KR20170089083A - Method for manufacturing metal grid structure and metal grid structure manufactured by the method - Google Patents

Abstract

The present invention relates to a production method of a metal lattice structure, and a metal lattice structure produced therefrom. The metal lattice structure can be precisely controlled by depositing a metal lattice-patterned structure on an interface between an electrolyte and an electrode using an electrohydraulic jet printing method, the amount of a deposition material is relatively simple.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for manufacturing a metal grid structure, and a metal grid structure formed therefrom,

The present invention relates to a method of manufacturing a metal grid structure and a metal grid structure formed therefrom, wherein a grid pattern structure made of metal at the interface between the electrolyte and the electrode is deposited using an electrohydraulic jet printing method, The present invention relates to a method for manufacturing a metal lattice structure capable of improving electrochemical performance in a battery and the like, and a metal lattice structure fabricated therefrom.

Solid oxide fuel cells are emerging as promising energy conversion devices due to their high efficiency, potential for merging with thermal power plants, and environmentally friendly advantages. However, since the performance of a solid oxide fuel cell is determined not only by the performance of a single cell but also by the contact resistance between the intermediate current collector and the anode layer or the cathode layer, studies on effective current collection / need.

The reduction in performance due to surface conductance and contact resistance is a practical reason to make the stack system of the fuel cell difficult. Moreover, even in a single cell, accurate electrochemical performance evaluation would be difficult without current collection / distribution devices. Therefore, many researchers have been working on current collectors / distributors and electrochemical performance evaluation. For example, Jiang and Noh's team reported that the performance increases as the contact area of the current collecting / distributing device and the anode increases (Non-Patent Documents 1 and 2). In addition, Jiang's team reported that uneven current distribution at the electrolyte / electrode interface increases ohmic and polarization resistance (Non-Patent Document 1), and Guillodo's team observed that the type of material and current collector affects electrochemical performance (Non-Patent Document 3). However, systematic experiments on the structure of the optimized current collecting / distributing device and its role have not yet been conducted, as well as the relationship with the electrochemical performance.

Platinum (Pt) or silver (Ag) paste and gratings are typical methods for constructing current collectors / distributors, but these methods are not suitable for precise control of current collector / distributor structures. Furthermore, deposition on the electrolyte / electrode interface will block the actual reaction area, so application at the interface is not possible. As an alternative to this, Choi's team formed a current collecting / distributing device by depositing a porous Ag layer at the electrolyte / electrode interface using a DC sputtering method (Non-Patent Document 4).

However, precise control of the current collecting / distributing device is still difficult, and the deposited Ag layer loses porosity in the operating environment of the fuel cell and causes a decrease in electrochemical performance. Therefore, there is still a need for a technique capable of improving the electrochemical performance of a fuel cell or the like as a current collecting / distributing device by depositing it on the interface between an electrolyte and an electrode.

 S.P. Jiang, J.G. , &Quot; Solid State Ion., &Quot; 160, 15-26 (2003), " Love, and L.Apateanu, " Effect of Contact Between Electrode and Current Collector on the Performance of Solid Oxide Fuel Cells,  H.S. Noh, J. Hwang, K. Yoon, B.-K. Kim, H.-W. Lee, J.-H. Lee, and J.-W. Son, "Optimization of Current Collection to Reduce the Lateral Conduction Loss of Thin-Film-Processed Cathodes," J. Power Sources, 230, 109-114 (2013)  M. Guillodo, P. Vernoux, and J. Fouletier, "Electrochemical Properties of Ni-YSZ Cermet in Solid Oxide Fuel Cells," Solid State Ion., 127, 99-107 (2000)  S.H. Choi, C.S. Hwang, and M.H. Lee, " Performance Enhancement of Freestanding Micro-SOFCs with Ceramic Electrodes by the Insertion of a YSZ-Ag Interlayer, " ECS Electrochem. Lett., 3, 57-59 (2014)

An object of the present invention is to provide a method for manufacturing a metal grid structure in which a metal grid structure is precisely deposited by using an electrohydraulic jet printing technique at the interface between an electrolyte and an electrode, and a metal grid structure manufactured thereby.

According to another aspect of the present invention, there is provided a method of fabricating a metal grid structure, including: preparing an ink solution containing a metal; And electrohydraulic jet printing the ink solution to form a lattice pattern structure.

Wherein the metal is at least one of titanium (Ti), nickel (Ni), copper (Cu), gold (Au), silver (Ag), platinum (Pt), iron (Fe), and palladium And the ink solution may contain 1 to 80% by weight of the polymer, 5 to 90% by weight of the solvent, and 5 to 90% by weight of the metal powder, based on 100% by weight of the ink solution.

The electrohydraulic jet printing can be performed at a flow rate of 0.1 to 10 ㎕ / min, a voltage of 0.5 to 10 kV, and a printing speed of 10 to 2000 / / s.

The lattice structure may form a lattice spacing of 10-2000 [mu] m.

The present invention can provide a metal grid structure manufactured by the above manufacturing method, and the metal grid structure can be used as a current collecting and distributing device.

In addition, the present invention can provide a battery including an electrolyte, an electrode, and a metal grid structure deposited on an interface between the electrolyte and the electrode. The electrode may be a cathode or a cathode.

The battery may be any one of a primary battery, a secondary battery, a fuel cell, and a solar cell.

The method of manufacturing a metal lattice structure according to the present invention is advantageous in that the metal grid structure can be precisely controlled and the amount of the evaporation material can be controlled by using the electrohydraulic jet printing method.

Electrohydraulic jet printing also has the advantage of providing a highly industrialized deposition technique because it allows for high reproducibility, improved quality, rapid process, and large area production.

In addition, since the metal grid structure manufactured by the manufacturing method of the present invention improves the electrochemical performance, it can be applied as a current collecting / distributing device in various fields such as batteries.

FIG. 1 shows a result of observing a silver lattice pattern structure according to an embodiment of the present invention with a scanning electron microscope (SEM) (lattice spacing - (a) 100 μm, (b) 200 μm, c) 400 [mu] m).
FIG. 2 is a SEM image of a cross section of a semi-conductive paper produced according to an embodiment of the present invention.
3 is an impedance graph showing the results of measuring the electrochemical performance of a half-cell produced according to an embodiment of the present invention.
4 is an Arrhenius graph showing the results of measuring the electrochemical performance of a half-cell produced according to an embodiment of the present invention.
5 is a graph showing the results of measuring the electrochemical performance of a half-cell produced according to an embodiment of the present invention.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

The present invention relates to a method of manufacturing a metal lattice structure and a metal lattice structure fabricated therefrom, and precisely adjusting the lattice structure of the metal lattice structure at the interface between the electrolyte and the electrode using an electrohydraulic jet printing method, A method of manufacturing a metal grid structure capable of improving electrochemical performance in various fields such as batteries and the like, and a metal grid structure fabricated therefrom can be provided.

The electrohydraulic jet printing method is widely used for forming a transparent electrode using a metal grid due to its high reproducibility and quality, and has a high industrialization potential because it can be processed rapidly and can be produced in a large area. Therefore, in the present invention, the metal lattice structure can be manufactured by precisely controlling the metal lattice structure using this method.

First, a method for fabricating a metal grid structure according to the present invention includes the steps of: preparing an ink solution containing a metal; And electrohydraulic jet printing the ink solution to form a lattice pattern structure.

The step of preparing the ink solution is a step of preparing an ink solution for electrohydraulic jet printing.

The type of metal contained in the ink solution of the present invention is not particularly limited as long as it is a metal that can be applied to electrohydraulic jet printing. Preferably, the metal is titanium (Ti), nickel (Ni), copper At least one of silver (Ag), platinum (Cu), gold (Au), silver (Ag), platinum (Pt), iron (Fe), and palladium can do.

The ink solution contains 1 to 80 wt% of a polymer, 5 to 90 wt% of a solvent, 5 to 90 wt% of a metal powder, preferably 1 to 10 wt% of a polymer, 60 to 85 wt% of a solvent %, And 10 to 30 wt% of the metal powder. When the content of each component is out of the above range, a smooth electrohydraulic jet can not be formed and the shape of the metal grid structure is not formed properly.

The polymer is not particularly limited as long as it is a polymer that can be applied to electrohydraulic jet printing and preferably at least one of polyethylene oxide (PEO), polyvinyl pyrrolidone (PVP), and polyacrylonitrile (PAN) .

The solvent is not particularly limited as long as it is a solvent that can be applied to printing, and preferably it may include at least one of water and an organic solvent. The organic solvent may be alcohol or chloroform, and the alcohol may preferably be ethanol.

The electrohydraulic jet printing is carried out at a flow rate of 0.1 to 10 / / min, a voltage of 0.5 to 10 kV, a printing speed of 10 to 2000 / / s, preferably a flow rate of 0.1 to 0.5 / / min, a voltage of 1.2 to 1.6 kV, 150 to 700 mm / s. If the thickness is out of the above range, there is a problem that a smooth electrohydraulic jet is not formed and the shape of the metal grid structure is not formed properly.

The metal lattice structure of the present invention can form a lattice pattern having a lattice spacing of 10 to 2000 μm, preferably 50 to 500 μm, more preferably 100 to 400 μm. When the lattice spacing is less than 10 탆, there is a problem of covering the surface of the electrolyte and a place where a substantial electrochemical reaction occurs. If the lattice spacing is more than 2000 탆, the effect of the lattice structure is deteriorated.

And the metal grid structure is deposited on the interface between the electrolyte and the electrode.

The electrolyte is not particularly limited as long as it can be used in a battery. Preferably, the electrolyte is YSZ or GDC, which is a solid electrolyte, and the electrode is not particularly limited as long as it can be used as a positive electrode or a negative electrode. BSCF, LSM, LSC, SSC and the like, and Ni-YSZ, Ni-GDC and the like.

The present invention can provide a metal grid structure manufactured by the above manufacturing method, and the metal grid structure can be used as a current collecting and distributing device.

In addition, the present invention can provide a battery including an electrolyte, an electrode, and a metal grid structure deposited on an interface between the electrolyte and the electrode. The electrode may be a positive electrode or a negative electrode, and may preferably be a positive electrode.

The battery may be any one of a primary cell, a secondary battery, a fuel cell, and a solar cell, and may be preferably a fuel cell, more preferably a solid oxide fuel cell.

Hereinafter, the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of protection defined by the appended claims.

Example  One: Electrohydrodynamics  Jet For printing  Ink solution preparation

In order to produce an ink solution for electrohydraulic jet printing, a mixed solvent obtained by mixing polyethylene oxide (PEO, 1,300,000 MW) as a polymer and water and ethanol in a volume ratio of 3: 2 as a solvent was used, Silver nano powder was prepared. First, 3 wt% of polyethylene oxide was mixed with the mixed solvent, and 25 wt% of silver nanopowder was added thereto, followed by stirring using an electromagnetic stirring device.

Example  2: formation of silver lattice structure

In the present invention, printing was performed while maintaining the humidity at 45 to 47% and the temperature at 20 to 25 ° C. Printing was deposited symmetrically on and below the Y _{0 .16} Zr _{0 .92} O ₂ (YSZ, 8 mol%, 500 ㎛ thick) substrate used as a traditional electrolyte material. Printing was performed under conditions of a flow rate of 0.3 / / min, a voltage of 1.45 kV, a gap between the nozzle and the substrate of 500 쨉 m, and a printing speed of 500 ㎜ / s.

In order to observe the electrochemical performance change of the fuel cell according to the lattice spacing, the lattice spacing was adjusted from 100 μm to 400 μm at intervals of 100 μm. The sintering process was carried out at 200 ° C for 2 hours to bond the particles of the silver lattice structure and to evaporate the solvent and the polymer.

The silver lattice structure deposited by the electrohydraulic jet printing method was observed with a scanning electron microscope (JSM700F, JEOL). As shown in Fig. 1, the lattice pattern was well formed for each of the lattice spacings 100 (a), 200 (b), and 400 (c).

Example  3: Deposition of anode

A screen printing technique was used to deposit a cathode on a YSZ substrate with a lattice spacing of 100-400 ㎛ deposited with a silver lattice structure. For the preparation of positive electrode ink for screen printing, the anode material powder and the binder for screen printing were mixed at a ratio of 1: 1 by mass. Sm _{0 .5} Sr _{0 .5} CoO ₃ (SSC) was used as a material of the anode, and a sintering process was performed at 800 ° C. for 8 hours to form a microstructure of the anode and to evaporate the binder for screen printing. .

The microstructure and shape of the silver lattice structure and the SSC anode layer of the prepared battery were observed by a scanning electron microscope. As a result, it was confirmed that the SSC anode layer was deposited by 38 탆 by the screen printing method. It can be said that there is no difference in the electrochemical performance due to the thickness of the cell and the microstructure in view of the same thickness and microstructure of the cell having no lattice structure (FIG. 2).

<Electrochemical Impedance Measurement>

An electrochemical impedance measurement method was used to measure the electrochemical performance of a silver halide deposited silver lattice structure. Impedance was measured from frequency 0.01 to 10 ⁶ Hz through an analytical instrument (GAMRY reference 600, GMARY INC.) And during the measurement, the inverting cell was operated in an electric furnace where both the top and bottom were exposed to air.

As shown in FIG. 3, as the silver lattice spacing decreases, the supply of electrons at the interface between the electrolyte and the anode layer becomes smooth and the sheet resistance decreases, so that the ohmic resistance (the resistance value corresponding to the first intersection point of the x axis of the semicircle) decreases. In addition, the polarizing resistance (the resistance value corresponding to half of the value between the x-axis intersections of the semicircle) also decreased because the polarity was actively generated due to the smooth supply of electrons in the place where the electron supply was not smooth.

The Arrhenius graph of FIG. 4 shows the activation energy of oxygen ion diffusion. The activation energy of the oxygen ion diffusion is the same as the activation energy of a half-cell with a lattice structure deposited at intervals of 100 탆, a half cell without a lattice structure, And that the decrease in the ohmic resistance of FIG. 3 is due to a decrease in the sheet resistance, not a change in the diffusion mechanism of the electrolyte.

FIG. 5 shows a board graph of a half-cell without a lattice structure and a half-cell with a lattice interval of 100 μm (P100), 200 μm (P200), and 400 μm (P400) 10000 Hz) decreased with decreasing lattice spacing. The intermediate frequency region represents a mechanism corresponding to the mechanism of electron transfer phenomenon. From the above results, it can be seen that electrons are distributed smoothly as the lattice spacing decreases, thereby improving the electron transfer phenomenon.

Therefore, it can be confirmed that the electrochemical performance is improved by facilitating the electron supply by depositing the metal lattice structure at the interface between the electrolyte and the electrode.

Although the configuration of the present invention has been proven by the above embodiments, the present invention is not necessarily limited to the above configuration, and various permutations, modifications and variations are possible without departing from the technical idea of the present invention. Therefore, the above description does not limit the scope of the present invention, which is defined by the limitations of the following claims.

Claims (10)

Preparing an ink solution containing a metal; And
And forming a lattice pattern structure by electrohydraulic jet printing the ink solution. The method according to claim 1,
Wherein the metal is at least one of titanium (Ti), nickel (Ni), copper (Cu), gold (Au), silver (Ag), platinum (Pt), iron (Fe), and palladium Wherein the metal lattice structure is formed by a method comprising the steps of: The method according to claim 1,
Wherein the ink solution comprises 1 to 80 wt% of a polymer, 5 to 90 wt% of a solvent, and 5 to 90 wt% of a metal powder, based on 100 wt% of the ink solution. The method according to claim 1,
Wherein the electrohydraulic jet printing is performed at a flow rate of 0.1 to 10 ㎕ / min, a voltage of 0.5 to 10 kV, and a printing rate of 10 to 2000 / / s. The method according to claim 1,
Wherein the lattice structure forms a lattice spacing of between 10 and 2000 &lt; RTI ID = 0.0 &gt; um. &Lt; / RTI &gt; A metal lattice structure produced by the method of any one of claims 1 to 5. The method according to claim 6,
Wherein the metal grid structure is used as a current collecting and distributing device. A battery comprising the electrolyte, the electrode, and the metal grid structure of claim 6 deposited at the interface of the electrolyte and the electrode. 9. The method of claim 8,
Wherein the electrode is a positive electrode or a negative electrode. 9. The method of claim 8,
Wherein the battery is any one of a primary cell, a secondary battery, a fuel cell, and a solar cell.

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