KR101328303B1 - Anode electrode plate for electro-forming, method for preparing the same and method for preparing metal supporting body by using the same - Google Patents

Abstract

The present invention relates to a method for manufacturing a Fe-Ni alloy metal support for solid oxide fuel cells, a plate used for the method and the manufacturing method for the plate. The plate is conductive for electroforming to manufacture metal foil using an electro-deposition reaction. The plate for electroforming comprises a width of 30 to 500�� a plurality of protrusions. The protrusions are provided at a range of 10 to 90%. [Reference numerals] (AA) Intaglio unit;(BB) Metal seed layer;(CC) Silicon wafer

Description

Technical Field [0001] The present invention relates to an electroforming base plate, an electroforming base plate, a manufacturing method thereof, and a method of manufacturing a metal support using the same.

The present invention relates to a fuel cell, in particular, a method for manufacturing a Fe-Ni alloy metal support for a solid oxide fuel cell (SOFC), a base plate used therefor, and a method for manufacturing the base plate.

Solid Oxide Fuel Cell (SOFC) is a device that directly generates electrical energy by electrochemically reacting fuel and oxidizer. At this time, a solid oxide which can permeate oxygen or hydrogen ions is used as an electrolyte, and the fuel cell operates in the range of 650 ° C to 1000 ° C, which is the highest operating temperature of the existing fuel cell. Therefore, solid oxide fuel cells are capable of generating thermal combined power using not only electric energy but also waste heat and hot water, so the theoretical efficiency is higher than 80% and the commercialized products are 40 ~ 60%.

Based on these advantages, the technology development is being promoted in order to utilize the power generation system of 100 ~ kW to several tens of megawatts, the small power generation system of household size for 1 kW to 10 kW scale, and the auxiliary power source for automobiles.

Such a solid oxide fuel cell is composed of unit cells based on a fuel electrode / electrolyte / air electrode, and the power generation capacity obtained from one unit cell per unit area is about 1V. Therefore, in order to output power required for actual power generation facilities, a plurality of unit cells are connected in series and in parallel, and a stack is formed by inserting a separator plate and a current collector between cells.

Until now, it has been difficult to commercialize fuel cells because the larger the area of the unit cell is, the lower the efficiency and the lower the fracture toughness due to sealing, thermal shock and physical impact. Particularly, in the case of the ceramic support type solid oxide, since the fracture toughness is basically low, it is very vulnerable to impact. To solve this problem, development of a metal support type solid oxide fuel cell is underway.

In general, the requirements for the metal support include (1) high electrical conductivity, (2) ensuring a fuel injection path to the anode, (3) excellent impact properties, (4) And the coefficient of thermal expansion is similar to that of the material. As a research direction currently being pushed toward the metal support which satisfies such conditions, there is a laser drilling processing method, a method of sintering metal powder, and the like.

However, the laser drilling method is usually difficult to secure pores of several tens of micrometers or less, and the productivity is low because laser drilling should be performed on the obtained metal support. On the other hand, when the metal powder is sintered, it is difficult to uniformly distribute the pores, and there is a possibility that the generation and propagation of microcracks at the powder grain boundaries is easy, causing brittle fracture.

The present invention provides a method of manufacturing a metal foil used as a metal support for a solid oxide fuel cell by precisely controlling the size and distribution of pores through which fuel passes using electroforming, Thereby securing the long-term operation stability of the oxide fuel cell.

Furthermore, the present invention is to provide a base plate and a method for producing the base plate used in the production of the metal support by electroforming. By using a durable base plate to produce a porous metal support by electroforming, it is possible to prevent the blockage of the hole, the base plate can be used repeatedly, to increase the efficiency in the manufacturing process.

The present invention relates to an electroforming conductive base plate used to produce a metal foil by using electrolytic precipitation of electroforming, wherein the base plate is a flexible metal having a thickness of 30-500 μm and having a plurality of flat surfaces. Including a protrusion, the protrusion provides an electroforming base plate present in the range of 10 to 90% of the bed area.

It is preferable that the protrusions have a maximum diameter of 1 to 50 탆 and a height of 50 to 200 탆 on a circular basis, and the protrusions may include a cylinder having a constant cross-sectional area, a cylinder having an upwardly reduced sectional area, a circular cone, A polygonal column having a constant cross-sectional area, a polygonal column or polygonal pyramid having a cross-sectional area reduced upward, or a combination of these shapes. Furthermore, the protrusion may have a step in the height direction.

The mother plate may have an upper end of the protrusion open.

In addition, an oxide film may be formed on a surface of the mother plate, and the oxide film may be a TiO ₂ film.

Furthermore, the flat surface may have a surface roughness of 1-100 nm.

On the other hand, the present invention relates to a method for producing a base plate for electroforming used for the production of metal foil using the electrolytic precipitation reaction of electroforming, provided at least as a power source, a cathode electrode, an anode electrode, the metal is electrodeposited from the electrolyte solution Using an electroforming device comprising a primary mother plate, and electrolyte supply means for supplying the electrolyte solution to the cathode electrode and the anode electrode, and supplying an electrolyte solution containing metal ions to at least the primary mother plate; A current is applied to the primary mother plate and the cathode electrode, and a metal is electrolytically precipitated from the electrolyte to be electrodeposited on the surface of the primary mother plate; And separating the metal electrodeposition layer electrodeposited on the surface of the primary mother plate from the primary mother plate, wherein the primary mother plate includes a plurality of protrusions on a flat surface, and the protrusions include 10 to 10 times of the primary mother plate area. It exists in the 90% range, and may include an oxide film on the surface.

The primary mother plate may be obtained by etching the surface of the Si wafer by a lithography process and an ion silicon etching process to form protrusions on the flat surface, and forming a conductive metal seed layer for electrodeposition of metal on the flat surface of the Si wafer. .

In addition, the conductive metal seed layer may be a Ti layer, the Ti layer may be formed by sputtering.

Further, the Ti layer may be heat treated to form a TiO ₂ film.

In this case, the electric casting device may be a drum type electric casting device.

In addition, the protrusions may have a maximum diameter of 1 to 50 μm and a height of 50 to 200 μm on a circular basis.

Furthermore, a surface roughness of 1 to 100 nm may be given to the Ti seed layer.

Furthermore, the present invention relates to a method of manufacturing a metal support, provided at least as a power source, a cathode electrode, an anode electrode, the mother plate provided in accordance with the present invention, the metal is electrodeposited from the electrolyte solution, and the electrolyte solution to the cathode electrode and the anode electrode A method of manufacturing a metal support for a solid oxide fuel cell using an electroforming device comprising an electrolytic solution supplying means, the method comprising the steps of: supplying an electrolyte containing metal ions to at least the mother plate; Applying a current to the base plate and the cathode electrode to deposit a metal on the surface of the base plate by electrolytic deposition of the metal from the electrolyte solution; Separating the metal electrodeposition layer deposited on the surface of the mother plate from the mother plate.

The electroforming device may be a drum type pole device or a horizontal pole device, wherein the horizontal pole device is supplied with a base plate horizontally in a predetermined direction, the base plate is immersed in an electrolyte, and applied to the base plate and the anode electrode. The metal electrodeposition layer may be formed on the surface of the mother plate by a current.

The electrolytic solution may include 40-50 g of a nickel precursor and 6-12 g of an iron precursor based on 1 L of water, and the iron precursor is at least one selected from the group consisting of iron sulfate, iron chloride, iron nitrate and iron sulfamide, The nickel precursor may be at least one member selected from the group consisting of nickel sulfate, nickel chloride, nickel nitrate and nickel sulfamide.

The metal support is preferably a Ni or Fe-Ni alloy having a Ni content of 40-100% by weight, more preferably a Fe-Ni alloy having a Ni content of 45-90% by weight.

Further, the metal support preferably has a thickness of 30-200 탆, more preferably 50-100 탆.

In addition, the metal support preferably has an opening ratio of 20-70% of the area.

A metal foil is manufactured by electroforming using a base plate having protrusions formed in a predetermined pattern on the surface thereof to prevent clogging of the inner hole patterns formed in the metal foil by protrusions already formed on the base plate during the electroforming process The metal foil satisfying the pore conditions required for the metal support can be stably produced.

Furthermore, another aspect of the present invention can simply manufacture a cathode electrode mother plate having protrusions by utilizing the electroforming material prepared on the primary mother substrate as a secondary mother substrate using the electroforming method.

By using the metal foil obtained by the electroforming as the base plate of the electroforming, a flexible metal thin plate can be obtained. Therefore, it is easy to maintain and maintain the shape of the roll. Not only can it be prevented, it can also mass-produce metal supports.

In addition, since the metal support proposed in the present invention is excellent in strength and impact characteristics compared to the metal support manufactured by the sintering method, the thickness of the metal support can be reduced. Therefore, a lower external pressure is required in the stack construction, great.

According to the present invention, a metal support manufactured by electroforming using a cathode electrode mother plate having protrusions can prevent hole clogging and can finely control the pores of the metal foil, and thus, the anode of the fuel cell. Since a uniform fuel can be supplied to the whole, power generation efficiency can be further improved.

1 is a view schematically showing a basic configuration of an electroforming apparatus capable of showing the basic driving concept of electroforming.
2 is a schematic view of a drum type electroforming apparatus.
3 is a view schematically showing an example of a horizontal electroforming apparatus.
4 is a view schematically showing a cross section of an example of a primary mother plate having an intaglio portion according to the present invention.
Figure 5 is a photograph of the microstructure of the Fe-Ni metal foil prepared by electroforming using the mother plate of the present invention.

The present invention relates to a method of manufacturing a fuel cell, particularly a Fe-Ni alloy metal support for a solid oxide fuel cell (SOFC).

The inventors of the present invention, while developing a metal support as a way to secure the long-term operation stability of the solid oxide fuel cell, while researching how to improve the power generation efficiency by controlling the size and shape of the pores through which the fuel is moved, manufactured using the electroforming method The present invention was completed by recognizing that the advantages of the existing metal support can be accommodated while the disadvantages of the metal support can be compensated for. By using the electroforming method to produce a metal foil having a projection, by using this as a secondary mother substrate to produce a metal foil having pores can be obtained a metal support.

Hereinafter, a method for producing a metal support for a solid oxide fuel cell according to the present invention will be described in detail.

The metal support is preferably produced by an electroforming method. The electroforming method is a method of manufacturing a substrate using an electroforming apparatus having an electrolytic bath, an anode electrode, a cathode electrode, and a power source, and an example of the electroforming apparatus is shown in FIG.

When a metal support is produced using the above electroforming method, it is possible to obtain a thin metal support having excellent flexibility, easy winding and development, and excellent workability and workability. As a result, a lower external pressure is required inside the unit cell for current collection, and a thinner and lighter stack configuration is possible. Further, since the fuel can be efficiently supplied to the anode during the operation of the fuel cell by uniformly controlling the size and distribution of the pores as well as mechanical characteristics such as strength and hardness, which are characteristics inherent to the metal substrate, .

Hereinafter, an electroforming apparatus applicable to the present invention will be described first.

The apparatus for electroforming in the present invention is not particularly limited, but may be suitably used as long as the metal from the electrolytic solution can be electrolytically deposited and electrodeposited on the surface of the base plate. The basic concept of the electroforming apparatus applicable to the present invention is as shown in Fig.

1, the electroforming apparatus 100 is provided with a cathode electrode 104 and an anode electrode 106 inside the electrolytic bath 102 and the cathode electrode 104 and the anode electrode 106, Are positioned to maintain a predetermined gap. The cathode electrode 104 and the anode electrode 106 are electrically connected to the power source 108 so that current flows. When a current is applied to the cathode electrode 104 and the anode electrode 106 immersed in the electrolytic solution 110 and the metal foil 10 is applied to a part of the surface of the cathode electrode 104, And separating the metal foil 112 from the cathode electrode 104, the metal foil 112 can be used as a metal support.

A typical example of such an electroforming apparatus is a drum electroforming apparatus 200 as shown in Fig. The method of manufacturing the metal foil 212 by electrodeposition in the drum type electroforming apparatus 200 of FIG. 2 is as described above with reference to FIG. 1 except that the drum 204 is used as a base plate of the cathode electrode 204. The skilled person in the art to which the present invention pertains can easily understand from the description of FIG. 1 or from known techniques, and thus detailed descriptions thereof will be omitted.

A metal support can be obtained by separating the metal foil 212 formed by electrodeposition of metal from the electrolytic solution on the surface of the cathode electrode drum 204 by the drum type electroforming apparatus 200. Such a metal support can be wound as needed, thereby facilitating the storage of the metal support.

On the other hand, in manufacturing the metal support of the present invention it is possible to use a horizontal type electroforming apparatus 300 as shown in FIG.

3 is an example of the horizontal electroforming apparatus 300, the horizontal electroforming apparatus 300 used in the manufacture of the metal support by the electroforming method according to an embodiment of the present invention is not limited to FIG. If necessary, you can remove components or add other components as appropriate.

The horizontal electroforming apparatus 300 includes a mother plate supply device 10, a horizontal cell 30, an electrolyte supply device and a metal foil separating device 51.

In the present invention, the 'electroforming cell' refers to an electrolyte flowing through a flow path formed by the base plate 11 and the anode electrode 32 provided as a cathode, and metal ions in the electrolyte are electrolyzed on the surface of the base plate. It can be defined as a unit cell in which a reaction in which an electrodeposition is formed by a precipitation reaction to form an electrodeposition layer occurs. In addition, after the base plate 11 is supplied into the electroforming cell, the constant direction means that the moving direction of the base plate 11 does not change until it exits the electroforming cell. In this specification, the moving direction of the base plate 11 may be referred to as a 'horizontal direction' or simply 'horizontal' in some cases. Furthermore, the base plate 11 advances the electroforming cell in a horizontal direction, and thus the metal in the electrolyte solution. In order to indicate that ions (iron ions and nickel ions) are electrolytically deposited on the base plate 11, the electroforming cell is also referred to as a 'horizontal cell 30'.

For the continuous supply of the base plate 11, the base plate 11 is not limited thereto, but the base plate wound in the form of a coil can be supplied into the horizontal cell 30, and furthermore, all of these base plates 11 are supplied. In this case, the mother plate 11 wound in the form of another coil can be continuously supplied following the mother plate 11 supplied previously. At this time, if necessary, the rear end of the preceding base plate and the leading end of the following base plate can be joined by a predetermined bonding method such as welding and continuously supplied. Furthermore, in order to easily join, each terminal joined can also be processed to a suitable shape.

The base plate 11 is contacted with the widthwise edge portion of the base plate 11 so that the horizontal cell 30 is formed by a pair of conductor rolls 31 and 31 ′ which transfer the base plate 11 into the horizontal cell 30. Can be fed in a horizontal direction. At this time, the electrolytic solution may be supplied to one side of the mother plate 11 supplied into the horizontal cell 30 to perform electroforming on one side, and the electrolytic solution may be supplied to both sides to electrolytically deposit metal ions on both sides. You can increase the speed.

When the mother plate 11 is supplied into the horizontal cell 30 as described above, the electrolyte is supplied to the one or both sides of the mother plate 11 through the electrolyte supply nozzle, and the horizontal formed by the mother plate 11 and the anode electrode 32. As the electrolyte moves through the flow path, metal is electrolytically precipitated due to the action between the base plate 11 serving as the anode electrode and the anode electrode 32 by the applied current to form an electrodeposition layer on the surface of the base plate 11.

The mother plate feeding device 10 may include a mother plate winding device 72 for supplying the mother plate 11. In order to continuously supply the base plate 11, a plurality of the platen winding devices 72 may be installed, and in the case where the platen 11 is exhausted in one platen winding device 72, the other platen winding device 72 may be used. In the new bed plate 11 can be supplied. For the continuous supply of such base plate 11, a bonding apparatus 12 for joining the end of the base plate 11 provided in advance and the tip of the base plate 11 to be provided next may be additionally included as necessary.

On the other hand, the electrodeposition layer electrodeposited on the base plate 11 transfers the surface roughness of the base plate 11, so that the surface roughness of the base plate 11 is expressed almost the same in the metal foil 50 obtained. Therefore, the grinding means 13 may be further included as necessary to control the surface roughness of the mother plate (11). Such polishing means 13 is not particularly limited, and may include mechanical polishing such as polishing, chemical polishing such as etching, and chemical mechanical polishing such as a CMP method mainly used in semiconductor processes. The chemical polishing, mechanical polishing and chemical mechanical polishing means may be used alone or in combination thereof. By this polishing means, the surface of the base plate 11 can be arbitrarily evenly and conveniently adjusted to the desired surface roughness as necessary.

Since impurities may be present on the surface of the mother plate 11, additional washing may be necessary as necessary to remove them, and thus, the pre-cleaning device 14 may be additionally included as necessary. The cleaning of the surface of the base plate 11 may use an acid solution such as diluted hydrochloric acid or sulfuric acid or water. Furthermore, after washing, a drying apparatus (not shown) for drying the mother plate 11 may be further included as necessary. Drying can be performed by adding air at high pressure, or adding a hot gas, or it can also be performed by heating a base plate.

The horizontal cell 30 is spaced apart from the pair of conductor rolls 31 and 31 ′, which serve to transfer the base plate 11 and connect the cathode power source, to the base plate 11 at regular intervals. And a power supply for supplying a current having a negative charge and a positive charge to the anode electrode 32, the conductor rolls 31 and 31 ′, and the anode electrode 32 disposed on one surface of the mother plate 11, respectively. An electrolyte solution supply device including an electrolyte solution tank 34 for storing and containing an electrolyte solution, and an electrolyte solution supply nozzle 38 for supplying an electrolyte solution to the surface of the base plate 11.

The conductor rolls 31 and 31 ′ serve as transfer means for transferring the base plate 11 into the horizontal cell 30 and discharging it from the horizontal cell 30, while the base plate 11 and the power source 33 are provided. By connecting the cathode power of the electrolytic precipitation reaction to the iron and nickel ions to be deposited on the base plate 11 by the electrolytic reaction of the anode electrode 32 and the base plate 11 is performed. These conductor rolls 31 and 31 'contact the both edges in the width direction of the base plate 11 to transfer the base plate 11 into the horizontal cell 30 and discharge it from the horizontal cell 30.

The base plate 11 may use a flexible conductive base plate, in which case, when passing through the horizontal cell 30, a drooping phenomenon may occur due to its own weight. In this case, the base plate 31 and the anode electrode 32 and Since the spacing may change, causing a difference in current density, a metal foil of uniform thickness may not be obtained. Therefore, in order to prevent stiction of the base plate 11, the rotational speeds of the inlet side conveying roll 31 and the outlet side conveying roll 31 'are different from each other, that is, rotation of the outlet side conveying roll 31' The speed of the inlet side conduit roll 31 can be made faster than the rotational speed of the inlet side conduit roll 31, thereby preventing the buckling due to the self weight of the base plate 11. [

On the other hand, the conductor rolls 31 and 31 'transfer the current supplied from the power supply 33 to the base plate 11 so that the base plate 11 can function as a cathode electrode and thus with the anode electrode 32. The electrolytic precipitation reaction can be caused by the action.

The anode electrode 32 may be spaced apart from the base plate 11 at regular intervals on one surface of the base plate 11 so that an electrolytic precipitation reaction of iron and nickel occurs on the base plate 11.

The anode electrode 32 and the mother plate 11 are spaced apart to provide a flow path through which the electrolyte is supplied and distributed therebetween, and as described above, the cathode plate 32 and the anode electrode 32 act as a cathode electrode. An electrolytic reaction may occur that electrolytically deposits metal ions on the mother plate. On the other hand, by supplying the electrolyte at a high speed, it is possible to increase the electrodeposition rate of iron and nickel ions to the surface of the base plate (11). In addition, since the flow path of the electrolyte is formed flat, it is possible to prevent a drop in the speed of the flow field with respect to the supply of the electrolyte.

The electrolyte may supply the electrolyte at a Reynolds number (Re) of up to 5,000 through an electrolyte flow path formed horizontally by the base plate 11 and the anode electrode 32, and the relative speed may be appropriately adjusted according to the traveling speed of the base plate 11. Can be increased or decreased. In addition, depending on the state of the electrodeposition reaction, the electrolyte may be supplied at a flow rate of laminar flow (the flow of fluid supplied in a straight line without shaking the water, having straightness), and a high speed turbulence (water stem) after a stable electrodeposition reaction is formed. Can be supplied at a flow rate).

If the flow rate of the electrolyte is increased during initial electrodeposition, the electrodeposition layer may come off and electrodeposition may fail.If the electrodeposition layer grows to several micro levels, the adhesion may be improved by the stress generated in the electrodeposition layer, thereby enabling the use of a high speed flow field. It is. On the other hand, the fluid supply speed region limited when using a high speed flow field is preferably supplied at a flow rate below the surface tension between the electrodeposition layer and the base plate 11, and the surface tension between the electrodeposition layer and the base plate 11 When the electrolyte is supplied at a flow rate exceeded, the shear stress between the flow field and the electrodeposition layer due to the supply of the electrolyte exceeds the surface tension between the electrodeposition layer and the mother plate 11, and thus the electrodeposition layer may be peeled off.

The electrolyte is supplied to the surface of the base plate 11 through the electrolyte nozzle 38 from the electrolyte storage tank 34 containing the electrolyte, which is supplied in the same direction and in the opposite direction to the traveling direction of the base plate 11. Can be. By doing in this way, the electrodeposition rate of the metal component with respect to the surface of the base plate 11 can be raised further.

On the other hand, the electrolyte used for electrodeposition can be recovered to the electrolyte storage tank 34 as needed. In this case, the recovered electrolyte solution may be lowered than the concentration required for electrodeposition because the metal ions are consumed in electrodeposition, so that the metal ions may be appropriately replenished to adjust the predetermined concentration.

The power source 33 supplies (-) current and (+) current to the conductive rolls 31 and 31 'and the anode electrode 32, respectively, and may be applied to the present invention without particular limitation as long as it can be generally applied. As can be, a detailed description thereof will be omitted.

The electrolyte supply apparatus includes an electrolyte storage tank 34 for storing and containing an electrolyte solution and an electrolyte supply nozzle 38 for supplying an electrolyte solution to the surface of the base plate 11. The electrolyte is transferred from the electrolyte reservoir 34 to the electrolyte supply nozzle 38 through an electrolyte supply pipe. The electrolyte supply nozzle 38 may be installed to be supplied only to one surface of the mother plate 11, or may be installed on both sides of the electrolyte supply to both surfaces of the mother plate 11.

Meanwhile, the electrolyte storage tank 34 includes an electrolyte heater 35 for heating the electrolyte, an electrolyte filter 36 for removing impurities such as sludge contained in the electrolyte, and an electrolyte pump for supplying the electrolyte to the horizontal cell 30. (37) etc. can be further included as needed.

On the other hand, compared to the central portion of the base plate 11, the amount of deposition of iron and nickel is increased at both edges in the width direction in some cases, resulting in thickness variation of the metal foil, and a metal foil of uniform thickness may not be obtained as a whole. have. Also, in such a case, a post-treatment process may be necessary to cut the edges so that the metal foil separated from the base plate 11 has a uniform thickness. Accordingly, this problem can be solved by preventing the deposition of metal at the edge portion of the base plate 11 to prevent thickness variation. For this purpose, an edge mask is prevented so that an electrolyte solution is not supplied to the edge of the base plate 11. (Not shown) may be provided. By providing such an edge mask, formation of the metal electrodeposition layer which has the thickness difference in the edge of the base plate 11 can be prevented.

The electrolyte supply nozzle 38 may supply the electrolyte at a high speed through a horizontal passage formed by the mother plate 11 and the anode electrode 32. In this case, the electrolyte may be installed such that the electrolyte is supplied in the same direction and in the opposite direction to the traveling direction of the base plate 11 with respect to the electrolyte supply nozzle 38. By doing in this way, the effect of electrodeposition substantially can be acquired. That is, the electrolyte solution supplied in the opposite direction can obtain the effect of primary electrodeposition, in which a relatively small amount of short time for the electrolyte solution to contact the mother plate 11 is electrodeposited due to the difference in relative speed with the mother plate 11, and the same. The electrolytic solution supplied in the direction may contact the base plate 11 for a longer time, thereby obtaining the effect of secondary electrodeposition in which a relatively large amount of electrodeposits are electrodeposited compared to the primary electrodeposition.

The electrodeposition process through the horizontal cell 30 as described above may be performed a plurality of times in succession. In this way, when the electrodeposition process through the horizontal cell 30 is performed a plurality of times, the thickness of the metal electrodeposition layer obtained by electrodeposition in each horizontal cell 30 can be increased, so that the thickness of the metal electrodeposition layer is required. According to the present invention, even when the mother plate 11 is supplied at a higher speed, a metal electrodeposition layer having a desired thickness can be obtained, thereby improving productivity. When a plurality of electrodeposition processes are performed, the process conditions and the composition of the electrolyte solution may be the same or different in the plurality of electrodeposition processes. The number of repetitions of the electrodeposition process is not limited, and may be appropriately selected depending on the desired degree of electrodeposition.

Furthermore, a plurality of horizontal cells 30 as described above may be installed in series in the advancing direction of the base plate 11. Even if a plurality of horizontal cells 30 are installed, the electrodeposited layer is peeled from the mother plate 11 during movement by being disposed in series in the mother plate 11 traveling direction. By providing a plurality of horizontal cells, an electrodeposition layer having a desired thickness can be formed on the base plate 11 even though the base plate 11 is advanced at a higher speed while reducing the amount of electrodeposition through one cell. It can improve the productivity.

The metal foil 50 can be obtained by separating the metal electrodeposition layer from the mother plate 11. The base plate 11 on which the electrodeposition layer is formed is discharged through the outlet-side conductor roll 31 ', and after discharge, the metal foil layer is separated from the base plate 11 by the metal foil separator 51. Get 50. Since the metal electrodeposition layer is bonded by surface tension with respect to the surface of the base plate 11 on which an oxide film is formed on the surface, the metal electrodeposition layer may be separated from each other by a difference in shear force between the metal electrodeposition layer and the base plate 11. Therefore, the metal foil separation device 51 is preferably capable of imparting a shear stress for separating the metal electrodeposition layer from the mother plate 11, for example, may be provided with a plurality of rollers. In addition, the difference in the moving speed of the metal electrodeposition layer and the mother plate 11 may be separated by the simultaneous or time difference between the upper and lower metal electrodeposition layer.

The metal foil 50 used as the metal support of the fuel cell obtained by separating from the mother board 11 and the mother board 11 is wound by the metal separator winding device 55 and the mother board winding device 72, respectively. Can be. The winding devices 55 and 72 may be, for example, cylindrical winding machines. The winding devices 55 and 72 may be wound in an appropriate amount according to the winding amount, and may be wound and wound around another winding machine. Thus, any additional metal foil cutting device 54 and base plate cutting device 71 may be further included as needed for the cutting. The cutting is more preferably cut at the bonding site of the mother plate.

On the other hand, the horizontal electroplating apparatus 100 is discharged from the horizontal cell 30, if necessary, before or after separating the metal foil 50, if necessary, the substrate, metal electrodeposition layer and / or metal foil ( The aftertreatment device of 50) can be additionally installed as necessary. Such a post-treatment device may include a post-cleaning device 52, and / or a drying device (not shown).

Since electrolyte may remain on the surface of the metal electrodeposition layer formed on the mother plate 11, it is preferable to wash the surface of the metal electrodeposition layer arbitrarily as needed. Such washing may be performed using an acidic solution or water, and in addition, a flexible brush or the like may be used to effectively remove the residual electrolyte.

The acid solution may be any one known to be usable for washing the metal surface, and is not particularly limited. Such washing may be performed in a state in which metal is deposited on the base plate 11 to form a metal electrodeposition layer, and the metal foil 50 may be washed after separating the metal electrodeposition layer from the base plate 11.

After washing, the surface of the metal electrodeposition layer or metal foil 50 may be optionally dried by necessity by spraying high pressure air or hot gas or heating the metal electrodeposition layer or metal foil 50.

In the above description, the horizontal type electroforming apparatus has been described in detail. However, unless the technically impossible case, the configuration employed in the horizontal type electroforming apparatus 300 may be applied to the drum type electro casting apparatus 200. Those skilled in the art will understand.

In the present invention, to form a projection on the surface of the mother plate to electrodeposit the metal on the surface of the mother plate by the electroforming method to obtain a metal support in which uniform pores are uniformly distributed. A base plate for forming pores and a method for producing the base plate will be described in detail.

Hereinafter, although the mother plate used in the electric casting apparatus 100 shown in FIG. 1 or the horizontal type electric casting apparatus 300 of FIG. 3 is used, this is used as the mother plate of the drum type electric casting apparatus 200 of FIG. As can be applied to the drum to be, it will be easily understood by those skilled in the art. Therefore, in the present invention, the base plate may be understood to include a drum used as a base plate of the drum-type electroforming apparatus 200.

In manufacturing the metal support for a solid oxide fuel cell by the electroforming of the present invention, the metal foil formed by the electroforming can be used as the base plate of the cathode electrode. The mother plate of the cathode electrode according to the invention comprises a plurality of projections on the surface. Therefore, in order to manufacture the base plate which has such a processus | protrusion, the primary base plate for said base plate manufacture is calculated | required. Hereinafter, a primary base plate for manufacturing a base plate that can be used in the electroforming of the present invention will be described. This will be described with reference to FIG. 4. 4 is a view schematically showing a primary mother plate for producing a mother plate having protrusions by electroforming.

In the present invention, when producing a base plate having protrusions by electroforming, protrusions or intaglio portions are formed on the surface of the primary base plate used as the cathode electrode. Such protrusions or indentations may be formed, for example, on a Si wafer through a lithography process and an etching process using an ion silicon etching apparatus (DRIE).

Ion silicon etching is a process of making a reactive gas into a plasma state and then dry etching by contacting the surface of the silicon wafer to produce a surface shape having a high aspect ratio. In this process, a pattern is formed using a photoresist film material on the surface for selective etching of the wafer surface, so that the portion below the photoresist film material can be controlled not to be etched.

In a general semiconductor process, after a certain depth of etching is performed in order to form a precise protrusion shape in the vertical direction, a multi-step process of etching after masking with a photosensitive film material is performed. Eggplants are manufactured by peeling after manufacturing on the mother board. In the process of manufacturing the projections of the mother board, the wedge-shaped intaglio portion can be manufactured by performing multi-step etching while gradually decreasing the size of the mask pattern through the photoresist material. have. Through such wedge-shaped intaglio, a primary mother plate of a metal foil having conical protrusions can be obtained, and a secondary mother plate having protrusions can be obtained by electroforming using the primary mother plate.

In the present invention, a method using an ion silicon etching apparatus (DRIE) of a Si wafer is provided for a method of forming a protrusion or an intaglio portion on a cathode electrode primary substrate, but may be formed by various forms in addition to the etching method. It does not specifically limit.

On the other hand, the high aspect ratio etching process aimed at the general semiconductor industry requires a perfectly vertical structure in the height direction, but the protrusion or the intaglio portion of the cathode electrode primary substrate used in the present invention is essentially vertical in the height or depth direction. It does not need to be a structure, and the protrusion part of the said primary mother plate does not specifically limit the shape. For example, a cylinder having a constant cross-sectional area, a cylinder having an upward cross-sectional area, a cone, an arc, a semicircle, an inverted circle, a polygonal prism having a constant cross-sectional area, a polygonal prism having a cross- And the protrusion of such a shape may be formed with two or more steps in the height direction. Furthermore, the form of the cross section of the protrusion is not particularly limited as long as it can form pores.

Hereinafter, the protrusion or the intaglio may be formed on the surface of the primary mother plate, and the following description will be made based on forming the intaglio. However, unless specifically contradicted in technical terms, the protrusion corresponds to the intaglio, and the height may be understood as an expression corresponding to the depth.

The intaglio portion of the primary base plate obtained in the present invention is transferred as it is by electroforming, so that a metal base plate having a protrusion almost identical to the shape of the intaglio portion of the primary base plate can be manufactured, and by electroforming using such a base plate A metal support for a solid oxide fuel cell is prepared. In this case, the metal support has a porous structure, wherein the pore size may be 50 μm or less, preferably 1 to 50 μm, and more preferably 1 to 10 μm. If the pore size on the metal support is more than 50 탆, it may be difficult to manufacture the unit cell because the anode and the electrolyte are easily broken during the process of manufacturing the unit cell of the fuel cell. Therefore, the maximum diameter of the protrusion is 50 μm or less, 1-50 μm, more preferably 1-10 μm so that the protrusion formed on the primary mother plate can form pores of the same size on the metal support by electroforming. Can be. Further, the protrusions formed on the base plate are not particularly limited, but may be 50-200 mu m in height.

In the fuel cell metal support, the pores formed on the surface of the metal support have an opening ratio of about 10-90% of the area, and the size and distribution of the metal support are preferably uniformly controlled. Otherwise, power generation efficiency is low and it is difficult to secure stable power. Therefore, the protrusions formed on the primary mother plate preferably have protrusions having a size sufficient to form pores of the same size, and are uniformly distributed on the surface of the primary mother plate, and the plurality of protrusions are formed on the primary mother plate. It is preferable to occupy about 10 to 90% of the area. Such protrusions may have a predetermined pattern with respect to the primary mother plate, but such patterns are appropriately selected and are not particularly limited herein.

When a silicon wafer is used as the substrate of the cathode electrode primary mother plate, it is necessary to form a metal seed layer so that it can be energized on the silicon wafer substrate. It is preferable that the metal seed layer has a high bonding strength with the Si wafer for peeling the metal foil formed by electroforming on it, but not a high bonding strength with the metal foil formed on the seed layer by electroforming.

Accordingly, the metal seed layer is preferably a Ti seed layer, and the Ti seed layer is preferably formed through an E-beam. By forming the Ti seed layer on the Si wafer by E-beam, the Ti seed layer and the Si wafer can be firmly bonded through ionic bonding, and further, a TiO ₂ oxide layer is formed on the surface of the Ti seed layer through proper heat treatment. Since it can form, the metal foil formed on a metal seed layer can be easily peeled off through an electroforming method, and the mother board for forming a solid oxide fuel cell by electroforming can be obtained.

It is preferable that the flat layer of the primary mother plate used as the cathode electrode has a certain level of surface roughness. If the surface roughness is too low, the metal foil generated during the electroforming process tends to fall off from the cathode electrode. If the surface roughness is too high, the metal foil is excessively strongly bonded to the surface of the cathode electrode to damage the metal foil in the subsequent peeling process. there is a problem. Therefore, the surface roughness of the cathode electrode flat layer may be in the range of 1 to 100nm. As described above, in the case of providing a constant surface roughness to the surface of the primary mother plate, the same surface roughness can be formed on the metal foil finally obtained by electroforming.

Such surface roughness may include mechanical polishing such as polishing, chemical polishing such as etching, and chemical mechanical polishing such as the CMP method mainly used in semiconductor processes. The chemical polishing, mechanical polishing and chemical mechanical polishing means may be used alone or in combination thereof. Such polishing means can provide a constant surface roughness to the surface of the primary mother plate.

When the metal is electrodeposited on the primary mother plate by the electroforming to form a metal electrodeposition layer, the metal foil which can be used as the mother plate can be obtained by peeling and separating the metal electrodeposition layer from the mother plate of the cathode electrode. The surface shape of the primary mother plate may be transferred to the surface of the separated metal foil as it is, thereby obtaining a metal foil having the same surface shape, and the metal support to be obtained in the present invention may be manufactured using the obtained metal foil as the mother plate. have.

In manufacturing the mother plate for producing such a metal support, the electroforming apparatus is not particularly limited, and any electroforming apparatus shown in FIGS. 1 to 3 may be used. More preferably, it is preferable to use a drum type electric casting device. In the case of using the electroforming apparatus of FIG. 1 or the horizontal electroforming apparatus of FIG. 3, continuous production is not easy when using a constant size plate, and a long length of the plate is required for continuous production. It is necessary to form protrusions or intaglio with respect to the surface processing of the primary mother plate can be a burden. However, in the case of using a drum type electroforming device, it is possible to obtain a base plate by electroforming continuously by forming a constant protrusion or intaglio on the drum surface, and does not require special operation for continuous production. Moreover, the metal foil for baseplates obtained by this can be wound up and stored, and it is convenient.

In preparing the mother plate by electroforming from the primary mother plate as described above, the electrolyte solution in the present invention, the electrolyte solution comprises a metal ion, the metal ion is particularly that the electrolytic precipitation reaction can occur by the electroforming method It does not limit, For example, Cu, Fe, Ni, Ti, Zn, Cr, Co, Ag, Pd, Al, Sn, or these alloys etc. are mentioned, More preferably, Cu, Ni, Fe, or these It may be an alloy of.

The obtained sheet metal foil may include a step of washing to remove impurities such as an electrolyte solution, an etching solution and the like present on the surface as needed. At this time, the washing is not particularly limited, and the electrolytic solution remaining on the surface of the metal foil can be cleaned using an acidic solution and a washing solution.

It is also possible to open at least a part of the projections by polishing or etching the surface of the obtained metal foil by mechanical, physical or chemical means. As a result, when the metal support is manufactured by electroforming using the metal foil as a mother plate, pores can be formed on the metal support obtained.

Although the thickness of the obtained metal foil for baseplate is not specifically limited, For example, it is preferable that it is 30-500 micrometers. When the thickness of the metal foil is less than 30 μm, handling may be difficult due to the process such as tearing of the foil during the peeling process, and when it exceeds 500 μm, productivity is reduced in manufacturing the metal foil for the mother board.

On the other hand, the metal foil for the mother plate preferably includes an oxide film on the surface. When the electrodeposition layer is formed on the surface of the mother plate by forming the oxide film, peeling from the electrodeposition layer may be easy. Such an oxide film is not particularly limited and is not particularly limited as long as it can be generally used, including a method of forming an oxide film on the surface of the metal foil by heat treatment.

The metal support to be obtained in the present invention can be produced by electroforming using the obtained metal foil as a mother plate. At this time, the process of electroforming is not different from manufacturing the metal foil for the mother board using the primary mother board.

However, in manufacturing the metal support, it is not necessarily limited, but it is preferable to use the horizontal cell electroforming apparatus shown in FIG. As described above, since the metal foil for the mother board can be continuously manufactured using the drum type pole apparatus, there is no particular problem in the production of the continuous metal support when the horizontal cell pole apparatus is used, thereby improving productivity. It can plan, and it is more preferable.

Moreover, it is preferable that the said metal support obtained by this is Ni or Fe-Ni alloy. Since Ni is excellent in electric conductivity, Fe is light and flexible, and excellent strength or hardness is secured, cracks or fractures due to physical impact are hardly generated, which is advantageous in terms of heat dissipation and durability. In addition, since the production cost is low, mass production is possible, it is advantageous from the viewpoint of productivity and easily changes into a roll-like form. Therefore, it is easy to store and it is easy to control the size of the substrate .

It is more preferable that the metal support is an alloy of Ni and Fe. Thus, when a substrate is manufactured as an Fe-Ni alloy, the coefficient of thermal expansion can be optimized to be applicable to a metal support for a fuel cell through the control of the content of Ni. In addition, the Fe-Ni alloy is an easy material to ensure corrosion resistance, and at the same time, when the metal support is manufactured by using the electroforming method, the Fe-Ni alloy can be easily formed.

The metal support may be a Ni metal or Fe-Ni alloy having a Ni content of 40 to 100% by weight, and more preferably a Fe-Ni alloy having a Ni content of 45 to 90% by weight. When the Ni content is out of the above range, the difference in coefficient of thermal expansion becomes large, and thus, deterioration of characteristics of the cell electrode due to thermal stress may occur, and thus it may be difficult to be applied as a metal support for a fuel cell.

In the case of manufacturing the metal support of the Fe-Ni alloy, the electrolyte solution added to the electrolytic cell for this includes a Fe precursor and Ni precursor. Examples of the Ni precursor include nickel sulfate, nickel chloride, nickel nitrate, nickel sulfide, or a mixture thereof. Examples of the Ni precursor include iron sulfate, ferric chloride, ferric nitrate, iron sulfamide, And the like.

The content of the iron precursor and the nickel precursor in the electrolyte is not particularly limited and can be suitably adjusted according to the moving speed of the base plate, the supply rate of the electrolyte, and the composition ratio of Fe and Ni in the Fe-Ni alloy electrodeposited layer (thin film) . At this time, an example for producing the metal support Fe-Ni alloy, when the composition of the electrolyte solution per 1 L of water, the Ni precursor is 40 to 50g, it is preferable to make the Fe precursor to 6 to 12g.

In addition, the electrolytic solution may contain other unavoidable impurities. Such other impurities can not be excluded because they can be inevitably incorporated from the raw material or the surrounding environment in a usual production process. These impurities can be recognized by those skilled in the art, and a detailed description thereof will be omitted here.

The electrolytic solution may contain other additives such as a conductive additive, a complexing agent and the like in an amount commonly used in this technical field. In order to facilitate the electroforming, the temperature of the electrolytic solution is preferably controlled at 50 to 60 ° C and the pH of the electrolytic solution is controlled at 1.5 to 3.5. In addition, a pH buffer may be added to adjust the pH of the electrolytic solution to the above range, and the pH buffer may include 10 to 30 g / L of boric acid. Furthermore, a surfactant such as sodium dodecyl sulfate, sodium lauryl sulfate, or a stress relaxation agent such as saccharin may be further added so as to reduce the stress of the substrate and easily detach the substrate from the cathode electrode base plate.

The metal foil for the mother plate obtained in the present invention may have a pore size of 50 μm or less, preferably 1 to 50 μm, and more preferably 1 to 10 μm. If the pore size on the metal support is more than 50 탆, the anode and the electrolyte may be easily broken in the process of raising the electrolyte, so that it may be difficult to manufacture the cell. In addition, the size and distribution of the pores must be uniformly controlled. Otherwise, the power generation efficiency is low and it may be difficult to obtain stable power.

On the other hand, the metal support needs to be controlled to have a similar thermal expansion coefficient to the cell components of the fuel cell. This is because as the temperature rises or falls, there may be a difference in the stresses exerted on the metal support or the materials deposited thereon, which can lead to cracking or fracture of the metal support or other materials Because.

Further, if necessary, a step of opening the protrusions by using a polishing means or the like as described in the present invention may be included in order to open the protrusions formed on the metal foil for the metal support.

Example

Hereinafter, an Example is given and this invention is demonstrated more concretely. However, the following examples are related to one example of the present invention, and are not intended to limit the present invention thereby.

Example  One

A silicon wafer was used as the first negative electrode substrate, and an intaglio shape was manufactured through an ion silicon etching process. The intaglio had an average diameter of 50 mu m and an interval of 150 mu m. A Ti seed layer was formed to a thickness of 1000 판 through an E-beam on the surface of the mother plate and then heat treated at 550 ° C. to form a TiO ₂ film.

50 g of nickel chloride, 12 g of iron chloride, 20 g of boric acid and 0.4 g of saccharine were added per liter of water to prepare an electrolytic solution of the present invention.

An electroforming apparatus 100 as shown in FIG. 1 having a power source 108, an anode electrode 106 connected to the power source, and an electrolyzer 102 carrying an electrolyte solution was used, and the prepared mother plate was a cathode electrode ( 104) to connect with the power supply. Subsequently, the electrolyte 110 was filled in the electrolytic cell 102 to immerse the anode electrode 106 and the cathode electrode 104 in the electrolyte 110.

After the electrolyte solution 110 had a pH of 2.0 and a temperature of 55 ° C., electric casting was performed by applying a current. At this time, the current density was 5 A / dm 2.

After the Fe-Ni electrodeposition layer having a thickness of 80 µm was formed on the surface of the cathode by such electroforming, the Fe-Ni electrodeposition layer was separated to obtain a Fe-Ni metal foil. A Ti seed layer was formed on the obtained metal foil through an E-beam, and then heat-treated at 550 ° C. to form a TiO ₂ film.

The base plate of the Fe-Ni alloy was used as the base plate 11 of the horizontal electroforming apparatus 300 as shown in FIG. 3 to prepare a metal foil used as a metal support.

The metal foil of the Fe-Ni alloy manufactured in the horizontal cell 30 of the horizontal electroforming apparatus 300 was introduced into the base plate 11, and an electrolyte solution was applied to 1000 Reynolds numbers while applying current to the base plate and the anode electrode. The electroforming was performed by feeding the surface of the mother plate at a rate of. At this time, the current density was 5 A / dm 2, and the same electrolyte was used as the electrolyte used for preparing the mother plate.

After the 50-micrometer Fe-Ni electrodeposition layer was formed in the mother board surface by the said electroforming, the Fe-Ni electrodeposition layer formed on the mother board was isolate | separated, and the Fe-Ni metal foil with a thickness of 50 micrometers was obtained.

The microstructure of the metal foil prepared by the above process is shown in FIG. 5. As can be seen from FIG. 5, it could be visually confirmed that the manufactured metal support has uniform and even pores by the shape of the mother plate protrusion.

As can be seen from the above, it is possible to produce a metal support having uniform size and distribution of pores and excellent strength and impact characteristics by using the method for producing a solid oxide fuel cell metal support of the present invention.

100: electroforming apparatus
102: electrolyzer 104: base plate (cathode electrode)
106: anode electrode 108: power source
110: electrolytic solution 112: metal foil
200: drum electroforming apparatus
202: electrolytic bath 204: drum (cathode electrode)
206: anode electrode 208: power source
210: electrolyte solution 212: metal foil
300: horizontal electric casting device
10: Bed plate feeder 11: Bed plate (cathode electrode)
12: bonding means 13: polishing means
14: electric cleaning device 30: horizontal cell
31, 31 ': Conductor roll 32: anode electrode
33: power source 34: electrolyte reservoir
35: Electrolyte heater 36: Electrolyte filter
37: Electrolyte pump 38: Electrolyte nozzle
50: metal foil 51: thin film separator (peel roll)
52: post-cleaning device 54: metal separator cutting device
55: metal foil winding device 71: bed plate cutting device
72: base plate winding device 300: horizontal pole

Claims (23)

A conductive base plate for electroforming used to produce a metal foil using an electrolytic precipitation reaction of electroforming, wherein the base plate is a flexible metal, has a thickness of 30-500 μm, and includes a plurality of protrusions on a flat surface. The projections are electroforming cast plate is present in the range of 10 to 90% of the bed area.
2. The electroforming base plate according to claim 1, wherein the protrusions have a maximum diameter of 1 to 50 mu m and a height of 50 to 200 mu m on a circular basis.
[2] The method of claim 1, wherein the protrusions have a cylindrical shape having a constant cross-sectional area, a cylindrical shape having a cross-sectional area reduced upward, a cone, an arc, a semicircle, an inverted ellipse, a polygonal prism having a constant cross-sectional area, a polygonal prism having a cross- Or a combination of these shapes.
The electroforming base plate according to claim 3, wherein the projections have a height difference in height direction.
According to claim 1, The base plate is electroforming casting base plate of the upper end of the projection.
2. The electroplating mother plate according to claim 1, wherein the mother plate has an oxide film formed on a surface thereof.
The mother plate for electroforming according to claim 6, wherein the oxide film is a TiO ₂ film.
The mother plate for electroforming according to any one of claims 1 to 7, wherein the mother plate has a surface roughness of 1-100 nm on a flat surface.
An electric casting apparatus provided at least as a power source, a cathode electrode, and an anode electrode, the primary mother plate to which metal is electrodeposited from an electrolyte solution, and an electrolyte supply means for supplying the electrolyte solution to the cathode electrode and the anode electrode,
Supplying an electrolyte solution containing metal ions to at least the primary mother plate;
A current is applied to the primary mother plate and the anode electrode, and metal is electrolytically precipitated from the electrolyte to be electrodeposited on the surface of the primary mother plate; And
Separating the metal electrodeposition layer deposited on the surface of the primary mother plate from the primary mother plate,
The primary base plate includes a plurality of protrusions or intaglio on a flat surface, wherein the protrusions or intaglio is present in the range of 10 to 90% of the area of the primary base plate, the surface of the electroforming casting plate manufacturing method comprising an oxide film on the surface.
10. The method of claim 9, wherein the primary mother plate is formed by etching the surface of the Si wafer by a lithography process and an ion silicon etching process to form protrusions or indentations on the flat surface, the conductive metal seed for electrodeposition of the metal on the flat surface of the Si wafer A method for producing an electroforming mother plate obtained by forming a layer.
The method of claim 10, wherein the conductive metal seed layer is a Ti layer.
12. The method of claim 11, wherein the Ti layer is formed through an E-beam.
The method of claim 12, wherein the Ti layer is heat-treated to form a TiO ₂ film.
12. The method of claim 11, wherein a surface roughness of 1 to 100 nm is given to the Ti seed layer.
10. The method of claim 9, wherein the primary mother plate is a cathode drum of a metal plate or a drum type electroforming device.
10. The method of claim 9, wherein the protrusion or the intaglio portion has a maximum diameter of 1 to 50 µm and a height of 30 to 500 µm on a circular basis.
An electroforming apparatus provided with at least a power supply, a cathode electrode, and an anode electrode, the electroforming apparatus including a base plate on which a metal is electrodeposited from an electrolyte, and an electrolyte supply means for supplying the electrolyte solution to the cathode electrode and the anode electrode, A method for producing a metal support,
Supplying an electrolytic solution containing metal ions to at least the base plate;
Applying a current to the base plate and the cathode electrode to deposit a metal on the surface of the base plate by electrolytic deposition of the metal from the electrolyte solution; And
Separating the metal electrodeposition layer deposited on the surface of the base plate from the base plate,
The said base plate is a metal support body manufacturing method of any one of Claims 1-7.
18. The apparatus of claim 17, wherein the electroforming device is a drum type pole or a horizontal type pole die,
The horizontal pole is supplied to the mother plate horizontally in a predetermined direction, the electrolyte is supplied to the surface of the mother plate through the electrolyte flow channel formed by the mother plate and the cathode electrode,
And a metal electrodeposition layer is formed on the surface of the mother plate by the current applied to the mother plate and the anode electrode.
18. The method of claim 17, wherein the electrolyte solution comprises 40-50 g of Ni precursor and 6-12 g of Fe precursor with respect to 1 L of water.
The method of claim 19, wherein the electrolyte is at least one iron precursor selected from the group consisting of iron sulfate, iron chloride, iron nitrate and iron sulfamate and at least one type selected from the group consisting of nickel sulfate, nickel chloride, nickel nitrate and nickel sulfamate Metal support manufacturing method comprising a nickel precursor.
18. The method of claim 17, wherein the metal support is Ni metal or Fe-Ni alloy having a Ni content of 40-100% by weight, and has a thickness of 30-200 µm.
The method of claim 17, wherein the metal support has a pore of 1 to 50㎛.
18. The method of claim 17, wherein the metal support has an opening ratio of 10-90% of the area.

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