JP5802641B2 - Method for removing conductive layer of titanium fuel cell separator material - Google Patents
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- 239000000463 material Substances 0.000 title claims description 180
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 120
- 239000010936 titanium Substances 0.000 title claims description 120
- 229910052719 titanium Inorganic materials 0.000 title claims description 120
- 239000000446 fuel Substances 0.000 title claims description 111
- 238000000034 method Methods 0.000 title claims description 70
- 239000007864 aqueous solution Substances 0.000 claims description 92
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 74
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 33
- 229910017604 nitric acid Inorganic materials 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 17
- 239000004020 conductor Substances 0.000 claims description 16
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- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Fuel Cell (AREA)
- Processing Of Solid Wastes (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
本発明は、純チタンまたはチタン合金からなる基材上に、炭素系導電性材料を含む導電層を被覆したチタン製燃料電池セパレータ材からの導電層除去方法に関する。 The present invention relates to a method for removing a conductive layer from a titanium fuel cell separator material in which a conductive layer containing a carbon-based conductive material is coated on a substrate made of pure titanium or a titanium alloy.
水素等の燃料と酸素等の酸化剤を供給し続けることで継続的に電力を取り出すことができる燃料電池は、乾電池等の一次電池や鉛蓄電池等の二次電池とは異なり、発電効率が高く、システム規模の大小にあまり影響されず、また、騒音や振動も少ないため、多様な用途・規模をカバーするエネルギー源として期待されている。燃料電池は、具体的には、固体高分子型燃料電池（ＰＥＦＣ）、アルカリ電解質型燃料電池（ＡＦＣ）、リン酸型燃料電池（ＰＡＦＣ）、溶融炭酸塩型燃料電池（ＭＣＦＣ）、固体酸化物型燃料電池（ＳＯＦＣ）、バイオ燃料電池等として開発されている。中でも、燃料電池自動車や、家庭用燃料電池（家庭用コジェネレーションシステム）、携帯電話やパソコン等の携帯機器向けとして、固体高分子型燃料電池の開発が進められている。 Unlike primary batteries such as dry batteries and secondary batteries such as lead-acid batteries, fuel cells that can continuously extract power by continuing to supply fuel such as hydrogen and oxidants such as oxygen have high power generation efficiency. It is expected to be an energy source that covers a wide range of applications and scales because it is not significantly affected by the size of the system and has little noise and vibration. Specifically, the fuel cell includes a polymer electrolyte fuel cell (PEFC), an alkaline electrolyte fuel cell (AFC), a phosphoric acid fuel cell (PAFC), a molten carbonate fuel cell (MCFC), and a solid oxide. It has been developed as a type fuel cell (SOFC) and biofuel cell. In particular, solid polymer fuel cells are being developed for mobile devices such as fuel cell vehicles, household fuel cells (household cogeneration systems), mobile phones and personal computers.
固体高分子型燃料電池（以下、燃料電池という）は、固体高分子電解質膜を、アノード電極とカソード電極とで挟んだものを単セルとし、ガス（水素、酸素等）の流路となる溝が形成されたセパレータ（バイポーラプレートとも呼ばれる）を介して、前記単セルを複数個重ね合わせたスタックとして構成される。燃料電池は、スタックあたりのセル数を増やすことで、出力を高くすることができる。 A polymer electrolyte fuel cell (hereinafter referred to as a fuel cell) is a single cell in which a solid polymer electrolyte membrane is sandwiched between an anode electrode and a cathode electrode, and a groove serving as a gas (hydrogen, oxygen, etc.) flow path. Is formed as a stack in which a plurality of the single cells are overlapped via a separator (also called a bipolar plate) formed with. The output of the fuel cell can be increased by increasing the number of cells per stack.
そして、燃料電池用のセパレータは、発生した電流を燃料電池の外部へ取り出すための部品であるので、その材料には、接触抵抗（電極とセパレータ表面との間で、界面現象のために電圧降下が生じることをいう）が低く、それがセパレータとしての使用中に長期間維持されるものでなければならない。 Since the separator for a fuel cell is a component for taking out the generated current to the outside of the fuel cell, the material has a contact resistance (a voltage drop due to an interface phenomenon between the electrode and the separator surface). Must be maintained for a long time during use as a separator.
さらに、燃料電池セル内部は高温・酸性雰囲気であるので、燃料電池用のセパレータは、このような雰囲気下でも高い導電性を長期間維持する必要がある。この性能を発揮するには、セパレータの基材上に導電層を良好に被覆させる必要がある。 Further, since the inside of the fuel cell is in a high temperature / acid atmosphere, the separator for the fuel cell needs to maintain high conductivity for a long time even in such an atmosphere. In order to exhibit this performance, it is necessary to satisfactorily coat the conductive layer on the separator substrate.
そして、このセパレータの基材としては、燃料電池スタックの小型化・薄型化・軽量化のニーズから、金属基材（金属製の箔等）の使用が検討され、導電層を形成する材料としては、導電性と安定性に優れるとともに安価である炭素系導電材料の使用が検討されている。さらに、この金属基材としては、特に、軽量で且つ耐食性に優れる純チタンまたはチタン合金からなる基材（以下、適宜、チタン材という）が志向される傾向にあり、このチタン材に炭素系導電材料を種々の方法により被覆してセパレータを製造する技術が多く提案されている。 As the base material of this separator, the use of a metal base material (metal foil, etc.) has been studied in order to reduce the size, thickness and weight of the fuel cell stack. The use of carbon-based conductive materials that are excellent in conductivity and stability and are inexpensive has been studied. Further, as this metal base material, a base material made of pure titanium or a titanium alloy that is lightweight and excellent in corrosion resistance (hereinafter, appropriately referred to as a titanium material) tends to be oriented. Many techniques for manufacturing a separator by coating a material by various methods have been proposed.
例えば、金属基材の表面に、ラマン分光法によるＧ／Ｄ比が０．５以下となる炭素層が形成されているセパレータ（特許文献１）や、金属基材の表面に、アモルファスカーボン層と黒鉛部から構成される炭素層が形成されているセパレータ（特許文献２）等が提案されている。 For example, a separator (Patent Document 1) in which a carbon layer having a G / D ratio of 0.5 or less by Raman spectroscopy is formed on the surface of the metal substrate, or an amorphous carbon layer on the surface of the metal substrate. The separator (patent document 2) etc. in which the carbon layer comprised from a graphite part is formed are proposed.
前記の特許文献１および特許文献２のように、燃料電池セパレータ材として求められる導電性および耐久性を満足し、且つ、このような燃料電池セパレータ材を低コストで製造する技術については種々検討されている。しかし、使用後の燃料電池セパレータ材や、燃料電池セパレータ材を製造する工程で生じた端材から導電層を除去し、もとの基材（チタン材）を回収し、リサイクルする技術についてはあまり検討されておらず、有効な手法が見出されていない。
詳細には、使用後のチタン製燃料電池セパレータ材等は、チタン材上に炭素系導電材料を含む導電層が形成されているので、そのままではチタン材として再利用することが出来ない。よって、導電層を除去してチタン材のみを回収する必要がある。また、導電層を除去する際にチタン材の大きなロスが生じてしまうような手法では、歩留まり低下（リサイクル効率の低下）の問題が発生してしまう。
As described in Patent Document 1 and Patent Document 2, various technologies have been studied for satisfying the electrical conductivity and durability required as a fuel cell separator material and manufacturing such a fuel cell separator material at low cost. ing. However, there is not much about the technology to remove the fuel layer from the used fuel cell separator material or the scrap material generated in the process of manufacturing the fuel cell separator material, recover the original base material (titanium material), and recycle it. It has not been studied and no effective method has been found.
In detail, since the titanium fuel cell separator material after use has a conductive layer containing a carbon-based conductive material on the titanium material, it cannot be reused as it is. Therefore, it is necessary to remove the conductive layer and recover only the titanium material. In addition, a technique that causes a large loss of the titanium material when removing the conductive layer causes a problem of yield reduction (reduction in recycling efficiency).
本発明は、このような問題に鑑みてなされたものであり、基材であるチタン材のロスを抑えつつ、チタン製燃料電池セパレータ材から炭素系導電性材料を含む導電層を除去する方法を提供することを目的とする。 The present invention has been made in view of such problems, and a method for removing a conductive layer containing a carbon-based conductive material from a titanium fuel cell separator while suppressing loss of a titanium material as a base material. The purpose is to provide.
前記課題を解決するために、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、純チタンまたはチタン合金からなる基材上に炭素系導電性材料を含む導電層が形成され、前記基材と前記導電層との間にチタンカーバイドを含む中間層が形成されてなるチタン製燃料電池セパレータ材から前記導電層を除去する導電層除去方法であって、前記チタン製燃料電池セパレータ材を、水溶液に浸漬させ、前記水溶液は、硝酸、過酸化水素水、硝酸と過酸化水素とを混合した水溶液、過酸化水素と硫酸とを混合した水溶液、もしくは、硝酸と過酸化水素と硫酸とを混合した水溶液であることを特徴とする。 In order to solve the above problems, the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention includes forming a conductive layer containing a carbon-based conductive material on a base material made of pure titanium or a titanium alloy, A conductive layer removal method for removing the conductive layer from a titanium fuel cell separator material in which an intermediate layer containing titanium carbide is formed between a base material and the conductive layer, the titanium fuel cell separator material comprising: , immersed in water solution, the aqueous solution, nitric acid, hydrogen peroxide, aqueous solution of a mixture of nitric acid and hydrogen peroxide, hydrogen peroxide and aqueous solution was mixed with sulfuric acid or, nitric acid and hydrogen peroxide and sulfuric acid wherein the aqueous solution der Rukoto mixed with.
このように、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、所定の水溶液にチタン製燃料電池セパレータ材を浸漬させることで、チタン製燃料電池セパレータ材の基材と導電層との間に形成されている中間層が溶解する。その結果、基材から導電層が剥がれ、導電層を除去することができる。
また、所定の水溶液には、基材（チタン材）はほとんど溶解しないことから、ロスを抑えてチタン製燃料電池セパレータ材から導電層を除去することができる。
Thus, the method for removing the conductive layer of the titanium fuel cell separator material according to the present invention includes immersing the titanium fuel cell separator material in a predetermined aqueous solution, and the base material of the titanium fuel cell separator material and the conductive layer. The intermediate layer formed during the dissolution is dissolved. As a result, the conductive layer is peeled off from the substrate, and the conductive layer can be removed.
Moreover, since the base material (titanium material) hardly dissolves in the predetermined aqueous solution, the conductive layer can be removed from the titanium fuel cell separator material with reduced loss.
また、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、前記水溶液が硝酸を含む水溶液であることが好ましい。
そして、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、前記水溶液中の前記硝酸の濃度が０．５〜５０．０質量％であることが好ましい。
In the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention, the aqueous solution is preferably an aqueous solution containing nitric acid.
And it is preferable that the density | concentration of the said nitric acid in the said aqueous solution is 0.5-50.0 mass% for the conductive layer removal method of the titanium fuel cell separator material which concerns on this invention.
このように、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、硝酸を含むとともに、当該硝酸の濃度を規定していることにより、基材を溶解することなく、チタン製燃料電池セパレータ材から導電層を短時間で迅速に除去することができる。 Thus, the method for removing the conductive layer of the titanium fuel cell separator material according to the present invention includes nitric acid and regulates the concentration of the nitric acid, so that the titanium fuel cell does not dissolve the base material. The conductive layer can be quickly removed from the separator material in a short time.
また、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、前記水溶液が過酸化水素を含む水溶液であることが好ましい。
そして、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、前記水溶液中の前記過酸化水素の濃度が２．０〜３０．０質量％であることが好ましい。
In the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention, the aqueous solution is preferably an aqueous solution containing hydrogen peroxide.
And it is preferable that the density | concentration of the said hydrogen peroxide in the said aqueous solution is 2.0-30.0 mass% for the conductive layer removal method of the titanium fuel cell separator material which concerns on this invention.
このように、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、過酸化水素を含むとともに、当該過酸化水素の濃度を規定していることにより、基材を溶解することなく、チタン製燃料電池セパレータ材から導電層を短時間で迅速に除去することができる。 Thus, the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention includes hydrogen peroxide and regulates the concentration of the hydrogen peroxide without dissolving the substrate. The conductive layer can be quickly removed from the titanium fuel cell separator material in a short time.
また、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、前記水溶液は過酸化水素と硫酸とを含む水溶液であり、前記水溶液中の当該硫酸の濃度が１．０〜４０．０質量％であることが好ましい。 The conductive layer removal process of titanium fuel cell separator material according to the present invention, the aqueous solution is including aqueous hydrogen peroxide and sulfuric acid, the concentration of the sulfuric acid in the aqueous solution is 1.0 to 40. It is preferably 0% by mass.
このように、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、水溶液がさらに硫酸を所定量含むことから、チタン製燃料電池セパレータ材から導電層を除去するために要する時間をさらに短縮することができる。 Thus, the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention further increases the time required to remove the conductive layer from the titanium fuel cell separator material because the aqueous solution further contains a predetermined amount of sulfuric acid. It can be shortened.
また、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、前記チタン製燃料電池セパレータ材を前記水溶液に浸漬させる前の前工程として、前記チタン製燃料電池セパレータ材を裁断する工程を含むことが好ましい。 The method for removing a conductive layer of a titanium fuel cell separator material according to the present invention includes a step of cutting the titanium fuel cell separator material as a pre-process before immersing the titanium fuel cell separator material in the aqueous solution. It is preferable to include.
このように、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、チタン製燃料電池セパレータ材を裁断することにより、裁断箇所（面）に中間層を露出させ、露出した中間層を起点として中間層全体を迅速に溶解させることができるため、チタン製燃料電池セパレータ材から導電層を除去するために要する時間をさらに短縮することができる。 Thus, the method for removing the conductive layer of the titanium fuel cell separator material according to the present invention cuts the titanium fuel cell separator material to expose the intermediate layer at the cut portion (surface), and to remove the exposed intermediate layer. Since the entire intermediate layer can be rapidly dissolved as a starting point, the time required to remove the conductive layer from the titanium fuel cell separator material can be further shortened.
また、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、前記チタン製燃料電池セパレータ材を前記水溶液に浸漬させる前の前工程として、前記チタン製燃料電池セパレータ材の導電層に傷を付ける工程を含むことが好ましい。 Further, the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention includes a step of scratching the conductive layer of the titanium fuel cell separator material as a pre-process before immersing the titanium fuel cell separator material in the aqueous solution. It is preferable to include the process of attaching.
このように、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、導電層に傷を付けることにより水溶液が中間層まで浸透しやすくなるため、チタン製燃料電池セパレータ材から導電層を除去するために要する時間をさらに短縮することができる。 As described above, the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention makes it easier for the aqueous solution to penetrate to the intermediate layer by scratching the conductive layer. Therefore, the conductive layer is removed from the titanium fuel cell separator material. The time required for removal can be further shortened.
また、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、前記チタン製燃料電池セパレータ材を前記水溶液に浸漬させる前の前工程として、前記チタン製燃料電池セパレータ材を酸化雰囲気中において３５０〜７５０℃で熱処理する工程を含むことが好ましい。 Further, the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention includes a step of immersing the titanium fuel cell separator material in an oxidizing atmosphere as a pre-process before immersing the titanium fuel cell separator material in the aqueous solution. It is preferable to include the process of heat-processing at 350-750 degreeC.
このように、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、酸化雰囲気中において３５０〜７５０℃の温度で熱処理することにより、炭素系導電性材料を含んで構成される導電層の少なくとも一部を分解させ、水溶液が中間層まで浸透しやすくなるため、チタン製燃料電池セパレータ材から導電層を除去するために要する時間をさらに短縮することができる。 Thus, the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention includes a conductive layer including a carbon-based conductive material by heat treatment at a temperature of 350 to 750 ° C. in an oxidizing atmosphere. Since at least a part of the aqueous solution is decomposed and the aqueous solution easily penetrates into the intermediate layer, the time required to remove the conductive layer from the titanium fuel cell separator material can be further shortened.
本発明に係るチタン製燃料電池セパレータ材の導電層除去方法は、硝酸および過酸化水素のうち少なくともいずれか一方を含む水溶液にチタン製燃料電池セパレータ材を浸漬させることで、基材であるチタン材のロスを抑えつつ、チタン製燃料電池セパレータ材から炭素系導電性材料を含む導電層を除去することができる。
したがって、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法によると、使用後のチタン製燃料電池セパレータ材や、チタン製燃料電池セパレータ材を製造する工程で生じた端材から、歩留まりよくチタン材を回収することができ、チタン材のリサイクルに資することができる。
The method for removing a conductive layer of a titanium fuel cell separator material according to the present invention includes immersing the titanium fuel cell separator material in an aqueous solution containing at least one of nitric acid and hydrogen peroxide, thereby forming a titanium material as a base material. Thus, the conductive layer containing the carbon-based conductive material can be removed from the titanium fuel cell separator material.
Therefore, according to the method for removing a conductive layer of a titanium fuel cell separator material according to the present invention, the yield of the titanium fuel cell separator material after use or the scrap material generated in the process of manufacturing the titanium fuel cell separator material is improved. Titanium material can be collected and can contribute to recycling of titanium material.
以下、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法の実施するための形態について、詳細に説明する。 Hereinafter, the form for implementing the conductive layer removal method of the titanium fuel cell separator material which concerns on this invention is demonstrated in detail.
≪本発明の対象となるチタン製燃料電池セパレータ材≫
まず、本発明の対象となるチタン製燃料電池セパレータ材について説明する。
チタン製燃料電池セパレータ材は、純チタンまたはチタン合金からなる基材と、当該基材上に被覆した導電層と、基材と導電層との間に形成された中間層と、から構成される。
なお、チタン製燃料電池セパレータ材は、導電層および中間層を基材の片面に形成したものでも、両面に形成したものでもよい。
<< Titanium Fuel Cell Separator Material Subject to the Present Invention >>
First, a titanium fuel cell separator material that is an object of the present invention will be described.
A titanium fuel cell separator material is composed of a base material made of pure titanium or a titanium alloy, a conductive layer coated on the base material, and an intermediate layer formed between the base material and the conductive layer. .
The titanium fuel cell separator material may be formed on one side or both sides of the conductive layer and the intermediate layer.
そして、チタン製燃料電池セパレータ材は、前記層構成のものであれば特に限定されず、セパレータとして燃料電池に使用された後のものであってもよいし、セパレータを製造する工程において端材として生じたものであってもよい。
また、チタン製燃料電池セパレータ材は、どのような形状のものであってもよく、例えば、プレス加工されることにより流路が形成されていたり、穴加工が施されていたり、回収される際に変形してしまっていてもよい。
The titanium fuel cell separator material is not particularly limited as long as it has the above layer structure, and may be a material after being used in a fuel cell as a separator, or as an end material in a process of manufacturing a separator. It may have occurred.
Further, the titanium fuel cell separator material may have any shape, for example, when a flow path is formed by pressing, a hole is drilled, or is recovered. You may have transformed into.
＜基材＞
基材は、純チタンまたはチタン合金からなり、特定の組成の純チタン、チタン合金に限定されるものではない。そして、基材の厚さについても、特に限定されるものではない。
<Base material>
The base material is made of pure titanium or a titanium alloy, and is not limited to pure titanium or a titanium alloy having a specific composition. Further, the thickness of the base material is not particularly limited.
＜導電層＞
導電層は、炭素系導電性材料を含んで構成され、基材上に形成（後記の中間層を介して基材上に形成）される層である。
詳細には、導電層は、樹脂中にカーボンブラック粉末や各種黒鉛粉末といった炭素粉末、炭素繊維が分散して形成されている層であったり、わずかなバインダ成分を含みほぼ黒鉛のみから構成される層であったり、もしくは、ＰＶＤ法やＣＶＤ法などの気層成膜法により形成された非晶質炭素の層のことをいう。つまり、導電層とは、炭素の高い導電性を活用する目的で形成された層のことを示す。
また、炭素系導電性材料とは、炭素を含有する物質であれば特に限定されず、人造のものであっても天然のものであってもよく、また結晶質のものであっても非晶質のものであってもよい。さらに、導電層の厚さについても、特に限定されるものではない。
<Conductive layer>
The conductive layer is a layer that includes a carbon-based conductive material and is formed on the base material (formed on the base material via an intermediate layer described later).
Specifically, the conductive layer is a layer formed by dispersing carbon powder such as carbon black powder and various graphite powders and carbon fibers in the resin, or is composed of only graphite including a slight binder component. It is a layer or an amorphous carbon layer formed by a vapor deposition method such as a PVD method or a CVD method. In other words, the conductive layer refers to a layer formed for the purpose of utilizing the high conductivity of carbon.
The carbon-based conductive material is not particularly limited as long as it is a substance containing carbon, and may be man-made or natural, and may be crystalline or amorphous. It may be of quality. Further, the thickness of the conductive layer is not particularly limited.
＜中間層＞
中間層は、チタンカーバイドを含んで構成され、基材と導電層との間に形成される層である。
通常、純チタンやチタン合金からなる基材は大気雰囲気化で自然酸化膜を形成するが、この自然酸化膜は絶縁膜であるため、その上に導電層を形成しても接触抵抗が高くなる。また、この自然酸化膜が形成されている状態では基材と導電層の密着性が低いため好ましくない。したがって、基材と導電層との密着性を高め、さらに接触抵抗を下げるには、基材上に炭素系導電材料の導電層を形成した後非酸化雰囲気下で熱処理を行い導電層中の炭素をチタン基材表面に拡散させて界面にチタンカーバイドを含む層を形成させるのが好ましい。また、導電層をＰＶＤ法やＣＶＤ法などの気層成膜法により形成する場合には、真空中で一旦基材表面の自然酸化膜を除去し、下地膜としてチタンカーバイド層を形成し、その上に非晶質炭素層を形成するような工程により行われるのが好ましい。
本発明は、基材と導電層との密着性を高めるとともに接触抵抗を下げるために中間層を設けたチタン製燃料電池セパレータ材を対象としている。言い換えると、中間層を設けることにより、基材と導電層との密着性が向上することで、基材から導電層を除去し難いと考えられるチタン製燃料電池セパレータ材を対象としている。
なお、中間層の厚さについては、特に限定されるものではない。
<Intermediate layer>
The intermediate layer is a layer that includes titanium carbide and is formed between the base material and the conductive layer.
Usually, a base material made of pure titanium or a titanium alloy forms a natural oxide film in an atmosphere, but since this natural oxide film is an insulating film, contact resistance is increased even if a conductive layer is formed thereon. . Further, in the state where the natural oxide film is formed, the adhesion between the base material and the conductive layer is low, which is not preferable. Therefore, in order to increase the adhesion between the base material and the conductive layer and further reduce the contact resistance, after forming a conductive layer of carbon-based conductive material on the base material, heat treatment is performed in a non-oxidizing atmosphere, and the carbon in the conductive layer Is preferably diffused on the surface of the titanium substrate to form a layer containing titanium carbide at the interface. Further, when the conductive layer is formed by a gas layer deposition method such as PVD method or CVD method, the natural oxide film on the surface of the substrate is temporarily removed in vacuum, and a titanium carbide layer is formed as a base film. It is preferably performed by a process that forms an amorphous carbon layer thereon.
The present invention is directed to a titanium fuel cell separator material provided with an intermediate layer in order to increase the adhesion between the base material and the conductive layer and reduce the contact resistance. In other words, by providing the intermediate layer, the adhesion between the base material and the conductive layer is improved, so that the titanium fuel cell separator material considered to be difficult to remove the conductive layer from the base material is targeted.
Note that the thickness of the intermediate layer is not particularly limited.
≪導電層除去方法≫
本発明に係る導電層除去方法は、チタン製燃料電池セパレータ材を所定の水溶液に浸漬させることにより、基材のロスを最小限にとどめて歩留まり良くチタン製燃料電池セパレータ材から基材を回収することができる。
導電層を構成する炭素は化学的に安定な物質であり、酸やアルカリでこの炭素を溶解することは困難である上、強力な酸やアルカリを用いるとチタン基材自体がダメージを受けて歩留まりが悪くなってしまう。そこで、本発明者らは鋭意検討し、チタン基材をなるべく溶解させずに、導電層と基材の中間に形成されているチタンカーバイド層を溶解させることで導電層を基材から剥離させるべく検討を行い、本発明に至った。
すなわち、純チタンまたはチタン合金からなる基材上に炭素系導電性材料を含む導電層が形成され、本導電層と基材との間にチタンカーバイドを含む中間層が形成されてなるチタン製燃料電池セパレータ材を後記する所定の水溶液に浸漬することによって、チタンカーバイドを含む中間層を溶解させて、基材から導電層を剥離除去できることを見出した。
≪Method for removing conductive layer≫
The method for removing a conductive layer according to the present invention recovers a base material from a titanium fuel cell separator material with a high yield by immersing the titanium fuel cell separator material in a predetermined aqueous solution with minimal loss of the base material. be able to.
Carbon that constitutes the conductive layer is a chemically stable substance, and it is difficult to dissolve this carbon with an acid or alkali, and if a strong acid or alkali is used, the titanium substrate itself is damaged and the yield is increased. Will get worse. Therefore, the present inventors have intensively studied, in order to peel the conductive layer from the base material by dissolving the titanium carbide layer formed between the conductive layer and the base material without dissolving the titanium base material as much as possible. The present invention has been studied and led to the present invention.
That is, a titanium fuel in which a conductive layer containing a carbon-based conductive material is formed on a substrate made of pure titanium or a titanium alloy, and an intermediate layer containing titanium carbide is formed between the conductive layer and the substrate. It has been found that by immersing the battery separator material in a predetermined aqueous solution described later, the intermediate layer containing titanium carbide can be dissolved, and the conductive layer can be peeled and removed from the substrate.
＜導電層除去方法に用いる水溶液＞
本発明に係る導電層除去に用いられる水溶液は、硝酸または過酸化水素のいずれか一方を含む水溶液、もしくは硝酸および過酸化水素を混合して含む水溶液である。
さらに、水溶液に硝酸が含まれる場合は、さらにフッ酸が含まれることが好ましく、水溶液に過酸化水素が含まれる場合は、さらに硫酸が含まれることが好ましい。
<Aqueous solution used for conductive layer removal method>
The aqueous solution used for removing the conductive layer according to the present invention is an aqueous solution containing either nitric acid or hydrogen peroxide, or an aqueous solution containing a mixture of nitric acid and hydrogen peroxide.
Furthermore, when nitric acid is contained in the aqueous solution, it is preferable that hydrofluoric acid is further contained. When the aqueous solution contains hydrogen peroxide, it is preferable that sulfuric acid is further contained.
（硝酸）
硝酸が水溶液に含まれる場合において、水溶液中の硝酸の好ましい濃度は０．５〜５０．０質量％である。０．５質量％未満では中間層（チタンカーバイド層）の溶解速度が遅く、導電層を剥離除去させるのに長時間を要するうえに、箇所によっては剥離が起こらず導電層が基材上に斑に残る恐れがある。一方、５０．０質量％を超えても導電層を剥離させる効果は飽和する。
なお、効率的に導電層を剥離させるための硝酸のより好ましい濃度範囲は、２．０〜４０．０質量％であり、さらに好ましくは５．０〜３０．０質量％である。
(nitric acid)
When nitric acid is contained in the aqueous solution, the preferred concentration of nitric acid in the aqueous solution is 0.5 to 50.0 mass%. If the content is less than 0.5% by mass, the dissolution rate of the intermediate layer (titanium carbide layer) is slow, and it takes a long time to peel off and remove the conductive layer. There is a risk of remaining. On the other hand, even if it exceeds 50.0% by mass, the effect of peeling off the conductive layer is saturated.
In addition, the more preferable concentration range of nitric acid for efficiently peeling the conductive layer is 2.0 to 40.0 mass%, and more preferably 5.0 to 30.0 mass%.
（過酸化水素）
過酸化水素が水溶液に含まれる場合において、水溶液中の過酸化水素の好ましい濃度は２．０〜３０．０質量％である。２．０質量％未満では中間層（チタンカーバイド層）の溶解速度が遅く、導電層を剥離除去させるのに長時間を要するうえに、箇所によっては剥離が起こらず導電層が基材上に斑に残る恐れがある。一方、３０．０質量％を超えても導電層を剥離させる効果は飽和する。
なお、効率的に導電層を剥離させるための過酸化水素のより好ましい濃度範囲は、５．０〜２８．０質量％であり、さらに好ましくは１０．０〜２５．０質量％である。
(hydrogen peroxide)
In the case where hydrogen peroxide is contained in the aqueous solution, the preferred concentration of hydrogen peroxide in the aqueous solution is 2.0 to 30.0% by mass. If the amount is less than 2.0% by mass, the dissolution rate of the intermediate layer (titanium carbide layer) is slow, and it takes a long time to peel and remove the conductive layer. There is a risk of remaining. On the other hand, even if it exceeds 30.0% by mass, the effect of peeling off the conductive layer is saturated.
In addition, the more preferable range of the concentration of hydrogen peroxide for efficiently peeling the conductive layer is 5.0 to 28.0% by mass, and more preferably 10.0 to 25.0% by mass.
（硝酸および過酸化水素を混合して含む水溶液）
硝酸および過酸化水素を混合して含む水溶液を用いると、中間層（チタンカーバイド層）の溶解がより効率的に進み、導電層剥離除去に要する時間が短縮される。なお、硝酸および過酸化水素を混合して用いる場合でも硝酸および過酸化水素の好ましい濃度範囲は、上記のそれぞれ単独で使用する場合と同様である。
(Aqueous solution containing nitric acid and hydrogen peroxide)
When an aqueous solution containing a mixture of nitric acid and hydrogen peroxide is used, dissolution of the intermediate layer (titanium carbide layer) proceeds more efficiently, and the time required for removing the conductive layer is shortened. Even when nitric acid and hydrogen peroxide are mixed and used, the preferred concentration ranges of nitric acid and hydrogen peroxide are the same as those when used alone.
（フッ酸）
硝酸が水溶液に含まれる場合において、さらにフッ酸が含まれると、導電層剥離除去に要する時間が短縮される。しかしながら、フッ酸の量が多すぎてしまうと、導電層剥離後にチタン材を溶解してしまう。
水溶液中のフッ酸の好ましい濃度は０．０１〜１．０質量％である。０．０１質量％未満ではフッ酸の添加効果はほとんど得られず、一方、１．０質量％を超えるとチタン材を溶解してしまう。
なお、導電層剥離除去時間の短縮化を要求される場合は、水溶液にフッ酸を含めるのが好ましいが、チタン材の歩留まりを要求される場合は、フッ酸は含めないのが好ましい。
(Hydrofluoric acid)
In the case where nitric acid is contained in the aqueous solution, if hydrofluoric acid is further contained, the time required for removing the conductive layer is shortened. However, if the amount of hydrofluoric acid is too large, the titanium material is dissolved after the conductive layer is peeled off.
A preferable concentration of hydrofluoric acid in the aqueous solution is 0.01 to 1.0% by mass. If it is less than 0.01% by mass, the effect of adding hydrofluoric acid is hardly obtained. On the other hand, if it exceeds 1.0% by mass, the titanium material is dissolved.
Note that hydrofluoric acid is preferably included in the aqueous solution when shortening of the conductive layer peeling and removing time is required, but it is preferable not to include hydrofluoric acid when the yield of the titanium material is required.
（硫酸）
過酸化水素が水溶液に含まれる場合において、さらに硫酸が含まれると、過酸化水素のみ含む場合と比べて中間層（チタンカーバイド層）の溶解がより効率的に進み、導電層剥離除去に要する時間が短縮される。
水溶液中の硫酸の好ましい濃度範囲は１．０〜４０．０質量％である。１．０質量％未満では硫酸の添加効果はほとんど得られず、一方、４０．０質量％を超えても添加効果は飽和する。
なお、前記添加効果を得るための硫酸のより好ましい濃度範囲は、５．０〜３５．０質量％であり、さらに好ましくは８．０〜３０．０質量％である。
(Sulfuric acid)
When hydrogen peroxide is contained in an aqueous solution, when sulfuric acid is further contained, the dissolution of the intermediate layer (titanium carbide layer) proceeds more efficiently than the case where only hydrogen peroxide is contained, and the time required for removing the conductive layer Is shortened.
A preferable concentration range of sulfuric acid in the aqueous solution is 1.0 to 40.0% by mass. If the amount is less than 1.0% by mass, the effect of adding sulfuric acid is hardly obtained. On the other hand, if the amount exceeds 40.0% by mass, the addition effect is saturated.
In addition, the more preferable concentration range of the sulfuric acid for obtaining the addition effect is 5.0 to 35.0% by mass, and more preferably 8.0 to 30.0% by mass.
なお、硝酸または過酸化水素のいずれかを含む水溶液、硝酸および過酸化水素を混合して含む水溶液、過酸化水素と硫酸を混合して含む水溶液に、導電層を形成していない基材（チタン材）を浸漬しても溶解はほとんど起こらない。 In addition, an aqueous solution containing either nitric acid or hydrogen peroxide, an aqueous solution containing a mixture of nitric acid and hydrogen peroxide, or an aqueous solution containing a mixture of hydrogen peroxide and sulfuric acid without a conductive layer (titanium Even if the material is immersed, dissolution hardly occurs.
上記水溶液の温度によって中間層（チタンカーバイド層）の溶解速度が変化し、導電層剥離除去に要する時間が変わる。室温程度でも導電層の剥離は進行するが、温度が高い方がより効率的であり、好ましくは３０℃以上、より好ましくは４０℃以上であるが、適宜調整して実施することができる。
上記のとおり、水溶液に浸漬する時間は、水溶液の液温が高いほうが短縮される。ただし、導電層が剥離し、基材が露出しても、基材の溶解は起こらないため、処理時間の上限は特に規定されない。なお、導電層の剥離は目視で確認することができる。
The dissolution rate of the intermediate layer (titanium carbide layer) changes depending on the temperature of the aqueous solution, and the time required for removing the conductive layer changes. The peeling of the conductive layer proceeds even at about room temperature, but the higher the temperature, the more efficient, preferably 30 ° C. or higher, and more preferably 40 ° C. or higher.
As described above, the time of immersion in the aqueous solution is shortened as the solution temperature of the aqueous solution is higher. However, even if the conductive layer is peeled off and the base material is exposed, the base material is not dissolved, so the upper limit of the treatment time is not particularly defined. In addition, peeling of a conductive layer can be confirmed visually.
上記のとおり、本発明の対象となるチタン製燃料電池セパレータ材は、様々な形状を呈する。しかし、本発明に係る導電層除去方法は、水溶液に浸漬するという手法を用いることから、どのような形状のものでも対応することができるため、本発明は、対象物の形状に左右されないという点でも優れているといえる。 As described above, the titanium fuel cell separator material that is the subject of the present invention exhibits various shapes. However, since the method for removing a conductive layer according to the present invention uses a technique of immersing in an aqueous solution, any shape can be supported, and therefore the present invention is not influenced by the shape of an object. But it can be said that it is excellent.
なお、このような手法によって導電層を除去して回収したチタン材は、上記のように様々な形状をしているため、そのままセパレータ材やその他の用途に再利用される可能性は低く、スクラップ材として再溶解されチタン原料として各種用途に利用されると考える。 In addition, since the titanium material recovered by removing the conductive layer by such a technique has various shapes as described above, it is unlikely to be reused as it is for a separator material or other applications. It is considered that it is redissolved as a material and used for various purposes as a titanium raw material.
本発明の対象となるチタン製燃料電池セパレータ材について、基材に対する導電層の被覆率が低い場合は、前記水溶液にチタン製燃料電池セパレータ材を浸漬した際、水溶液は導電層を通過し、中間層を溶解することとなる。よって、チタン製燃料電池セパレータ材を大きな板状のまま水溶液に浸漬させても、本発明の効果を奏する。
一方、基材に対する導電層の被覆率が極めて高い場合は、前記水溶液にチタン製燃料電池セパレータ材を浸漬しても、水溶液は導電層を通過し難いため、中間層の溶解に時間がかかってしまう場合がある。当該場合は、水溶液にチタン製燃料電池セパレータ材を浸漬する前に、当該セパレータ材を細かく裁断することで、裁断箇所（面）に中間層を露出させることができる。よって、水溶液に裁断したチタン製燃料電池セパレータ材を浸漬させることで、裁断箇所（面）に露出した中間層を起点として、中間層全体を迅速に溶解させることができる。また、中間層が溶解した部分での導電層の剥離を促すため、超音波振動発生装置などを用いて微振動を与えることも有効である。
For the titanium fuel cell separator material that is the subject of the present invention, when the coverage of the conductive layer relative to the substrate is low, when the titanium fuel cell separator material is immersed in the aqueous solution, the aqueous solution passes through the conductive layer, The layer will be dissolved. Therefore, even if the titanium fuel cell separator material is immersed in an aqueous solution in the form of a large plate, the effect of the present invention is exhibited.
On the other hand, when the coverage of the conductive layer to the substrate is extremely high, even if the titanium fuel cell separator material is immersed in the aqueous solution, the aqueous solution is difficult to pass through the conductive layer. May end up. In this case, before the titanium fuel cell separator material is immersed in the aqueous solution, the intermediate layer can be exposed at the cutting location (surface) by finely cutting the separator material. Therefore, by immersing the titanium fuel cell separator material cut into the aqueous solution, the entire intermediate layer can be rapidly dissolved starting from the intermediate layer exposed at the cut portion (surface). It is also effective to apply a slight vibration using an ultrasonic vibration generator or the like in order to promote peeling of the conductive layer at the portion where the intermediate layer is dissolved.
＜水溶液浸漬前の前工程＞
本発明に係る導電層除去方法は、チタン製燃料電池セパレータ材を所定の水溶液に浸漬する前工程として、前記したチタン製燃料電池セパレータ材を裁断する工程以外にも、導電層に傷を付ける工程、もしくは酸化雰囲気中において３５０〜７５０℃で熱処理する工程を行うことにより、水溶液が中間層まで浸透しやすくして導電層を除去するために要する時間を短縮することができる。
<Pre-process before immersion in aqueous solution>
The method for removing a conductive layer according to the present invention includes a step of scratching the conductive layer in addition to the step of cutting the titanium fuel cell separator material as a previous step of immersing the titanium fuel cell separator material in a predetermined aqueous solution. Alternatively, by performing a heat treatment at 350 to 750 ° C. in an oxidizing atmosphere, the aqueous solution can easily penetrate into the intermediate layer, and the time required to remove the conductive layer can be shortened.
（導電層に傷を付ける工程）
基材に対する導電層の被覆率が高い場合、前記水溶液にチタン製燃料電池セパレータ材を浸漬させる前に導電層に傷を付ける工程を行うことが好ましい。導電層に傷を付ける方法としては、先端が鋭利な冶具で導電層に傷を付ける方法や、ショットブラスト、ワイヤーブラシ、サンドペーパーを用いる方法などが挙げられる。また、剣山状の冶具で当該セパレータ材に細かな穴を開けることも有効と考えられる。このような前工程を行うことにより、水溶液が中間層にまで浸透しやすくなるため、効率良く導電層を除去することができる。
なお、傷とは、導電層に設けることにより、チタン製燃料電池セパレータ材を水溶液に浸漬させた際に、中間層が水溶液と接触する程度の深さの切れ目や穴等である。
(Process of scratching the conductive layer)
When the coverage of the conductive layer with respect to the substrate is high, it is preferable to perform a step of scratching the conductive layer before immersing the titanium fuel cell separator material in the aqueous solution. Examples of the method for scratching the conductive layer include a method for scratching the conductive layer with a jig having a sharp tip, a method using a shot blast, a wire brush, and sandpaper. It is also considered effective to make fine holes in the separator material with a sword-shaped jig. By performing such a pre-process, the aqueous solution can easily penetrate into the intermediate layer, so that the conductive layer can be efficiently removed.
In addition, a crack is a cut | interruption, a hole, etc. of the depth which an intermediate | middle layer contacts with aqueous solution when a titanium fuel cell separator material is immersed in aqueous solution by providing in a conductive layer.
（酸化雰囲気中において熱処理する工程）
また、同様に基材に対する導電層の被覆率が高い場合、前記水溶液にチタン製燃料電池セパレータ材を浸漬させる前に酸化雰囲気中において３５０〜７５０℃で熱処理する工程を行うことが好ましい。導電層は炭素系導電性材料を含んで構成されるため、酸化雰囲気中で熱処理を行うと少なくともその一部が酸化分解（酸素と反応して二酸化炭素となる）し、導電層が脆弱になる。また、導電層と基材界面に形成されている中間層（チタンカーバイド層）のうち導電層側が雰囲気中の酸素により酸化されて、導電層との密着性が低下し、導電層が剥離しやすくなる。このような前工程を行うことにより、導電層が剥離しやすくなるとともに、水溶液が中間層にまで浸透しやすくなるため、効率良く導電層を除去することができる。
熱処理の温度が３５０℃未満の場合は、導電層の酸化の進行が遅いため、本工程の有効性が低く、一方、熱処理の温度が７５０℃を超えると基材自体が著しく酸化されることとなり、その酸化皮膜を除去するのに時間を要することになる。よって、熱処理の温度は３５０〜７５０℃であり、好ましくは４００〜７００℃であり、より好ましくは４５０〜６５０℃である。
熱処理時間は、熱処理の温度により適宜調整するのが良く、低温側であれば時間を長く、一方、高温側であれば時間を短く調整する。
(Process of heat treatment in oxidizing atmosphere)
Similarly, when the coverage of the conductive layer on the substrate is high, it is preferable to perform a heat treatment at 350 to 750 ° C. in an oxidizing atmosphere before immersing the titanium fuel cell separator material in the aqueous solution. Since the conductive layer includes a carbon-based conductive material, at least part of the conductive layer undergoes oxidative decomposition (reacts with oxygen to carbon dioxide) when heat-treated in an oxidizing atmosphere, and the conductive layer becomes brittle. . In addition, the conductive layer side of the intermediate layer (titanium carbide layer) formed at the interface between the conductive layer and the substrate is oxidized by oxygen in the atmosphere, the adhesion with the conductive layer is lowered, and the conductive layer is easily peeled off. Become. By performing such a pre-process, the conductive layer can be easily peeled off and the aqueous solution can easily penetrate into the intermediate layer, so that the conductive layer can be efficiently removed.
When the heat treatment temperature is less than 350 ° C., the progress of oxidation of the conductive layer is slow, so the effectiveness of this step is low. On the other hand, when the heat treatment temperature exceeds 750 ° C., the substrate itself is significantly oxidized. Therefore, it takes time to remove the oxide film. Therefore, the temperature of heat processing is 350-750 degreeC, Preferably it is 400-700 degreeC, More preferably, it is 450-650 degreeC.
The heat treatment time is suitably adjusted according to the temperature of the heat treatment, and the time is adjusted to be longer if the temperature is low, while the time is adjusted to be short if the temperature is high.
以上、本発明の実施形態について説明したが、本発明は前記実施形態に限定されず、特許請求の範囲に記載した本発明の要旨を逸脱しない範囲で適宜設計変更可能である。 Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and the design can be appropriately changed without departing from the gist of the present invention described in the claims.
次に、本発明に係るチタン製燃料電池セパレータ材の導電層除去方法について、本発明の要件を満たす実施例（試験Ｎｏ．１〜１４）と本発明の要件を満たさない比較例（試験Ｎｏ．１５〜２０）とを比較して具体的に説明する。 Next, with respect to the method for removing the conductive layer of the titanium fuel cell separator material according to the present invention, the examples satisfying the requirements of the present invention (Test Nos. 1 to 14) and the comparative examples not satisfying the requirements of the present invention (Test No. 1). 15-20) will be described in detail.
［被試験材］
基材にはＪＩＳ １種の純チタン材を用い、基材の両面に膨張化黒鉛粉を含むスラリーを塗布後、２段ロールプレス機を用いて圧着処理を行い、その後真空雰囲気（６．７×１０−３Ｐａ）において７００℃にて６０分間保持後に炉冷するという条件で熱処理を行った。上記処理により、純チタンからなる基材上（両面）に炭素系導電性材料が導電層として被覆され、当該導電層と基材との間にチタンカーバイドを含む中間層が形成されてなる被試験材を製造した。
なお、製造した被試験材は、基材の厚さが約０．２ｍｍ、中間層の厚さが約１．５μｍ（片面）、導電層の厚さが約３．０μｍ（片面）であった。そして、当該被試験材を２０×３０ｍｍのサイズに切断加工し、導電層除去試験に用いた。
[Test material]
JIS 1 type pure titanium material is used for the base material, a slurry containing expanded graphite powder is applied on both sides of the base material, and then a pressure-bonding treatment is performed using a two-stage roll press, and then a vacuum atmosphere (6.7) The heat treatment was performed under the condition that the furnace was cooled after being held at 700 ° C. for 60 minutes at × 10 −3 Pa). By the above treatment, a carbon-based conductive material is coated as a conductive layer on a base material (both sides) made of pure titanium, and an intermediate layer containing titanium carbide is formed between the conductive layer and the base material. The material was manufactured.
The manufactured material to be tested had a base material thickness of about 0.2 mm, an intermediate layer thickness of about 1.5 μm (single side), and a conductive layer thickness of about 3.0 μm (single side). . And the said to-be-tested material was cut into the size of 20x30 mm, and was used for the conductive layer removal test.
［導電層除去試験］
硝酸、過酸化水素、フッ酸、硫酸、塩酸を用い、表１に示す各種水溶液を作製し、それぞれの水溶液３０ｍｌを蓋付きのＰＰ製容器（５０ｍｌ容量）に入れ、液温を室温（約２５℃）もしくは５０℃に調整して試験を行った。なお、液温５０℃の場合は、ウォーターバスを使用して液温を５０℃に調整して導電層除去試験に用いた。
水溶液の温度が目的の温度になったことを確認後、上記被試験材を水溶液に浸漬し、導電層が剥離するまでの時間を計測した。
[Conductive layer removal test]
Various aqueous solutions shown in Table 1 were prepared using nitric acid, hydrogen peroxide, hydrofluoric acid, sulfuric acid, and hydrochloric acid, and 30 ml of each aqueous solution was placed in a PP container (50 ml capacity) with a lid, and the liquid temperature was room temperature (about 25 ° C) or 50 ° C. When the liquid temperature was 50 ° C., the liquid temperature was adjusted to 50 ° C. using a water bath and used for the conductive layer removal test.
After confirming that the temperature of the aqueous solution reached the target temperature, the test material was immersed in the aqueous solution, and the time until the conductive layer peeled was measured.
［導電層除去の評価］
導電層の剥離（除去）は目視にて判断した。剥離が起こる場合は、時間の経過にしたがい導電層に「膨れ」が発生し、それが被試験材の表面全体に広がり、やがて基材から導電層が脱落するのが目視にて判断できる。被試験材浸漬開始より導電層の脱落が確認されるまでの時間を計測し比較した。
[Evaluation of conductive layer removal]
The peeling (removal) of the conductive layer was judged visually. When peeling occurs, it can be visually determined that “swelling” occurs in the conductive layer as time passes, and this spreads over the entire surface of the material under test, and eventually the conductive layer falls off from the substrate. The time from the start of immersion of the test material to the confirmation of the removal of the conductive layer was measured and compared.
使用した水溶液の種類および濃度、液温度、導電層剥離の有無および剥離に要した時間を表１にまとめた。導電層剥離の有無については、浸漬開始後１０時間までに剥離が起こったもの（厳密には、基材から全ての導電層が脱落したもの）を○、剥離が起こらなかったものを×とし、剥離が起こったもののみ「剥離に要した時間」を記入した。 Table 1 summarizes the type and concentration of the aqueous solution used, the liquid temperature, the presence or absence of the conductive layer peeling, and the time required for the peeling. Regarding the presence or absence of peeling of the conductive layer, the case where peeling occurred within 10 hours after the start of immersion (strictly, the case where all the conductive layers were removed from the base material) was marked with ○, and the case where peeling did not occur was marked with ×, Only the time when peeling occurred was entered as “time required for peeling”.
試験Ｎｏ.１〜１４は、本発明に規定する水溶液を使用しているため、導電層を剥離除去することができた。特に硝酸と過酸化水素の混合溶液を使用した試験Ｎｏ.４および５、過酸化水素と硫酸の混合溶液を使用した試験Ｎｏ.１１〜１３、硝酸と過酸化水素と硫酸の混合溶液を使用したＮｏ.１４では、短時間で導電層を剥離させることができ、かつ基材の溶解がないため好ましいことがわかった。 Since Test Nos. 1 to 14 used the aqueous solution specified in the present invention, the conductive layer could be peeled off. In particular, Test Nos. 4 and 5 using a mixed solution of nitric acid and hydrogen peroxide, Test Nos. 11 to 13 using a mixed solution of hydrogen peroxide and sulfuric acid, and a mixed solution of nitric acid, hydrogen peroxide and sulfuric acid were used. No. 14 was found to be preferable because the conductive layer can be peeled off in a short time and the base material does not dissolve.
なお、硝酸とフッ酸の混合溶液を使用した試験Ｎｏ.６〜８は導電層の剥離は起こったものの、基材が若干溶解しているため歩留まりの点ではやや不利と考えられる。ただ、試験Ｎｏ．２と比較すると、剥離に要した時間を大幅に短縮できることがわかった。 In Test Nos. 6 to 8 using a mixed solution of nitric acid and hydrofluoric acid, although peeling of the conductive layer occurred, the base material was slightly dissolved, so it is considered somewhat disadvantageous in terms of yield. However, test no. Compared with 2, it was found that the time required for peeling can be greatly shortened.
一方、試験Ｎｏ.１５および１６では、フッ酸のみの水溶液での処理であるため、導電層が基材より剥離する前に、激しく発泡して基材に穴が開く様子などが観察され、チタン基材の著しい溶解が起こってしまった。
また、試験Ｎｏ.１７〜２０では１０時間の浸漬でも導電層の剥離が起こらず、目的の効果を得ることができなかった。
On the other hand, in Test Nos. 15 and 16, since treatment with an aqueous solution containing only hydrofluoric acid, before the conductive layer was peeled off from the base material, it was observed that the foam was vigorously foamed and a hole was formed in the base material. Substantial dissolution of the substrate has occurred.
In Test Nos. 17 to 20, peeling of the conductive layer did not occur even after 10 hours of immersion, and the intended effect could not be obtained.
なお、表１の試験Ｎｏ.３の水溶液浸漬前後の試料の断面ＳＥＭ観察結果を図１に示した。図１（ａ）に示すように、浸漬前ではチタン材上に炭素系導電性材料を含む導電層が存在し、チタン材と導電層との間にチタンカーバイドを含む中間層が確認される。一方、図１（ｂ）に示すように、この被試験材を３０％硝酸に浸漬させると、中間層の表層側が溶解して導電層が除去されており、チタン材までは溶解していないことがわかった。 In addition, the cross-sectional SEM observation result of the sample before and behind immersion of the aqueous solution of test No. 3 of Table 1 was shown in FIG. As shown in FIG. 1A, before immersion, a conductive layer containing a carbon-based conductive material exists on the titanium material, and an intermediate layer containing titanium carbide is confirmed between the titanium material and the conductive layer. On the other hand, as shown in FIG. 1B, when this test material is immersed in 30% nitric acid, the surface layer side of the intermediate layer is dissolved and the conductive layer is removed, and the titanium material is not dissolved. I understood.
実施例１と同様の工程にて、純チタンからなる基材上（両面）に炭素系導電性材料が導電層として被覆されるとともに、当該導電層と基材との間にチタンカーバイドを含む中間層が形成されてなる材料を作製し、当該材料を２０×３０ｍｍのサイズに切断加工した。
その後、一部のものを除き、大気雰囲気下にて３５０〜７５０℃で所定時間熱処理を行い、被試験材を作製した。
In the same process as in Example 1, a carbon-based conductive material is coated as a conductive layer on a base material (both sides) made of pure titanium, and an intermediate containing titanium carbide between the conductive layer and the base material. A material in which a layer was formed was produced, and the material was cut into a size of 20 × 30 mm.
Then, except for a part of them, heat treatment was performed at 350 to 750 ° C. for a predetermined time in an air atmosphere to prepare a material to be tested.
［導電層除去試験］
導電層除去試験では、１０質量％ 硝酸、０．２質量％ フッ酸水溶液を用い、この水溶液３０ｍｌを蓋付きのＰＰ製容器（５０ｍｌ容量）に入れ、液温を室温５０℃に調整して試験を行った。なお、液温の調整は、実施例１と同様にウォーターバスを用いて行った。
水溶液の温度が目的の温度になったことを確認後、上記被試験材を水溶液に浸漬し、５分経過する毎に容器ごと超音波洗浄装置（出力：２００Ｗ、周波数：３６ｋＨｚ）内に入れ１０秒間微振動を与え、これを繰り返し行い、導電層が剥離するまでの時間を計測して比較した。
[Conductive layer removal test]
In the conductive layer removal test, 10 mass% nitric acid, 0.2 mass% hydrofluoric acid aqueous solution was used, 30 ml of this aqueous solution was placed in a PP container (50 ml capacity) with a lid, and the liquid temperature was adjusted to room temperature 50 ° C. Went. The liquid temperature was adjusted using a water bath in the same manner as in Example 1.
After confirming that the temperature of the aqueous solution has reached the target temperature, the material to be tested is immersed in the aqueous solution, and the container is placed in an ultrasonic cleaning device (output: 200 W, frequency: 36 kHz) every 5 minutes. A slight vibration was applied for 2 seconds, this was repeated, and the time until the conductive layer peeled was measured and compared.
［導電層除去の評価］
導電層除去の評価については、実施例１と同じ方法で評価を行った。
そして、熱処理条件（温度、時間）、導電層剥離の有無および剥離に要した時間を表２にまとめた。表２の導電層剥離の有無についても、実施例１（表１）と同じ判断基準を用い、剥離が起こったものについて「剥離に要した時間」を記入した。なお、試験Ｎｏ.２１は熱処理を行わずに導電層除去試験に供した。
[Evaluation of conductive layer removal]
About the evaluation of conductive layer removal, it evaluated by the same method as Example 1. FIG.
Table 2 summarizes the heat treatment conditions (temperature, time), the presence or absence of conductive layer peeling, and the time required for peeling. Regarding the presence / absence of peeling of the conductive layer in Table 2, the same judgment criteria as in Example 1 (Table 1) were used, and “time required for peeling” was entered for those where peeling occurred. Test No. 21 was subjected to a conductive layer removal test without performing heat treatment.
試験Ｎｏ.２２〜２６の条件で熱処理した被試験材は、熱処理を行わなかった試験Ｎｏ.２１と比べて導電層剥離までの時間が短縮され、特に４００℃および５００℃の熱処理（試験Ｎｏ.２３、２４）が有効であった。一方、７５０℃を超える温度での熱処理を行った試験Ｎｏ.２７は、熱処理時に酸化膜が厚く成長したために、導電層の除去は可能であるものの、熱処理を行わない場合よりも長時間を要した。 The material to be tested heat-treated under the conditions of Test Nos. 22 to 26 has a shorter time to peel off the conductive layer than Test No. 21 in which heat treatment was not performed, and in particular, heat treatment at 400 ° C. and 500 ° C. (Test No. 23, 24) was effective. On the other hand, in Test No. 27 in which the heat treatment at a temperature exceeding 750 ° C. was performed, the conductive layer could be removed because the oxide film grew thick during the heat treatment, but it took a longer time than when the heat treatment was not performed. did.
Claims (9)
前記チタン製燃料電池セパレータ材を、水溶液に浸漬させ、
前記水溶液は、硝酸、過酸化水素水、硝酸と過酸化水素とを混合した水溶液、過酸化水素と硫酸とを混合した水溶液、もしくは、硝酸と過酸化水素と硫酸とを混合した水溶液であることを特徴とするチタン製燃料電池セパレータ材の導電層除去方法。 A titanium fuel cell in which a conductive layer containing a carbon-based conductive material is formed on a base material made of pure titanium or a titanium alloy, and an intermediate layer containing titanium carbide is formed between the base material and the conductive layer. A conductive layer removing method for removing the conductive layer from a separator material,
Wherein the titanium fuel cells separator material is immersed in water solution,
The aqueous solution, nitric acid, hydrogen peroxide, aqueous solution of a mixture of nitric acid and hydrogen peroxide, hydrogen peroxide and aqueous solution was mixed with sulfuric acid or, Ru aqueous der of a mixture of nitric acid and hydrogen peroxide and sulfuric acid A method for removing a conductive layer from a titanium fuel cell separator.
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| WO2000044059A1 (en) * | 1999-01-21 | 2000-07-27 | Asahi Glass Company, Limited | Solid polymer electrolyte fuel cell |
| TW200810198A (en) * | 2006-06-15 | 2008-02-16 | Nippon Steel Corp | Pure titanium or titanium alloy separator for solid polymer fuel cell and method for producing the same |
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