Sensor device for contacting hydrogen, use of such a sensor device in a fuel cell system, a hydrogen high-pressure storage system, a hydrogen internal combustion engine system, or a hydrogen distribution system, and a method for manufacturing such a sensor device

Abstract

The present invention relates to a sensor device (1) for contact with hydrogen, comprising a sensor diaphragm (11) intended for contact with a hydrogen atmosphere. Furthermore, the sensor diaphragm (11) comprises at least one steel material, including stainless steel or anticorrosive steel, or a nickel-based alloy, the sensor diaphragm (11) having a hydrogen protection layer (20). Furthermore, the present invention relates to a method for manufacturing such a sensor device (1) for contact with hydrogen.

Description

[Technical field]

[0001] The present invention relates to a sensor device suitable and intended for contact with hydrogen, which may in particular be a component of a fuel cell system, a hydrogen high-pressure storage system, a hydrogen internal combustion engine system or a hydrogen distribution system, and furthermore a method for manufacturing such a sensor device. [Background technology]

[0002] Typically, components, for example in fuel cell systems or high-pressure storage systems, have high mechanical stability. In addition to mechanical stability, high media resistance must also often be present. In particular, high hydrogen resistance is required in fuel cell systems, hydrogen-internal combustion engine systems, hydrogen-high-pressure storage systems or even hydrogen-distribution systems.

[0003] Patent Document 1 describes a fuel cell system having a hydrogen pressure tank from which hydrogen can be extracted for supply to at least one anode of the fuel cell system. Therefore, for a long service life of the fuel cell system or the hydrogen pressure tank, high hydrogen resistance is required for the components of the fuel cell system and the hydrogen pressure tank.

[0004] In particular, the sensor device must have a high hydrogen resistance for a safe and reliable functioning. Materials currently used for the sensor membrane in the sensor device are, for example, martensitic precipitation-hardened stainless steels (maraging steels, e.g. 1.4542). However, they are characterized by a high incidence of hydrogen embrittlement, which makes their use costly in terms of safety engineering. Furthermore, materials of this type exhibit a high hydrogen permeability, which can lead to impairment of the mechanical material properties and interference with the measurement signal of the sensor device.

[0005] As an alternative to maraging steel, austenitic stainless special steels are often used. However, they have a relatively low strength. For use as a sensor membrane in a sensor device, a relatively large thickness is therefore required. The elastic deformations that can be achieved by the applied pressure are relatively small when a relatively large membrane thickness is applied. In that case, the measurement of the pressure signal based on the small elastic deformations cannot be directly applied with sufficient accuracy for pressure measurement.

[0006] Steel materials can exhibit a degradation of their mechanical properties under hydrogen atmosphere and mechanical load, which is called hydrogen embrittlement. The tendency to embrittlement depends on factors such as the microstructure (e.g. ferrite, martensite, austenite) and strength, as well as on the ingress of hydrogen into the material or component. One option to minimize hydrogen embrittlement is to prevent or hinder the ingress of hydrogen into the material. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] DE 102012219061 A1 Summary of the Invention

[0008] The device according to the invention having the features of the characterizing part of claim 1 has the advantage that the risk of hydrogen ingress and hydrogen embrittlement in the device can be minimized in a simple manner.

[0009] To that end, the sensor device for contacting hydrogen comprises a sensor diaphragm intended for contacting a hydrogen atmosphere, the sensor diaphragm further comprising at least one stainless steel or anticorrosive steel or a steel material comprising a nickel-based alloy, the sensor diaphragm having a hydrogen barrier layer.

[0010] By means of the hydrogen protection layer the sensor device obtains protection against hydrogen embrittlement and in this way the mechanical properties of the sensor device are maintained, thereby ensuring a reliable and correct functioning of the sensor device.

[0011] In a first preferred development, the stainless steel or anti-corrosive steel is intended to include martensitic steels such as, for example, 1.4542, 1.4418, 1.4034.

[0012] The hydrogen barrier layer preferably comprises aluminum oxide or silicon oxide.

[0013] In that way, hydrogen embrittlement of the sensor device can be minimized in a simple manner by the selection of materials.

[0014] Additionally, materials that allow for relatively small membrane thicknesses due to large elastic deformation without plastic deformation in response to applied pressure are preferred. Larger elastic deformations lead to more accurate and easier measurement of pressure.

[0015] In a preferred development, it is provided that the hydrogen barrier layer has a thickness d between 0.1 and 5 μm.

[0016] Furthermore, according to the invention, a use of the sensor device for a fuel cell system is proposed.

[0017] Furthermore, according to the invention, a use of the sensor device for a hydrogen high-pressure storage system is proposed.

[0018] Furthermore, according to the invention, a use of the sensor arrangement for a hydrogen internal combustion engine system is proposed.

[0019] Further according to the invention, a use of the sensor device for a hydrogen distribution system is proposed.

[0020] The invention further relates to a method for manufacturing a sensor device for contacting hydrogen, said method comprising the following method steps: a) a sensor device is fabricated from a raw material in the form of a rod, sheet or plate; b) a hydrogen barrier layer is created on the sensor device by coating with aluminum and / or silicon; c) For heat treatment of the sensor device to form aluminum oxide and / or silicon oxide, the sensor device is exposed to an atmosphere, e.g. air, at a temperature range between 450°C and 1100°C for a time range between 0.5 hours and 3 hours.

[0021] The invention further relates to a method for manufacturing a sensor device for contacting hydrogen, said method comprising the following method steps: a) a sensor device is fabricated from a raw material in the form of a rod, sheet or plate; b) A hydrogen barrier layer is produced on the sensor device by the application of aluminum oxide and / or silicon oxide by CVD (chemical vapor deposition).

[0022] The invention further relates to a method for manufacturing a sensor device for contacting hydrogen, said method comprising the following method steps: a) a sensor device is fabricated from a raw material in the form of a rod, sheet or plate; b) A hydrogen barrier layer is produced on the sensor device by application of aluminum oxide and / or silicon oxide by PVD (physical vapor deposition).

[0023] The invention further relates to a method for manufacturing a sensor device for contacting hydrogen, said method comprising the following method steps: a) a sensor device is fabricated from a raw material in the form of a rod, sheet or plate; b) A hydrogen barrier layer is created on the sensor device by application of aluminum oxide and / or silicon oxide by dip coating.

[0024] In this way, a protective layer can be provided in a simple manner to the sensor device, which protects the sensor device from hydrogen embrittlement and mechanical damage due to contact with hydrogen, and furthermore, an optimal and reliable functioning of the sensor device can be achieved in this way.

[0025] The drawings show an embodiment of a sensor device according to the invention for contacting hydrogen and its use in a fuel cell system, a hydrogen high-pressure storage system, a hydrogen internal combustion engine system or a hydrogen distribution system. [Brief description of the drawings]

[0026] [Figure 1] FIG. 2 is a simplified schematic diagram showing one possible embodiment of a sensor apparatus for contacting hydrogen. [Diagram 2] 2 is a simplified schematic diagram illustrating the use of the embodiments of FIG. 1 in a fuel cell system, a hydrogen high pressure storage system, a hydrogen internal combustion engine system, and a hydrogen distribution system. [Diagram 3] 1 is a flow chart of a method of manufacturing a sensor device for contacting hydrogen. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] 1 shows in a simplified schematic diagram one possible embodiment of a sensor device 1 for contacting hydrogen. The sensor device 1 comprises a sensor element housing 10 with a sensor diaphragm 11 intended for contacting hydrogen on a pressure-biased side 18. On this pressure-biased side 18 a hydrogen protection layer 20 is formed.

[0028] The pressure of the medium, here hydrogen, leads to an elastic deformation in the sensor diaphragm 11. Furthermore, a glass-coated electrical isolation layer 16 with isolated module elements 14, e.g. a Wheatstone bridge, is arranged on the sensor diaphragm 11, in which the elastic deformation is converted into a resistance change that can be assigned to pressure. In this way, pressure detection is possible via the sensor device 1.

[0029] The sensor diaphragm 11 includes at least one stainless steel or anti-rust steel, or a steel material including a nickel-based alloy. The stainless steel or anti-rust steel may include a martensitic steel, such as 1.4542, 1.4418, or 1.4034, for example.

[0030] The sensor membrane 11 further comprises a hydrogen barrier layer 20, which comprises aluminum oxide or silicon oxide, and the hydrogen barrier layer 20 further comprises a thickness d between 0.1 μm and 5 μm.

[0031] The sensor device 1 is utilized for application in a fuel cell system 70, a hydrogen high pressure storage system 71, a hydrogen internal combustion engine system 72 or a hydrogen distribution system 73 (see FIG. 2).

[0032] The invention further relates to a method 500 for manufacturing a sensor device 1 for contacting hydrogen, comprising the following method steps: a) a sensor device 1 is fabricated 50 from a raw material in the form of a rod, sheet or plate; b) a hydrogen barrier layer 20 is produced 51 on the sensor device 1 by application of aluminum and / or silicon, c) For heat treatment of the sensor device 1 to form aluminum oxide and / or silicon oxide, the sensor device 1 is exposed 52 to an atmosphere, e.g. air, at a temperature range between 450°C and 1100°C for a time range between 0.5 hours and 3 hours.

[0033] The invention further relates to a method 500 for manufacturing a sensor device 1 for contacting hydrogen, comprising the following method steps: a) a sensor device 1 is fabricated 50 from a raw material in the form of a rod, sheet or plate; b) A hydrogen barrier layer 20 is produced 51 on the sensor device 1 by application of aluminum oxide and / or silicon oxide by CVD (chemical vapor deposition).

[0034] At this time, the starting materials required for the creation of the hydrogen barrier layer are heated and the hydrogen barrier layer 20 is formed by a chemical reaction in the starting materials of the sensor membrane 11, often under reduced pressure.

[0035] The invention further relates to a method 500 for manufacturing a sensor device 1 for contacting hydrogen, comprising the following method steps: a) a sensor device 1 is fabricated 50 from a raw material in the form of a rod, sheet or plate; b) A hydrogen barrier layer 20 is produced 51 on the sensor device 1 by application of aluminum oxide and / or silicon oxide by PVD (physical vapor deposition).

[0036] By physical methods, the material used for the hydrogen barrier layer is converted into the gas phase and transferred to the sensor device 1, in particular to the sensor diaphragm 11, and a hydrogen barrier layer is formed on the sensor diaphragm 11 by condensation.

[0037] The invention further relates to a method 500 for manufacturing a sensor device 1 for contacting hydrogen, comprising the following method steps: a) a sensor device 1 is fabricated 50 from a raw material in the form of a rod, sheet or plate; b) A hydrogen barrier layer 20 is produced 51 on the sensor device 1 by application of aluminium oxide and / or silicon oxide by dip coating.

[0038] Dip coating is one possible form of CVD (chemical vapor deposition) in which the sensor device 1 is immersed in a solution and a hydrogen barrier layer is solidified and formed on the sensor device 1 by a chemical reaction.

[0039] FIG. 3 shows a possible flow chart of the above method 500 with method steps 50 , 51 , 52 . [Explanation of symbols]

[0040] 1 Sensor device 11 Sensor diaphragm 20 Hydrogen protection layer 50 production 51 generation 52 Exposure 70 Fuel Cell System 71 Hydrogen High Pressure Storage System 72 Hydrogen and internal combustion engine systems 73 Hydrogen Distribution System 500 ways

Claims

1. A sensor device (1) for contact with hydrogen, comprising a sensor diaphragm (11) intended for contact with a hydrogen atmosphere, characterized in that the sensor diaphragm (11) comprises at least one stainless steel or anticorrosive steel, or a steel material comprising a nickel-based alloy, and the sensor diaphragm (11) has a hydrogen protection layer (20).

2. 2. The sensor arrangement (1) according to claim 1, characterized in that the stainless steel or anti-corrosive steel comprises a martensitic steel such as, for example, 1.4542, 1.4418, 1.4034.

3. 3. The sensor device (1) according to claim 1 or 2, characterized in that the hydrogen barrier layer (20) comprises aluminum oxide or silicon oxide.

4. The sensor device (1) according to any one of the preceding claims, characterized in that the hydrogen protection layer (20) has a thickness (d) between 0.1 μm and 5 μm.

5. Use of a sensor device (1) according to any one of the preceding claims in a fuel cell system (70).

6. Use of a sensor device (1) according to any one of claims 1 to 4 in a hydrogen high pressure storage system (71).

7. 5. Use of a sensor device (1) according to any one of claims 1 to 4 in a hydrogen internal combustion engine system (72).

8. Use of a sensor device (1) according to any one of claims 1 to 4 in a hydrogen distribution system (73).

9. A method (500) for manufacturing a sensor device (1) for contact with hydrogen according to any one of claims 1 to 4, comprising the steps of: a) a sensor device (1) is fabricated (50) from a raw material in the form of a rod, sheet or plate; b) a hydrogen barrier layer (20) is produced (51) on the sensor device (1) by application of aluminum and / or silicon; c) A method comprising the method steps of exposing (52) the sensor device (1) to an atmosphere, e.g. air, at a temperature range between 450° C. and 1100° C. for a time range between 0.5 hours and 3 hours for a heat treatment of the sensor device (1) to form aluminum oxide and / or silicon oxide.

10. A method (500) for manufacturing a sensor device (1) for contact with hydrogen according to any one of claims 1 to 4, comprising the steps of: a) a sensor device (1) is fabricated (50) from a raw material in the form of a rod, sheet or plate; b) A method comprising the method steps in which a hydrogen protection layer (20) is produced (51) on said sensor device (1) by application of aluminium oxide and / or silicon oxide by CVD (chemical vapour deposition).

11. A method (500) for manufacturing a sensor device (1) for contact with hydrogen according to any one of claims 1 to 4, comprising the steps of: a) a sensor device (1) is fabricated (50) from a raw material in the form of a rod, sheet or plate; b) A method comprising the respective method steps, in which a hydrogen protection layer (20) is produced (51) on said sensor device (1) by application of aluminium oxide and / or silicon oxide by PVD (physical vapour deposition).

12. A method (500) for manufacturing a sensor device (1) for contact with hydrogen according to any one of claims 1 to 4, comprising the steps of: a) a sensor device (1) is fabricated (50) from a raw material in the form of a rod, sheet or plate; b) A method comprising the method steps in which a hydrogen protection layer (20) is produced (51) on said sensor device (1) by application of aluminum oxide and / or silicon oxide by dip coating.

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