JP2018181458A - Plasma device and separator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film forming apparatus which suppresses deformation of a work due to a temperature difference between a central portion and an outer peripheral portion. SOLUTION: A first mold 110 and a second mold 120 arranged to face each other are provided, and the first mold 110 has a first flat surface portion 111 and a first hollow portion in which a hollow separator 10 is arranged from the first flat surface portion 111. A vacuum container 100 having a portion 114, a masking member 21 arranged between the first flat surface portion 111 and the second mold, and a masking member arranged between the first flat surface portion 111 and the second mold 120. An insulating member 35 that contacts the member 21, a separating member that separates the masking member 21 from the first flat surface portion 111 and the second mold 120, and a power application unit 70 that applies power to the separator 10 and the masking member 21. The masking member 21 is a plasma device for forming a film on the separator 10 having a notch or an opening at a position corresponding to the power generation region S1 involved in power generation and the connection region where the cell monitor terminal is connected in the separator 10. 200. [Selection diagram] Fig. 4

Description

  The present invention relates to a plasma device and a separator.

  As a plasma apparatus, Patent Document 1 describes an apparatus for forming a film by holding a substrate between two vertically divided film forming containers and filling a film forming container with a gas.

JP, 2009-062579, A

  In the apparatus described in Patent Document 1, since the outer peripheral portion of the substrate is sandwiched between the film forming containers, it is difficult to be exposed to plasma during film formation, and a temperature difference occurs between the central portion and the outer peripheral portion of the substrate to deform the workpiece. There was a fear.

  The present invention has been made to solve the above-described problems, and can be realized as the following modes.

(1) According to one aspect of the present invention, there is provided a plasma device for forming a film on a separator used in a fuel cell. The plasma apparatus is a vacuum vessel including a first mold and a second mold disposed opposite to each other, wherein the first mold is recessed from the first flat portion and the first flat portion and the separator is disposed. A vacuum vessel having a first recess; a masking member at least a portion of which is disposed between the first flat portion and the second mold; and the first flat portion and the second type An insulating member disposed between and in contact with the masking member; a spacing member for spacing the masking member away from the first flat portion and the second mold; power application for applying power to the separator and the masking member The masking member is a power generation area involved in power generation of the fuel cell among the separators, and a cell monitor terminal located on an outer peripheral portion of the power generation area and capable of detecting the voltage of the fuel cell A connection region connected to the corresponding position, with a notch or opening.
In such a plasma device, the separator is disposed in the first depression where plasma is generated, and the masking member has a notch or opening in the power generation region and the connection region of the outer periphery of the separator. The temperature difference between the central portion and the outer peripheral portion of the separator during film formation can be reduced, and deformation of the separator due to the temperature difference can be suppressed. In addition, since the masking member has notches or openings in the connection region, the connection region can be formed into a film, so that the strength of the connection region can be improved and the contact resistance can be reduced.

(2) According to another aspect of the present invention, a separator for use in a fuel cell is provided. The separator includes: a power generation area involved in power generation of the fuel cell; a connection area located at an outer peripheral portion of the power generation area and to which a cell monitor terminal capable of detecting the voltage of the fuel cell is connected; It comprises: a seal area in which a seal member to be sealed is disposed; and a conductive film formed on the power generation area and the connection area except for the seal area.
With such a separator, it is possible to achieve an improvement in the strength of the connection region and a reduction in the contact resistance. In addition, sealing defects between the separators can be suppressed.

  The present invention can also be realized in various forms other than the above-described plasma apparatus. For example, it can be realized in the form of a method of forming a film on a separator, a fuel battery cell provided with a separator, or the like.

FIG. 1 is a perspective view showing a schematic configuration of a fuel cell stack to which a separator in an embodiment of the present invention is applied. The top view which shows schematic structure of a separator. The figure which shows the example in which a cell monitor terminal is connected to the connection area | region of a separator. BRIEF DESCRIPTION OF THE DRAWINGS The schematic sectional drawing which shows the structure of the plasma apparatus in one Embodiment of this invention. The disassembled perspective view of a plasma apparatus. The elements on larger scale of a plasma device. FIG. 7 is a process diagram showing a method of forming a separator with a plasma device. FIG. 7 is a view showing a plasma device in a modification 2; FIG. 16 is a view showing a plasma device in a third modification.

A. Embodiment:
A1. Fuel Cell Stack Configuration:
FIG. 1 is a perspective view showing a schematic configuration of a fuel cell stack 400 to which a separator 10 according to an embodiment of the present invention is applied. The fuel cell stack 400 is formed by stacking a plurality of fuel cells 300 along the stacking direction SD. The fuel cell 300 is also referred to as a single cell.

  Inside the fuel cell stack 400, manifolds 11m to 16m are formed. The manifold 11 m supplies the fuel cell 300 with hydrogen gas which is a fuel gas. The manifold 12 m discharges the anode side off gas discharged from the fuel cell 300 to the outside of the fuel cell stack 400. The manifold 13m supplies air, which is an oxidant gas, to the fuel cell 300, and the manifold 14m discharges the cathode side off gas discharged from the fuel cell 300 to the outside of the fuel cell stack 400. The manifold 15 m supplies a cooling medium to the fuel cell 300, and the manifold 16 m discharges the cooling medium discharged from the fuel cell 300 to the outside of the fuel cell stack 400. The six manifolds 11m to 16m are all extended in parallel to the stacking direction SD.

  The fuel cell 300 includes an MEGA plate 46 and a pair of separators 10. The MEGA plate 46 includes an MEGA (Membrane Electrode and Gas Diffusion Layer Assembly) 42 and a support frame 40. The MEGA 42 has a configuration in which a solid polymer electrolyte membrane, an anode catalyst electrode layer, a cathode catalyst electrode layer, an anode gas diffusion layer, and a cathode gas diffusion layer are stacked in the stacking direction SD. A through hole is provided in the central portion of the support frame 40 in the thickness direction. The MEGA 42 is disposed in the through hole of the support frame 40.

  The pair of separators 10 are arranged to sandwich the MEGA plate 46 in the stacking direction SD. The seal member 48 is disposed between the adjacent separators 10 when the fuel cells 300 are stacked. The seal member 48 is disposed for the purpose of suppressing the leakage of the reaction gas, the cooling medium, and the like. The seal member 48 is formed of rubber. As the rubber, for example, butyl rubber or silicone rubber may be employed.

  Each fuel battery cell 300 is provided with six substantially rectangular openings 11 to 16 in the outer peripheral portion. The openings 11 to 16 correspond to six manifolds 11 m to 16 m formed inside the fuel cell stack 400. Specifically, when the plurality of fuel cells 300 are stacked and the fuel cell stack 400 is assembled, the openings 11 to 16 of the fuel cells 300 overlap in the stacking direction SD, so that six manifolds 11m to 16m is formed. The number, the shape, and the like of the openings 11 to 16 can be changed as appropriate.

A2. Composition of separator:
FIG. 2 is a plan view showing a schematic configuration of the separator 10. The separator 10 is a substantially rectangular plate-like member having conductivity. In the present embodiment, the separator 10 is made of titanium (Ti). The separator 10 includes a power generation area S1, a connection area S2, and a seal area S3. Moreover, the separator 10 is provided with the electroconductive film | membrane formed in electric power generation area | region S1 and connection area | region S2 except seal | sticker area | region S3. In FIG. 2, the conductive films are shown shaded. In the present embodiment, the outer peripheral end portions S4, S5, S6 of the power generation region S1 of the separator 10 also have a conductive film, similarly to the power generation region S1 and the connection region S2. In the present embodiment, the conductive film is a carbon-based thin film. In the present embodiment, a conductive film is formed on the other surface of the separator 10 shown in FIG. 2 as in the case shown in FIG.

  The power generation region S <b> 1 is a region of the separator 10 involved in the power generation of the fuel cell 300. The power generation region S1 is located at the central portion of the separator 10, and faces the MEGA 42 shown in FIG. An uneven shape is formed in the power generation region S1. This uneven shape forms an in-cell gas flow path through which the reaction gas (fuel gas or oxidant gas) flows, and also forms a flow path for the cooling medium between the separators 10 of the adjacent fuel cells 300.

  Connection region S2 is located at the outer peripheral portion of power generation region S1. The connection area S2 is an area to which a cell monitor terminal is connected. The cell monitor terminal is a terminal capable of detecting the voltage of the fuel cell 300, and is connected to the voltage sensor. The cell monitor terminal may have conductivity and be connected to the connection area S2, and may sandwich the connection area S2, or may be fixed to the connection area S2 by a spiral or the like. FIG. 3 is a view showing an example in which the cell monitor terminal 310 is connected to the connection area S2 of the separator 10. As shown in FIG.

  Returning to FIG. 2, the seal area S3 is located at the outer peripheral portion of the power generation area S1. The seal area S3 is an area different from the connection area S2. The seal area S3 is an area where the seal member 48 (FIG. 1) for sealing between the separators 10 of the fuel cell 300 is disposed.

A3. Configuration of plasma device:
FIG. 4 is a schematic cross-sectional view showing the configuration of a plasma device 200 according to an embodiment of the present invention. FIG. 5 is an exploded perspective view of the plasma device 200. As shown in FIG. In FIGS. 4 and 5, mutually orthogonal XYZ axes are shown. In addition, orthogonal means including the range of +/- 20 degrees. In the present embodiment, the Y direction indicates a vertical direction, the X direction indicates a horizontal direction, and the Z direction indicates a direction perpendicular to the Y axis and the X axis. The same applies to the following figures.

  The plasma apparatus 200 is an apparatus for forming a film on the separator 10 using plasma. In the present embodiment, the plasma device 200 forms a conductive carbon-based thin film on the power generation region S1, the connection region S2, and the outer peripheral end portions S4 to S6 of the separator 10 by the plasma CVD method. The cross section of the separator 10 shown in FIG. 4 is a 4-4 cross section of the separator 10 shown in FIG.

  The plasma apparatus 200 includes a vacuum vessel (chamber) 100, masking members 21 and 22, an insulating member 30, seal members 61 and 62 as separating members, and a power application unit 70. The plasma apparatus 200 further includes an opening / closing device 50, a transfer device 55, a gas supply device 80, an exhaust device 90, a control unit 95, and a pallet 130. In FIG. 5, the opening / closing device 50, the transfer device 55, the power application unit 70 and its power introduction unit 71, the gas supply device 80 and the supply port 81, the exhaust device 90 and the exhaust port 91, and the control unit 95. And are not shown. The separator 10 and the masking members 21 and 22 are collectively referred to as “work W”.

  The vacuum vessel 100 is a dividable vessel. In the present embodiment, the vacuum vessel 100 is divided in the + Y direction and the −Y direction. The vacuum vessel 100 is a metal vessel, and is formed of, for example, stainless steel (SUS). The vacuum vessel 100 includes a first mold 110 and a second mold 120 disposed opposite to each other. The first mold 110 includes a first flat portion 111 and a first hollow portion 114 in which the hollow separator 10 is disposed from the first flat portion 111. In a state where the separator 10 is disposed in the vacuum vessel 100, the first recess 114 is recessed in a direction away from the separator 10. In the present embodiment, the first recess 114 is recessed upward (in the + Y direction) when viewed from the upper surface side of the separator 10. You In addition, the first recess 114 includes a side 112 and a bottom 113. In the present embodiment, the connection point between the first recess 114 and the first flat portion 111 is located on the same YZ plane as the end of the separator 10. In the present embodiment, the second mold 120 includes a second flat portion 121 and a second hollow portion 124 in which the hollow separator 10 is disposed from the second flat portion 121. When the separator 10 is disposed in the vacuum vessel 100, the second recess 124 is recessed downward (in the −Y direction) when viewed from the lower surface side of the separator 10. The second recess 124 includes a side 122 and a bottom 123. The second flat surface portion 121 is disposed in a portion corresponding to the first flat surface portion 111 of the first mold 110. In the present embodiment, the connection point between the second recess 124 and the second flat surface 121 is located on the same YZ plane as the end of the separator 10. In the present embodiment, the first flat surface portion 111 and the second flat surface portion 121 are parallel to the XZ plane. The first mold 110 and the second mold 120 have a supply port 81 for supplying a gas from the gas supply device 80 into the vacuum vessel 100 and an exhaust port 91 for exhausting the inside of the vacuum vessel 100 by the exhaust system 90. And. The supply port 81 and the exhaust port 91 are provided with valves that can be opened and closed. The second mold 120 also includes a power introducing unit 71 for applying a voltage to the separator 10 and the masking members 21 and 22. An insulating member 35 electrically insulates between the second mold 120 and the power introducing portion 71. In the present embodiment, the vacuum vessel 100 has a ground potential.

  The masking members 21 and 22 have an opening 24 and a notch 25 at positions corresponding to the power generation region S1 and the connection region S2 in the separator 10. In the present embodiment, the masking members 21 and 22 cover the non-processing target portion 10B of the separator 10 including the seal area S3, have an opening 24 at a position corresponding to the power generation area S1, and at a position corresponding to the connection area S2. It has a notch 25. In the present embodiment, the masking members 21 and 22 also have the notches 25 at positions corresponding to the outer peripheral end portions S4 to S6 of the separator 10. In the present embodiment, the masking member 21 (upper masking member 21) is disposed on the side of the first mold 110 of the separator 10. The masking member 22 (lower masking member 22) is disposed on the second mold 120 side of the separator 10. In the present embodiment, the lower masking member 22 supports the separator 10. The masking members 21, 22 are at least partially disposed between the first flat portion 111 and the second mold 120. In the present embodiment, parts of the masking members 21 and 22 are disposed in the first recess 114 and the second recess 124, and the other portions are between the first flat portion 111 and the second flat portion 121. Is located in The masking members 21 and 22 are formed of conductive members, and can be made of titanium (Ti), aluminum (Al), stainless steel (SUS) or the like. The separator 10 and the masking members 21 and 22 are electrically connected by contact. The masking members 21 and 22 may have openings at positions corresponding to the connection region S2 or the outer peripheral end portions S4 to S6.

The insulating member 30 is disposed between the first flat portion 111 of the first mold 110 and the second mold 120 and is in contact with the masking member 22. In the present embodiment, the insulating member 30 is disposed between the first flat portion 111 and the second flat portion 121 and contacts the masking member 22 to support the lower masking member 22. The insulating member 30 is made of, for example, a ceramic such as alumina (Al ₂ O ₃ ) or silicon dioxide (SiO ₂ ).

  The pallet 130 is a plate member made of metal. The pallet 130 is also a member for transporting the masking members 21 and 22 and the separator 10 into the vacuum vessel 100. The pallet 130 is disposed between the first flat portion 111 of the first mold 110 and the second mold 120. In the present embodiment, the insulating member 30, the lower masking member 22, the separator 10 and the upper masking member 21 are loaded in this order in the + Y direction in this embodiment, and the pallet 130 is masked via the insulating member 30. The members 21 and 22 and the separator 10 are held. In the present embodiment, the pallet 130 has an edge 130 t exposed outside the vacuum vessel 100 in a state where the vacuum vessel 100 is closed. The edge 130 t is a portion that contacts the pallet 130 when the conveying device 55 described later conveys the pallet 130. In the present embodiment, the pallet 130 has a ground potential. The pallet 130 is formed of aluminum (Al), stainless steel (SUS), titanium (Ti) or the like.

  The seal members 61 and 62 are disposed between the first flat portion 111 of the first mold 110 and the second mold 120. The sealing members 61 and 62 are members for keeping the inside of the vacuum vessel 100 airtight. The seal members 61 and 62 are insulating members, and in the present embodiment, are annular members made of rubber. In the present embodiment, the seal members 61 and 62 use O-rings. In the present embodiment, the seal member 61 is fitted in a groove provided in the first mold 110. The seal member 62 is fitted in a groove provided in the second mold 120. In the present embodiment, the seal members 61 and 62 are also separating members that separate the masking members 21 and 22 from the first flat portion 111 and the second mold 120.

  The opening and closing device 50 is a device for opening and closing the vacuum vessel 100. In the present embodiment, the opening / closing device 50 moves the first mold 110 in the + Y direction to open the vacuum vessel 100, and moves the first mold 110 in the −Y direction to close the vacuum vessel 100.

  The transfer device 55 is a device for transferring the pallet 130 into the vacuum vessel 100 and transferring the pallet 130 out of the vacuum vessel 100. In the present embodiment, the transport device 55 contacts the edge 130t of the pallet 130, and the insulating member 30, the masking members 21 and 22, and the separator stacked on the pallet 130 and the pallet 130 in a state where the vacuum vessel 100 is opened. 10 are transferred into the vacuum vessel 100. Further, the transport device 55 places the pallet 130 on the second mold 120 via the seal member 62 by moving the transported pallet 130 downward. The transfer device 55 can also transfer the pallet 130 moved upward to the outside of the vacuum vessel 100 by moving the pallet 130 along the XZ plane.

  The power application unit 70 is a device for applying power to the separator 10 and the masking members 21 and 22. The power application unit 70 generates an electric field for plasmatizing the source gas supplied into the vacuum vessel 100. In the present embodiment, the power introducing portion 71, the separator 10 and the masking members 21 and 22 are cathodes, and the first mold 110, the second mold 120 and the pallet 130 are anodes. In the present embodiment, the power application unit 70 applies a bias voltage to the separator 10 through the lower masking member 22. The power application unit 70 can apply, for example, a voltage of −3000 V to the power introduction unit 71. In the present embodiment, the vacuum vessel 100 and the pallet 130 are connected to the ground (0 V).

The gas supply device 80 supplies the carrier gas and the source gas into the vacuum vessel 100 via the supply port 81. In the present embodiment, the gas supply device 80 supplies, for example, nitrogen (N ₂ ) gas or argon (Ar) gas as a carrier gas, and supplies, for example, pyridine (C ₅ H ₅ N) gas as a source gas. The gas supply device 80 is connected to a tank that stores different types of gas. The gas supply device 80 can switch the type of gas supplied to the supply port 81 by operating a switching valve provided between each tank and the supply port 81. In addition, the gas supply device 80 may, for example, be placed in the vacuum container 100 after film formation by the plasma device 200 in order to return the pressure in the vacuum container 100 to a pressure that allows the opening / closing device 50 to open the vacuum container 100. Nitrogen gas is supplied to decompress the vacuum vessel 100.

  The exhaust device 90 exhausts the inside of the vacuum vessel 100 via the exhaust port 91. The exhaust device 90 is configured of, for example, a rotary pump, a diffusion pump, a turbo molecular pump, and the like.

  The control unit 95 controls the overall operation of the plasma device 200. Control unit 95 includes a CPU and a memory. The CPU controls the plasma device 200 by executing a program stored in the memory. This program may be recorded on various recording media. For example, the control unit 95 controls the opening / closing device 50 to open the vacuum container 100, and controls the transfer device 55 to transfer the pallet 130. After the pallet 130 is transported into the vacuum vessel 100, when the control unit 95 closes the vacuum vessel 100, the sealing members 61 and 62 as separating members come in contact with the pallet 130, thereby the masking members 21 and 22 and the first The flat portion 111 and the second mold 120 are separated. Further, the control unit 95 controls the exhaust device 90 to exhaust the inside of the vacuum vessel 100, controls the gas supply device 80 to supply gas into the vacuum vessel 100, and controls the power application unit 70 to perform the separator 10. And apply power to the masking members 21 and 22.

  FIG. 6 is a partial enlarged view of the plasma device 200. As shown in FIG. In FIG. 6, an X portion indicated by a broken line in FIG. 4 is shown. FIG. 6 shows points (contact points P1 and P2) at which the masking members 21 and 22 and the insulating member 30 are in contact with each other. The contact point P1 is a portion facing the first flat portion 111 among the portions where the masking members 21 and 22 contact the insulating member 30. The contact point P1 is the closest contact point to the first flat portion 111 among the contact points between the masking members 21 and 22 and the insulating member 30 in the cross section of the plasma device 200 (FIG. 6). The contact point P2 is a portion facing the second flat portion 121 among the portions where the masking members 21 and 22 and the insulating member 30 contact with each other. The contact point P2 is the contact point closest to the second flat portion 121 among the contact points between the masking members 21 and 22 and the insulating member 30 in the cross section of the plasma device 200 (FIG. 6). Further, FIG. 6 shows the distance A1 between the contact point P1 and the first flat portion 111 and the distance B1 between the separator 10 and the bottom portion 113 of the first hollow portion 114. The distance A1 is the shortest distance between the contact point between the masking members 21 and 22 and the insulating member 30, and the first flat portion 111. The distance B1 is the distance between the separator 10 facing the first recess 114 and the bottom 113 of the first recess 114, and is the shortest distance between the bottom 113 of the first recess 114 and the separator 10. Further, FIG. 6 shows a distance A2 between the contact point P2 and the second flat portion 121, and a distance B2 between the separator 10 and the bottom portion 123 of the second hollow portion 124. The distance A2 is the shortest distance between the contact point between the masking members 21 and 22 and the insulating member 30 and the second flat portion 121. The distance B2 is the distance between the separator 10 facing the second recess 124 and the bottom 123 of the second recess 124, and is the shortest distance between the bottom 123 of the second recess 124 and the separator 10. In the plasma device 200, the distance A1 is smaller than the distance B1. In other words, the space formed by the masking members 21 and 22 and the first flat portion 111 is smaller than the space formed by the separator 10 and the first recess 114. Further, in the present embodiment, the distance A2 is smaller than the distance B2. In other words, the space formed by the masking members 21 and 22 and the second flat portion 121 is smaller than the space formed by the separator 10 and the second hollow portion 124.

  In the present embodiment, the distance A1 and the distance A2 indicate that the workpiece W and the vacuum container 100 (first flat portion) when power is applied between the workpiece W including the separator 10 and the masking members 21 and 22 and the vacuum container 100. 111, shorter than the distance of the sheath formed between the second flat portion 121). In the present embodiment, the distances A1 and A2 are 2.0 mm or less. From the viewpoint of sufficiently maintaining the insulation between the vacuum container 100 and the work W, the distances A1 and A2 are preferably 0.5 mm or more.

  Further, in FIG. 6, the connection point Q1 between the first recess 114 and the first flat surface 111 and the connection point Q2 between the second recess 124 and the second flat surface 121 to the X-axis from the contact points P1 and P2 The shortest distance C along is shown. The distance C is also the shortest distance along the X-axis from the side 112 of the first recess 114 and the side 122 of the second recess 124 to the contact points P1 and P2. In the present embodiment, the distance C is greater than 0 (zero). In the present embodiment, the distance C is 10 mm or more.

A4. Separator film formation method:
FIG. 7 is a process diagram showing a film forming method of the separator 10 by the plasma device 200. As shown in FIG. Hereinafter, a method of forming a film on the power generation region S1, the connection region S2, and the outer peripheral end portions S4 to S6 of the separator 10 by the plasma device 200 will be described as an example. In the film formation by the plasma apparatus 200, first, a conveyance step is performed in which the separator 10 and the masking members 21 and 22 are conveyed into the vacuum vessel 100 (step S10). In the present embodiment, the insulating member 30, the lower masking member 22, and the separator 10 are loaded on the pallet 130, and the upper masking member 21 is loaded on the separator 10. By doing this, the non-processing target portion 10B including the seal area S3 of the separator 10 is covered by the masking members 21 and 22. Thereafter, the first mold 110 of the vacuum vessel 100 is moved in the + Y direction by the opening / closing device 50, and the pallet 130 on which the insulating members 30, the masking members 21 and 22 and the separators 10 are loaded Transported to The transported pallet 130 is disposed on the second mold 120 via the seal member 62. In the transfer process, when the pallet 130 is placed on the second mold 120, the vacuum vessel 100 is closed. In the present embodiment, the first mold 110 is moved by the opening / closing device 50 in the −Y direction. When the vacuum vessel 100 is closed, the seal members 61 and 62 as separating members come in contact with the pallet 130, and the masking members 21 and 22 and the first flat portion 111 and the second mold 120 are separated. As a result, a gap is formed between the masking members 21 and 22 and the first flat portion 111, and a gap is formed between the masking members 21 and 22 and the second flat portion 121. Further, the distance A1 between the contact point P1 and the first flat surface portion 111 is smaller than the distance B1 between the separator 10 and the first hollow portion 114. The distance A2 between the contact point P2 and the second flat portion 121 is smaller than the distance B2 between the separator 10 and the second hollow portion 124.

  Next, an exhaust process is performed in which the gas in the vacuum vessel 100 is exhausted (step S20). In the present embodiment, the plasma device 200 is installed, for example, in a nitrogen gas atmosphere. In the exhaust process, nitrogen gas in the vacuum vessel 100 is exhausted by the exhaust device 90 through the exhaust port 91, and the inside of the vacuum vessel 100 is vacuumized.

  Next, a gas supply step of supplying the source gas into the vacuum vessel 100 is performed (step S30). In the gas supply step, the carrier gas and the source gas are supplied by the gas supply device 80 through the supply port 81. In the vacuum vessel 100, for example, hydrogen gas and argon gas are supplied as a carrier gas. In addition, nitrogen gas and pyridine gas are supplied as source gases. In the gas supply process, the pressure value in the vacuum vessel 100 is, for example, 11 Pa.

  Next, a power application process is performed in which power is applied to the separator 10 and the masking members 21 and 22 (step S40). In the power application process, a power of, for example, -3000 V is applied to the separator 10 and the masking members 21 and 22 by the power application unit 70. When power is applied to the separator 10 and the masking members 21 and 22 by the power application unit 70, plasma is generated in the first recess 114 and the second recess 124, and the power generation region S1 of the separator 10, the connection region S2 A thin film is formed on the outer peripheral end portions S4 to S6. In the power application process, by applying power to the separator 10 and the masking members 21 and 22, the temperature in the first hollow portion 114 and the second hollow portion 124 of the vacuum vessel 100 is increased. For example, the temperature of the central portion of the separator 10 disposed in the first recess 114 and the second recess 124 reaches 600 ° C. When the power application process is completed, the supply of the source gas and the application of the power are stopped.

  Next, a repressurization step is performed in which the pressure in the vacuum vessel 100 is adjusted (step S50). In the present embodiment, in order to return the pressure in the vacuum vessel 100 to a pressure at which the vacuum vessel 100 can be opened by the opening / closing device 50, nitrogen gas is supplied into the vacuum vessel 100 by the gas supply device 80. . When the pressure in the vacuum vessel 100 is adjusted, the first mold 110 is moved in the + Y direction by the opening and closing device 50, and the conveying member 55 has the insulating members 30, the masking members 21 and 22, and the separator 10 stacked. The pallet 130 is carried out of the vacuum vessel 100. As described above, a series of processing by the plasma device 200 is completed.

A5. effect:
A5-1. Effect 1:
The separator 10 according to the present embodiment includes the conductive film formed in the power generation region S1 and the connection region S2 except for the seal region S3, so that the strength of the connection region S2 is improved and the contact resistance is reduced. Can. Therefore, as compared with the case where the conductive film is not provided in connection region S2, deformation of separator 10 due to connection of cell monitor terminal 310 can be suppressed, and the voltage sensor connected to cell monitor terminal 310 can be used. The voltage of the fuel cell 300 can be acquired more accurately. In addition, sealing failure of the seal member 48 between the separators 10 can be suppressed.

A5-2. Effect 2:
When the outer peripheral portion of the power generation region S1 of the separator 10 is entirely covered with the masking members 21 and 22, the temperature difference between the power generation region S1 and the outer peripheral portion becomes large during film formation, and the separator 10 is warped. There is a fear. In the plasma device 200 of the present embodiment, the separator 10 is disposed in the first recess 114 where plasma is generated, and the masking members 21 and 22 are cut into the power generation region S1 and the connection region S2 of the outer peripheral portion of the separator. Since the notch 25 or the opening 24 is provided, the temperature difference between the central portion and the outer peripheral portion of the separator 10 during film formation can be reduced, and deformation of the separator 10 due to the temperature difference can be suppressed. Further, since the masking member 21 does not cover the connection region S2, the connection region S2 can be formed into a film, so that the strength of the connection region S2 can be improved and the contact resistance can be reduced.

  Further, in the plasma device 200 of the present embodiment, since the seal region S3 is covered with the masking members 21 and 22 and is not formed into a film, the seal of the seal member 48 between the separators 10 when the fuel cell 300 is stacked. Defects can be suppressed.

  Further, in the plasma device 200 of the present embodiment, since the masking members 21 and 22 do not cover the outer peripheral end portions S4 to S6, the temperature difference between the central portion and the outer peripheral portion of the separator 10 at the time of film formation is further reduced. As a result, deformation of the separator 10 can be further suppressed.

A5-3. Effect 3:
In the plasma apparatus 200 of the present embodiment, in a state where the vacuum vessel 100 is closed, the masking members 21 and 22 are partially disposed between the first flat portion 111 and the second mold 120, and the insulating member 30 is It is disposed between the first flat portion 111 and the second mold 120 to be in contact with the masking members 21, 22. The distance A1 between the contact point (contact point) P1 between the masking members 21 and 22 and the insulating member 30 and the first flat portion 111 is smaller than the distance B1 between the separator 10 and the bottom portion 113 of the first recess 114 Therefore, the plasma is prevented from entering the space formed by the masking members 21 and 22 and the first flat portion 111 from the first recess 114 and the second recess 124. Therefore, the amount of plasma at the contact point P1 is reduced, so that the occurrence of abnormal discharge can be suppressed.

  Similarly, the distance A2 between the contact point (contact point) P2 between the masking members 21 and 22 and the insulating member 30 and the second flat portion 121 is the distance B2 between the separator 10 and the bottom 123 of the second recess 124. Since it is smaller than the above, it is possible to suppress the plasma from entering the space formed by the masking members 21 and 22 and the second flat surface portion 121 from the second depression 124 and the first depression 114. Therefore, since the amount of plasma at the contact point P2 is reduced, the occurrence of abnormal discharge can be suppressed.

  Further, a distance C along the X axis from the connection point Q1 of the first recess 114 and the first plane part 111 and the connection point Q2 of the second recess 124 and the second plane part 121 to the insulating member 30 is Since it is larger than 0 (zero), the space where the plasma formed by the first recess 114 and the second recess 124 is generated is apart from the contact points P 1 and P 2 between the masking members 21 and 22 and the insulating member 30. ing. Therefore, the amount of plasma at the contact points P1 and P2 is further reduced, so that the occurrence of abnormal discharge can be further suppressed.

  Further, the distance A1 between the contact point P1 between the masking members 21 and 22 and the insulating member 30 and the first flat portion 111 is a sheath formed between the masking members 21 and 22 and the first flat portion 111. Since it is shorter than the distance, it is possible to prevent plasma from being generated between the masking members 21 and 22 and the first flat portion 111. Further, the distance A2 between the contact point P2 between the masking members 21 and 22 and the insulating member 30 and the second flat portion 121 is a sheath formed between the masking members 21 and 22 and the second flat portion 121. Since the distance is shorter than the distance, it is possible to prevent the generation of plasma between the masking members 21 and 22 and the second flat portion 121. Therefore, the amount of plasma at the contact points P1 and P2 is effectively reduced, so that the occurrence of abnormal discharge can be effectively suppressed.

  Further, since the distance A1 and the distance A2 are 2.0 mm or less, the space formed by the masking members 21 and 22 and the first flat portion 111, and the masking members 21 and 22 and the second flat portion 121 are formed. The penetration of plasma from the first recess 114 and the second recess 124 into the space is further suppressed. In addition, it is possible to prevent plasma from being generated between the masking members 21 and 22 and the first flat portion 111. Further, plasma can be prevented from being generated between the masking members 21 and 22 and the second flat portion 121. Therefore, the amount of plasma at the contact points P1 and P2 is further reduced, so that the occurrence of abnormal discharge can be further suppressed.

  In the plasma device 200, the separator 10 is disposed in the first recess 114 and the second recess 124, and the insulating member 30 and the end of the masking members 21 and 22 (the end of the masking member 22) Is located between the first flat portion 111 and the second flat portion 121. Therefore, the plasma device 200 can be miniaturized as compared with the case where the separator 10 and the masking members 21 and 22 (the entire work W) are accommodated in the space where the plasma is generated. Further, in the plasma apparatus 200, since the space for exhausting the film for film formation is small, the time required for the exhaust can be shortened, and the time required for forming the film on the separator 10 can be shortened.

B. Modification:
B1. Modification 1:
In the above-described embodiment, the separator 10 includes the conductive film in the power generation region S1, the connection region S2, and the outer peripheral end portions S4 to S6 except the seal region S3. On the other hand, the separator 10 may be provided with a conductive film in the power generation area S1 and the connection area S2 except for the seal area S3. For example, the separator 10 may be provided with a conductive film in all areas except the seal area S3. The masking members 21 and 22 may have notches or openings in the area other than the seal area S3. That is, the masking members 21 and 22 may cover only the seal area S3. If the masking members 21 and 22 cover only the seal area S3, it is possible to further reduce the temperature difference between the power generation area S1 and the outer peripheral portion of the separator 10 at the time of film formation. It can be further suppressed.

B2. Modification 2:
FIG. 8 is a view showing a plasma device 200m in the second modification. In the plasma apparatus 200m of this modification, the first recess 114m and the second recess 124m extend in the direction along the separator 10 (direction along the XZ plane) more than the first embodiment described above. The contact points P1 and P2 between the masking members 21 and 22 and the insulating member 30 from the connection point Q1 between the first recess 114m and the first flat surface 111m and the connection point Q2 between the second recess 124m and the second flat surface 121m. The shortest distance along the first plane portion 111m up to is 0 (zero). In the present modification, the connection point Q2 and the contact point P2 are located in the same YZ plane. Therefore, in the vacuum vessel 100m, the upper masking member 21 is located in the first recess 114m further from the first flat portion 111 of the first mold 110m than in the above-described embodiment, and the lower masking member 22 Are exposed in the second recess 124m of the second mold 120m more than the above-described embodiment. Also in this modification, as in the above-described embodiment, the separator 10 is disposed in the first recess 114m, and the masking members 21 and 22 are located at positions corresponding to the power generation area S1 and the connection area S2, respectively. It has a notch 25 or opening 24 and covers the sealing area S3 included in the non-processed portion 10B. Furthermore, also in this modification, the distance between the contact point P1 and the first flat surface portion 111m is smaller than the distance between the separator 10 and the bottom portion 113m of the first hollow portion 114m, as in the above-described embodiment. Further, the distance between the contact point P2 and the second flat portion 121m is smaller than the distance between the separator 10 and the bottom portion 123m of the second hollow portion 124m. The above-described effects 1 to 3 are exhibited also by such a plasma apparatus 200 m.

  Further, according to the plasma device 200m, the first hollow portion 114m and the second hollow portion 124m spread more in the direction along the separator 10 (the direction along the XZ plane) than in the above-described embodiment. Compared to one embodiment, the capacities of the masking members 21 and 22 positioned in the first recess 114 m and the second recess 124 m are large. Therefore, at the time of film formation, the temperature of the masking members 21 and 22 in contact with the outer peripheral portion of the separator 10 rises compared to the above-described embodiment, so the separator 10 is deformed due to the temperature difference between the central portion and the outer peripheral portion of the separator 10 Can be effectively suppressed.

B3. Modification 3:
FIG. 9 is a view showing a plasma device 200b in the third modification. Unlike the plasma device 200 of the embodiment, the plasma device 200 b performs film formation or etching only on the first recessed portion 114 side of the separator 10. Therefore, in the present modification, there is no space between the second mold 120b of the vacuum vessel 100b and the separator 10, the insulating member 30b contacts the second mold 120b, and the lower masking member on the insulating member 30b. 22b contacts and the lower entire surface of the separator 10 contacts on the lower masking member 22b. Further, in the present modification, the plasma device 200 b does not include the pallet 130. Further, in the present modification, the power introducing unit 71 is provided on the side of the first mold 110 b. In the plasma device 200b, the insulating member 30b contacts the masking member 22b between the first flat portion 111 and the second mold 120b. In the plasma apparatus 200b, the insulating seal member 61 and the insulating member 30b correspond to separating members for separating the masking members 21 and 22b from the first flat portion 111 and the second mold 120b. Also in this modification, as in the above-described embodiment, the separator 10 is disposed in the first recess 114, and the masking member 21 is notched at a position corresponding to the power generation region S1 and the connection region S2. Alternatively, it has an opening 24 and covers the seal area S3 included in the non-processed portion 10B. Furthermore, also in this modification, the distance between the contact point P1b between the masking member 22b and the insulating member 30b and the first flat portion 111 is smaller than the distance between the separator 10 and the bottom portion 113 of the first recess 114. . Therefore, the above-described effects 1 to 3 are exhibited also by such a plasma device 200b.

B4. Modification 4:
In the above-described embodiment, film formation is performed on the power generation region S1 and the connection region S2 of the separator 10 by the plasma device 200. The plasma device 200 can also perform film formation on a member having conductivity other than the separator 10. In addition, the plasma device 200 may perform etching on a conductive member. When the etching is performed, in the gas supply step (FIG. 7) of the above-described processes, a gas mainly containing, for example, argon may be supplied into the vacuum vessel 100.

B5. Modification 5:
In the above embodiment, the distance A1 between the contact point P1 and the first flat surface portion 111 is shorter than the distance of the sheath formed between the masking members 21 and 22 and the first flat surface portion 111, and The distance A2 to the second flat surface portion 121 is shorter than the distance of the sheath formed between the masking members 21 and 22 and the second flat surface portion 121. On the other hand, any one of the distance A1 and the distance A2 may be larger than the distance of the sheath, and both may be larger than the distance of the sheath. Moreover, in the above-mentioned embodiment, distance A1 and distance A2 are 2.0 mm or less. On the other hand, any one of the distance A1 and the distance A2 may be larger than 2.0 mm, and both may be larger than 2.0 mm.

B6. Modification 6:
In the above-mentioned embodiment, although the 1st hollow part 114 is provided with the side part 112 and the bottom part 113, the 1st hollow part 114 should just be depressed from the 1st plane part 111 in the direction away from separator 10. For example, it may be hemispherical. In this case, the bottom 113 of the first recess 114 may be the portion most distant from the separator 10 facing the first recess 114, and the distance between the separator 10 and the bottom 113 of the first recess 114 is B1 may be the distance between the separator 10 facing the first recess 114 and the portion of the first recess 114 farthest from the separator 10.

B7. Modification 7:
In the above-described embodiment, the vacuum vessel 100 and the pallet 130 are at the ground potential, but the vacuum vessel 100 and the pallet 130 may not be at the ground potential. The power application unit 70 may apply power for forming the separator 10 between the vacuum container 100 and the separator 10 and the masking members 21 and 22.

  The present invention is not limited to the above-described embodiment and modifications, and can be realized in various configurations without departing from the scope of the invention. For example, technical features in the embodiments and modifications corresponding to the technical features in the respective forms described in the section of the summary of the invention can be used to solve some or all of the problems described above, or Replacements and combinations can be made as appropriate to achieve part or all of the effects. Moreover, elements other than the element described in the independent claim in the component in the embodiment and each modification which were mentioned above are additional elements, and can be omitted suitably.

DESCRIPTION OF SYMBOLS 10 ... Separator 10B ... Non-processing target part 11, 12, 13, 14, 15, 16 ... Opening part 11m, 12m, 13m, 14m, 15m, 16m ... Manifold 21, 22, 22b ... Masking member 24 ... Opening 25 ... Cutting Notches 30, 30b: Insulating members 35: Insulating members 40: Support frame 42: MEGA
DESCRIPTION OF SYMBOLS 46 ... MEGA plate 48 ... Seal member 50 ... Opening / closing device 55 ... Conveyance device 61, 62 ... Seal member 70 ... Power application part 71 ... Power introduction part 80 ... Gas supply device 81 ... Supply port 90 ... Exhaust device 91 ... Exhaust port 95 ... Control unit 100, 100b, 100m ... Vacuum vessel 110, 110m ... First mold 111, 111m ... First plane section 112 ... Side section 113, 113m ... Bottom section 114, 114m ... First recessed section 120, 120b, 120m ... Second mold 121, 121 m: second flat portion 122: side portion 123, 123 m: bottom portion 124, 124 m: second depression portion 130: pallet 130 t: edge portion 200, 200 b, 200 m: plasma device 300: fuel cell 310 ... Cell monitor terminal 400 ... Fuel cell stack A1, A2, B1, B2, C ... Distance P1, P1b P2 ... contact point Q1, Q2 ... connection points S1 ... power generation region S2 ... connection region S3 ... seal area S4, S5, S6 ... outer edge SD ... stacking direction W ... workpiece

Claims (2)

A plasma apparatus for forming a film on a separator used in a fuel cell, comprising:
A vacuum vessel comprising a first mold and a second mold arranged opposite to each other, wherein the first mold has a first flat portion and a first hollow portion in which the separator is placed from the first flat portion. A vacuum vessel having
A masking member at least a part of which is disposed between the first flat portion and the second mold;
An insulating member disposed between the first flat portion and the second mold and in contact with the masking member;
A separating member for separating the masking member from the first flat portion and the second mold;
A power application unit that applies power to the separator and the masking member;
Equipped with
Among the separators, the masking member is a power generation area involved in the power generation of the fuel cell, and a connection area to which a cell monitor terminal located on an outer peripheral portion of the power generation area and capable of detecting the voltage of the fuel cell is connected. And at corresponding positions, with notches or openings,
Plasma device. A separator used for a fuel cell,
A power generation area involved in the power generation of the fuel cell;
A connection area to which a cell monitor terminal located at an outer peripheral portion of the power generation area and capable of detecting the voltage of the fuel cell is connected;
A seal area in which a seal member for sealing between the separators is disposed;
It comprises the power generation area and the conductive film formed in the connection area except for the seal area.
Separator.

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