for a super capacitor having the above advantages.

In addition, another technical problem to be solved by the present invention is to provide a super capacitor including an electrode, a counter electrode, and an electrolyte containing a nanoporous transition metal alloy having the above-described advantages.

According to an embodiment of the present invention, the first phase is a high entropy alloy composed of a ternary or higher metal selected from the group consisting of Ni, Ti, Zr, Nb, Cr, Cu, Fe, and Co, uniformly distributed on a nano scale. And a nanoporous transition metal alloy in which the second phase is selectively removed from a high entropy alloy comprising a second phase that is composed of at least one transition metal selected from the group consisting of Al and Mn and is not miscible with the first phase. Can be provided.

According to an embodiment, the elements constituting the first phase tend to have similar atomic sizes and crystal structures, and the transition metal constituting the second phase is compared with the transition metal constituting the first phase. As the value (Hmix) is large, negative or positive, the tendency of electrochemical corrosion may be large.

According to an embodiment, the thickness of the nanoporous transition metal alloy may range from 20 μm to 300 μm, and the size of the nanoporosity may range from 20 nm to 200 nm.

According to an embodiment, the porosity of the nanoporous transition metal alloy may be 30 to 70% by volume.

According to another embodiment of the present invention, a ternary or higher metal selected from the group consisting of Ni, Ti, Zr, Nb, Cr, Cu, Fe, and Co constituting the first phase, which is a high entropy alloy, and the first phase Preparing a molten metal in which a precursor of at least one transition metal selected from the group consisting of Al and Mn constituting a second phase that is not mixed with is melted; Solidifying the molten metal by a rapid solidification method to generate a high-entropy alloy in which a first phase that is a high-entropy alloy and a second phase that is not miscible with the first phase are uniformly distributed on a nano scale; And selectively removing the second phase from the high entropy alloy. A method of manufacturing a nanoporous transition metal alloy may be provided.

In one embodiment, the elements constituting the first phase tend to have similar atomic sizes and crystal structures, and the transition metal constituting the second phase is the value of the heat of mixing compared to the transition metal constituting the first phase. While (Hmix) is large, the tendency of electrochemical corrosion may be large. The porosity of the alloy may be controlled by adjusting the composition ratio of the metal constituting the first phase and the second phase. The composition ratio of the transition metal constituting the first phase and the second phase is A(100-x)Bx (where x is the composition ratio of the transition metal constituting the second phase among the total transition metals and has a range of 10 to 70 ) Can be.

In one embodiment, the transition metal constituting the first phase may achieve an equiatomic ratio within an error tolerance of 5 to 40 at.%.

In an embodiment, the step of generating the high entropy alloy may include rapidly solidifying the molten metal while controlling the molten metal at a cooling rate of 104 K/sec to 106 K/sec.

In one embodiment, the rapid solidification step may be performed by a melt spinning method.

In one embodiment, the step of selectively removing the second phase may include electrochemical corrosion by immersing the high entropy alloy in an acidic or basic solution.

In one embodiment, the first phase may remain in the nanoporous transition metal alloy as a passivation phenomenon.

In an embodiment, in the step of selectively removing the second phase, the porosity of the alloy may be controlled by adjusting the concentration and immersion time of the acidic or basic solution.

According to another embodiment of the present invention, a super capacitor including the nanoporous transition metal alloy according to claim 1 may be provided.

According to the present invention, a precursor alloy having a uniform distribution of multiple phases can be provided by rapidly solidifying a multi-element transition metal molten metal (or a high entropy alloy molten metal) having a phase separation phenomenon and having different electrochemical corrosion tendency. have.

In addition, by selectively removing an electrochemically activated phase among a plurality of uniform phases of the multi-element transition metal alloy, it is possible to provide a transition metal alloy having uniform porosity on a nano scale.

In addition, by adjusting the composition ratio of the electrochemically activated phase and the deactivated phase, or by controlling the degree of removal of the electrochemically activated phase, the size and porosity of the nanopores distributed on the surface or inside of the transition metal alloy can be easily improved. Can be controlled.

In addition, the nano-scale transition metal alloy having uniform porosity can significantly improve dynamic properties and life stability when used as an electrode material for a super capacitor, and as a result, an improvement having high capacity, high energy density and semi-permanent life. Super capacitors can be provided.

1 is a flowchart illustrating a method of manufacturing a transition metal alloy having uniform porosity on a nano scale according to an embodiment of the present invention.
2 is a schematic diagram for explaining the structure of a melt spinning apparatus for producing a transition metal alloy in which at least two or more phases are uniformly distributed according to an embodiment of the present invention.
3 is a view for explaining a method for selectively removing an electrochemically activated phase of a multi-element transition metal alloy according to an embodiment of the present invention.
4 is a cross-sectional view of a precursor alloy having a uniform distribution of multiple phases according to an embodiment of the present invention.
5 is an electron scanning microscope (SEM) photograph for comparing changes in the surface of an alloy before and after electrochemical decorrosion according to an embodiment of the present invention.
6 is an X-ray diffraction analysis result graph for comparing changes in the surface of an alloy before and after electrochemical decorrosion according to an embodiment of the present invention.

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

The embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art, and the following examples may be modified in various other forms, and the scope of the present invention is as follows. It is not limited to the examples. Rather, these embodiments are provided to make the present disclosure more faithful and complete, and to completely convey the spirit of the present invention to those skilled in the art.

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

The terms used in this specification are used to describe specific embodiments, and are not intended to limit the present invention. As used herein, the singular form may include the plural form unless the context clearly indicates another case. Further, when used herein, "comprise" and/or "comprising" refers to the presence of the mentioned shapes, numbers, steps, actions, members, elements and/or groups thereof. And does not exclude the presence or addition of one or more other shapes, numbers, actions, members, elements, and/or groups.

1 is a flowchart illustrating a method of manufacturing a transition metal alloy having uniform porosity on a nano scale according to an embodiment of the present invention.

Referring to Figure 1, the manufacturing method is a first step of preparing a molten metal in which a multi-element metal precursor is melted, and by rapidly solidifying the molten metal, uniformly distributed multi-element transition metal elements or phases are formed. A second step of generating a transition metal alloy having, and a third step of removing elements or phases having different electrochemical corrosion tendency from the transition metal alloy.

The multi-element metal precursor may include at least three or more transition metal elements. In one embodiment, the transition metal element is titanium (Ti), zirconium (Zr), niobium (Nb), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni) And copper (Cu). However, the present invention is not limited to these transition metal elements. For example, the multi-element metal precursor may further include a post-transition metal element such as aluminum (Al) or a metalloid element such as boron and silicon.

In an embodiment of the present invention, the multi-element metal precursor is at least one of Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Hf and W It includes five or more metal elements, and may include a high-entropy alloy exhibiting a phase separation phenomenon of nanoscale. The phase separation phenomenon may appear as each metal component of the high entropy alloy, or may appear as an alloy component including at least two metal components. Alternatively, phase separation of one metal component and phase separation of an alloy component including a plurality of metal components may be mixed.

In one embodiment, at least one metal element or at least one phase constituting the high entropy alloy may have different electrochemical corrosion tendencies. Specifically, certain metal elements or phases may have a high electrochemical corrosion tendency, other metal elements or phases may have a small electrochemical corrosion tendency, and other metal elements or phases may not undergo electrochemical corrosion.

In one embodiment, the high-entropy alloy is Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Hf, and more than five elements selected from the group consisting of W It may include a high entropy alloy in which two or more phases appear as a metal. The first phase contains a large amount of an element that makes the passivation film well or refers to a phase that is electrochemically inactivated compared to the second phase, and the second phase contains a large amount of an alloying element having strong corrosion tendency or is electrochemically compared to the first phase. May refer to an activated phase. For example, in a high entropy alloy composed of Ni, Co, Cr, Fe and Al, the second phase composed of Al may be selectively corroded.

The second step may be performed through a rapid solidification method such as a melt spinning method to be described later. By rapidly solidifying the molten metal through the melt spinning, a high entropy alloy including at least two or more phases of a nanoscale uniformly distributed may be produced. The at least two or more phases may be classified into an electrochemically activated phase and an electrochemically deactivated phase, and the electrochemically activated phase may be subdivided and classified according to a degree of corrosion tendency. The present invention is a rapid solidification method, and a melt spinning method is used, but the present invention is not limited thereto, and any method capable of forming a nanoscale uniformly distributed phase in a high entropy alloy can be applied. .

Thereafter, from a high entropy alloy comprising at least two or more phases of uniformly distributed nanoscale produced in the second step, optionally at least one electrochemically, to form a nanoscale uniform porous transition metal alloy. A third step of removing the activated phase may be performed.

In the third step, electrochemical corrosion occurs after the high-entropy alloy is immersed in an acidic solution or an alkaline solution, thereby selectively corroding the electrochemically activated phase of the high-entropy alloy. At this time, the electrochemically deactivated phase of the high entropy alloy exhibits a passivation phenomenon, so that the electrochemically deactivated phase remains without corrosion.

Referring back to FIG. 1, in selecting a metal element for conceiving a high entropy alloy, a merchant who is electrochemically deactivated in consideration of at least one of the value of the heat of mixing (Hmix) and the degree of electrochemical corrosion tendency of each transition metal. The first phase and the electrochemically activated second phase may be divided into constituent elements and selected.

In addition, the transition metal selected as a constituent material of the high entropy alloy may include a characteristic in which a phase separation phenomenon occurs. In particular, in selecting the transition metal elements representing the first phase and the second phase, a more complete phase separation between the first phase and the second phase can be induced by simultaneously considering the mixing heat of the transition metal and the degree of electrochemical corrosion tendency. have. In addition, since the transition metal of the second phase has a relatively high tendency of electrochemical corrosion, not only the second phase can be selectively and easily removed in the subsequent corrosion process, but also it is easy to control the removal rate of the second phase. The porosity control of the transition metal alloy can be facilitated.

According to an embodiment of the present invention, the transition metal constituting the first phase tends to be similar to each other as the difference in heat of mixing (ΔHmix) is less than ±10 kJ/mole of atom, and the transition metal constituting the second phase Compared to the transition metal constituting the first phase, the value of the heat of mixing (Hmix) may be large and the tendency of electrochemical corrosion may be large.

Specifically, the elements constituting the first phase are composed of Al, Co, Cr, Fe, and Ni (a phase in which Fe-Cr is contained in a large amount compared to the second phase in the high entropy alloy, and the second phase is the first phase. It is a phase containing a large amount of Al-Ni compared to the phase. In the Al-Co-Cr-Fe-Ni composition, the Al-Ni content is higher than that of the first phase) All five-element high-entropy alloys (Al-Co-Cr-Fe-Ni) are composed of the composition.) However, this application In the invention, the transition metal, post-transition metal, and metalloid are not limited to these elements.

In order to form the high entropy alloy, it may be desirable to select and use elements having similar atomic sizes and crystal structures. In one embodiment, the high entropy alloy may be separated into the first phase and the second phase by a difference in the value of heat of mixing (Hmix) within the alloying element. In addition, the second phase may be a phase having a high electrochemical potential compared to the first phase. Specifically, the transition metal constituting the second phase may be one or more transition metals relatively activated in the alloy. The phase separation phenomenon between the transition metals of the first and second phases may be confirmed by a metal cooling process to be described later.

According to an embodiment of the present invention, the fraction of the phase may be adjusted by adjusting the composition ratio of the transition metal constituting the first phase and the second phase, and the phase constituting the first phase and the second phase is A _{( 100-x)} B _x (In this case, A represents the phase constituting the first phase, B represents the phase constituting the second phase, and x is the fraction of the phase constituting the second phase among the total phases, 30% by volume To 70% by volume). In the fraction of the phases constituting the first phase and the second phase, if x is less than 30, the porosity of the finally prepared nanoporous transition metal alloy ribbon may be too low, and if x exceeds 70, the nanoporous transition The porosity of the metal alloy ribbon can be maintained high, but the mechanical properties of the nanoporous transition metal ribbon may be deteriorated.

According to an embodiment of the present invention, it may be preferable for the formation of a high entropy alloy that the content ratio of the transition metal constituting the first phase is an equiatomic ratio within an error tolerance of 5 to 40 at.%. have.

The second step is a step of generating a high entropy alloy in which the first phase and the second phase are uniformly distributed on a nano scale. Specifically, the high-entropy alloy may be prepared in the form of a ribbon by a rapid solidification method.

According to an embodiment of the present invention, in order to uniformly distribute the first phase and the second phase on a nanoscale, the molten metal is rapidly solidified while adjusting the cooling rate at a cooling rate of 10 ⁴ K/sec to 10 ⁶ K/sec. I can make it. Since it may be important to control the cooling rate in the rapid solidification process in order to manufacture a high-entropy alloy having a uniform phase distribution of nano-scale, it may be desirable to maintain the cooling rate range suggested above.

2 is a schematic diagram for explaining the structure of a melt spinning device, which is one of the rapid coagulation methods.

Referring to FIG. 2, the melt spinning apparatus 10 includes an electric furnace (Furnace, 12) equipped with a heater 11 to maintain the molten alloy obtained by melting the alloy raw material in a molten state, and to extrude the molten alloy. The piston 13 disposed on the upper part of the electric furnace 12, the ceramic nozzle 14 provided at the lower part of the electric furnace 12 to discharge the molten alloy from the electric furnace 12, and the ceramic nozzle 14 In order to rapidly solidify the molten alloy flowing out through the molten alloy to form a ribbon shape, a rotating wheel 15 made of a copper material may be provided below the ceramic nozzle 14.

Below the ceramic nozzle 14, a rotating wheel 15 made of copper material that rotates at high speed is provided, whereby the molten alloy discharged from the electric furnace 12 comes into contact with the rotating wheel 15 and can be rapidly solidified. . At this time, by controlling the rotation speed of the rotating wheel 15 and the cooling speed of the molten alloy, the first phase and the second phase in the alloy ribbon can be uniformly distributed on a nano scale. For example, the rotational speed of the rotation wheel 15 may maintain a high speed of 3,000 rpm or more, and specifically, the rotation speed may be adjusted within the range of 4,000 rpm to 6,000 rpm. In addition, the molten alloy in contact with the rotating wheel 15 can be rapidly solidified at a cooling rate of about 10 ³ K/sec or more, and specifically, the cooling rate of the molten alloy is within the range of 10 ³ K/sec to 10 ⁶ K/sec. Can be adjusted in The cooling rate can be increased by increasing the rotational speed of the metal rotating body, and can be controlled by increasing the difference between the temperature of the molten alloy and the solidification temperature. The rotating wheel 15 may be configured in a single roll or twin roll form, and may be rotated using a conventional driving source such as a motor. The thickness of the high entropy alloy manufactured by performing the above rapid cooling may be adjusted in the range of 50 μm to 200 μm.

The third step of FIG. 1 is a step of preparing a nanoporous transition metal alloy by selectively removing the second phase from the high entropy alloy.

Specifically, by selectively removing the second phase from the high-entropy alloy in which the first and second phases are uniformly distributed, the first phase, which is a high-entropy alloy, is left, and nanopores are formed in the portion from which the second phase is removed. Porous transition metal alloys can be prepared. In order to selectively remove the second phase from the high entropy alloy, an electrochemical decorrosion process is performed. Specifically, the decorrosion process is performed by immersing the high entropy alloy in an acidic or basic solution and maintaining it for several minutes to tens of hours. Can be done. The porosity of the nanoporous alloy may be adjusted by changing the type and concentration of the acid or base solution, the immersion time, and the immersion temperature as the decorrosion process conditions. In addition, the effect of maximizing the porosity by completely removing the second phase distributed in the alloy can be expected, but depending on the purpose, the porosity may be adjusted through the remaining of the second phase.

3 is a schematic diagram for explaining the decorrosion process, when a specimen of a high entropy alloy is immersed in an acid solution, the second phase of the first and second phases in the high entropy alloy can be selectively removed. In this case, the acid solution may be an inorganic acid such as nitric acid, hydrochloric acid, or sulfuric acid, or an organic acid such as acetic acid, but is not limited to these materials. The type and concentration of these acid solutions, immersion time, immersion temperature, and other decorrosion conditions can be important factors for controlling the porosity, and these decorrosion conditions can be appropriately adjusted.

4 is a schematic diagram for explaining in more detail the selective de-corrosion process. At this time, the term'passivation' may refer to a state in which the corrosion rate is markedly reduced and excellent corrosion resistance is exhibited if the corrosion potential is maintained high even though the metal has a high corrosion tendency. Representative metals exhibiting such a passivation behavior may include transition metals such as Ni, Ti, Zr, Ti, Nb, Cr, Fe, and Co. These are immersed in an acid solution and are called a passivity layer having a thickness of several nm. An oxide film is formed and may not be easily corroded in an acid solution. On the other hand, Al and Mn as transition metals have a large electrochemical corrosion tendency, and can be easily corroded in an acid solution because a passive film is not formed by being immersed in an acid solution.

5 is an electron scanning microscope (SEM) for comparing the surface of an alloy ribbon specimen before and after a decorrosion process as an embodiment of the present invention.

Referring to FIG. 5, according to the photograph 500 before decorrosion, it can be seen that the first phase, which is a high entropy alloy, and the second phase, which has a high electrochemical corrosion tendency, are uniformly distributed on a nano scale. In addition, according to the picture after decorrosion (510), it can be seen that pores are formed in the portion from which the second phase has been removed.

6 is an X-ray diffraction analysis diagram for comparing the surface of an alloy ribbon specimen before and after a decorrosion process as an embodiment of the present invention.

Referring to FIG. 6, according to the results of X-ray diffraction analysis, the second phase (Al-Ni rich phase) was present in the alloy ribbon specimen before electrochemical decorrosion, but the content of the second phase in the alloy ribbon specimen after decorrosion. It can be seen that this is significantly reduced.

As described above, in the present invention, a transition metal exhibiting a phase separation phenomenon is included as an alloy raw material, but a specific transition metal exhibiting a passivation tendency is classified as a first phase constituent element, and a specific transition metal not exhibiting a passivation tendency is It is classified and included as a constituent element of the second phase, and in the alloying process, these two phases are uniformly phase-separated on a nanoscale by a rapid solidification method, and the second phase is selectively removed through a decorrosion process, resulting in a uniform size on the surface and inside of the alloy Nano pores can be provided with

The thickness of the nanoporous transition metal alloy prepared by the above method may range from 20 µm to 200 µm, and nanoscale pores are evenly distributed on the surface and inside of the alloy ribbon, and the pore size is 20 nm To 100 nm, and the porosity may range from 30% to 70% by volume.

According to an embodiment of the present invention, the nanoporous transition metal alloy may be used as a chemical or electrochemical catalyst or a carrier because nanoporosity is uniformly distributed on the surface and inside of the alloy to increase a specific surface area. In addition, the nanoporous transition metal alloy ribbon has utility as an electrode of a battery and can be applied as a new optical material.

In addition, the present invention provides an electrode for a super capacitor including the nanoporous transition metal alloy prepared above, and a super capacitor including the electrode.

According to an embodiment of the present invention, the super capacitor includes a negative electrode, a positive electrode, and an electrolyte positioned between the negative electrode and the positive electrode, and at least one of the negative electrode and the positive electrode is an electrode including a nanoporous transition metal alloy ribbon. I can. The super capacitor may further include a separator.

The cathode and anode may be the same or different from each other. As the negative electrode, any negative electrode known in the art may be used. The electrolyte positioned between the negative electrode and the positive electrode may be a solid electrolyte or a liquid electrolyte. The liquid electrolyte may be a solution obtained by dissolving a salt in an organic solvent.

The organic solvent used in the liquid electrolyte is acetonitrile, dimethyl ketone, ethyl methyl ketone, diethyl ketone, ethylene carbonate, propylene carbonate, gamma butyrolactone, dioxymethane, dioxyethane, 2-methyltetrahydrofuran and sulfur. It may be one or more selected from the group consisting of incubation.

The salts are H2SO4, Na2SO4, Li2SO4, LiPF6, lithium perchlorate, lithium triflate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bistrifluoromethylsulfonylimide, tetramethylammonium tetrafluoroborate, tetra Ethyl ammonium tetrafluoroborate, KCl, KOH and 1-ethyl-3-methylimidazoliium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]) can be at least one selected from the group consisting of have. The liquid electrolyte has a concentration of 0.5 to 3 M, and is electrically inert in the operating voltage range of the super capacitor.

The separator may divide the inner space of the super capacitor into a cathode and an anode, and may be disposed between the electrodes to prevent an electrical short. The separator material may be polyethylene (PE), polypropylene (PP), Teflon, or the like, but is not limited thereto.

The present invention has been described above through preferred embodiments, but the above-described embodiments are only illustrative of the technical idea of the present invention, and various changes are possible within the scope not departing from the technical idea of the present invention. Those of ordinary knowledge will understand. Therefore, the scope of protection of the present invention should be interpreted not by specific embodiments, but by the matters described in the claims, and all technical ideas within the scope equivalent thereto should be interpreted as being included in the scope of the present invention.

Claims (15)

Ni, Ti, Zr, Nb, Cr, Cu, Fe, Co, Al and Mn consisting of five or more metals selected from the group consisting of a nano-porous high entropy alloy having a first phase distributed in a nano scale, ,
The porosity of the nanoporous high entropy alloy is in the range of 30% by volume to 70% by volume,
The first phase is defined as a phase in which the content of at least one first metal of Ni, Ti, Zr, Nb, Cr, Cu, Fe, and Co is relatively higher than the content of at least one second metal of Al and Mn,
The second phase separated from the first phase is defined as a phase in which the content of the second metal is relatively higher than that of the first metal,
The metal elements of Ni, Ti, Zr, Nb, Cr, Cu, Fe and Co each have a content of 5 at.% to 40 at.%, and an electrode for a super capacitor having an equiatomic ratio. The method of claim 1,
Metal elements constituting the first phase tend to have similar atomic sizes and crystal structures,
The metal element constituting the second phase has a negative or positive heat of mixing value (H _mix ) compared to the (transition) metal constituting the first phase, and has a large electrochemical corrosion tendency. The method of claim 1,
The thickness of the nanoporous high entropy alloy has a range of 20 μm to 100 μm,
The nanoporous high entropy alloy has a pore size in the range of 20 nm to 100 nm. The method of claim 1,
The pores of the nanoporous high entropy alloy are formed by selectively removing the second phase separated from the first phase. Ni, Ti, Zr, Nb, Cr, Cu, Fe, Co, Al, and preparing a molten metal of five or more metals selected from the group consisting of Mn;
Solidifying the molten metal by a rapid solidification method, thereby producing a high entropy alloy including a first phase and a second phase that are phase-separated from each other; And
And selectively removing the second phase from the high entropy alloy to form a nanoporous high entropy alloy,
The porosity of the nanoporous high entropy alloy is in the range of 30% by volume to 70% by volume,
The first phase is defined as a phase in which the content of at least one first metal of Ni, Ti, Zr, Nb, Cr, Cu, Fe, and Co is relatively higher than the content of at least one second metal of Al and Mn,
The second phase is defined as a phase in which the content of the second metal is relatively higher than that of the first metal,
The metal elements of Ni, Ti, Zr, Nb, Cr, Cu, Fe and Co each have a content of 5 at.% to 40 at.%, and a method of manufacturing an electrode for a super capacitor having an equiatomic ratio . The method of claim 5,
Metal elements constituting the first phase tend to have similar atomic sizes and crystal structures,
The metal element constituting the second phase has a greater heat of mixing (H _mix ) than the transition metal constituting the first phase and has a large electrochemical corrosion tendency. The method of claim 5,
A method of manufacturing a super capacitor electrode for controlling the pore size and specific surface area of the nanoporous high entropy alloy by controlling the size of the phases constituting the first and second phases. The method of claim 5,
The phase constituting the first phase and the second phase is defined as A _(100-x) B _x ,
The x is a fraction of the phase constituting the second phase among the entire phase, and has a range of 30% by volume to 70% by volume,
A _(100-x) refers to the first phase in the range of 100-x,
B _x refers to the second phase in the x range of the method of manufacturing an electrode for a super capacitor. The method of claim 5,
A method of manufacturing an electrode for a super capacitor in which phase separation occurs in a size of 20 nm to 100 nm in the first and second phases. The method of claim 5,
A method of manufacturing an electrode for a super capacitor comprising the step of rapidly solidifying the molten metal at a cooling rate of 10 ⁴ K/sec to 10 ⁶ K/sec. The method of claim 10,
The rapid solidification step is a method of manufacturing an electrode for a super capacitor performed by a melt spinning method. The method of claim 5,
The step of selectively removing the second phase,
A method of manufacturing an electrode for a super capacitor comprising the step of electrochemically corroding the high entropy alloy by immersing it in an acidic or basic solution. The method of claim 12,
The first phase is a passivation phenomenon that remains in the nanoporous transition metal alloy, a method of manufacturing an electrode for a super capacitor. The method of claim 12,
The step of selectively removing the second phase,
A method of manufacturing a super capacitor electrode for controlling the porosity of an alloy by controlling the concentration and immersion time of the acidic or basic solution. delete

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