Plasmonic electrocatalyst for water-based and flexible metal-air battery and manufacturing method thereof

Abstract

The present application relates to a plasmonic electrode catalyst for a metal-air battery and a manufacturing method thereof, the plasmonic electrode catalyst comprising: a perovskite oxide represented by chemical formula 1; and plasmonic particles formed on the surface of the perovskite oxide, wherein the perovskite oxide is in the form of nanofibers. [Chemical formula 1] A(1-x)BxC(1-y)C'yO3-δ In chemical Formula 1, A is Sr, La, Pr, or Ba; B is Ag, Au, Pt, Mg, or Cu; C and C' each are Nb, Co, Fe, Mn, or Ni; x is 0.01-0.1; y is 0.01-1, and δ may correspond to 0.

Description

Plasmonic electrocatalyst for aqueous and flexible metal-air batteries and method for manufacturing the same

[0001] The present invention relates to a plasmonic electrode catalyst for a metal-air battery and a method for manufacturing the same.

[0002] Zinc-air batteries are receiving significant attention as next-generation batteries because they theoretically have a higher energy density compared to existing commercial batteries, and utilize environmentally friendly and inexpensive materials. A zinc-air battery consists of an air electrode (anode), a separator, an electrolyte, and a negative electrode; the air electrode is composed of a double-layer structure consisting of a catalyst layer and a gas diffusion layer. The catalyst layer supports an anode catalyst that activates oxygen reduction and oxygen generation reactions (oxygen oxidation reactions), while the gas diffusion layer provides a flow path for external air. Since the oxygen reduction and oxygen generation reactions occurring at the anode proceed much more slowly than the oxidation rate at the negative electrode, the reaction in the zinc-air battery depends on the rate of the oxygen reduction reaction at the anode. Accordingly, research is continuously being conducted to improve the performance of the anode catalyst where these reactions take place. Furthermore, the oxidation / reduction reactions at the negative electrode proceed at approximately -1.25 V, while the oxygen reduction and oxidation reactions at the anode proceed at approximately +0.4 V. During battery charging, the voltage difference between the oxygen evolution reaction and the carbon corrosion reaction is only about 0.12 V, so there is a possibility that side reactions other than the oxygen evolution reaction may proceed. Therefore, in order to produce a highly stable and high-performance battery, a catalyst that is good for both the oxygen reduction reaction and the oxygen generation reaction must be utilized.

[0003] [Prior Art Literature]

[0004] [Patent Literature]

[0005] Korean Registered Patent Publication No. 2138261.

[0006] The present invention aims to provide a plasmonic electrode catalyst for metal-air batteries and a method for manufacturing the same.

[0007] However, the problems that this invention seeks to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by a person skilled in the art from the description below.

[0008] The first aspect of the present invention provides a plasmonic electrode catalyst for a metal-air battery comprising: a perovskite oxide represented by the following chemical formula 1; and plasmonic particles formed on the surface of the perovskite oxide, wherein the perovskite oxide is in the form of nanofibers:

[0009] [Chemical Formula 1]

[0010] A (1-x) B x C (1-y) C' y O 3-δ ,

[0011] In the above chemical formula 1, A is Sr, La, Pr, or Ba, B is Ag, Au, Pt, Mg, or Cu, C and C' are each Nb, Co, Fe, Mn, or Ni, x is 0.01 to 0.1, and y is 0.01 to 1.

[0012] A second aspect of the present invention provides an electrode for a metal-air battery comprising a plasmonic electrode catalyst for a metal-air battery according to a first aspect.

[0013] A third aspect of the present invention provides a metal-air battery comprising an electrode for a metal-air battery according to a second aspect.

[0014] The fourth aspect of the present invention provides a method for manufacturing a plasmonic electrode catalyst for a metal-air battery, comprising mixing a perovskite precursor, a polymer, and a solvent to obtain a polymer solution; obtaining polymer nanofibers from the polymer solution using an electrospinning process; calcining the polymer nanofibers to obtain perovskite oxide nanofibers; and calcining the perovskite oxide nanofibers to form plasmonic particles on the surface, wherein the perovskite oxide is represented by Formula 1.

[0015] The plasmonic electrode catalyst for a metal-air battery according to the embodiments of the present invention not only acts as a catalyst for the electrode reaction based on the intrinsic properties of the metal of the plasmonic particles, but may also exhibit a plasmonic phenomenon when irradiated with light, thereby further enhancing catalytic activity.

[0016] The plasmonic electrode catalyst for a metal-air battery according to the embodiments of the present invention comprises a perovskite oxide in the form of a nanofiber containing a hollow space, so that light can reach the interior of the perovskite oxide and the plasmonic phenomenon can occur uniformly.

[0017] The metal-air battery according to the embodiments of the present invention may have a higher maximum output power and stable charge / discharge performance compared to a metal-air battery containing a conventional commercial catalyst (e.g., Pt / C+RuO2).

[0018] FIG. 1 shows a schematic diagram of the synthesis process of nanofiber perovskite oxide (a), scanning electron microscopy (SEM) images (b and c), transmission electron microscopy (TEM) images (d and e), and energy-dispersive X-ray spectroscopy (EDS) analysis results (f and g) of nanofiber perovskite oxide in one embodiment of the present invention.

[0019] FIG. 2 shows the results of the oxygen reduction reaction (ORR) (a to c) and oxygen evolution reaction (OER) (d to f) performance evaluation of the electrode of the present invention in one embodiment of the present invention, the overpotential measurement results (g), the electrochemical surface area (ECSA) analysis results (h), and the plasmonic phenomenon results (i).

[0020] FIG. 3 shows, in one embodiment of the present invention, a schematic diagram of a zinc-air battery (a), an open circuit voltage (OCV) graph (b), current-voltage measurement results (c), current density under various voltage conditions (d), current-voltage measurement results (e), charge-discharge test results (f), and energy efficiency change during charge-discharge cycles (g).

[0021] FIG. 4 shows, in one embodiment of the present invention, a schematic diagram (a) of a flexible zinc-air battery, a photograph and a photograph with the LED voltage turned on (b), a graph of the open circuit voltage (OCV) of the flexible zinc-air battery (c), current-voltage analysis results (d and e), a change in performance according to the degree of bending (f), and a change in energy efficiency during charge-discharge cycles (g).

[0022] Hereinafter, embodiments and examples of the present invention are described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments and examples described herein. Furthermore, in order to clearly explain the present invention in the drawings, parts unrelated to the explanation have been omitted, and similar parts throughout the specification have been given similar reference numerals.

[0023] Throughout this specification, when a part is described as being "connected" to another part, this includes not only cases where they are "directly connected," but also cases where they are "electrically connected" with other elements interposed between them.

[0024] Throughout this specification, when a component is described as being located "on" another component, this includes not only cases where a component is in contact with another component, but also cases where another component exists between the two components.

[0025] Throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0026] Terms of degree used in this specification, such as “about,” “substantially,” etc., are used to mean at or near the stated value when inherent manufacturing and material tolerances are presented in the stated meaning, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which precise or absolute values ​​are mentioned to aid in understanding the invention.

[0027] The terms “step of” or “step of” as used throughout this specification do not mean “step for”.

[0028] Throughout this specification, the term “combination(s) of these” included in the Markush-type expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush-type expression, and means including one or more selected from the group consisting of said components.

[0029] Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

[0030] Embodiments of the present invention have been described in detail below, but the present invention may not be limited thereto.

[0031] The first aspect of the present invention provides a plasmonic electrode catalyst for a metal-air battery comprising: a perovskite oxide represented by the following chemical formula 1; and plasmonic particles formed on the surface of the perovskite oxide, wherein the perovskite oxide is in the form of nanofibers:

[0032] [Chemical Formula 1]

[0033] A (1-x) B x C (1-y) C' y O 3-δ ,

[0034] In the above chemical formula 1, A is Sr, La, Pr, or Ba, B is Ag, Au, Pt, Mg, or Cu, C and C' are each Nb, Co, Fe, Mn, or Ni, x is 0.01 to 0.1, and y is 0.01 to 1.

[0035] In one embodiment of the present invention, the perovskite oxide may be in the form of nanofibers and may be manufactured using an electrospinning method.

[0036] In one embodiment of the present invention, the diameter of each fiber of the nanofiber may be about 50 nm to about 1,000 nm, but is not limited thereto.

[0037] In one embodiment of the present invention, the nanofiber form may include a hollow formed between each fiber.

[0038] In one embodiment of the present invention, the diameter of the hollow may be about 10 nm to about 200 nm, but is not limited thereto.

[0039] In one embodiment of the present invention, the plasmonic particle may include B of Formula 1.

[0040] In one embodiment of the present invention, the plasmonic particles may be formed by heat-treating the perovskite oxide to dissolve B of Formula 1. By being formed by dissolution, the plasmonic particles may be uniformly distributed on the surface of the perovskite oxide, have a small variation in diameter, and have excellent bonding strength to the perovskite oxide.

[0041] In one embodiment of the present invention, the average diameter of the plasmonic particles may be about 10 nm to about 100 nm, but is not limited thereto.

[0042] In one embodiment of the present invention, the plasmonic particles not only act as a catalyst for the electrode reaction according to the intrinsic properties of the metal, but also, when irradiated with light, a plasmonic phenomenon is manifested to change the electrochemical reaction pathway of the catalyst, thereby further enhancing the catalytic activity.

[0043] In one embodiment of the present invention, the plasmonic particles may exhibit a plasmonic phenomenon when irradiated with light in the wavelength range of about 500 nm to about 600 nm.

[0044] In one embodiment of the present invention, since the perovskite oxide is in the form of a nanofiber containing a hollow space, light can reach the interior of the perovskite oxide and plasmonic phenomena can occur uniformly.

[0045] A second aspect of the present invention provides an electrode for a metal-air battery comprising a plasmonic electrode catalyst for a metal-air battery according to a first aspect.

[0046] Detailed explanations have been omitted for parts that overlap with the first aspect of the present invention, but the content explained in the first aspect of the present invention may be applied in the same way even if such explanations are omitted in the second aspect of the present invention.

[0047] In one embodiment of the present invention, the electrode may be an air electrode of a metal-air battery.

[0048] In one embodiment of the present invention, the electrode may include a plasmonic electrode catalyst for the metal-air battery and a conductor, but may not be limited thereto.

[0049] In one embodiment of the present invention, the conductor may be a carbon conductor and, as a non-limiting example, may include Ketjen black, graphene, carbon nanofiber, carbon nanotube, graphene, Ketjen black, or super P.

[0050] In one embodiment of the present invention, the electrode may additionally include a water electrolysis electrode catalyst.

[0051] A third aspect of the present invention provides a metal-air battery comprising an electrode for a metal-air battery according to a second aspect.

[0052] Detailed descriptions of parts that overlap with the first and second aspects of the present invention have been omitted, but the descriptions of the first and second aspects of the present invention may be applied in the same way even if such descriptions are omitted in the third aspect of the present invention.

[0053] In one embodiment of the present invention, the metal-air battery may be irradiated with light in the wavelength range of about 500 nm to about 600 nm to induce a plasmonic phenomenon of the plasmonic particles when driven.

[0054] In one embodiment of the present invention, the plasmonic particles may act as a catalyst for the electrode for the metal-air battery to improve the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance of the electrode.

[0055] A metal-air battery according to one embodiment of the present invention may have a higher maximum output power and stable charge / discharge performance compared to a metal-air battery containing a conventional commercial catalyst (e.g., Pt / C+RuO2).

[0056] In one embodiment of the present invention, the maximum output power of the metal-air battery is approximately 190 mW cm⁻¹ -2 Above, or about 190 mW cm -2 Up to about 200 mW cm -2 It could be.

[0057] In one embodiment of the present invention, the high power range of the metal-air battery is 50 mA cm⁻¹ -2 The charge / discharge overvoltage may be about 0.7 V to about 0.9 V.

[0058] In one embodiment of the present invention, the metal-air battery exhibits a charge-discharge overvoltage value similar to that of the initial cycle (1 to 10 cycles) even after about 60 or more charge-discharge cycles, so the charge-discharge performance can be stable.

[0059] In one embodiment of the present invention, the metal-air battery may be a flexible battery.

[0060] In one embodiment of the present invention, the flexible battery may comprise, but is not limited to, a flexible substrate (a polyethylene terephthalate (PET) substrate as a non-limiting example), an electrode for the metal-air battery as an air electrode, a polymer gel electrolyte, and a zinc electrode.

[0061] In one embodiment of the present invention, the metal-air battery may be a zinc-air battery, a lithium-air battery, an aluminum-air battery, or a magnesium-air battery, but may not be limited thereto.

[0062] A fourth aspect of the present invention provides a method for manufacturing a plasmonic electrode catalyst for a metal-air battery, comprising mixing a perovskite precursor, a polymer, and a solvent to obtain a polymer solution; obtaining polymer nanofibers from the polymer solution using an electrospinning process; calcining the polymer nanofibers to obtain perovskite oxide nanofibers; and calcining the perovskite oxide nanofibers to form plasmonic particles on the surface, wherein the perovskite oxide is represented by the following chemical formula 1:

[0063] [Chemical Formula 1]

[0064] A (1-x) B x C (1-y) C' y O 3-δ ,

[0065] In the above chemical formula 1, A is Sr, La, Pr, or Ba, B is Ag, Au, Pt, Mg, or Cu, C and C' are each Nb, Co, Fe, Mn, or Ni, x is 0.01 to 0.1, and y is 0.01 to 1.

[0066] Detailed explanations have been omitted for parts that overlap with the first aspect of the present invention, but the content described in the first aspect of the present invention may be applied in the same way even if such explanations are omitted in the fourth aspect of the present invention.

[0067] In one embodiment of the present invention, the plasmonic particle may include B of Formula 1.

[0068] In one embodiment of the present invention, the perovskite precursor may comprise a precursor of each element (A, B, C, and C') of the perovskite oxide of Formula 1.

[0069] In one embodiment of the present invention, the solvent may comprise one or more selected from dimethylformamide (DMF), water, ethanol, methanol, propanol, butanol, isopropanol (IPA), acetone, toluene, and tetrahydrofuran, but is not limited thereto.

[0070] In one embodiment of the present invention, the polymer may comprise one or more selected from polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylpyrrolidone (PVP), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polystyrene (PS), and polyvinylidene fluoride (PVDF), but is not limited thereto.

[0071] In one embodiment of the present invention, the electrospinning process may be performed in a voltage range of about 10 kV to about 20 kV, about 14 kV to about 16 kV, or about 15 kV.

[0072] In one embodiment of the present invention, the polymer nanofiber is calcined at about 700°C to about 1300°C, about 700°C to about 1200°C, about 700°C to about 1100°C, about 700°C to about 1000°C, about 800°C to about 1300°C, about 800°C to about 1200°C, about 800°C to about 1100°C, about 800°C to about 1000°C, about 900°C to about 1300°C, about 900°C to about 1200°C, about 900°C to about 1100°C, about 900°C to about 1000°C, about 1000°C to about 1300°C, about 1000°C to about 1200°C, or about 1000°C to about It may be performed in a temperature range of 1100℃.

[0073] In one embodiment of the present invention, the calcination of the polymer nanofiber may be performed for about 1 hour to about 10 hours, about 4 hours to about 6 hours, or about 5 hours.

[0074] In one embodiment of the present invention, the heat treatment of the perovskite oxide nanofiber may be performed in a temperature range of about 200°C to about 500°C, about 300°C to about 400°C, about 300°C to about 350°C, or about 325°C.

[0075] In one embodiment of the present invention, the heat treatment of the perovskite oxide nanofiber may be performed for about 30 minutes to about 5 hours, about 30 minutes to about 3 hours, or about 1 hour.

[0076] In one embodiment of the present invention, the heat treatment of the perovskite oxide nanofiber may be performed under an oxygen and hydrogen gas atmosphere.

[0077] The present invention will be explained in more detail below using examples, but the following examples are merely illustrative to aid in understanding the present invention, and the content of the present invention is not limited to the following examples.

[0078] [Example]

[0079] 1. Preparation of Nanofiber Perovskite Oxide Catalyst

[0080] Nanofiber perovskite oxide (Sr 0.95 Ag 0.05 Nb 0.1 Co 0.9 O 3-d The structure was synthesized according to the following procedure (Fig. 1a): 1) Sr(NO3)2, AgNO3, Co(NO3)26H2O, C 10 H5NbO 20 ..., and citric acid monohydrate were dissolved in DMF (Dimethyl formamide) at 80°C. 2) Polyacrylonitrile (PAN) was added and stirred at the same temperature for 12 hours. 3) It was synthesized in the form of a nanofiber structure using the electrospinning method (15 kV voltage condition). 4) Perovskite (Sr) was produced by calcination at 1000°C for 5 hours. 0.95 Ag 0.05 Nb 0.1 Co 0.9 O 3-d ) The material was synthesized. 6) The exsolution of Ag nanoparticles was completed by maintaining the H2:N2 ratio at 1:10 at 325℃ for 1 hour. Finally, Sr having a plasmonics antenna of Ag nanoparticles 0.95 Ag 0.05 Nb 0.1 Co 0.9 O 3-d Nanofibers (p-SANC NF) were manufactured.

[0081] Referring to Figures 1b and 1c, the appearance of the catalyst before and after the leaching of Ag metal can be confirmed through scanning electron microscopy (SEM) analysis (fibers with a diameter of about 200 nm). Figures 1d and 1e are the results of transmission electron microscopy (TEM) analysis of the catalyst, confirming that Ag metal with a diameter of about 25 nm to 30 nm has been leached. Figures 1f and 1g further confirm that the leached metal is Ag material through EDS mapping analysis.

[0082] 2. Electrode Manufacturing

[0083] An electrode containing the catalyst of 1 was prepared according to the following procedure. 8 mg of catalyst of 1, 2 mg of conductive carbon (Ketjen Black), and 2.5 mg of the binder material Nafion were mixed and dispersed in 1 mL of solution. The 1 mL solution consisted of water and ethanol mixed in a 1:1 ratio. To increase the dispersion of the solution, a sonication process was performed for 24 hours, after which the solution was applied to the surface of each electrode at a concentration of 1 mg cm⁻¹. -2 It was loaded in an amount of [amount]. In the case of a zinc-air battery, the solution was loaded onto the surface of a carbon paper electrode, and in the case of a leaded zinc-air battery, the solution was loaded onto a carbon cloth electrode.

[0084] 3. Zinc-Air Battery Manufacturing

[0085] A zinc-air battery including electrode 2 was prepared according to the following procedure. Electrode 2 was used as the air electrode, and a zinc metal (0.25 mm thick) electrode was used as the zinc electrode. A solution of 6 M KOH + 0.2 M Zn(Ac)2 was used as the electrolyte.

[0086] 4. Manufacturing of flexible zinc-air batteries

[0087] A flexible zinc-air battery containing electrode 2 was fabricated. Electrode 2 was utilized as the air electrode, and a zinc metal electrode (1.5 mm thick) was utilized as the zinc electrode. As an all-solid electrolyte, a gel-type electrolyte was prepared and used. For the synthesis of the gel electrolyte, 1.0 g of polyvinyl alcohol (PVA) powder was dispersed in 10 mL of water and maintained at 90°C for 2 hours. Subsequently, 2.0 mL of 18 M KOH and 0.1 M ZnCl2 were added, and the solution was maintained at 90°C for 1 hour. The final gel electrolyte was completed by cooling the solution at -20°C for 18 hours. The completed gel electrolyte was placed between the zinc electrode and the air electrode, and the entire structure was bonded together with PET material.

[0088] [Experimental Example]

[0089] 1. Evaluation of Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) Performance of Electrodes

[0090] The ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) performance of the electrode of Example 2 was evaluated using an RRDE (Rotating Ring Disk Electrode) device.

[0091] Figures 2a to 2c show the ORR performance evaluation results. Referring to Figure 2a, the p-SANC NF catalyst (orange graph) shows an ORR of approximately -6 mA cm⁻¹, which is similar to that of the commercial catalyst (Pt / C, black graph). -2 The limiting current was shown. After the plasmonic phenomenon was manifested (p-SANC NF (532 nm), red graph), the limiting current was approximately -7 mA cm⁻¹. -2 Up to -8 mA cm -2It was confirmed that the value improved. In addition, through Tafel slope analysis, it was confirmed that the electrochemical reaction rate of the p-SANC NF catalyst is similar to that of commercial catalysts (Fig. 2b). Furthermore, stable ORR performance over time was confirmed (Fig. 2c).

[0092] Figures 2d to 2f show the results of the OER performance evaluation. Referring to Figure 2d, the p-SANC NF (532 nm) catalyst exhibiting plasmonic phenomena (red graph) showed the best OER performance, confirming that it outperformed the commercial catalyst (RuO2, black graph). Through Tafel slope analysis, it was also confirmed that the electrochemical reaction rate was superior to that of the commercial catalyst (Figure 2e). Furthermore, stable OER performance over time was confirmed (Figure 2f).

[0093] Referring to g in Fig. 2, the p-SANC NF catalyst exhibits 30 mA cm⁻¹ in the absence of plasmonic phenomena (i.e., without light irradiation). -2 Under the conditions, OER and approximately 3 mA cm -2 It was confirmed that the overpotential between the two reactions was approximately 0.99 V when the ORR reaction was carried out under these conditions. On the other hand, when the plasmonic phenomenon occurred (i.e., when light was irradiated), the overpotential decreased to 0.91 V under the same conditions. Additionally, it was confirmed that the overpotential for the commercial catalyst (Pt / C+RuO2) was 0.95 V under the same conditions. In other words, the catalyst of the example of the present invention (p-SANC NF (532 nm)) exhibited the lowest overpotential result.

[0094] Through ECSA (electrochemical surface area) analysis, it was confirmed that the p-SANC NF (532 nm) catalyst exhibited the highest electrochemical surface area value (Fig. 2h). By assessing the degree of plasmonic enhancement, it was confirmed that plasmonic phenomena were exhibited in both ORR and OER (Fig. 2i).

[0095] 2. Zinc-Air Battery Performance Test

[0096] The performance of the zinc-air battery of Example 3 was evaluated. Fig. 3a is a schematic diagram of the zinc-air battery of the present invention. Fig. 3b shows the results of the open circuit voltage (OCV) measurement, indicating a stable cell voltage value. Fig. 3c shows the results of the current-voltage (IV) measurement, yielding the maximum output value. In the case of the commercial catalyst (Pt / C+RuO2), the maximum output was approximately 120 mW cm⁻¹. -2 In contrast, for the p-SANC NF (532 nm) plasmonic catalyst, the maximum output is approximately 190 mW cm⁻¹. -2 It was significantly high.

[0097] Referring to Fig. 3d, under various voltage conditions from 1.2 V to 0.6 V, the p-SANC NF (532 nm) plasmonic catalyst exhibited superior current density values ​​compared to commercial catalysts and was also confirmed to have excellent reproducibility.

[0098] Referring to Figure 3e, IV analysis confirmed that the discharge and charge performance of the plasmonic catalyst is also superior to that of commercial catalysts.

[0099] Referring to f in Fig. 3, the high current (50 mA cm⁻¹) -2 As a result of performing charge-discharge tests in ), the charge-discharge overvoltage of the commercial catalyst rose to 1.938 V over 60 cycles, whereas the battery utilizing the plasmonic catalyst of the present invention showed stable performance at approximately 0.892 V.

[0100] Referring to g in Fig. 3, it was confirmed that the energy efficiency of the plasmonic catalyst of the present invention was maintained at a high level of approximately 60% during the charge-discharge test.

[0101] 3. Performance Test of Leaded Zinc-Air Battery

[0102] The performance of the flexible zinc-air battery of Example 4 was evaluated. Fig. 4a is a schematic diagram of a flexible zinc-air battery fabricated using a gel polymer. Fig. 4b shows a photograph of the flexible zinc battery and a photograph with the LED voltage turned on. Fig. 4c confirms the stable OCV voltage value of the flexible zinc battery. Fig. 4d is an IV analysis graph, confirming that the plasmonic catalyst (p-SANC NF (532 nm)) is superior to the commercial catalyst in both discharge and charge performance. Fig. 4e shows the IV analysis results, indicating that for the plasmonic catalyst (p-SANC NF (532 nm)), the maximum output was approximately 40 mW cm⁻¹. -2 In contrast, for commercial catalysts, the maximum output is approximately 22 mW cm⁻¹ -2 It was confirmed that it was.

[0103] Figure 4f confirms the change in performance according to the degree of bending. Approximately 1 mA cm regardless of the degree of bending. -2 It was confirmed that stable charge-discharge performance is exhibited under current density conditions. Referring to g in Fig. 4, it can be seen that the device operates while maintaining an energy efficiency of approximately 60% stably during the charge-discharge test. Therefore, it was confirmed that the plasmonic catalyst of the present invention can be utilized in zinc-air batteries as a replacement for commercial catalysts, and furthermore, can be applied to all-solid-state flexible battery systems.

[0104] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will understand that other specific forms can be easily modified without altering the technical concept or essential features of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single unit may be implemented in a distributed manner, and components described as distributed may likewise be implemented in a combined form.

[0105] The scope of the present invention is defined by the claims set forth below rather than by the detailed description above, and all modifications or variations derived from the meaning and scope of the claims and the concept of equivalents thereof should be interpreted as being included within the scope of the present invention.

Claims

1. A perovskite oxide represented by the following chemical formula 1; and A plasmonic electrode catalyst for a metal-air battery comprising plasmonic particles formed on the surface of the above-mentioned perovskite oxide, Plasmonic electrode catalyst for metal-air batteries, wherein the above perovskite oxide is in the form of nanofibers: [Chemical Formula 1] A (1-x) B x C (1-y) C' y O 3-δ , In the above chemical formula 1, A is Sr, La, Pr, or Ba, and B is Ag, Au, Pt, Mg, or Cu, and C and C' are Nb, Co, Fe, Mn, or Ni, respectively, and x is 0.01 to 0.1, and y is 0.01 to 1.

2. In Paragraph 1, A plasmonic electrode catalyst for a metal-air battery, wherein the above-mentioned nanofiber form includes a hollow structure.

3. In Paragraph 1, A plasmonic electrode catalyst for a metal-air battery, wherein the plasmonic particle comprises B of Chemical Formula 1.

4. In Paragraph 1, A plasmonic electrode catalyst for a metal-air battery, wherein the average diameter of the plasmonic particles is 10 nm to 100 nm.

5. An electrode for a metal-air battery comprising a plasmonic electrode catalyst for a metal-air battery according to claim 1.

6. A metal-air battery comprising an electrode for a metal-air battery according to claim 5.

7. In Paragraph 6, The above metal-air battery is a flexible battery, a metal-air battery.

8. In Paragraph 6, The metal-air battery is a zinc-air battery, a lithium-air battery, an aluminum-air battery, or a magnesium-air battery.

9. Mixing a perovskite precursor, a polymer, and a solvent to obtain a polymer solution; Obtaining polymer nanofibers from the above polymer solution using an electrospinning process; Calcining the above polymer nanofibers to obtain perovskite oxide nanofibers; and Heat-treating the above perovskite oxide nanofibers to form plasmonic particles on the surface A method for manufacturing a plasmonic electrode catalyst for a metal-air battery, comprising: A method for manufacturing a plasmonic electrode catalyst for a metal-air battery, wherein the perovskite oxide is represented by the following chemical formula 1. [Chemical Formula 1] A (1-x) B x C (1-y) C' y O 3-δ , In the above chemical formula 1, A is Sr, La, Pr, or Ba, and B is Ag, Au, Pt, Mg, or Cu, and C and C' are Nb, Co, Fe, Mn, or Ni, respectively, and x is 0.01 to 0.1, and y is 0.01 to 1.

10. In Paragraph 9, A method for manufacturing a plasmonic electrode catalyst for a metal-air battery, wherein the plasmonic particles include B of Chemical Formula 1.

11. In Paragraph 9, A method for manufacturing a plasmonic electrode catalyst for a metal-air battery, wherein the above electrospinning process is performed in a voltage range of 10 kV to 20 kV.

12. In Paragraph 9, A method for manufacturing a plasmonic electrode catalyst for a metal-air battery, wherein the above-mentioned polymer nanofibers are calcined at a temperature range of 700°C to 1300°C.

13. In Paragraph 9, A method for manufacturing a plasmonic electrode catalyst for a metal-air battery, wherein the heat treatment of the perovskite oxide nanofiber is performed in a temperature range of 200°C to 500°C.

Images