KR20230143370A - 3d-on-1d hybrid nanoarchitecture and manufacturing method thereof, supercapacitor containing the same, catalyst for oxygen evolution reaction(oer) containing the same - Google Patents

Abstract

The present invention discloses a 3D-on-1D hybrid nanoarchitecture, a production method thereof, a supercapacitor containing the same, and a catalyst for oxygen evolution reaction (OER) containing the same. The present invention comprises: at least one nanocone grown on carbon cloth; and at least one nanoparticle grown on the nanocone, wherein the nanocone and the nanoparticle contain dual metal phosphides of cobalt nickel phosphide-cobalt phosphide (CoNiP-CoP_2). It is possible to improve electrochemical performance while achieving process simplification by directly synthesizing dual metal phosphides of CoNiP-CoP_2 on highly flexible carbon cloth (CF) using a first-step hydrothermal technique.

Description

3D-on-1D Hybrid Nanoarchitecture and method of manufacturing same, supercapacitor including same, catalyst for oxygen evolution reaction (OER) including same {3D-ON-1D HYBRID NANOARCHITECTURE AND MANUFACTURING METHOD THEREOF, SUPERCAPACITOR CONTAINING THE SAME, CATALYST FOR OXYGEN EVOLUTION REACTION(OER) CONTAINING THE SAME}

The present invention relates to a 3D-on-1D Hybrid Nanoarchitecture and a method of manufacturing the same, a supercapacitor including the same, and a catalyst for oxygen evolution reaction (OER) including the same, and more specifically, , The present invention provides a CoNiP-CoP ₂ 3D-on-1D hybrid nanostructure based on a one-step hydrothermal synthesis method for a long-life hybrid cell and oxygen evolution reaction, a method for manufacturing the same, a supercapacitor containing the same, and an oxygen evolution reaction (OER) containing the same. It's about catalysts.

The recent boom in portable electronics and electric vehicles has highlighted the importance of rechargeable electrochemical systems and green hydrogen production. It is well known that active substances play a key role in both of the above-mentioned systems. Therefore, the cost of an electrochemical system depends on the active material and its preparation.

So far, it has been manufactured using various manufacturing methods such as chemical vapor deposition, thermal evaporation, sputtering, inkjet printing, and electrospinning, but these methods involve high energy consumption equipment, hazardous chemicals/solvents, heavy equipment, and complex operations, so they require no electricity. Increases the production cost of chemical systems.

Therefore, in order to reduce the production cost of electrochemical systems, it is necessary to simplify the process of electrode materials, and research is needed to lower costs and increase environmental safety.

Republic of Korea Patent No. 1883005, “Electrode, manufacturing method thereof, and supercapacitor using the same” Republic of Korea Patent No. 2019-0042268, “Composition for forming supercapacitor electrodes and supercapacitor using the same”

Embodiments of the present invention include dual metal phosphides of CoNiPCoP ₂ (cobalt nickel phosphide-cobalt phosphide) containing nanocones and nanoparticles grown on carbon cloth (CF), thereby demonstrating their flexible properties. The aim is to provide a 3D-on-1D hybrid nanostructure having high area capacity and electrochemical properties, a method for manufacturing the same, a supercapacitor containing the same, and a catalyst for oxygen evolution reaction (OER) containing the same.

An embodiment of the present invention is a 3D-on method that simplifies the process and improves electrochemical performance by directly synthesizing the dual metal phosphide of CoNiP-CoP ₂ on highly flexible carbon cloth (CF) using a one-step hydrothermal synthesis method. -The aim is to provide a 1D hybrid nanostructure, a method for manufacturing the same, a supercapacitor containing the same, and a catalyst for oxygen evolution reaction (OER) containing the same.

The 3D-on-1D hybrid nanostructure according to an embodiment of the present invention includes at least one nanocone grown on carbon cloth; and at least one nanoparticle grown on the nanocone, wherein the nanocone and the nanoparticle include dual metal phosphides of CoNiP-CoP ₂ (cobalt nickel phosphide-cobalt phosphide). .

The CoNiP-CoP ₂ may have a heterojunction structure of CoNiP and CoP ₂ .

The average size of the nanoparticles may be 850 nm to 900 nm.

The contact angle of the 3D-on-1D hybrid nanostructure may be 0°.

A supercapacitor according to an embodiment of the present invention includes a cathode including a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention; cathode (anode); and an electrolyte disposed between the anode and the cathode.

An electrode catalyst for oxygen evolution reaction (OER) according to an embodiment of the present invention includes a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention.

A method of manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention includes preparing a carbon cloth; Preparing a growth solution containing a nickel precursor, a cobalt precursor, a phosphorus precursor, and a solvent; It includes adding the carbon cloth to the growth solution and growing at least one nanocone and at least one nanoparticle on the carbon cloth by hydrothermal synthesis.

The growth solution may further include a surfactant that vertically grows Co-Ni phosphide nuclei formed on the carbon cloth.

In the step of adding a carbon cloth to the growth solution and growing at least one nanocone and at least one nanoparticle on the carbon cloth by hydrothermal synthesis, the growth temperature may be 130°C to 170°C.

In the step of adding a carbon cloth to the growth solution and growing at least one nanocone and at least one nanoparticle on the carbon cloth by hydrothermal synthesis, the growth time may be 3 to 7 hours.

Adding a carbon cloth to the growth solution and growing at least one nanocone and at least one nanoparticle on the carbon cloth by hydrothermal synthesis (S130) includes at least one nanocone and at least one nanoparticle grown on the carbon cloth. A step of drying the nanoparticles may be further included.

According to an embodiment of the present invention, a flexible phosphide comprising dual metal phosphides of CoNiP-CoP ₂ (cobalt nickel phosphide-cobalt phosphide) containing nanocones and nanoparticles grown on carbon cloth (CF) It is possible to provide a 3D-on-1D hybrid nanostructure with flexible properties and high areal capacity and electrochemical properties, a method for manufacturing the same, a supercapacitor containing the same, and a catalyst for oxygen evolution reaction (OER) containing the same. there is.

According to an embodiment of the present invention, the dual metal phosphide of CoNiP-CoP ₂ is directly synthesized on highly flexible carbon cloth (CF) using a one-step hydrothermal synthesis method, thereby simplifying the process and improving electrochemical performance. An -on-1D hybrid nanostructure and a method for manufacturing the same, a supercapacitor including the same, and a catalyst for oxygen evolution reaction (OER) including the same can be provided.

Figure 1 is a schematic diagram showing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing a supercapacitor according to an embodiment of the present invention.
Figure 3 is a schematic diagram showing a method of manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention.
Figure 4 is an image showing an image of a 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention and the results of FE-SEM (field-emission scanning electron microscope) measurement at low to high magnification.
Figure 5a is an image showing the contact angle measurement results of carbon cloth and 3D-on-1D hybrid nanostructures manufactured according to Examples 1 to 3 of the present invention.
Figure 5b is a graph showing the EDS (X-ray spectroscopy) spectrum of the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention, Figure 5c is an element mapping image, and Figure 5d is an XRD (X -ray diffraction) pattern, Figure 5e is a transmission electron microscope (TEM) image, selected area electron diffraction (SAED) pattern, and element mapping image recorded in TEM measurements, Figure 5f is Ni 2p, Co 2p and This is a graph showing the HR XPS spectrum of P 2p element.
Figure 6a is a graph showing the CV curve at 5mV s ^-1 of the 3D-on-1D hybrid nanostructures prepared according to Comparative Example 1, Comparative Example 2, and Examples 1 to 3 of the present invention, and Figure 6b is 2mA cm It is a graph showing the galvanostatic charge-discharge (GCD) curve at ^-2 , and Figure 6c is a graph showing area capacity values.
Figure 6d is a graph showing the CV curves recorded at various sweep rates of the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention, and Figure 6e is the logarithm of the sweep rate and A graph showing the relationship between peak currents, Figure 6f is a graph showing the relationship between v ^1/2 versus i/v ^1/2 , and Figure 6g is a graph showing the relationship between diffusion and capacity control ( It is a graph showing the results of current contribution (diffusion- and capacitive-controlled), Figure 6h is a graph showing the GCD curve, Figure 6i is a graph showing area capacitance values at different current densities, and Figure 6j is 7 mA cm. It is a graph showing the results of the durability test conducted at ^-2 and 10 mA cm ^-2 , and Figure 6k is a graph showing the fitted Nyquist plot before and after the durability test.
Figure 7 shows a schematic diagram of the Operando FIG. 9 is a graph showing the CV curves of CNP-CP-150 and AC electrodes measured in the corresponding voltage window to estimate the optimal voltage window of the supercapacitor manufactured according to 0. It is a graph showing the CV curve within a voltage window of -1.5V, Figure 10 is a graph showing the GCD curve within a voltage window of 0-1.5V, and Figure 11 is a graph showing the Ni K-edge and Co K-edge This is a graph showing the XANES spectrum.
FIG. 12 is a graph showing the specific/area capacitance values at different current densities of the supercapacitor manufactured according to Example 4 of the present invention, and FIG. 13 is a graph showing the specific/area energy and power density values. 14 is a graph showing the results of the speed performance test, Figure 15 is a graph showing the results of the durability test, Figure 16 is a graph showing the Nyquist plot obtained before and after the durability test, and Figure 17 is a graph showing the results of the durability test. It is a graph showing the CV curve at various sweep speeds, Figure 18 is a graph showing the GCD curve at various sweep speeds, and Figure 19 is the area/specific capacity of QSSD (quasi-solid-state device; Example 5). It is a graph showing the values, and Figure 20 is an image showing a QSSD (quasi-solid-state device) designed in the form of a bracelet (bracelet-like set-up).
Figure 21 shows the LSV ( ^linear It is a graph showing the sweep voltammograms profile, and Figure 22 is a graph showing the OP (onset overpotential) value of the catalyst required to drive a current density of 8.5 10 mA cm ^-2 or 10 mA cm ^-2 , and Figure 23 is the Tafel slope. It is a graph showing the (Tafel slope), and Figure 24 is a graph comparing the Tafel slope of the catalyst containing the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention and the reference materials, Figure 25 is a graph showing the results of a time potentiometer test performed on the catalyst containing the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention at 10 mA cm ^-2 for 24 hours.
Figure 26 is an image showing the TEM results and SAED pattern of catalyst nanoparticles containing the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention after the OER stability test, and Figure 27 is an image showing the nanocone This is an image showing the TEM results and SAED pattern, Figure 28 is a graph showing the EDS spectrum, and Figure 29 is an element mapping image of HNA.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described in the accompanying drawings, but the present invention is not limited or limited by the embodiments.

The terminology used herein is for describing embodiments and is not intended to limit the invention. As used herein, singular forms also include plural forms, unless specifically stated otherwise in the context. As used in the specification, “comprises” and/or “comprising” does not exclude the presence or addition of one or more other components or steps.

As used herein, “embodiment,” “example,” “aspect,” “example,” etc. should be construed to mean that any aspect or design described is better or advantageous than other aspects or designs. It's not like that.

Additionally, the term 'or' means an inclusive OR 'inclusive or' rather than an exclusive OR 'exclusive or'. That is, unless otherwise stated or clear from the context, the expression 'x uses a or b' means any of the natural inclusive permutations.

Additionally, as used in this specification and claims, the singular expressions “a” or “an” generally mean “one or more,” unless otherwise indicated or it is clear from the context that the singular refers to singular forms. It should be interpreted as

The terms used in the description below have been selected as general and universal in the related technical field, but there may be different terms depending on technological developments and/or changes, customs, technicians' preferences, etc. Accordingly, the terms used in the description below should not be understood as limiting the technical idea, but should be understood as illustrative terms for describing embodiments.

In addition, in certain cases, there are terms arbitrarily selected by the applicant, and in this case, the detailed meaning will be described in the relevant description. Therefore, the terms used in the description below should be understood based on the meaning of the term and the overall content of the specification, not just the name of the term.

Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used with meanings that can be commonly understood by those skilled in the art to which the present invention pertains. Additionally, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless clearly specifically defined.

Meanwhile, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. In addition, the terminology used in this specification is a term used to appropriately express the embodiments of the present invention, and may vary depending on the intention of the user or operator or the customs of the field to which the present invention belongs. Therefore, definitions of these terms should be made based on the content throughout this specification.

Figure 1 is a schematic diagram showing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention.

The 3D-on-1D hybrid nanostructure according to an embodiment of the present invention includes at least one nanocone 122 grown on carbon cloth 110 and at least one nanoparticle 123 grown on the nanocone. And the nanocones 122 and nanoparticles 123 include dual metal phosphides of CoNiP-CoP ₂ (cobalt nickel phosphide-cobalt phosphide).

Therefore, the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention is a double metal of CoNiP-CoP ₂ including nano 122 cones and nanoparticles 123 grown on carbon cloth (CF; 220). By including phosphide, it can have flexible properties and at the same time have high area capacity and electrochemical properties.

In the double metal phosphide of CoNiP-CoP ₂ , CoNiP and CoP ₂ may have a heterojunction structure. Therefore, the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention promotes rapid electron transfer by forming a heterojunction between CoNiP and CoP ₂ and changes the electronic structure of the active site of the material to generate charge. It can reduce movement resistance and improve supercapacitor and electrocatalytic activity performance.

The 3D-on-1D hybrid nanostructure according to an embodiment of the present invention includes carbon cloth 110.

Carbon cloth 110 can be used as a substrate and can be formed into a fabric form to have flexibility.

Therefore, the carbon cloth 110 can serve as an efficient current collector with excellent electrical conductivity in a flexible energy storage device.

The 3D-on-1D hybrid nanostructure according to an embodiment of the present invention includes a double metal phosphide of CoNiP-CoP ₂ formed on carbon cloth 110, and the double metal phosphide of CoNiP-CoP ₂ has at least one nanocone. (122) and at least one nanoparticle (123) grown on the nanocone.

The nanocone 122 includes one end in contact with the carbon cloth 110 and the other end not in contact with the carbon cloth 110, and the other end is vertically grown in the carbon cloth 110 to have a sharp edge to provide a high surface area. there is.

The nanoparticles 123 may have a cashew fruit shape, and the cashew fruit shape may have a width profile in which the width changes from one end to the other based on both ends of the nanoparticle.

Therefore, the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention has increased surface roughness by the nanocones 122 and nanoparticles 123, so that it can form a nanosheet with a rough outer surface.

The shape of 3D-on-1D hybrid nanostructures is an important parameter controlling the electrochemical properties in supercapacitors or oxygen evolution reaction (OER). The morphological size, surface area, porosity and reasonable structural properties are related to the accessibility of active sites, Mass diffusion and charge transport processes can be controlled. Reducing the size of any form to the nanoscale range significantly increases the surface area, which can control the number of electrochemically active sites.

Therefore, the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention has a 3D structure because the double metal phosphide of CoNiP-CoP ₂ includes at least one nanocone 122 and at least one nanoparticle 123. Electrochemical properties can be improved by increasing the surface area of the -on-1D hybrid nanostructure shape and increasing the number of electrochemically active sites.

The average length (height) of the nano cones may be nanometers to micrometers, and preferably, the average length (height) of the nano cones may be 1.1 ㎛. For example, if the average length of a nanocone is micro-sized, it may not provide all the active sites that contribute in the electrochemical reaction, so having a nano-sized size increases the active surface area and provides more active sites to improve electrochemical performance. can be improved.

The average size (width) of the nanoparticles may be nano-sized, and preferably may be 850 nm to 900 nm. For example, if the average size of nanoparticles is micro, it may not provide all active sites contributing to the electrochemical reaction, so having a nano size can provide more active sites.

The contact angle of the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention may be 0°.

More specifically, hydrophilicity is an important property of electrodes because electrodes cannot absorb electrolytes if they are hydrophobic, so to carry out electrochemical reactions in energy storage or conversion fields, electrodes must be in contact with liquid/gel electrolytes. Bare carbon cloth exhibits a high contact angle of 123°, showing high hydrophobicity, but the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention exhibits a contact angle of 0°, so it has high hydrophilicity and can be used while measuring electrochemical properties. Because it improves the interaction between the active material and the electrolyte, the active material can be completely wetted by the electrolyte and cause many electrochemical reactions.

Therefore, the 3D-on-1D hybrid nanostructure according to the embodiment of the present invention forms a double metal phosphide of CoNiP-CoP ₂ on the hydrophobic carbon cloth 110, thereby providing high hydrophilicity to the embodiment of the present invention. The interaction between the 3D-on-1D hybrid nanostructure and the electrolyte is improved, so that the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention can be completely wetted by the electrolyte, causing more electrochemical reactions.

3D-on-1D hybrid nanostructures according to embodiments of the present invention can exhibit not only excellent OER activity but also energy storage performance thanks to their high redox chemistry, morphology, and fast electrokinetics. That is, the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention exhibits stable electrocatalytic activity for 24 hours in a stability test conducted at 10 mA cm ^-2 and can exhibit excellent durability over 30,000 cycles or more. The practicality of the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention can be applied by manufacturing a quasi-solid hybrid cell and then supplying power to electronic components.

Therefore, the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention can be used as an electrode or electrode catalyst for an energy storage device or an OER device, but is not limited thereto, and can be used in various energy materials for energy storage and catalyst applications. may be included.

Preferably, the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention can be used as an electrode of a supercapacitor or an electrode catalyst of an OER device.

More specifically, the flourishing of wearable and portable electronics in recent years has stimulated the exploration of flexible and long-lasting powered devices. Supercapacitors (SCs) and lithium-ion batteries (LIBs), among other energy storage systems, are leading the way in powering portable electronics.

In particular, supercapacitors (SCs) are receiving increasing attention over lithium-ion batteries (LIBs) in terms of safety, durability, power density, and flexibility. Supercapacitors (SCs) with hybrid cell configurations using highly redox-active battery-type materials and porous carbon-related materials as anodes and cathodes respectively achieve higher energy densities.

The adaptability of supercapacitors (SCs) in flexible electronics is only conceivable if they are fabricated with highly flexible electrodes. Conductive fiber/fabric-based substrates with flexible fibers and woven textures have been attracted as suitable current collectors for fabricating flexible supercapacitors (SCs) due to their impressive shape elasticity, high electrical conductivity and light weight. Among several conductive fibers/fabrics, carbon fiber (CF) exhibits high mechanical strength, chemical stability, corrosion resistance, and thermal conductivity in addition to the above-mentioned properties. Considering these characteristics of carbon fiber (CF), it is advantageous to form the active material directly on the surface by removing the binder and additives, and the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention is made using a one-step hydrothermal synthesis method. By synthesizing the dual metal phosphide of CoNiP-CoP ₂ directly on the carbon cloth 110, the current collector, binder, and additives are eliminated to simplify the process and reduce the process cost, while simultaneously maintaining the flexibility and electrochemical properties of the electrode. It can be improved.

Additionally, apart from energy storage, producing green energy sources is also indispensable in the scenario of rapid consumption of fossil fuels and environmental problems. Producing hydrogen (H ₂ ) using electrochemical water splitting technology without emitting carbon monoxide into the environment is considered an ideal source of future energy. The water splitting process consists of two key redox reactions: oxygen evolution reaction (OER) and hydrogen evolution reaction at the anode and cathode, respectively. Therefore, catalysts with high OER activity should be prepared without noble metals through facile synthetic routes to reduce ecological scarcity and production costs.

Transition metal phosphides (TMPs), which have high electrochemical activity, metalloid structure, high chemical stability, and multiple electronic orbitals, have recently attracted attention as potential electrode candidates for energy storage, water splitting, etc.

The 3D-on-1D hybrid nanostructure according to an embodiment of the present invention includes a double metal phosphide of CoNiP-CoP ₂ grown on carbon cloth, and the double metal phosphide of CoNiP-CoP ₂ , which is a transition metal phosphide (TMP), is Because cobalt is composed of transition metals, has closer atomic and electronic structures, and cobalt (Co) or nickel (Ni) has high redox chemistry, multivalent states, high electrical conductivity, and excellent durability, the practice of the present invention The 3D-on-1D hybrid nanostructure according to the example can be used as an electrode material in the field of energy storage and as a potential catalyst in water splitting technology.

Accordingly, the electrode catalyst for oxygen evolution reaction (OER) according to an embodiment of the present invention includes a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention.

Figure 2 is a schematic diagram showing a supercapacitor according to an embodiment of the present invention.

A supercapacitor according to an embodiment of the present invention includes an anode (cathode) including a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention, a cathode (anode), and an electrolyte disposed between the anode and the cathode.

A supercapacitor according to an embodiment of the present invention includes a cathode including a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention.

Since the 3D-on-1D hybrid nanostructure according to an embodiment of the present invention is the same as that described in FIG. 1, description of the same components will be omitted.

Conventionally, various conductive substrates such as nickel foam/foil, copper foam/foil, titanium foil, stainless steel foil, graphite sheet, etc. were used as current collectors to manufacture the anode. However, the conductive substrate is rigid and inflexible, making it a flexible energy storage system. There was a problem with not being able to manufacture.

However, since the supercapacitor according to an embodiment of the present invention uses a 3D-on-1D hybrid nanostructure containing a double metal phosphide of CoNiP-CoP ₂ grown on carbon cloth as an anode, carbon cloth is used as a conductive substrate. , by using the double metal phosphide of CoNiP-CoP ₂ as an active material, a flexible energy storage system with flexibility in various physical deformation conditions such as bending, rolling, twisting, and folding can be manufactured.

A supercapacitor according to an embodiment of the present invention includes a cathode (anode).

The negative electrode may include a negative electrode coating layer coated on the negative electrode current collector.

The negative electrode coating layer may include an active material, and the active material may be formed of a carbon material containing carbon. For example, the active material may include petroleum pitch, coal-based pitch, raw coke, Calcination can be formed using carbon materials such as coke and coke dust.

The active material formed of a carbon material may include, but is not limited to, at least one of activated carbon, graphite, fullerene (C60), soft carbon, and carbon black. It may contain materials that can meet the required properties.

Depending on the embodiment, the cathode coating layer may further include a binder, and the binder may be carboxymethylcellulose (CMC), linear polyvinylidene fluoride (PVDF), or branched polyvinylidene fluoride (PVDF). , polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyethylene (PE), polypropylene (PP), and polyvinyl alcohol (PVA). However, the embodiment is not limited thereto and may include materials that can satisfy the properties required for the binder.

Depending on the embodiment, the cathode coating layer may further include a conductive agent, and the conductive agent is carbon black (CB), acetylene black, ketjen black, graphite, or super-P. -p) may be included.

The current collector may include a conductive metal, and the conductive metal is made of aluminum (Al), gold (Au), silver (Ag), stainless steel (STS), nickel (Ni), copper (Cu), and combinations thereof. It may include at least one of the alloys.

A supercapacitor according to an embodiment of the present invention includes an electrolyte disposed between an anode and a cathode.

The electrolyte may be an electrolyte solution or a gel electrolyte. If a gel electrolyte is used, stability can be improved. Additionally, the electrolyte may include a solid electrolyte.

The electrolyte solution may be an aqueous electrolyte solution or a non-aqueous electrolyte solution. Aqueous electrolytes have excellent electrical properties. In detail, aqueous electrolytes have excellent electrical conductivity, so supercapacitors using electrolytes can reduce internal resistance. However, when using an aqueous electrolyte, the operating voltage of the supercapacitor, that is, the driving voltage, is low, which has the disadvantage of lowering the energy density of the supercapacitor.

On the other hand, non-aqueous electrolytes have lower electrical conductivity and higher viscosity than aqueous electrolytes, but can be used in supercapacitors in high temperature and high voltage environments due to the high applicable potential difference. Additionally, when using a non-aqueous electrolyte, the supercapacitor can be miniaturized.

The electrolyte solution may include a solvent and an electrolyte salt, and the solvent and electrolyte salt are not particularly limited and may include materials that can meet the characteristics required for a supercapacitor. there is.

Gel electrolytes may include polymers and liquid electrolytes.

Polymers include polyvinyl alcohol, poly2-Acrylamido-2-methyl-1-propanesulfonic acid (PAMPS), polyacrlic acid, and poly(N-pyrrolidone). )), polysaccharide, hydroxyethyl methacrylate (HEMA), acryl amide, and dimethylacrylamide.

The liquid electrolyte may include an ionic liquid or an organic electrolyte.

Depending on the embodiment, the supercapacitor according to the embodiment of the present invention may further include a separator disposed between the anode and the cathode. The separator may be included separately or may be formed integrally with the electrolyte.

When a gel electrolyte or a solid electrolyte is used as the electrolyte, each of the anode and cathode may be coated and disposed so that the anode and cathode are electrically insulated from each other.

The separator is made of at least one of polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, polyacrylonitrile porous separator, poly(vinylidene fluoride) hexafluoropropane copolymer porous separator, cellulose porous separator, kraft paper, and rayon fiber. It may include, but is not limited to, the separator 230 may include a material that can satisfy the characteristics required for the separator of a supercapacitor.

Figure 3 is a schematic diagram showing a method of manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention.

The method of manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention includes preparing a carbon cloth 110 (S110), preparing a growth solution containing a nickel precursor, a cobalt precursor, a phosphorus precursor, and a solvent. A step (S120) and a step (S130) of adding carbon cloth 110 to a growth solution and growing at least one nanocone 122 and at least one nanoparticle 123 on the carbon cloth 110 by hydrothermal synthesis. Includes.

Therefore, the method for manufacturing 3D-on-1D hybrid nanostructures according to an embodiment of the present invention is a one-step hydrothermal synthesis method using hydrothermal synthesis, which is an easy and efficient method for manufacturing electrode materials, and CoNiP is formed on a very flexible carbon cloth 110. By directly synthesizing the dual metal phosphide of -CoP ₂ , the process can be simplified and the electrochemical performance can be improved at the same time.

The method for manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention proceeds with the step of preparing carbon cloth (110) (S110).

The carbon cloth 110 may preferably be a carbon cloth fiber, and the carbon material included in the carbon cloth 110 is not particularly limited.

The method for manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention proceeds with a step (S120) of preparing a growth solution containing a nickel precursor, a cobalt precursor, a phosphorus precursor, and a solvent.

Nickel precursors may include nickel salts, for example, NiCl ₂ , Ni(NO ₃ ) ₂ ·6H ₂ O, Ni(CH ₃ CO ₂ )·H ₂ O, and NiSO ₄ ·6H ₂ O. It may include at least one of, but is not limited to, and preferably, the nickel precursor may include NiCl ₂ .

The cobalt precursor may include a cobalt salt, for example, CoCl _2, Co(NO ₃ ) ₂ ·6 H ₂ O, Co(CH ₃ CO ₂ )·4 H₂O, and CoSO ₄ ·6H ₂ O. It may include at least one of, but is not limited to, and preferably, the cobalt precursor may include CoCl ₂ .

The phosphorus precursor may include, but is not limited to, at least one of NaPO ₂ H _2, Na ₃ PO ₄ , and ((NH ₄ ) ₃ PO _4. Preferably, the phosphorus precursor is It may include NaPO ₂ H ₂ .

The solvent may be any substance used in the art without limitation.

The growth solution may further include a surfactant that vertically grows Co-Ni phosphide nuclei formed on the carbon cloth 110.

The surfactant may include at least one of urea, NH ₄ F, EDTA (C ₁₀ H ₁₆ N ₂ O ₈ ), and HMTA (C ₆ H ₁₂ N ₄ ), but is not limited thereto, and is preferably used as a surfactant. The activator may include urea.

The method for manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention is to place carbon cloth 110 in a growth solution and form at least one nanocone 122 and at least one nanocone 122 on the carbon 110 cloth by hydrothermal synthesis. The step (S130) of growing the above nanoparticles 123 is performed.

Step 130 is a step of forming a Co-Ni phosphide thin film 121 on the carbon cloth 110 (S131), in which the Co-Ni phosphide nuclei of the Co-Ni phosphide thin film 121 grow vertically to form at least one nanocone ( 122) may include forming (S132) and forming at least one nanoparticle 123 on at least one nanocone 122 (S133).

In addition, the Co-Ni phosphide thin film 121 is used as a seed layer to form a dual metal phosphide of CoNiP-CoP ₂ on carbon (110) cloth, and is continuously formed in the Co-Ni phosphide thin film 121. Nano cones 122 and nanoparticles 123 can be grown.

More specifically, in step S130, metal cations (CO ²⁺ and Ni ²⁺ ) liberated from the nickel precursor and cobalt precursor through hydrothermal synthesis react with H ₂ PO ₂ ^- ions to form Co-Ni on the surface of the carbon cloth (110). A phosphide thin film 121 is formed.

Thereafter, as the reaction time passes, the basicity gradually increases in the reaction medium, further accelerating the precipitation of Co-Ni phosphide nuclei, and at this time, the surfactant causes the Co-Ni phosphide nuclei to grow vertically. A nano cone 122 can be formed.

In addition, even after the nanocone 122 is formed, the accessibility of numerous metal cations (CO ²⁺ and Ni ²⁺ ) is increased due to the presence of H ₂ PO ₂ ^- ions, but they do not diffuse to the surface of the carbon cloth 110, causing excessive Due to the ions, cashew fruit-shaped nanoparticles 123 may be randomly deposited on the nano cone 122 without a specific direction.

Therefore, the method for manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention uses a 3D-on-1D hybrid nanostructure of cashew fruit-shaped nanoparticles 123 and nano cones 122 through a one-step sequence. The dual metal phosphide of CoNiP-CoP ₂ can be synthesized directly on a highly flexible carbon cloth (110) substrate using a synthetic method.

In the method of manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention, electrochemical properties can be adjusted depending on the growth temperature.

In the method of manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention, nanoparticles 123 can be formed as the growth temperature increases, but if the growth temperature is too high, cracks and overcoating may occur. there is. For example, if the growth temperature is too low (e.g., 150°C), nanoparticles 123 are not formed, resulting in fewer active sites, and if the growth temperature is too high (e.g., 170°C), electrochemical damage occurs due to cracking and overcoating. Unable to carry out reactions, cracks can impede charge transport and durability.

That is, since the response of 3D-on-1D hybrid nanostructures is due to the higher deposition active mass (nanocones and nanoparticles) and hybrid morphology, nanoparticles (123) provide auxiliary active sites in addition to nanocones (122), thereby Since electrochemical reactions can be induced, the active sites of nanocones 122 and nanoparticles 123 can enable numerous reversible redox reactions in the potential range measured in an alkaline electrolyte.

In the method of manufacturing a 3D-on-1D hybrid nanostructure according to an embodiment of the present invention, the structure of the double metal phosphide of CoNiP-CoP ₂ can be adjusted depending on the growth temperature.

In the step (S130) of adding a carbon cloth to a growth solution and growing at least one nanocone and at least one nanoparticle on the carbon cloth by hydrothermal synthesis, the growth temperature may be 130°C to 170°C. If the growth temperature is less than 130°C, nanoparticles are not formed due to too low a growth temperature, and if the growth temperature exceeds 170°C, there is a problem of cracks occurring due to overgrowth.

More specifically, if the growth temperature is less than 130°C, only the nanocone 120 is formed, so no nanostructure is formed except the nanomembrane. On the other hand, if the growth temperature exceeds 170°C, a large number of cracks are generated, which may lead to serious cracking or overcoating.

In the step (S130) of growing at least one nanocone 122 and at least one nanoparticle 123 on the carbon (110) cloth by hydrothermal synthesis by adding the carbon cloth (110) to the growth solution, the growth time is 3 It can be from 1 hour to 7 hours, preferably, the growth time can be 5 hours.

If the growth time is less than 3 hours, the production of well-defined nano cones 122 and nanoparticles 120 in the shape of nano cashew fruits is low, so the effect is insignificant due to the small number, and if it exceeds 7 hours, Overcoatings/cracks or lumps may form on the carbon cloth 110, impeding electrolyte penetration and charge rate.

In addition, the method for manufacturing 3D-on-1D hybrid nanostructures according to an embodiment of the present invention does not require a separate cooling process because growth proceeds at low temperature (e.g., 150°C), enabling process simplification.

The step (S130) of growing at least one nanocone 122 and at least one nanoparticle 123 on the carbon cloth 110 by hydrothermal synthesis by adding the carbon cloth 110 to the growth solution is performed on the carbon cloth. It may further include drying the grown at least one nanocone and at least one nanoparticle.

The drying step may be performed using a hot air oven.

Example 1: CNP-CP-130

Chloride salts of cobalt (CoCl ₂ ·6H ₂ O, 0.43 g) and nickel (NiCl ₂ ·6H ₂ O, 0.48 g) were mixed in a Teflon liner containing 60 mL of demineralized water (DMW). . Then, sodium hypophosphite (NaPO ₂ H ₂ , 0.14 g) and urea (CH ₄ N ₂ O, 0.47 g) were added to the above solution, and this growth solution was incubated for about 10 minutes until all chemicals were completely dissolved. It was left for a minute.

Meanwhile, the carbon cloth (CF) substrate was attached to a glass slide using Teflon tape to allow the active material to grow only on a surface area of 1 Х 1 cm ² , and then oxidized in a muffle furnace to make the CF substrate hydrophilic. .

CF was immersed in the growth solution, and the growth solution was heated in an autoclave reaction system at 130°C and maintained for 5 hours.

After cooling the autoclave, the CF substrate loaded with CNP-CP was washed several times with DMW and then dried in an oven overnight.

Example 2: CNP-CP-150

It was prepared in the same manner as Example 1, except that the growth temperature was 150°C.

Example 3: CNP-CP-170

It was prepared in the same manner as Example 1 except that the growth temperature was 170°C.

Comparative Example 1: CP-150

The chloride salt of cobalt (CoCl ₂ ·6H ₂ O, 0.43 g) was mixed in a Teflon liner containing 60 mL of demineralized water (DMW). Then, sodium hypophosphite (NaPO ₂ H ₂ , 0.14 g) and urea (CH ₄ N ₂ O, 0.47 g) were added to the above solution, and this growth solution was incubated for about 10 minutes until all chemicals were completely dissolved. It was left for a minute.

Meanwhile, the CF substrate was attached to a glass slide using Teflon tape so that the active material could be grown only on a surface area of 1 Х 1 cm ² and then oxidized in a muffle furnace to make the CF substrate hydrophilic.

CF was immersed in the growth solution, and the growth solution was heated in an autoclave reaction system at 130°C and maintained for 5 hours.

After cooling the autoclave, the CF substrate loaded with CNP-CP was washed several times with DMW and then dried in an oven overnight.

That is, conventional cobalt phosphide can be produced in the same manner as Example 1, except that the nickel precursor is not added in Example 1.

Comparative Example 2: NP-150

The chloride salt of nickel (NiCl ₂ ·6H ₂ O, 0.48 g) was mixed in a Teflon liner containing 60 mL of demineralized water (DMW). Then, sodium hypophosphite (NaPO ₂ H ₂ , 0.14 g) and urea (CH ₄ N ₂ O, 0.47 g) were added to the above solution, and this growth solution was incubated for about 10 minutes until all chemicals were completely dissolved. It was left for a minute.

Meanwhile, the CF substrate was attached to a glass slide using Teflon tape so that the active material could be grown only on a surface area of 1 Х 1 cm ² and then oxidized in a muffle furnace to make the CF substrate hydrophilic.

CF was immersed in the growth solution, and the growth solution was heated in an autoclave reaction system at 130°C and maintained for 5 hours.

After cooling the autoclave, the CF substrate loaded with CNP-CP was washed several times with DMW and then dried in an oven overnight.

That is, conventional nickel phosphide can be produced in the same manner as Example 1, except that the cobalt precursor is not added in Example 1.

Example 4: Supercapacitor with hybrid cell configuration

The 3D-on-1D hybrid nanostructure (CNP-CP-150) according to Example 2, microporous filter paper, activated carbon-supported CF substrate (AC@CF), and 2m KOH solution serve as an anode, separator, cathode, and electrolyte, respectively. Hybrid cells were assembled.

A mixture of activated carbon (AC) powder, Super P carbon black, and PVDF powder at a weight ratio of 80:10:10, respectively, was placed in an agate mortar. Next, the mixture was well pulverized for about 30 minutes, then a sufficient amount of NMP solvent was added dropwise to the mixture, and the mixture was pulverized for another 10 minutes. Finally, the viscous slurry was loaded onto the cleaned CF substrate within an active area of ¹ The AC loaded CF (AC@CF) electrode (cathode) was compressed to ~3 MPa. The mass of the AC material on a carbon cloth (CF) substrate is ~3.5 mg cm ^-2 .

Example 5: QSSD

It was prepared in the same manner as Example 4, except that PVA-KOH gel polymer-electrolyte was used instead of KOH solution.

PVA-KOH gel polymer-electrolyte was prepared as follows.

2 g of PVA was added to 20 mL of DMW, the solution was vigorously stirred using magnetic beads for about 5 minutes, and then heated at 80°C until the PVA in the stirred solution was completely dissolved in DMW.

Then, KOH solution (2 m in 10 mL DMW) was added dropwise to the stirred solution, and the entire solution was heated again under stirring to form a gel due to evaporation of excess water, and the gel was applied to both the anode and cathode after cooling.

Finally, the two electrodes were overlapped with each other and packed with paraffin film.

Figure 4 is an image showing an image of a 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention and the results of FE-SEM (field-emission scanning electron microscope) measurement at low to high magnification.

Referring to FIG. 4, it can be seen that the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention has flexibility favorable for various physical deformations such as rolling, bending, and twisting.

In addition, the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention, unlike the smooth surface of the carbon cloth fiber, has cashew fruit-shaped nanoparticles and nanocones formed on the surface of the carbon cloth fiber by hydrothermal synthesis, resulting in a rough surface. It can be seen that it has a surface.

In addition, in the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention, it can be seen that the double metal phosphide of CoNiP-CoP ₂ was formed uniformly without cracks on the surface of the carbon cloth fiber.

Figure 5a is an image showing the contact angle measurement results of carbon cloth and 3D-on-1D hybrid nanostructures manufactured according to Examples 1 to 3 of the present invention.

123°의 높은 접촉각을 나타내나, 본 발명의 실시예 1 내지 실시예 3에 따라 제조된 3D-on-1D 하이브리드 나노 구조물은 0°의 낮은 접촉각을 나타내는 것을 알 수 있다.Referring to Figure 5A, the carbon cloth fiber substrate exhibits hydrophobic properties.

Although it shows a high contact angle of 123°, the 3D-on-1D hybrid nanostructure manufactured according to Examples 1 to 3 of the present invention shows a low contact angle of 0°.

Therefore, the 3D-on-1D hybrid nanostructures prepared according to Examples 1 to 3 of the present invention have improved interaction between the active material and the electrolyte through high hydrophilicity, so that the active material is completely wetted by the electrolyte, resulting in more electrochemical activity. It can be seen that it triggers a reaction.

Figure 5b is a graph showing the EDS (X-ray spectroscopy) spectrum of the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention, Figure 5c is an element mapping image, and Figure 5d is an XRD (X -ray diffraction) pattern, Figure 5e is a transmission electron microscope (TEM) image, selected area electron diffraction (SAED) pattern, and element mapping image recorded in TEM measurements, Figure 5f is Ni 2p, Co 2p and This is a graph showing the HR XPS spectrum of P 2p element.

25.8°에서 높은 강도의 넓은 피크가 검출되고,

43.4° 및

55.7°에서 다른 두 피크가 검출되는 것으로 보아, 탄소 천 기판을 확인할 수 있고, 다른 날카로운 회절 피크는 아나타제(anatase) CoNiP(#71-2336) 및 CoP₂(#77-0263) 상의 특징적인 피크가 검출되는 것으로 보아, 본 발명의 실시예 2에 따라 제조된 3D-on-1D 하이브리드 나노 구조물이 탄소 천 및 CoNiP-CoP₂의 이중 금속 인화물을 포함하는 것을 알 수 있다.Referring to Figures 5b to 5f,

A broad peak of high intensity is detected at 25.8°,

43.4° and

The detection of two other peaks at 55.7° confirms the carbon cloth substrate, and the other sharp diffraction peaks are characteristic peaks for anatase CoNiP (#71-2336) and CoP ₂ (#77-0263). From the detection results, it can be seen that the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention includes carbon cloth and a double metal phosphide of CoNiP-CoP ₂ .

In addition, the inside of the nanocone appears relatively transparent compared to the nanoparticle because the crystal structure of the CoP ₂ phase is dominant.

Figure 6a is a graph showing the CV curve at 5mV s ^-1 of the 3D-on-1D hybrid nanostructures prepared according to Comparative Example 1, Comparative Example 2, and Examples 1 to 3 of the present invention, and Figure 6b is 2mA cm It is a graph showing the galvanostatic charge-discharge (GCD) curve at ^-2 , and Figure 6c is a graph showing area capacity values.

Referring to FIGS. 6A to 6C, it can be seen that the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention exhibits a redox reaction with the largest CV area and higher anode and cathode currents.

Therefore, the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention includes nanocones and nanoparticles to form auxiliary active sites, thereby increasing electrochemical reactions, especially CoNiP and CoP ₂ activities. The site enables numerous reversible redox reactions (see Equations 1 and 2 below) in the range of potentials measured in alkaline electrolytes.

[Equation 1]

CoNiP + 2OH ^- CoP _x OH + NiP _1x OH + 2e

[Equation 2]

CoP _x OH + OH ^- CoP _x O + H ₂ O + e

In addition, the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention is compared to the 3D-on-1D hybrid nanostructure manufactured according to Comparative Example 1, Comparative Example 2, and Examples 1 and 2 of the present invention. It can be seen that it has a long charge and discharge time.

This shows that the nanocones and nanoparticles formed on the carbon cloth create more electroactive sites and improve the partial redox reaction.

It can be seen that the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention exhibits a higher areal capacity of 82.8 μAh cm ^-2 at 2mA cm ^-2 . It can be seen that the specific capacity of the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention is 82.8 mAh g ^-1 .

Figure 6d is a graph showing the CV curves recorded at various sweep rates of the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention, and Figure 6e is the logarithm of the sweep rate and A graph showing the relationship between peak currents, Figure 6f is a graph showing the relationship between v ^1/2 versus i/v ^1/2 , and Figure 6g is a graph showing the relationship between diffusion and capacity control ( It is a graph showing the results of current contribution (diffusion- and capacitive-controlled), Figure 6h is a graph showing the GCD curve, Figure 6i is a graph showing area capacitance values at different current densities, and Figure 6j is 7 mA cm. It is a graph showing the results of the durability test conducted at ^-2 and 10 mA cm ^-2 , and Figure 6k is a graph showing the fitted Nyquist plot before and after the durability test.

Referring to FIGS. 6D to 6K, the redox peak of the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention shows excellent electrical properties as all CV profiles are well maintained, especially at a high scan rate of 20mVs ^-1 . It can be seen that it shows chemical reversibility.

In addition, the capacity value of the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention is 82.8 μAh cm ^-2 , which is higher than the previously reported metal phosphide-based material. .

In addition, the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention exhibits cycling stability at current densities of 7 mAcm ^-2 and 10mAcm ^-2 at the end of the durability test, and the initial Maintaining 96.9% and 90.3% of capacity, the Rs and Rct values of the Nyquist diagram measured before the stability test (2.4 Ω cm ^-2 and 4.7 Ω cm ^-2 , respectively) and these values after the stability test (2.65 Ω, respectively) cm ^-2 and 5.1 Ω cm ^-2 ) do not change substantially, indicating excellent electrical conductivity and fast electrokinetics.

In addition, the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention does not peel or crack due to the dual metal phosphide of CoNiP-CoP ₂ being densely coated on the carbon cloth fiber even after the durability test. From this, it can be seen that the carbon cloth fiber and the dual metal phosphide of CoNiP-CoP ₂ exhibit strong adhesion and have excellent structural stability.

Therefore, the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention showed excellent electrochemical performance in both cyclic voltammetry and constant current charge/discharge tests performed at a constant sweep rate and current density. You can see what it represents.

Figure 7 shows a schematic diagram of the Operando FIG. 9 is a graph showing the CV curves of CNP-CP-150 and AC electrodes measured in the corresponding voltage window to estimate the optimal voltage window of the supercapacitor manufactured according to 0. It is a graph showing the CV curve within a voltage window of -1.5V, Figure 10 is a graph showing the GCD curve within a voltage window of 0-1.5V, and Figure 11 is a graph showing the Ni K-edge and Co K-edge This is a graph showing the XANES spectrum.

7 to 11 show HC and In situ/operando measurements were performed using .

The supercapacitor manufactured according to Example 4 of the present invention was produced as a hybrid battery (HC) using CNP-CP-150 and activated carbon as the anode and cathode.

Referring to FIG. 7, in situ/operando This is performed by illuminating the K ^- edge spectrum, and in situ/operando

Referring to Figures 8 to 11, in situ/operando After the durability test of the supercapacitor manufactured according to Example 4 of the present invention, the transformation to the (Ni,Co)OOH phase on the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention was ex. This was confirmed by situ XRD and X-ray photoelectron spectroscopy (XPS) analysis.

It can be seen that the CV and GCD profiles of the supercapacitor manufactured according to Example 4 of the present invention maintain the contour well even under high test conditions, showing a well-balanced charge and excellent reversibility of the hybrid cell.

FIG. 12 is a graph showing the specific/area capacitance values at different current densities of the supercapacitor manufactured according to Example 4 of the present invention, and FIG. 13 is a graph showing the specific/area energy and power density values. 14 is a graph showing the results of the speed performance test, Figure 15 is a graph showing the results of the durability test, Figure 16 is a graph showing the Nyquist plot obtained before and after the durability test, and Figure 17 is a graph showing the results of the durability test. It is a graph showing the CV curve at various sweep speeds, Figure 18 is a graph showing the GCD curve at various sweep speeds, and Figure 19 is the area/specific capacity of QSSD (quasi-solid-state device; Example 5). It is a graph showing the values, and Figure 20 is an image showing a QSSD (quasi-solid-state device) designed in the form of a bracelet (bracelet-like set-up).

The quasi-solid-state device (QSSD) includes the 3D-on-1D hybrid nanostructure manufactured according to Example 2 of the present invention as an electrode, but the separator and liquid electrolyte are poly(vinyl alcohol) ( PVA) and KOH gel electrolyte, QSSD exhibits an areal capacity of 23.7μAh cm ^-2 .

Additionally, the practicality of the QSSD was tested by designing a bracelet-like configuration by combining two QSSDs in a series connection to extend the voltage range and then wrapping them with scotch tape. The bracelet-like shape could potentially be used to connect a green light-emitting diode (LED) and a motor. It can supply power to the fan.

12 to 20, the supercapacitor manufactured according to Example 4 of the present invention at a maximum operating voltage of 0-1.5V has a maximum areal capacity of 43 μAh cm ^-2 at 2mA cm ^-2. (17.23 mAh g ^-1 ), and it can be seen that it still maintains 30.1 μAh cm ^-2 (12 mAh g ^-1 ) even at a high current density of 20mA cm ^-2 with excellent speed performance of 78.3%.

Additionally, the supercapacitor manufactured according to Example 4 of the present invention maintained almost the same value for 50 more cycles, revealing high rate performance.

In addition, the supercapacitor manufactured according to Example 4 of the present invention exhibits maximum energy density and power density values of 31 μWh·cm ^-2 and 10.9 mW·cm ^-2 , respectively, and 95.8% at the end of 30,000 charge/discharge cycles. It can be seen that the maintenance rate shows excellent durability.

Figures 21 to 29 show the results of an oxygen evolution reaction (OER) activity test using a catalyst.

Figure 21 shows the LSV ( ^linear It is a graph showing the sweep voltammograms profile, and Figure 22 is a graph showing the OP (onset overpotential) value of the catalyst required to drive a current density of 8.5 10 mA cm ^-2 or 10 mA cm ^-2 , and Figure 23 is the Tafel slope. It is a graph showing the (Tafel slope), and Figure 24 is a graph comparing the Tafel slope of the catalyst containing the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention and the reference materials, Figure 25 is a graph showing the results of a time potentiometer test performed on the catalyst containing the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention at 10 mA cm ^-2 for 24 hours.

The electrocatalytic activity of the catalyst containing the 3D-on-1D hybrid nanostructures prepared according to Comparative Example 1, Comparative Example 2, and Examples 1 to 3 of the present invention was linear sweep voltammetry at 2 mV s ^-1 at a low sweep speed. The oxygen evolution reaction (OER) was tested in an alkaline medium by measuring the LSV.

21 to 29, the catalyst containing the 3D ^- on-1D hybrid nanostructure prepared according to Example 2 of the present invention has a low onset overpotential of 230 mV ( It can be seen that the highest OER activity is observed in the OP) value.

The catalyst containing the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention showed a lower Tafel slope of 38mV dec ^-1 and more stable catalytic activity (24 hours) than other catalysts. .

Figure 26 is an image showing the TEM results and SAED pattern of catalyst nanoparticles containing the 3D-on-1D hybrid nanostructure prepared according to Example 2 of the present invention after the OER stability test, and Figure 27 is an image showing the nanocone This is an image showing the TEM results and SAED pattern, Figure 28 is a graph showing the EDS spectrum, and Figure 29 is an elemental mapping image of HNA.

In addition, after the OER stability test, ex situ Further confirmation shows that the “real-active sites” of the metal phosphide-based material are (Ni,Co)OOH species.

Therefore, the method for manufacturing 3D-on-1D hybrid nanostructures according to embodiments of the present invention can produce inexpensive electrode materials for energy storage systems and electrocatalytic activities using a one-step hydrothermal synthesis method, while improving electrochemical performance. It can be seen that it can be applied in multi-functional application fields.

As described above, although the present invention has been described using limited embodiments and drawings, the present invention is not limited to the above embodiments, and various modifications and variations can be made from these descriptions by those skilled in the art. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the claims and equivalents thereof as well as the claims described later.

110: carbon cloth 121: nanomembrane
122: nano cone 123: nanoparticle

Claims (11)

At least one nanocone grown on carbon cloth; and
At least one nanoparticle grown on the nanocone;
Including,
The nanocone and the nanoparticle are 3D-on-1D hybrid nanostructures, characterized in that they contain dual metal phosphides of CoNiP-CoP ₂ (cobalt nickel phosphide-cobalt phosphide) Hybrid Nanoarchitecture).
According to paragraph 1,
The double metal phosphide of CoNiP-CoP ₂ is a 3D-on-1D hybrid nanostructure characterized in that CoNiP and CoP ₂ have a heterojunction structure.
According to paragraph 1,
A 3D-on-1D hybrid nanostructure, characterized in that the average size of the nanoparticles is 850 nm to 900 nm.
According to paragraph 1,
A 3D-on-1D hybrid nanostructure, characterized in that the contact angle of the 3D-on-1D hybrid nanostructure is 0°.
An anode comprising the 3D-on-1D hybrid nanostructure according to claim 1;
cathode (anode); and
an electrolyte disposed between the anode and the cathode;
A supercapacitor comprising:
An electrode catalyst for oxygen evolution reaction (OER) comprising the 3D-on-1D hybrid nanostructure according to claim 1.
Preparing carbon cloth;
Preparing a growth solution containing a nickel precursor, a cobalt precursor, a phosphorus precursor, and a solvent;
Adding the carbon cloth to the growth solution and growing at least one nanocone and at least one nanoparticle on the carbon cloth by hydrothermal synthesis;
A method of manufacturing a 3D-on-1D hybrid nanostructure comprising a.
In clause 7,
The growth solution is a method of producing a 3D-on-1D hybrid nanostructure, characterized in that it further contains a surfactant that vertically grows Co-Ni phosphide nuclei formed on the carbon cloth.
In clause 7,
In the step of adding carbon cloth to the growth solution and growing at least one nanocone and at least one nanoparticle on the carbon cloth by hydrothermal synthesis, the growth temperature is 130°C to 170°C. 3D-on-1D Method for manufacturing hybrid nanostructures.
In clause 7,
In the step of adding carbon cloth to the growth solution and growing at least one nanocone and at least one nanoparticle on the carbon cloth by hydrothermal synthesis, the growth time is 3 to 7 hours. 3D-on-1D Method for manufacturing hybrid nanostructures.
In clause 7,
The step (S130) of adding a carbon cloth to the growth solution and growing at least one nanocone and at least one nanoparticle on the carbon cloth by hydrothermal synthesis,
A method for manufacturing a 3D-on-1D hybrid nanostructure, further comprising drying at least one nanocone and at least one nanoparticle grown on a carbon cloth.