Patent Application
20230092377
The present application relates to a negative electrode, a secondary battery including the same, and a method for manufacturing the same, and more particularly, to a metal negative electrode, a secondary battery including the same, and a method for manufacturing the same.
As mid-to-large high-energy applications such as electric vehicles and energy storage systems (ESS) are rapidly growing beyond the existing secondary batteries for small devices and home appliances, the market value of the secondary battery industry was only about 22 billion dollars in 2018, but is expected to grow to about 118 billion dollars by 2025. As such, in order for secondary batteries to be used as medium and large-sized energy storage media, price competitiveness, energy density and stability that are significantly improved more than a current level are required.
According to the technical needs, various electrodes for secondary batteries have been developed.
For example, Korean Unexamined Patent Publication No. 10-2019-0139586 discloses an electrode for a lithium-air battery, which includes a carbon nanotube and RuO2 deposited on a surface of the carbon nanotube, in which the RuO2 is deposited on a defective surface site of the carbon nanotube; the RuO2 has a particle size of 1.0 to 4.0 nm; and the RuO2 inhibits carbon decomposition at a surface defect site of the carbon nanotube and promotes the decomposition of Li2O2 formed on the surface of the carbon nanotube.
One technical object of the present application is to provide a metal negative electrode, a secondary battery including the same, and a method for manufacturing the same.
Another technical object of the present application is to provide a metal negative electrode with a low fabricating cost and a simple fabricating process, a secondary battery including the same, and a method for manufacturing the same.
Still another technical object of the present application is to provide a metal negative electrode with flexibility improved by controlling a ratio of surface area and thickness through a patterning process, a metal-air battery including the same, and a method for manufacturing the same.
Still another technical object of the present application is to provide a metal negative electrode with an improved charge/discharge capacity, a secondary battery including the same, and a method for manufacturing the same.
Still another technical object of the present application is to provide a metal negative electrode with a long lifespan and high stability, a secondary battery including the same, and a method for manufacturing the same.
The technical objects of the present application are not limited to the above.
To solve the above technical objects, the present application may provide a metal negative electrode.
According to one embodiment, in the metal negative electrode, as a result of XRD analysis, a peak value corresponding to (002) crystal plane may be lower than a peak value corresponding to (100) crystal plane, and a peak value corresponding to (101) crystal plane may be higher than a peak value corresponding to other crystal planes.
According to one embodiment, the metal negative electrode may include a first surface and a second surface facing the first surface, and a plurality of grooves spaced apart from each other may be provided in the first surface.
According to one embodiment, in a plan view, the plurality of grooves may have a circular shape, and the flexibility of the metal negative electrode may be improved by controlling a ratio of a surface area of the metal negative electrode to a thickness of the metal negative electrode through a method of providing the plurality of grooves spaced apart from each other on the first surface.
According to one embodiment, as a result of XRD analysis, a peak value corresponding to (102) crystal plane, a peak value corresponding to (103) crystal plane, and a peak value corresponding to (110) crystal plane may be further observed, but may be lower than a peak value corresponding to (101) crystal plane.
According to one embodiment, the metal negative electrode may be a zinc electrode.
To solve the above technical objects, the present application may provide a metal-air battery.
According to one embodiment, the metal-air battery may include a metal negative electrode according to the embodiment described above, a positive electrode catalyst on the metal negative electrode, and an electrolyte between the metal negative electrode and the positive electrode catalyst.
According to one embodiment, the metal-air battery may include a metal negative electrode having a plurality of grooves on a surface thereof, a positive electrode on the metal negative electrode, and a solid electrolyte between the metal negative electrode and the positive electrode catalyst, in which the solid electrolyte may include a network formed by providing a plurality of base complex fibers combined with cellulose and chitosan, and the positive electrode may include a compound of a transition metal, phosphorus, and a chalcogen element.
According to one embodiment, in each of the metal negative electrode and the solid electrolyte, a peak value corresponding to (101) crystal plane may be higher than a peak value corresponding to other crystal planes.
According to one embodiment, the metal negative electrode and the solid electrolyte may face each other.
According to one embodiment, an interphase layer in contact with the solid electrolyte may be provided on a surface of the metal negative electrode and the interphase layer may include a compound having fluorine and a metal element contained in the metal negative electrode, and a compound having sulfur and a metal element contained in the metal negative electrode.
According to one embodiment, as charging and discharging are performed, a ratio of the compound including fluorine and the metal element contained in the metal negative electrode to the compound including sulfur and the metal element contained in the metal negative electrode may increase on the interphase layer.
According to one embodiment, the metal-air battery may be provided in the form of a pouch cell.
To solve the above technical objects, the present application may provide a method for fabricating a metal negative electrode.
According to one embodiment, the method for fabricating the metal negative electrode may include: preparing a flat base metal substrate; disposing a plurality of beads on the base metal substrate; forming a mask layer on the base metal substrate on which the plurality of beads are disposed; removing the plurality of beads to expose a region to be etched of the base metal substrate, which is not covered with the mask layer; and etching the exposed region to be etched of the base metal substrate by using the mask layer as a mask to form a metal negative electrode.
According to one embodiment, the method for fabricating the metal negative electrode may further include: reducing a size of the plurality of beads before forming the mask layer.
According to one embodiment, the method for fabricating the metal negative electrode may further include: hydrophilizing a surface of the base metal substrate before disposing the plurality of beads.
According to one embodiment, the region to be etched may include a bonding surface between the base metal substrate and the plurality of beads.
The metal negative electrode according to an embodiment of the present application may be fabricated by a method of sequentially forming the plurality of beads and the mask layer on the flat base metal substrate, removing the plurality of beads, and etching the base metal substrate by using the mask layer as a mask.
Accordingly, the metal negative electrode having a plurality of grooves may be fabricated with a high yield by a simple method.
In addition, the flexibility and the mechanical properties of the metal negative electrode may be improved by controlling a ratio of a surface area of the metal negative electrode to a thickness of the metal negative electrode through a method of providing a plurality of grooves spaced apart from each other on a surface of the metal negative electrode.
Furthermore, an energy density of the metal-air battery including the metal negative electrode may be improved by adjusting a thickness of the metal negative electrode and/or a depth and diameter of the plurality of grooves.
Moreover, a side reaction at an interphase with a solid electrolyte may be minimized by the plurality of grooves provided in the metal negative electrode, and thus a dendrite growth may be minimized in a process of charging and discharging the metal-air battery including the metal negative electrode.
Besides, a specific crystal plane (e.g., (101) crystal plane) of the metal negative electrode may be developed by a simple method of controlling the depth and diameter of the plurality of grooves of the metal negative electrode, and thus the electrochemical properties of the metal negative electrode may be improved.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments, but may be realized in different forms. The embodiments introduced herein are provided to sufficiently deliver the spirit of the present invention to those skilled in the art so that the disclosed contents may become thorough and complete.
Further, in the various embodiments of the present specification, the terms such as first, second, and third are used to describe various elements, but the elements are not limited to the terms. The terms are used only to distinguish one element from another element. Accordingly, an element mentioned as a first element in one embodiment may be mentioned as a second element in another embodiment. The embodiments illustrated here include their complementary embodiments. Further, the term “and/or” in the specification is used to include at least one of the elements enumerated in the specification.
In the specification, the terms of a singular form may include plural forms unless otherwise specified. Further, the terms “including” and “having” are used to designate that the features, the numbers, the steps, the elements, or combinations thereof described in the specification are present, and are not to be understood as excluding the possibility that one or more other features, numbers, steps, elements, or combinations thereof may be present or added. In addition, the term “connection” used herein may include the meaning of indirectly connecting a plurality of components, and directly connecting a plurality of components.
Further, in the following description of the present invention, a detailed description of known functions or configurations incorporated herein will be omitted when it may make the subject matter of the present invention unnecessarily unclear.
Referring to
The base metal substrate 10 may include a first surface and a second surface facing the first surface, and both the first surface and the second surface may be flat.
According to one embodiment, the base metal substrate 10 may include zinc.
A plurality of beads 110 may be disposed on the base metal substrate 10 (S120).
The plurality of beads 110 may be mixed with a solvent and then spin-coated on the base metal substrate 10. The plurality of beads 110 may be disposed to be spaced apart from each other on the base metal substrate 10. The plurality of beads 110 may be disposed on the first surface of the base metal substrate 10. For example, the plurality of beads 110 may be polystyrene beads.
Before disposing the plurality of beads 110 on the base metal substrate 10, the base metal substrate may be treated with HCl and washed. Accordingly, a native oxide layer on the base metal substrate 10 may be removed.
In addition, before disposing the plurality of beads 110 on the base metal substrate 10, the first surface of the base metal substrate 10 may be treated with hydrophilicity. For example, the first surface of the base metal substrate 10 may have a hydrophilic property by treating the first surface of the base metal substrate 10 with piranha solution. Accordingly, the plurality of beads 110 may be stably and easily provided on the first surface of the base metal substrate 10.
A size of the plurality of beads 110 may be reduced. For example, regions adjacent to the surfaces of the plurality of beads 110 may be removed by applying an oxygen plasma onto the base metal substrate 10 having the plurality of beads 110, and thus the size of the plurality of beads 110 may be reduced. As the size of the plurality of beads 110 is reduced, a distance between the plurality of beads 110 may increase.
Referring
The mask layer 120 may be formed of a polymer using a spin coating process, and thus may cover the base metal substrate 10 exposed between the plurality of beads 110. In addition, the mask layer 120 may not be provided on a bonding surface between the plurality of beads 110 and the base metal substrate 10.
A region to be etched 122 of the base metal substrate 10 which is not covered with the mask layer 120 may be exposed by removing the plurality of beads 110 (S140).
As described above, the mask layer 120 may not be provided on the bonding surface between the plurality of beads 110 and the base metal substrate 10, and thus the region to be etched 122 (the bonding surface), with which the plurality of beads 110 and the base metal substrate 10 used to come into contact, may be exposed after removing the plurality of beads 110.
Referring
The region to be etched 122 may be etched by using the mask layer 120 as a mask, so as to provide a plurality of grooves 124 in the negative electrode 100. The plurality of grooves 124 may correspond to the region to be etched 122. The plurality of grooves 124 may not penetrate the negative electrode 100. In other words, the plurality of grooves 124 may have a bottom surface and a side surface, and may have an opened top surface.
The region to be etched 122 may be etched by using an etching gas. According to one embodiment, the etching gas may include fluorine and sulfur. For example, the etching gas may include SF6.
According to one embodiment, a portion of an element included in the etching gas may remain on the bottom surface and/or the side surface of the plurality of grooves 124. Accordingly, the properties of the negative electrode 100 fabricated from the base metal substrate 10 to be described later may be improved. Specifically, an interphase layer may be formed on the surface (the first surface) of the negative electrode 100 in contact with the electrolyte in a process of charging and discharging the secondary battery including the negative electrode 100. In this case, the generation of the interphase layer may be induced by the element included in the etching gas remaining on the bottom surface and/or the side surface of the plurality of grooves 124, and thus the interphase layer may be stably and easily generated to improve the charge/discharge properties and lifespan properties of the secondary battery.
According to one embodiment, a diameter and a depth of the plurality of grooves 124 may be controlled. Specifically, the diameter of the plurality of grooves 124 may be adjusted by a method of controlling the diameter of the plurality of beads 110, and the diameter of the plurality of beads 110 may be controlled by a method of adjusting an initial size of the plurality of beads 110 coated on the base metal substrate 10, a degree of reduction in the size of the plurality of beads 110, etc. A depth of the plurality of grooves 124 may be adjusted according to process conditions (e.g., time, concentration, pressure, power, etc.) for providing the etching gas.
According to one embodiment, a crystal plane developed in the negative electrode 100 may be controlled according to a diameter and a depth of the plurality of grooves 124. Specifically, as the depth of the plurality of grooves 124 increases from 100 nm to 500 nm, (100) crystal plane and (101) crystal plane may be further developed; (002) crystal plane, (102) crystal plane, (103) crystal plane, and (110) crystal plane may be less developed; and (100) crystal plane and (101) crystal plane may be less developed as the depth increases from 500 nm to 5 μm. In addition, as the diameter of the plurality of grooves 124 increases from 100 nm to 500 nm, (100) crystal plane and (101) crystal plane may be further developed; and (100) crystal plane and (101) crystal plane may be less developed as the diameter increases from 500 nm to 1 μm.
Whether or not the crystal plane of the negative electrode 100 is developed may be confirmed through an XRD analysis. As described above, when the diameter and depth of the plurality of grooves 124 increase from 100 nm to 500 nm, a ratio of a peak value corresponding to (101) crystal plane to a peak value corresponding to (002) crystal plane ((101)/(002)) may increase. When the diameter and depth of the plurality of grooves 124 exceed 500 nm, a ratio of a peak value corresponding to (101) crystal plane to a peak value corresponding to (002) crystal plane ((101)/(002)) may decrease.
According to one embodiment, the electrochemical properties of the negative electrode 100 may be controlled according to a ratio of a peak value corresponding to (101) crystal plane to a peak value corresponding to (002) crystal plane ((101)/(002)). Specifically, as the ratio of the peak value corresponding to (101) crystal plane to the peak value corresponding to (002) crystal plane ((101)/(002)) increases, an overpotential value of the secondary battery including the negative electrode 100 may be reduced.
Accordingly, as the ratio of the peak value corresponding to (101) crystal plane to the peak value corresponding to (002) crystal plane ((101)/(002)) increases, the diameter and depth of the plurality of grooves 124 may be controlled, and thus the electrochemical properties of the negative electrode 100 may be improved. For example, the diameter and depth of the plurality of grooves 124 may be 500 nm.
In addition, according to one embodiment, a lattice constant of a unit cell of the negative electrode 100 may be controlled according to the diameter and depth of the plurality of grooves 124. Specifically, when the negative electrode 100 has a hexagonal crystal structure, an a-axis lattice constant of the unit cell of the negative electrode 100 may increase and a c-axis lattice constant thereof may decrease, as the diameter and depth of the plurality of grooves 124 increase.
The negative electrode 100 according to an embodiment of the present application may be fabricated by a method of sequentially forming the plurality of beads 110 and the mask layer 120 on the base metal substrate 10, removing the plurality of beads 110, and etching the base metal substrate 10 by using the mask layer 120 as a mask.
Accordingly, the metal negative electrode 100 having the plurality of grooves 124 may be fabricated with a high yield by a simple method
In addition, in a simple method of controlling the depth and diameter of the plurality of grooves 124 of the metal negative electrode 100, a specific crystal plane of the metal negative electrode 100 can be developed (for example, control the ratio of (002) crystal plane and (101) crystal plane to the crystal plane), thereby improving the electrochemical properties of the metal negative electrode 100.
In addition, a ratio of the surface area of the metal negative electrode 100 to the thickness of the metal negative electrode 100 may be controlled by the plurality of grooves 124 of the metal negative electrode 100, and thus flexibility of the metal negative electrode 100 may be improved. Specifically, in the case of providing a comparative electrode having the same thickness as the metal negative electrode 100, but with the plurality of grooves omitted, the metal negative electrode 100 may have high flexibility and mechanical stability compared to the comparative electrode.
Referring to
The metal negative electrode 100 may be the same as described with reference to
The solid electrolyte 200, the positive electrode 300, and the current collector 400 may be sequentially stacked and then bent, so that the positive electrode 100 may be disposed in between the bent solid electrolyte 200. In other words, the metal negative electrode 100 may be provided in a sandwiched form between the solid electrolyte 200, the positive electrode 300, and the current collector 400, which are stacked.
Hereinafter, the solid electrolyte 200 and the method for fabricating the same will be described with reference to
A chitosan derivative may be prepared. The chitosan derivative may be obtained by mixing a chitosan precursor in a solvent. According to one embodiment, the chitosan derivative may be obtained by adding a solubilizing agent to chitosan chloride and a solvent. Accordingly, the chitosan chloride may be easily dissolved in a solvent, and the chitosan derivative may be easily provided in a medium to be described later, so that cellulose to which chitosan is bound may be easily prepared.
For example, the solvent may be an aqueous acetic acid, and the solubilizing agent may include at least one of glycidyltrimethylammonium chloride, (2-aminoethyl)trimethylammonium chloride, (2-chloroethyl)trimethylammonium chloride, (3-carboxypropyl)trimethylammonium chloride, or (formylmethyl)trimethylammonium chloride.
The chitosan may have excellent thermal and chemical stability, have high ionic conductivity, and contain OH ions without a long-term loss. In addition, as will be described later, when used in the secondary battery the chitosan may have high compatibility with the negative electrode 100 and the positive electrode 300 compound structure of copper, phosphorus, and sulfur.
Chitosan bound to cellulose may be produced from the chitosan derivative. The step of producing the cellulose to which the chitosan is bound may include: preparing a culture medium having the chitosan derivative; and injecting and culturing a bacterial strain in the culture medium to produce a base complex fiber 110 including a cellulose 212 to which the chitosan 214 is bound. In this case, the cellulose 212 may be bacterial cellulose.
According to one embodiment, the cellulose 212, to which the chitosan 214 is bound, may be prepared by culturing a bacterial pellicle in the culture medium and then desalting the bacterial pellicle. The bacterial pellicle may be prepared by preparing a culture medium containing the chitosan derivative together with raw materials (for example, pineapple juice, peptone, disodium phosphate, citric acid) for culturing yeast and bacteria, and injecting and culturing a strain. For example, the strain may be Acetobacter xylinum.
The base complex fiber 210 including the cellulose 212, to which the chitosan 214 is bound, may be prepared by washing and drying the cultured bacterial pellicle, desalting with an acidic solution (for example, HCl), neutralizing and removing a solvent. In the desalting process, the remaining Na, K, or cell shielding materials and debris may be removed, so that the cellulose 212, to which the chitosan 214 of high purity is bound, may be prepared.
In addition, the chitosan 214 may be chemically bound to the cellulose 212. Accordingly, in the cellulose 212 to which the chitosan 214 is bound, a stretching vibration corresponding to C—N may be observed during an XPS analysis.
According to one embodiment, the surface of the cellulose 112 to which the chitosan 214 is bound, that is, the surface of the base complex fiber 210 may be oxidized using an oxidizing agent, so that the first complex fiber 210a may be prepared.
Specifically, the step of preparing a first complex fiber 210a may include the steps of: adding the base complex fiber 210 to an aqueous solution containing an oxidizing agent to prepare a source solution; adjusting the pH of the source solution to basic; adjusting the pH of the source solution to neutral; and washing and drying a pulp in the source solution to prepare the first complex fiber 210a.
For example, the aqueous solution containing the oxidizing agent may be an aqueous TEMPO solution. Alternatively, as another example, the aqueous solution containing the oxidizing agent may include at least one of 4-hydroxy-TEMPO, (diacetoxyiodo)benzene, 4-amino-TEMPO, 4-carboxy-TEMPO, 4-methoxy-TEMPO, TEMPO methacrylate, 4-acetamido-TEMPO, 3-carboxy-PROXYL, 4-maleimido-TEMPO, 4-hydroxy-TEMPO benzoate, or 4-phosphonooxy-TEMPO.
The source solution may further include a sacrificial reagent and an additional oxidizing agent for the oxidation reaction of the base complex fiber 210. For example, the sacrificial reagent may include at least one of NaBr, sodium iodide, sodium bromate, Sodium bromite, Sodium borate, sodium chlorite, or sodium chloride, and the additional oxidizing agent may include at least one of NaClO, potassium hypochlorite, lithium hypochlorite, sodium chlorite, sodium chlorate, perchloric acid, potassium perchlorate, lithium perchlorate, tetrabutylammonium perchlorate, zinc perchlorate, hydrogen peroxide, or sodium peroxide.
According to one embodiment, in the step of adjusting the pH of the source solution to be basic, the pH of the source solution may be adjusted to 10. Accordingly, the oxidation reaction may be easily induced while the precipitate is minimized, and a degree of oxidation of the first complex fiber 210a may be improved as compared to the reaction conditions at pH 8 to 9.
According to one embodiment, the additional oxidizing agent may be provided after the base complex fiber 210 and the sacrificial reagent are provided to the aqueous solution containing the oxidizing agent. In addition, the additional oxidizing agent may be provided by dropping. Accordingly, a rapid oxidation phenomenon of the base complex fiber 110 may be prevented, and as a result, the surface of the base complex fiber 210 may be uniformly and stably oxidized.
In addition, according to one embodiment, bromine may be bound to the surface of the cellulose 212 to which the chitosan 214 is bound, and a first functional group 216 containing nitrogen may be substituted with bromine, so that the second complex fiber 210b may be prepared.
The first functional group 216 may be represented as in <Formula 1> below, and the first functional group 216 may be bound with the chitosan 214 and/or the cellulose 212.
<Formula 1>
In other words, the second complex fiber 210b may have quaternary N.
Specifically, the step of preparing the second complex fiber 210b may include: dispersing the base complex fiber 210 in a first solvent and adding a bromine source to prepare a first source solution; adding a coupling agent to the first source solution and reacting to prepare a reaction suspension; filtering, washing and freeze-drying the reaction suspension to prepare a brominated base complex fiber; dispersing the brominated base complex fiber in a second solvent to prepare a second source solution; adding and reacting a precursor of the functional group 216 to the second source solution; filtering, washing, and freeze-drying the reacted solution to prepare the second complex fiber 210b.
For example, the first solvent and the second solvent may be the same as each other, and may include at least one of N,N-dimethylacetamide, acetamide, acetonitrile, ethanol, ethylenediamine, diethyl ether, or benzaldehyde.
For example, the bromine source may include at least one of LiBr, sodium bromide, or potassium bromide.
For example, the coupling agent may include N-bromosuccinimide and triphenylphosphine. Bromine can be easily bound to the surface of the base complex fiber 110 by the coupling agent. Specifically, bromine in N-bromosuccinimide may be bound with the base complex fiber 110, and triphenylphosphine may improve a reaction rate by reducing a bromine precursor (bromine source or N-bromosuccinimide).
As described above, after obtaining the brominated base complex fiber from the reaction suspension, the brominated base complex fiber may be freeze-dried. Accordingly, a loss of bromine in the brominated base complex fiber may be minimized, and secondary reaction of bromine with other elements may be minimized.
For example, the precursor of the first functional group 216 may include 1,4-diazabicyclo[2.2.2]octane.
A solid state electrolyte 200 may be prepared by using the cellulose 212 to which the chitosan 214 is bound.
The solid state electrolyte 200 may be prepared in the form of a membrane in which the base complex fiber 210 including the cellulose 212, to which the chitosan 214 is bound, forms a network. For this reason, the solid state electrolyte 200 may be provided with a plurality of pores therein, may have a high surface area, and may be excellent in flexibility and mechanical properties.
The solid state electrolyte 200 may be in a state in which a crystalline phase and an amorphous phase are mixed. More specifically, in the solid state electrolyte 200, the ratio of the amorphous phase may be higher than that of the crystalline phase. Accordingly, the solid state electrolyte 200 may have high ion mobility.
According to one embodiment, the solid state electrolyte 200 may be prepared by a gelatin process using the first complex fiber 210a and the second complex fiber 210b. In this case, the solid state electrolyte 200 may include the first complex fiber 210a and the second complex fiber 210b, but the first complex fiber 210a and the second complex fiber 110b may be cross-linked with each other. Due to the first complex fiber 210a, the number of OH ions in the solid state electrolyte 200 may be increased, ionic conductivity may be improved, a negative charge density may be increased, and swelling resistance may be improved. In addition, due to the second complex fiber 210b, a molecular weight may be increased to improve thermal stability, and ion exchange capacity may be improved to yield a high moisture impregnation rate and a high swelling resistance, improve cross-linking strength with the first complex fiber 210a, and provide a selectively high solubility (ion discerning selectivity) with regard to a specific solvent. Accordingly, the charge/discharge properties and life properties of the secondary battery including the solid state electrolyte 200 may be improved.
Specifically, the step of preparing the solid state electrolyte 200 may include the steps of: mixing the first complex fiber 210a and the second complex fiber 210b in a solvent to prepare a mixed solution; adding and reacting a crosslinking agent and an initiator to the mixed solution so as to prepare a suspension; casting and drying the suspension on a substrate to prepare a complex fiber membrane; and performing an ion exchange process on the complex fiber membrane.
For example, the solvent may include methylene chloride, 1,2-propanediol, acetone, and a mixed solvent thereof, the crosslinking agent may include glutaraldehyde, and the initiator may include N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide.
In addition, for example, an ion exchange process for the complex fiber membrane may include a step of providing a KOH aqueous solution and a ZnTFSI aqueous solution to the complex fiber membrane. Accordingly, the content of OH ions in the solid state electrolyte 200 may be improved.
As described above, according to an embodiment of the present application, the solid state electrolyte 200 may include the membrane, which has at least one of the base complex fiber 210, the first complex fiber 210a, or the second complex fiber 210b.
In the solid state electrolyte 200, the ratio of the chitosan 214 may be easily controlled depending on the content of the chitosan derivative provided in the culture medium. Depending on the ratio of the chitosan 214, the crystallinity, ionic conductivity, and swelling ratio of the solid state electrolyte 200 may be controlled. Specifically, as the ratio of the chitosan 214 increases, the crystallinity of the solid state electrolyte 200 may gradually decrease.
According to one embodiment, the content of the chitosan 214 may be more than 30 wt % and less than 70 wt %. If the content of the chitosan 214 is 30 wt % or less, or 70 wt % or more, the ionic conductivity of the solid state electrolyte 200 may be remarkably lowered, and the swelling rate may be remarkably increased.
However, according to an embodiment of the present application, the ratio of the chitosan 214 in the solid state electrolyte 200 may be more than 30 wt % and less than 70 wt %, and thus the solid state electrolyte 200 may have a low swelling ratio value while maintaining high ionic conductivity properties.
Hereinafter, the positive electrode 300 and the method for fabricating the same will be described with reference to
A first precursor having a chalcogen element, a second precursor having phosphorus, and a third precursor having a transition metal may be prepared.
According to one embodiment, the chalcogen element may include phosphorus. In this case, for example, the first precursor may include at least any one of dithiooxamide, dithiobiuret, dithiouracil, acetylthiourea, thiourea, N-methylthiourea, bis(phenylthio)methane, 2-imino-4-thiobiuret, N,N′ ammonium sulfide, methyl methanesulfonate, sulfur powder, sulphates, N,N-dimethylthioformamide, or davy reagent methyl.
Alternatively, according to another embodiment, the chalcogen element may include at least any one of oxygen, selenium, or tellurium.
For example, the second precursor may include at least any one of tetradecylphosphonic acid, ifosfamide, octadecylphosphonic acid, hexylphosphonic acid, trioctylphosphine, phosphoric acid, triphenylphosphine, ammonium phosphide, pyrophosphates, davy reagent methyl, cyclophosphamide monohydrate, phosphorus trichloride, phosphorus (V) oxychloride, thiophosphoryl chloride, phosphorus pentachloride, or phosphorus pentasulfide.
According to one embodiment, different heterogeneous types including phosphorus may be used as the second precursor. For example, a mixture of tetradecylphosphonic acid and ifosfamide at a ratio of 1:1 (M %) may be used as the second precursor. Accordingly, a stoichiometric ratio of the transition metal, phosphorus, and the chalcogen element may be controlled to 1:1:1. As a result, as will be described later, the positive electrode 300 according to an embodiment of the present application may have a covellite structure, and the electrochemical properties of the positive electrode 300 may be improved.
According to one embodiment, the transition metal may include copper. In this case, for example, the third precursor may include at least any one of copper chloride, copper(II) sulfate, copper(II) nitrate, copper selenide, copper oxychloride, cupric acetate, copper carbonate, copper thiocyanate, copper sulfide, copper hydroxide, copper naphthenate, or copper(II) phosphate.
Alternatively, according to another embodiment, the transition metal may include at least any one of copper, magnesium, manganese, cobalt, iron, nickel, titanium, zinc, aluminum, or tin.
A mixture may be prepared by mixing the first precursor, the second precursor, and the third precursor, and adding a first reducing agent.
The first precursor, the second precursor, and the third precursor may be mixed in solvent and the first reducing agent may be added. For example, the solvent may be a mixture of ethanol and ethylenediamine. Alternatively, for example, the solvent may be a mixture of ethanol and toluene.
According to one embodiment, the direction of the crystal plane of the electrode structure to be described later may be controlled according to the type and mixing ratio of the solvent. In other words, according to the type and mixing ratio of the solvent, whether the crystal plane 101 is developed or not in the positive electrode 300 may be controlled, and thus the electrochemical properties of the positive electrode 300 may be controlled.
According to an embodiment of the present application, in the same way as the (101) crystal plane is developed in the negative electrode 100, the solvent may be selected (for example, mixing ethanol and ethylenediamine at a volume ratio of 1:3) so that a crystal plane may be developed in the positive electrode 300, thereby improving the electrochemical properties (for example, ORR, OER, HER) of the positive electrode 300.
After the first precursor, the second precursor, and the third precursor are mixed in the solvent, nucleation and crystallization may proceed as shown in (a) of
For example, the first reducing agent may include at least any one of ammonium hydroxide, ammonium chloride, or tetramethylammonium hydroxide.
An intermediate product including a plurality of stems may be prepared by co-precipitating the mixture including the first precursor, the second precursor, the third precursor, the first reducing agent, and the solvent.
The mixture may be heat treated to form an intermediate product, as shown in (b) of
For example, the mixture to which the first reducing agent is added may be heat treated under reflux at 120° C., and then washed with deionized water and ethanol.
The first reducing agent may maintain pH and increase a reaction rate while performing a function of the reducing agent during heat treatment. Accordingly, the intermediate product having the plurality of stems may be easily absorbed. For example, when the transition metal is copper and the chalcogen element is sulfur, the intermediate structure may be CuPS having a covellite crystal structure.
A plurality of branches may branch off from the plurality of stems according to a method of adding a second reducing agent to the intermediate product and performing heat treatment under pressure, so as to prepare a plurality of fibrillated fibers including the transition metal, the chalcogen element, and phosphorus.
According to one embodiment, the intermediate product and the second reducing agent may be added to deionized water, and then a pressure heat treatment process may be performed.
For example, the second reducing agent may include at least any one of triton X-165, triton X-102, triton X-45, triton X-114, triton X-405, triton X-101, trimesic acid, diamide, peroxynitrite, formaldehyde, thimerosal, or chloramine-T.
According to one embodiment, a chalcogen element source having the chalcogen element may be further added along with the second reducing agent. Accordingly, the chalcogen element lost in the reaction process may be supplemented by the chalcogen element source, and the electrode structure having a sponge structure in which a plurality of fibrillated fibers to be described later form a network may be easily formed.
For example, when the chalcogen element is sulfur, the chalcogen element source may include at least any one of sodium bisulfite, sodium sulfate, sodium sulfide, sodium thiosulfate, sodium thiomethoxide, sodium ethanethiolate, or sodium methanethiolate.
A process of mixing the intermediate product and the second reducing agent in deionized water may be performed in a cooled state. The reaction rate may be prevented from excessively increasing due to the heat generated in the process of adding the second reducing agent, thereby improving the electrochemical properties of the electrode structure 300 to be described later.
As described above, a plurality of branches may branch off from the plurality of stems as shown in (c) of
The positive electrode 300 having a sponge structure may be immersed in liquid nitrogen after being washed with deionized water and ethanol. Accordingly, mechanical properties and flexibility of the electrode structure of the sponge structure may be improved.
In addition, after being immersed in liquid nitrogen, the positive electrode 300 of the sponge structure may be freeze-dried, and the remaining solvents may be removed to minimize a secondary reaction.
The positive electrode 300 may include a membrane of a sponge structure, in which a plurality of branches branch off from the plurality of stems and a plurality of fibers form a network as described above. Accordingly, the electrode structure may have a porous structure in which a plurality of pores having a size of 1 to 2 nm are provided, and may be flexible.
In addition, as described above, the type and ratio of the solvent mixed with the first precursor, the second precursor, and the third precursor may be controlled and thus a crystal plane 101 may be developed in the positive electrode 300. Accordingly, upon the XRD analysis of the positive electrode 300, a peak value corresponding to a crystal plane 101 may have a maximum value compared with a peak value corresponding to another crystal plane. Upon the XRD measurement, a peak value corresponding to a crystal plane 101 may be observed in a range of 2θ values of 19° to 21°.
The plurality of fibers forming the positive electrode 300 may include a compound of the transition metal, phosphorus, and the chalcogen element. For example, when the transition metal is copper and the chalcogen element is oxygen, the fiber may be represented by the following <Formula 1>.
CuPxSy <Formula 1>
When the fiber forming the positive electrode 300 is represented as above <Formula 1>, it may be x+y=1, 0.3≤x≤0.7, 0.3≤y≤0.7.
If, in above <Formula 1>, x is less than 0.3 or more than 0.7 and y is less than 0.3 or more than 0.7, ORR, OER, and HER properties of the positive electrode 300 may be deteriorated, and thus the positive electrode 300 may not react reversibly in a process of charging/discharging of the secondary battery including as a positive electrode 300, accordingly.
However, according to an embodiment of the present application, when the positive electrode 300 is represented by CuPxSy, a composition ratio of P may be 0.3 or more and 0.7 or less and a composition ratio of S may be 0.3 or more and 0.7 or less. Accordingly, the ORR, OER, and HER properties of the positive electrode 300 may be improved, and the charge/discharge property and life property of the secondary battery, which includes the positive electrode 300, may be improved.
When the secondary battery including the positive electrode 300 performs charging and discharging, a lattice spacing of the fibers included in the positive electrode may be reversibly changed. Specifically, when the secondary battery is charged, the lattice spacing may be 0.478 nm, and when the secondary battery is discharged, the lattice spacing may be 0.466 nm. The lattice spacing of the fibers may be confirmed by the HRTEM.
According to an embodiment of the present application, the positive electrode 300 having a membrane shape in which the plurality of fibrillated fibers form a network according to a method of mixing the first precursor having the chalcogen element, the second precursor having phosphorus, and the third precursor having the transition metal.
The positive electrode 300 having high electrochemical properties may be prepared by an inexpensive method.
In addition, the positive electrode 300 may be fabricated by co-precipitation and heat treatment under pressure, and thus may be easily mass-produced and subjected to a simple fabrication process, thereby providing the positive electrode 300 for the secondary battery.
Hereinafter, a specific experimental example of the present application, and results of evaluating properties will be described accordingly.
A zinc foil was prepared as a base metal substrate. The zinc foil was sonicated with HCl for five minutes and washed with deionized water and ethanol.
A piranha solution in which H2SO4, H2O and NH4OH are mixed at a ratio of 2.5:7:0.5 (v/v/v), and the zinc foil was treated with piranha solution to improve hydrophilic properties, washed with deionized water, and dried in an argon gas atmosphere.
Polystyrene beads were prepared and spin-coated on the zinc foil, after which oxygen plasma was applied under the conditions of 60 mTorr, 30 sccm flow rate, and 80 W RF, so as to etch the polystyrene beads and reduce a size thereof.
After that, a photosensitive material having chromium was coated on the zinc foil having polystyrene beads to prepare a mask layer, and the polystyrene beads were removed. Then, a plurality of grooves having a depth of 500 nm and a diameter of 500 nm were formed in the zinc foil by providing the etching gas containing argon gas and SF6 gas under the conditions of 0.1 Pa, 40 sccm flow rate, and 60 W RF using the mask film as a mask.
The mask layer was removed, sonicated with diluted H2SO4, and dried in an argon gas atmosphere, so as to fabricate a negative electrode according to Experimental Example 1-1.
The depth and diameter of the plurality of grooves were adjusted as shown in Table 1 below by controlling the flow rate and supply time of etching gas, and the time for applying oxygen plasma. The flow rate and supply time of the etching gas are as shown in <Table 2> in order to control the depth of the plurality of grooves to 100 nm, 500 nm, 1,000 nm, and 3,000 nm, and the time for applying the oxygen plasma is as shown in <Table 3> below in order to control the diameter of the plurality of grooves to 100 nm, 300 nm, 500 m, 1,000 nm, and 5,000 nm.
Referring to
As can be understood from
An unpatterned zinc foil was prepared as a metal negative electrode according to Experimental Example 1-2.
Acetobacter xylinum was provided as a bacterial strain, and a chitosan derivative was provided. The chitosan derivative was prepared by dissolving 1 g of chitosan chloride in 1% (v/v) aqueous acetic acid, treating with 1 M glycidyltrimethylammonium chloride at 65° C. for 24 hours in an N2 atmosphere, precipitating, filtering multiple times with ethanol.
A Hestrin-Schramm (HS) culture medium containing pineapple juice (2% w/v), yeast (0.5% w/v), peptone (0.5% w/v), disodium phosphate (0.27% w/v), citric acid (0.015% w/v), and chitosan derivative (2% w/v) was prepared and steam-sterilized at 121° C. for 20 minutes. In addition, Acetobacter xylinum was activated in a pre-cultivation Hestrin-Schramm (HS) culture medium at 30° C. for 24 hours, and acetic acid was added to maintain pH 6.
After that, Acetobacter xylinum was cultured in the Hestrin-Schramm (HS) culture medium at 30° C. for seven days.
The harvested bacterial pellicle was washed with deionized water to neutralize the pH of the supernatant and dehydrated in vacuum at 105° C. The resulting cellulose was demineralized by using 1 N HCl for 30 minutes (mass ratio 1:15, w/v) to remove an excessive amount of reagent, and then was purified by centrifugation several times with deionized water until the supernatant reached a neutral pH. Finally, all solvents were evaporated at 100° C. to prepare a base complex fiber (chitosan-bacterial cellulose (CBC)).
A first complex fiber (TEMPO-oxidized CBC (oCBCs)), in which a surface of the base complex fiber is oxidized, was designed according to a method of conjugating a base complex fiber (CBC) of hydroxymethyl and ortho-para directing acetamido to the oxide of TEMPO by an oxidation reaction using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), sodium bromide (NaBr) and sodium hypochlorite (NaClO) as shown in
Specifically, 2 g of the base complex fiber dispersed in a 2 mM TEMPO aqueous solution was reacted with NaBr (1.9 mM). 5 mM NaClO was used as an additional oxidizing agent.
The reaction suspension was stirred with ultrasonic waves, and the reaction was allowed to proceed at room temperature for three hours. The pH of the suspension was maintained at 10 by successive addition of 0.5M NaOH solution. Then, 1N HCl was added to the suspension to keep the pH neutral for three hours. The oxidized pulp produced in the suspension was washed three times with 0.5 N HCl, and the supernatant was brought to a neutral pH with deionized water.
The washed pulp was exchanged with acetone and toluene for 30 minutes and dried to evaporate the solvent, and finally a first complex fiber (oCBC) fiber was obtained.
As can be understood from
A second complex fiber (covalently quaternized CBC (qCBC)), in which a first functional group having nitrogen is bound to the base complex fiber, was prepared according to a method of conjugating a brominated base complex fiber (CBC) and a quaternary amine group by a coupling agent using 1,4-diazabicyclo[2.2.2]octane, as shown in
Specifically, 1 g of the base complex fiber dispersed in N,N-dimethylacetamide (35 ml) solution was reacted with LiBr (1.25 g) suspension while stirring for 30 minutes. N-bromosuccinimide (2.1 g) and triphenylphosphine (3.2 g) were used as a coupling agent. The two reaction mixtures were stirred for 10 minutes and reacted at 80° C. for 60 minutes.
Then, the reaction suspension was cooled to room temperature, added to deionized water, filtered, rinsed with deionized water and ethanol, and freeze-dried to obtain a brominated base complex fiber (bCBC) fiber.
The brominated base complex fiber was dissolved in 100 ml of N,N-dimethylformamide, and reacted with 1.2 g of 1,4-diazabicyclo[2.2.2]octane.
After that, the mixture was subjected to ultrasonic treatment for 30 minutes, and then reacted at room temperature for 24 hours. The resulting solution was mixed with diethyl ether, washed five times with diethyl ether/ethyl acetate, and freeze-dried to obtain a second complex fiber (covalently quaternized CBC (qCBC)).
As can be understood from
A solid state electrolyte was prepared by a gelatin process using the first complex fiber (oCBC) and the second complex fiber (qCBC), as shown in
Bubbles were removed from the gel suspension by using a vacuum chamber (200 Pa), and casted on a glass at 60° C. for six hours. The complex fiber membrane was peeled off while coagulating with deionized water, rinsed with deionized water, and vacuum dried.
A solid state electrolyte (CBCs) was prepared by an ion exchange with 1 M KOH aqueous solution and 0.1 M ZnTFSI at room temperature for six hours, respectively. After that, washing and immersion processes were performed with deionized water in an N2 atmosphere in order to avoid a reaction with CO2 and a formation of carbonate.
As can be understood from
In the process of preparing the solid electrolyte (CBCs), a ratio of the first complex fiber (oCBC) and the second complex fiber (qCBC) was adjusted as shown in Table 4 below.
According to Experimental Example 2-1 described above, a base complex fiber was prepared, but base complex fibers having different chitosan contents were prepared by adjusting an addition ratio of the chitosan derivative. After that, according to Experimental Example 2-6 described above, a solid electrolyte according to Experimental Examples 2-9 to 2-13 was prepared by using base complex fibers having different chitosan contents as shown in <Table 5>.
Dithiooxamide was prepared as a first precursor having sulfur, a mixture of tetradecylphosphonic acid and ifosfamide (1:1 M %) was prepared as a second precursor having phosphorus, copper chloride was prepared as a third precursor having copper, and a mixture of ethanol and ethylenediamine (1:3 v/v %) was prepared as a solvent.
The first to third precursors were added to the solvent and stirred to prepare a suspension.
After that, 2.5 M % ammonium hydroxide was added as a first reducing agent, stirred for two hours, and heat treated at 120° C. for six hours, after which an intermediate product was obtained, washed with deionized water and ethanol, and dried under vacuum at 50° C.
In an ice bath, the intermediate product was mixed and stirred in 20 ml of deionized water with Triton X-165 as a secondary reducing agent and sodium bisulfite as an elemental sulfur source. After that, heat treatment was performed under pressure at 120° C. for 24 hours to prepare a membrane which is formed of a compound of copper, phosphorus, and sulfur and in which a plurality of fibrillated fibers form a network.
The membrane was washed with deionized water and ethanol to adjust to neutral pH, stored at −70° C. for two hours, immersed in liquid nitrogen, and freeze-dried in vacuum, so as to prepare a CuPS electrode structure according to Experimental Example 1 in which a crystal plane 101 is developed.
In the process of fabricating the electrode structure according to Experimental Example 1, a ratio of the first precursor having sulfur and the second precursor having phosphorus was controlled to adjust a ratio of P and S in CuPS at 0.1:0.9, 0.2:0.8, 03:0.7, 0.5:0.5, 0.7.0.3, and 0.9:0.1, respectively.
Referring to
A secondary battery (zinc-air battery) according to Experimental Example 4 was fabricated in a pouch type by using a negative electrode having a plurality of grooves with a depth of 500 nm and a diameter of 500 nm according to Experimental Example 1-1, a solid electrolyte according to Experimental Example 2-6, and a CuPS positive electrode having a ratio of P and S of 0.5:0.5 according to Experimental Example 3.
Specifically, the positive electrode (90 wt %) according to Experimental Example 3, super P carbon (5 wt %), and PTFE (5 wt %) were mixed in N-methyl-pyrrolidone containing 0.5 wt % of Nafion solution so as to prepare a slurry. The slurry was coated on a stainless steel mesh and the solvent was evaporated. Then, the resulting product was cut into a size of 6 cm×1.5 and dried in vacuum.
After that, the positive electrode prepared and cut by the method described above and the solid electrolyte of Experimental Example 2-6 were stacked and bent, after which the negative electrode of Experimental Example 1-1 was placed in the bending region, and pressure was applied to prepare a secondary battery (zinc air battery) of Experimental Example 4.
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Furthermore, it can be confirmed that the peak values corresponding to (100) crystal plane and (101) crystal plane are increased when the diameter of grooves increases from 100 nm to 500 nm while the depth of grooves is fixed at 500 nm; the peak value corresponding to (002) crystal plane is increased when the diameter of grooves exceeds 500 nm; and the peak value corresponding to (002) crystal plane is greater than the peak value corresponding to (100) crystal plane when the peak value corresponding to (100) crystal plane decreases and thus the diameter of grooves is 5 μm.
Consequently, it can be confirmed that a ratio of peak value of (101) crystal plane to (002) crystal plane ((101)/(002)) increases as the diameter and depth of grooves increase from 100 nm to 500 nm, and a ratio of peak value of (101) crystal plane to (002) crystal plane ((101)/(002)) decreases when the diameter and depth of grooves exceed 500 nm.
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In addition, the metal negative electrode of Experimental Example 1-1 was measured to have an electric double layer capacitance of 126 uFcm−2, and the metal negative electrode of Experimental Example 1-2 was measured to have an electric double layer capacitance of 1.86 uFcm−2, and thus it can be confirmed that the metal negative electrode of Experimental Example 1-1 has significantly more electrochemically active surfaces compared to the metal negative electrode of Experimental Example 1-2. In other words, it can be confirmed that the metal negative electrode of Experimental Example 1-1 has a wide surface area and has a high capacity and a mass transfer rate.
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In other words, the fact that the peak value corresponding to (002) crystal plane is lower than the peak value corresponding to (100) crystal plane may refer to a material property caused by the method of fabricating the negative electrode according to the embodiment of the present application.
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In contrast, it can be confirmed that the negative electrode of Experimental Example 1-1 having a plurality of grooves obtained by the patterning process has no substantial change in resistance even after the bending process is performed 20,000 times or more.
In conclusion, it can be confirmed that the negative electrode of Experimental Example 1-1 has excellent mechanical properties and flexibility.
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In other words, it can be seen that an excellent interphase layer is formed on the surface of the zinc electrode and thus dendrite growth is suppressed by an interaction of the solid electrolyte having bacterial cellulose according to Experimental Example 2-6 and the zinc electrode having a plurality of grooves according to Experimental Example 1-1.
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It can be confirmed that bonds such as Zn—F and Zn—S present in the interphase layer are present in an amount of less than 5 at %, but perform an important function of stabilizing a surface of a zinc electrode, and the elastic properties of the solid electrolyte according to an embodiment of the present application having bacterial cellulose stabilize an interphase layer on the surface of the negative electrode together with the bonds of Zn—F and Zn—S.
In addition, it can be seen that a ratio of Zn—F to Zn—S(ZnF/ZnS) increases as a charge/discharge cycle is performed, and also increases up to about 8.6 at % after 6,000 times of charge/discharge cycles. This may be material and electrochemical properties caused by a combination of the solid electrolyte and the negative electrode according to an embodiment of the present application.
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In addition, it can be confirmed that the solid state electrolyte with the same ratio of the first complex fiber and the second complex fiber according to Experimental Example 2-6 has ionic conductivity higher than that of the solid state electrolytes according to Experimental Examples 2-4, 2-5, 2-7, and 2-8. As a result, it can be confirmed that controlling the ratio of the first complex fiber to more than 30 wt % and less than 70 wt %, and controlling the ratio of the second complex fiber to less than 70 wt % and more than 30 wt % is an efficient way to improve the ionic conductivity of OH ions.
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In addition, it can be confirmed that the solid electrolyte with 50 wt % of chitosan according to Experimental Example 2-11 has ion conductivity remarkably higher than that of a solid electrolytes according to Experimental Examples 2-9, 2-10, 2-12, and 2-13. As a result, it can be confirmed that controlling the ratio of chitosan to more than 30 wt % and less than 70 wt % in the solid electrolyte is an efficient way to improve the ion conductivity of OH ions.
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In conclusion, it can be seen that fabricating of the positive electrode having a crystal plane 101 developed and using the same as a positive electrode of a zinc-air battery is an efficient method for improving the charge/discharge properties of the zinc-air battery.
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In contrast, it can be confirmed that the secondary battery according to Experimental Example 4 of the present application is stably driven without any change in charge/discharge properties at various bending angles.
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In conclusion, it can be confirmed that it is preferable to control a thickness along with depth and diameter of grooves formed on a surface of the metal negative electrode in order to implement a metal-air battery having high energy density and high flexibility for a long time, and for example, it may be efficient to use a metal negative electrode with a thickness of 100 to 500 μm.
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However, as in the embodiment of the present application, when a plurality of grooves are formed on the surface, high flexibility may be implemented, and side reactions occurring in the charge/discharge process may be minimized by a combination of the solid electrolyte and the metal negative electrode according to the embodiment of the present application. Accordingly, zinc may be plated and stripped at high density and substantially uniformly during the charge/discharge process, and as a result, dendrite growth may be minimized.
Although the invention has been described in detail with reference to exemplary embodiments, the scope of the present invention is not limited to a specific embodiment and should be interpreted by the attached claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.
A metal negative electrode according to an embodiment of the present application may be used in various fields of industry such as secondary batteries, energy storage devices, batteries for electric cars, etc.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0021252 | Feb 2020 | KR | national |
| 10-2020-0021253 | Feb 2020 | KR | national |
| 10-2020-0021894 | Feb 2020 | KR | national |
| 10-2020-0164657 | Nov 2020 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/002217 | 2/22/2021 | WO |
