阅读说明：本技术 燃料电池用隔板的制造方法以及制造装置 (The manufacturing method and manufacturing device of separator for fuel battery ) 是由 高田智司 于 2019-05-17 设计创作，主要内容包括：一种燃料电池用隔板的制造方法以及制造装置。制造方法：准备工序,准备在至少一部分的表面具有钝化膜的金属制的基材；以及氧化钛膜形成工序,在85～92.5体积％的氮气氛下的室内,使用将包含钛的原料溶液以及氩气一同喷射的第一喷射单元,对金属制的基材的表面进行大气压等离子体处理。制造装置具有：输送单元,对在至少一部分的表面具有钝化膜的金属制的基材进行输送；85～92.5体积％的氮气氛下的处理室,供由输送单元输送的金属制的基材以能够通过的方式配置；以及第一喷射单元,在处理室内沿着金属制的基材的通过方向配置,一同喷射包含钛的原料溶液以及氩气而用于进行大气压等离子体处理。(A kind of manufacturing method and manufacturing device of separator for fuel battery.Manufacturing method: preparatory process prepares the metal substrate for having passivating film at least part of surface；And oxidation titanium film formation process, the interior under the nitrogen atmosphere of 85~92.5 volume % carry out atmospheric plasma treatment to the surface of metal substrate using the first injection unit for spraying the material solution comprising titanium and argon gas together.Manufacturing device includes supply unit, at least part of surface there is the metal substrate of passivating film to convey；Process chamber under the nitrogen atmosphere of 85~92.5 volume %, for the metal substrate that is conveyed by supply unit can be configured in a manner of；And first injection unit, being configured by direction along metal substrate in process chamber, together material solution of the injection comprising titanium and argon gas and be used to carry out atmospheric plasma treatment.)

1. a kind of manufacturing method of separator for fuel battery, wherein include:

Preparatory process prepares the metal substrate for having passivating film at least part of surface；With

Oxidation titanium film formation process, the interior under the nitrogen atmosphere of 85~92.5 volume % use the material solution that will include titanium And the first injection unit that argon gas sprays together, atmospheric plasma treatment is carried out to the surface of metal substrate.

2. the manufacturing method of separator for fuel battery according to claim 1, wherein

Further include nitridation process sequence before oxidation titanium film formation process, in the nitridation process sequence, is using the first spray The interior for penetrating unit carries out atmos plasma to the surface of metal substrate using the second injection unit of injection nitrogen Body processing, to carry out nitrogen treatment to the passivating film on at least part of surface of the metal substrate.

3. the manufacturing method of separator for fuel battery according to claim 1 or 2, wherein

Metal substrate is stainless steel.

4. the manufacturing method of separator for fuel battery described in any one of claim 1 to 3, wherein

Material solution comprising titanium includes trivalent titanium compound.

5. a kind of manufacturing device of separator for fuel battery, wherein include

Supply unit at least part of surface there is the metal substrate of passivating film to convey；

Process chamber under the nitrogen atmosphere of 85~92.5 volume %, wherein by the metal substrate of supply unit conveying with can It is configured by way of；And

First injection unit, being configured by direction along metal substrate in process chamber, injection includes the original of titanium together Expect solution and argon gas and is used to carry out atmospheric plasma treatment.

6. the manufacturing device of separator for fuel battery according to claim 5, wherein

Also there is the second injection unit, second injection unit being matched by direction relative to metal substrate in process chamber It is placed in the position on the front than the first injection unit, nitrogen is sprayed and is used to carry out atmospheric plasma treatment.

7. the manufacturing device of separator for fuel battery according to claim 5 or 6, wherein

Metal substrate is stainless steel.

8. the manufacturing device of the separator for fuel battery according to any one of claim 5~7, wherein

Material solution comprising titanium includes trivalent titanium compound.

Technical field

The present invention relates to the manufacturing method of separator for fuel battery and manufacturing devices.

Background technique

Fuel cell obtains electromotive force by being electrochemically reacted hydrogen and oxygen.It is produced with the power generation of fuel cell It is only water in raw product principle.Therefore, as there's almost no to earth environment generate burden clean electric power generation system by To attracting attention.

Fuel cell is to be configured with the membrane-electrode assembly of electrode catalyst layer on the two sides of dielectric film (hereinafter, also remembering It carries as " MEA ") is basic unit and constitutes.In the operating of fuel cell, by the fuel gas comprising hydrogen to anode (fuel Pole) side electrode catalyst layer supply, will wrap oxygen containing oxidizing gas to the electrode catalyst layer of cathode (air pole) side supply, To obtain electromotive force.Oxidation reaction is carried out on anode, reduction reaction is carried out on cathode, and electronic to external circuit supply Gesture.

In a fuel cell, gas diffusion layers, In are configured in the outside of each electrode catalyst layer of MEA under normal conditions Partition is also configured on the outside of gas diffusion layers, to constitute fuel-cell single-cell.Fuel cell is typically based on desired electricity Power, the combinations (hereinafter, being also recorded as " fuel cell unit ") of multiple fuel-cell single-cells as needs use.

Separator for fuel battery may with by fuel cell react generate water and burden charge move hydrogen from Sub (H+) contact.Therefore, separator for fuel battery needs higher electric conductivity and corrosion resistance.Therefore, as fuel cell With partition, usually used carbon or metallic material.As the metallic material of excellent corrosion resistance, stainless steel can be enumerated. However, stainless steel is under normal conditions on its surface, there are passivating films, therefore electric conductivity is lower.Therefore, developing makes stainless steel The technology that the electric conductivity and corrosion resistance on surface improve.

For example, patent document 1 describes a kind of anti-corrosion method of structuring, it is the side for improving the anti-corrosive properties of structuring (X) Method, which is characterized in that will be to TiO₂The resulting material of element of 5 valences such as the Nb of 0.01~0.2 weight % is added as thermal spray Material is carried out thermal spray to the surface of structuring and is formed a film by plasma thermal spraying method, atmospheric pressure plasma spraying method. The document describes the content that stainless steel can be used as to structuring X.In addition, the document also describes following content: by thermal jet Plating material becomes mist-like resulting material and supplies to plasma generating element as plasma stream, makes under air atmosphere Its thermal spray is attached to the surface of structuring X, to form titanium oxide semiconductor layer Y.

Patent document 2 describes a kind of high nitrogen solid solution stainless steel, which is characterized in that is made by plasma nitridation process Nitrogen is solid-solution in the surface of stainless steel with high concentration, to form the nitration case based on phase transformation in surface portion.

Patent document 3 describes a kind of low form separator for fuel battery, not by the austenite being made of defined ingredient Rust steel or the austenite ferrite stainless steel that is made of defined ingredient as substrate, be formed on its surface mainly by TiO₂The clad of the titanium oxide of the electric conductivity of composition, above-mentioned low form separator for fuel battery be characterized in that, the clad Containing the impurity for assigning electric conductivity, volume resistivity is adjusted to 10²Ω m or less.

The technology of separator for fuel battery, such as patent document are manufactured as the passivating film on the surface of stainless steel is removed 4 describe a kind of low contact resistance surface preparation to carbon on passive metal surface, which is characterized in that expensive by being attached with The grinding-material of metal grinds passive metal, to make noble metal be attached to immediately after eliminating surface oxidation epithelium The passive metal.

Patent document 5 describes a kind of manufacturing method of separator for fuel battery, which is characterized in that has: by made of metal Plate of material be formed as the stamping process in concavo-convex section；Only in the above-mentioned material plate for being formed as above-mentioned concavo-convex section Protrusion plating conductive metal plating process, the plating solution for making to maintain the plating solution of the ion comprising above-mentioned conductive metal protects Gripping member is only contacted with raised part, and is kept between material and above-mentioned material plate in the plating solution with defined current density (average electricity 5~26A/dm of current density²Except) be powered, to carry out above-mentioned plating process, and generated on the surface of above-mentioned material plate The passive state envelope on hydrogen and the surface that will be formed in above-mentioned material plate using the hydrogen restores, while leading above-mentioned material plate plating is above-mentioned Conductive metal.

In addition, the process for treating surface as stainless steel, such as patent document 6 describe a kind of atomic pile structuring, match It is placed in the inside of atomic pile cooling water (R), above-mentioned atomic pile structuring is characterized in that, in the irradiation atmosphere for being exposed to radiating light Structuring (X) surface configuration it is aerobic shortcoming construction titanium oxide semiconductor layer (Y).The document, which describes, to be able to use Content of the SUS304 stainless steel as structuring (X).

Patent document 1: Japanese Unexamined Patent Publication 9-324253 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2015-161011 bulletin

Patent document 3: No. 3980166 bulletins of Japanese Patent No.

Patent document 4: Japanese Unexamined Patent Publication 2002-134128 bulletin

Patent document 5: No. 5580444 bulletins of Japanese Patent No.

Patent document 6: Japanese Unexamined Patent Publication 8-201578 bulletin

As described above, there is known the conductions for making the surface of metal substrate as the stainless steel of excellent corrosion resistance Property and corrosion resistance improve technology.However, in these techniques, there are some projects.For example, as patent document 1 is remembered The method of load is such, in the case where the surface of stainless steel forms titanium oxide film under air atmosphere, resulting material Electric conductivity is lower.It should be the reason is that because there are passivating film (autoxidations being formed by between titanium oxide film and stainless steel Film).The film of electric conductivity is formed there is known after removing the passivating film on the surface of metal substrate for such project Technology (for example, patent document 4 and 5).Even if also having can however, the passivating film on the surface of metal substrate is removed During can be until to the film for forming electric conductivity, the surface of metal substrate occurs autoxidation and forms passivation again Film.Even if accordingly, there exist the removings of the passivating film on the surface for implementing metal substrate, it is also unable to get sufficient electric conductivity Project.

Summary of the invention

Therefore, the purpose of the present invention is to provide a kind of in the metal substrate that can be used as separator for fuel battery In, essence inhibits the formation of the passivating film on the surface of metal substrate as caused by autoxidation, and improves the made of metal Substrate surface electric conductivity unit.

The present inventor has carried out various researchs to the unit for solving the above subject.The inventors discovered that following thing Real: the interior under the nitrogen atmosphere of normal concentration carries out the surface of metal substrate by the inclusion of the material solution of titanium big Atmospheric pressure plasma processing, to be had compared with the case where carrying out atmospheric plasma treatment under air atmosphere The metal substrate of the surface envelope of more high conductivity.In addition, the present inventors have additionally discovered that following fact: passing through the above method The close property of the surface envelope of the obtained metal substrate with surface envelope is higher.The present inventor be based on above-mentioned opinion and Complete the present invention.

That is, the present invention includes mode and embodiment below.

(1) a kind of manufacturing method of separator for fuel battery, wherein include: preparatory process, prepare at least part of Surface has the metal substrate of passivating film；With oxidation titanium film formation process, under the nitrogen atmosphere of 85~92.5 volume % Interior, using the first injection unit for spraying the material solution comprising titanium and argon gas together, to the table of metal substrate Face carries out atmospheric plasma treatment.

(2) method according to documented by above embodiment (1), wherein

Further include nitridation process sequence before oxidation titanium film formation process, in the nitridation process sequence, is using the The interior of one injection unit carries out atmospheric pressure etc. to the surface of metal substrate using the second injection unit of injection nitrogen Gas ions processing, to carry out nitrogen treatment to the passivating film on at least part of surface of the metal substrate.

(3) method according to documented by above embodiment (1) or (2), wherein

Metal substrate is stainless steel.

(4) method according to documented by any one of above embodiment (1)~(3), wherein

Material solution comprising titanium includes trivalent titanium compound.

(5) a kind of manufacturing device of separator for fuel battery, wherein include

Supply unit at least part of surface there is the metal substrate of passivating film to convey；

Process chamber under the nitrogen atmosphere of 85~92.5 volume %, wherein by supply unit conveying metal substrate with It can be configured by way of；And

First injection unit, being configured by direction along metal substrate in process chamber, injection includes titanium together Material solution and argon gas and be used to carry out atmospheric plasma treatment.

(6) device according to documented by above embodiment (5), wherein

Also there is the second injection unit, the pass through side of second injection unit in process chamber relative to metal substrate To the position being configured at than the first injection unit on the front, sprays nitrogen and be used to carry out atmospheric plasma treatment.

(7) device according to above embodiment (5) or (6), wherein

Metal substrate is stainless steel.

(8) device according to documented by any one of above embodiment (5)~(7), wherein

Material solution comprising titanium includes trivalent titanium compound.

In accordance with the invention it is possible to provide can be used as separator for fuel battery come using metal substrate in, essence Inhibit the formation of the passivating film on the surface of metal substrate as caused by autoxidation, and improves the metal substrate The unit of the electric conductivity on surface.

Detailed description of the invention

Fig. 1 is the signal for indicating an embodiment of manufacturing method for the separator for fuel battery of one embodiment of the present invention Figure.

Fig. 2 is the signal for indicating an embodiment of manufacturing device for the separator for fuel battery of one embodiment of the present invention Figure.

Fig. 3 be the indoor nitrogen of processing in the manufacture to surface envelope SUS447 plate volume ratio, in the order described above The chart that the contact resistance of measurement and the relationship of clinging force are compared.

The explanation of appended drawing reference

11... supply unit；12... process chamber；13... the first injection unit；14... the second injection unit；21... base Material transport platform；22,25... high frequency electric source；It 23... include the material solution of titanium；24... carrier gas；26... nitrogen；100... combustion Expect the manufacturing device of battery separator.

Specific embodiment

Hereinafter, the preferred embodiments of the present invention is described in detail.

The manufacturing method > of 1. separator for fuel battery of <

One embodiment of the present invention is related to the manufacturing method of separator for fuel battery.The method of the method includes beam worker Sequence, oxidation titanium film formation process and according to circumstances existing nitridation process sequence.

[1-1. preparatory process]

The method of the method includes preparing the preparation for the metal substrate for having passivating film at least part of surface Process.

What is prepared in this process has the metal substrate of passivating film can be from as separator for fuel battery on surface Material and usually used a variety of materials properly select in this technical field.As such material, though do not limit, But such as stainless steel (for example, SUS447) can be enumerated.Metal substrate is preferably shaped to plate.Material illustrated by above-mentioned Stainless steel in material is cheap compared with titanium etc..In addition, stainless steel is compared with aluminium etc., corrosion resistance is higher.Material illustrated by above-mentioned Expect the passivating film that there is metal oxide at least part of surface.Therefore, the material illustrated by will be above-mentioned is applied to combustion In the case where expecting battery separator, it can be found that higher corrosion resistance under the use environment of fuel cell.

[1-2. oxidation titanium film formation process]

The method of the method is comprising oxidation titanium film formation process, the interior under the nitrogen atmosphere of normal concentration, and use will wrap The first injection unit that the material solution of titaniferous and carrier gas are sprayed together carries out atmospheric pressure etc. to the surface of metal substrate Gas ions processing.

For metal substrate used in this process, usually it is prepared in above explained preparatory process.In Metal substrate used in this process be it is above-mentioned illustrated by the case where material (for example, stainless steel), at least one The surface divided has the passivating film of metal oxide.It is therefore preferable that before this process or period, to used in this process At least part of surface of metal substrate carries out conductive treatment.As making at least part of of metal substrate The gimmick of surface conductance can for example enumerate the nitridation of passivating film though not limiting.It is preferred that passing through nitridation described below Treatment process carries out nitrogen treatment to the passivating film on at least part of surface of metal substrate before this process.It is logical Above-mentioned gimmick is crossed, it can be before this process or period is at least part of of metal substrate used in this process Surface carries out conductive treatment, and thus, it is possible to improve the electric conductivity on the surface of metal substrate.

The inventors discovered that following fact: the gas of the nitrogen concentration more than the nitrogen concentration (about 78 volume %) of air atmosphere Interior under atmosphere, if the material solution by the inclusion of titanium carries out atmospheric plasma treatment to the surface of metal substrate, Then with the interior carry out identical atmospheric plasma treatment under air atmosphere the case where compared with, obtain having more highly conductive The metal substrate of the surface envelope of property.In this process, using the first injection unit to the surface of metal substrate into The indoor nitrogen atmosphere of row atmospheric plasma treatment is the range of 85~92.5 volume %, preferably 85~90 volume %'s Range, even more preferably about 85 volume %.When the insufficient above-mentioned lower limit value of the indoor nitrogen atmosphere for carrying out atmospheric plasma treatment In the case where, there is a possibility that electric conductivity reduction on the surface of the metal substrate obtained as a result.In addition, carry out In the case that the indoor nitrogen atmosphere of atmospheric plasma treatment is more than above-mentioned upper limit value, as described below, exist A possibility that close property of the envelope on the surface of the metal substrate obtained as a result reduces.Therefore, by above-mentioned model Interior implementation this process under the nitrogen atmosphere enclosed, can be improved the electric conductivity on the surface of metal substrate, and can be improved table The close property of the envelope in face.

It, for example can be by though the electric conductivity on the surface of metal substrate does not limit in each mode of the invention Implement according to the contact resistance of the metal substrate of sequential determination below.In the metal obtained by oxidation titanium film formation process Gold-plated copper sheet is laminated in the film forming face of the substrate of system.Carbon paper is clamped between metal substrate and copper sheet.It is assigned from upper surface It provides the pressure of (for example, about 0.98MPa), and applies constant current between metal substrate and copper sheet.At this point, measurement gold Belong to the voltage value between the oxidation titanium film and carbon paper on the surface of the substrate of system.Based on resulting voltage value and additional electric current Value calculates contact resistance value (m Ω cm²)。

In each mode of the invention, though the close property of the envelope on the surface of metal substrate does not limit, for example It can be implemented by stud pull test.

In the first injection unit used in this process, it can apply usually used in atmospheric plasma treatment Various devices.Implement in the process chamber of atmospheric plasma treatment under atmospheric pressure, therefore can be real with cheap device It applies.On the other hand, by the way that other envelope formation are handled, such as ion sputtering process or aerosol deposition method are in metal In the case that the surface of the substrate of system forms envelope, is formed to carry out envelope in a vacuum, need the vacuum plant of high price.Separately Outside, atmospheric plasma treatment is i.e. implementable without being heated to metal substrate.On the other hand, passing through other Envelope formation processing, such as ion sputtering process, chemical vapor coating (CVD) method or sol-gel method and metal In the case that the surface of substrate forms envelope, need to carry out the heating of metal substrate.If adding to metal substrate Heat, it is likely that the passivating film generated by autoxidation is formed on surface.Therefore, implemented by atmospheric plasma treatment This process, so that inexpensively envelope can be formed on the surface of metal substrate compared with other envelopes form processing.

First injection unit used in this process can be applied usually used each in atmospheric plasma treatment Kind device.First injection unit is preferably the atmospheric pressure plasma device of remote mode.In the case where remote mode, pass through Contact the active material generated in discharge space with the surface of metal substrate, so as in the metal substrate Surface forms envelope.Therefore, the plasma with large energy can be substantially inhibited to contact with metal substrate.Cause This, implements this process by the first injection unit in the above described manner, can substantially inhibit metal substrate and institute's shape At envelope damage.

In this process, atmospheric pressure plasma is carried out using surface of the material solution comprising titanium to metal substrate Processing, to form the film comprising titanium oxide on the surface of the metal substrate.Oxidation titanium film can be showed because oxygen is short of Electric conductivity out.In addition, titanium oxide is cheap compared with other materials such as gold or tin oxide that can show electric conductivity.Cause Conductive cheap oxidation titanium film can be formed in the surface of metal substrate by implementing this process by this.

Material solution used in this process comprising titanium includes preferably trivalent titanium compound, more preferably comprising inorganic Trivalent titanium compound, such as titanium trichloride (TiCl₃), further include TiCl₃.In addition, the material solution comprising titanium is preferably also Comprising it is more than one it is above-mentioned illustrated by trivalent titanium compound aqueous solution.There is titanous oxygen to be short of characteristic, therefore include Film including the titanium oxide formed by trivalent titanium compound can show electric conductivity because oxygen is short of.Trivalent titanium compound it In, organic trivalent titanium compound is capable of forming after ionizing as caused by atmospheric plasma treatment as secondary product Organic compound.If such organic compound is mixed into the film comprising titanium oxide, there is the metal obtained as a result A possibility that electric conductivity on the surface of the substrate of system reduces.In addition, including tetravalent titanium compound (for example, titanium tetrachloride) in use Material solution in the case where, because oxygen shortcoming difference, thus the case where including the material solution of trivalent titanium compound with using It compares, there is a possibility that electric conductivity reduction on the surface of the metal substrate obtained as a result.Therefore, use comprising In the case where the material solution of tetravalent titanium compound (for example, titanium tetrachloride), in order to which titanic is reduced into titanous, need The reducibility gas such as hydrogen are used as carrier gas in first injection unit.Using such reducibility gas, need It will be in higher this process of indoor implementation of air-tightness.Therefore, by using the original for illustrated by above-mentioned including trivalent titanium compound Solution is expected to implement this process, conductive oxidation titanium film can be formed in metal base under the conditions of simple The surface of material.

Carrier gas used in this process is argon gas.In the case where using the reducibility gas such as hydrogen as carrier gas, need In higher this process of indoor implementation of air-tightness.Therefore, this process is implemented by using argon gas, it can be in simple condition Under, conductive oxidation titanium film is formed in the surface of metal substrate.

[1-3. nitridation process sequence]

The method of the method be preferably further include nitridation process sequence, before oxidation titanium film formation process, using the The interior of one injection unit carries out atmospheric pressure etc. to the surface of metal substrate using the second injection unit of injection nitrogen Gas ions processing, to carry out nitrogen treatment to the passivating film on at least part of surface of the metal substrate.

In this process, to carry out the surface of metal substrate by using the second injection unit of injection nitrogen big Atmospheric pressure plasma processing, thus nitrogenizes the passivating film on at least part of surface of the metal substrate.Pass through The passivating film on at least part of surface of metal substrate can be transformed to the nitride film of electric conductivity by nitrogen treatment.

As already explained, the surface of metal substrate used in oxidation titanium film formation process is preferably at least one Part is by carry out conductive treatment.The inventors discovered that following fact: before oxidation titanium film formation process, by using spray Second injection unit of radio-nitrogen gas and to the surface of metal substrate carry out atmospheric plasma treatment, thus to the metal The passivating film on at least part of surface of the substrate of system carries out nitrogen treatment, then implements oxidation titanium film formation process, thus The nitride film autoxidation of electric conductivity can substantially be inhibited and form passivating film again, can be formed on the surface of the nitride film Conductive oxidation titanium film.It therefore, can be in nitride film by implementing this process before oxidation titanium film formation process Surface forms oxidation titanium film, to obtain the metal substrate of electric conductivity with higher.

In this process, in the interior using the first injection unit, the second injection unit of injection nitrogen is used.That is, excellent It is selected in process chamber identical with the process chamber of oxidation titanium film formation process is implemented and implements this process.By in such a situa-tion Implement this process, can substantially inhibit the nitride film autoxidation of electric conductivity and form passivating film again, and can aoxidize Surface in titanium film formation process in the nitride film forms conductive oxidation titanium film.Therefore, by under the above conditions Implement this process and oxidation titanium film formation process, can the surface of nitride film formed oxidation titanium film, thus obtain have compared with The metal substrate of high electric conductivity.

In this process, if the surface to metal substrate carries out nitrogen treatment, on the surface of metal substrate The passivating film metal that is included oxide in, oxygen atom is replaced into nitrogen-atoms and forms the nitride of metal.Here, nitrogen The indoor nitrogen concentration of change processing is higher, then the nitride for being formed in the metal on the surface of metal substrate more increases.However, For the nitride of metal, and the compatibility of the combination of titanium oxide formed in oxidation titanium film formation process is lower.This Inventor has found following fact: if the interior in the case where being more than the atmosphere of defined nitrogen concentration, to the surface of metal substrate Carry out nitrogen treatment, then with the interior carry out identical nitrogen treatment under air atmosphere the case where compared with, obtain as a result Oxidation titanium film close property significantly reduce.In this process, using the second injection unit of injection nitrogen to metal base The range that the indoor nitrogen atmosphere of the surface progress atmospheric plasma treatment of material is 85~92.5 volume %, preferably 85~ The range of 90 volume %, even more preferably about 85 volume %.It is more than in the indoor nitrogen atmosphere for carrying out atmospheric plasma treatment In the case where above-mentioned upper limit value, exist the envelope on the surface of the metal substrate obtained as a result close property reduce can It can property.It therefore, can be locally to metal substrate by interior implementation this process under the nitrogen atmosphere of above range The passivating film on surface carries out nitrogen treatment.The electric conductivity on the surface of metal substrate is improved as a result, and can be improved surface The close property of envelope.

Second injection unit used in this process can be applied usually used each in atmospheric plasma treatment Kind device.Second injection unit is preferably the atmospheric pressure plasma device of direct mode.It, can in the case where direct mode Contact the plasma with large energy generated in discharge space directly with the surface of metal substrate.Therefore, energy It is enough that nitrogen treatment promptly is carried out to the passivating film on the surface of metal substrate.Therefore, by using the second of aforesaid way Injection unit can promptly implement this process.

Nitrogen used in this process can be pure nitrogen gas or comprising the gaseous mixture including nitrogen and other gases Any one of body.In the case where mixed gas, as other gases, it is arbitrary that oxygen and carbon dioxide etc. can be enumerated Gas.Due to cheap, it is advantageous to be the mixed gas comprising nitrogen and oxygen.In the case where mixed gas includes oxygen, if oxygen Concentration is higher, then there is a possibility that oxidation for excessively carrying out metal substrate.As the mixed gas comprising nitrogen and oxygen, In the case where supplying atmosphere by compressor etc. to carry out use, polluted as caused by the floating material in atmosphere in order to prevent, It is preferred that in the flow arrangement filter to the second injection unit supply gas.It is preferred that nitrogen used in this process has and implementation The identical nitrogen concentration of the indoor nitrogen concentration of oxidation titanium film formation process and nitridation process sequence.By using above-mentioned concentration Nitrogen can adjust the indoor nitrogen concentration for implementing oxidation titanium film formation process and nitridation process sequence in defined range It is interior.

It will indicate the schematic diagram of an embodiment of the manufacturing method of the separator for fuel battery of one embodiment of the present invention It is shown in Fig. 1.As shown in Figure 1, the method for the method quilt usually in the process chamber configured with the first atmospheric pressure plasma device Implement, wherein above-mentioned first atmospheric pressure plasma device has the first of material solution of the injection comprising titanium together and carrier gas Injection unit.In process chamber, metal substrate in a manner of can configure.In process chamber, it is preferable configured with tool There is the second atmospheric pressure plasma device of the second injection unit of injection nitrogen.In this case, the first spray It penetrates unit and the second injection unit to configure along the metal substrate can configure in a manner of, and the first injection is single The position that by direction is configured at than second injection unit rearward of the member relative to metal substrate.It is preferred that in the first injection Unit is connected with high frequency electric source, and is connected separately with the flow path of material solution of the supply comprising titanium and supplies the flow path of carrier gas. It is preferred that being connected with high frequency electric source in the second injection unit, and it is connected with the flow path of supply nitrogen.Nitrogen can be used in adjustment processing Indoor nitrogen concentration.In this case, nitrogen preferably includes the nitrogen with nitrogen concentration identical with indoor nitrogen concentration is handled And the mixed gas including other gases (for example, oxygen).

The metal substrate prepared in preparatory process is conveyed in process chamber with defined speed and direction.It is preferred that By the nitrogen sprayed from the second injection unit, the atmosphere of defined nitrogen concentration will be adjusted in process chamber.Here, using along By the second injection unit that the metal substrate that can be configured in a manner of configures, to the surface of metal substrate into Row atmospheric plasma treatment, and nitrogen treatment is carried out to the passivating film on at least part of surface of the metal substrate (nitridation process sequence).The passivating film on at least part of surface of metal substrate is transformed into the nitridation of electric conductivity as a result, Film.Then, using of the position being configured at by direction than the second injection unit rearward relative to metal substrate One injection unit carries out atmospheric plasma treatment (oxidation titanium film formation process) to the surface of metal substrate.As a result, On the surface of the nitride film formed by nitridation process sequence, conductive oxidation titanium film is formed.

By the method for the method, it can obtain that there is nitride film at least part of surface, and in the nitride film Surface has the metal substrate of oxidation titanium film.The metal substrate obtained by the method for the method is with higher to lead The close property of electrical and higher oxidation titanium film, therefore can be suitble to use in separator for fuel battery.Therefore, pass through we The method of formula can manufacture the separator for fuel battery of the close property of electric conductivity with higher and higher oxidation titanium film.

The manufacturing device > of 2. separator for fuel battery of <

Another mode of the invention is related to the manufacturing device of separator for fuel battery, the manufacture of the separator for fuel battery Device includes supply unit, at least part of surface there is the metal substrate of passivating film to convey；Regulation Nitrogen atmosphere under process chamber, wherein by supply unit conveying metal substrate can be configured in a manner of；And First injection unit, being configured by direction along metal substrate in process chamber, and injection includes the original of titanium together Expect solution and carrier gas and is used to carry out atmospheric plasma treatment.The device of the method can be suitable for carrying out the present invention A mode separator for fuel battery manufacturing method.

It is preferred that the device of the method also has the second injection unit, second injection unit is in process chamber relative to metal The substrate of system is configured at the position than the first injection unit on the front by direction, and sprays nitrogen and be used to carry out atmospheric pressure Corona treatment.That is, the first injection unit and the second injection unit are as separated unit in the device of the method (for example, separated atmospheric pressure plasma device) and configure.Configuration in this way can substantially inhibit due to the first spray It penetrates the nitride film autoxidation for the electric conductivity that unit is converted from passivating film and forms passivating film again, and can be in oxidation titanium film shape Conductive oxidation titanium film is formed at the surface in process in the nitride film.On the other hand, by the first injection unit And second injection unit configured as identical unit (for example, single atmospheric pressure plasma device) in the case where, Need the material solution comprising titanium and argon gas that will be used for the nitrogen of nitrogen treatment and be used for oxidation titanium film formation to the unit Alternative supply, and implement atmospheric plasma treatment.In this case, the plasma shape in the switching of active material A possibility that state becomes unstable, causes the activation of active material to become inadequate there are result.In addition, in order to passivation The surface of nitride film that film carries out nitrogen treatment and formed forms oxidation titanium film to obtain desired product, needs critically to control The conveying speed of the switching of active material and the metal substrate based on supply unit.Therefore, by the way that the first injection is single Member and the second injection unit are configured as separated unit, so as to form oxidation titanium film on the surface of nitride film, are obtained To the metal substrate of electric conductivity with higher.

Metal substrate, the material solution comprising titanium used in the device of the method, carrier gas and nitrogen can be from It is properly selected in material with above explained feature.

The signal of one embodiment of the manufacturing device for indicating the separator for fuel battery of the method is illustrated in Fig. 2.Such as Shown in Fig. 2, the device 100 of the method includes supply unit 11, to the metal at least part of surface with passivating film The substrate of system is conveyed；Process chamber 12, wherein the metal substrate conveyed by supply unit 11 is by can be in a manner of Configuration；And first injection unit 13, being configured by direction along metal substrate in process chamber 12, and together Material solution 23 of the injection comprising titanium and carrier gas 24.It is preferred that in process chamber 12 configured with injection nitrogen and be used to carry out atmosphere Press the second injection unit 14 of corona treatment.It is preferred that in process chamber 12, configured with for conveying metal substrate Substrate transport platform 21, the first atmospheric pressure plasma device with the first injection unit 13 and have the second injection unit 14 the second atmospheric pressure plasma device.In this case, the first injection unit 13 and the second injection are single Member 14 is configured along substrate transport platform 21, and the first injection unit 13 is configured at ratio by direction relative to metal substrate The position of second injection unit 14 rearward.Supply unit 11 can for example be configured to the metal substrate of plate from a side Coil extraction, and pass through it in substrate transport platform 21 with defined speed, and be wound in the coil of another party.It is preferred that First injection unit 13 is connected with high frequency electric source 22, and is connected separately with flow path and the confession of material solution 23 of the supply comprising titanium To the flow path of carrier gas 24.It is preferred that carrier gas 24 is supplied from the gas cylinder for the carrier gas for being sealed with high-purity.In this case, carrier gas 24 is supplied Flow path connect with gas cylinder.It is preferred that being connected with high frequency electric source 25 in the second injection unit 14, and it is connected with supply nitrogen 26 Flow path.Nitrogen 26 can be used in adjusting the nitrogen concentration in process chamber 12.In this case, nitrogen 26 preferably comprising have with Mixed gas including the nitrogen of the identical nitrogen concentration of nitrogen concentration in process chamber 12 and other gases (for example, oxygen).Supply As long as the flow path of the mixed gas of nitrogen and other gases is connect with nitrogen cylinder and other gas cylinders.In supply carrier gas 24 flow path and the flow path for supplying nitrogen 26 can be configured the filter of the removings such as floating material according to demand.

By the device of the method with above explained feature, the fuel electricity of one embodiment of the present invention can be implemented The manufacturing method of pond partition.Therefore, by the device of the method, electric conductivity with higher and higher oxygen can be manufactured Change the separator for fuel battery of the close property of titanium film.