Thermal-mechanical coupling electrochemical hydrogen permeation device and use method thereof

Abstract

The invention relates to the technical field of electrochemical hydrogen permeation devices, in particular to a thermodynamic coupling electrochemical hydrogen permeation device and a use method thereof.The thermodynamic coupling electrochemical hydrogen permeation device comprises a device body, a sample, an electrochemical workstation, a galvanostat and a data collection unit, and one side face of the sample is plated with nickel; the device body is internally provided with a cavity body, the sample is detachably mounted on the device body, the sample divides the cavity body into a cathode chamber and an anode chamber which are horizontally and oppositely arranged and mutually closed, the cathode chamber contains a 0.1 mol / L hydrogen chloride solution, and when the device is used, the sample is arranged between the cathode chamber and the anode chamber; under the action of a constant-temperature water circulation system, the solution in the anode chamber is circularly heated, then the solution in the cathode chamber is pressurized, so that the solution in the anode chamber is in a constant-temperature state, sample data are measured through an electrochemical workstation and a galvanostat, and the metal hydrogen permeation test at high temperature and high pressure is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of electrochemical hydrogen permeation devices, and in particular to a thermally coupled electrochemical hydrogen permeation device and a method for using the same. Background Art

[0002] As a type of clean energy, hydrogen energy has attracted much attention in recent years. However, problems such as penetration and damage caused by high pressure and high temperature environments have occurred in the storage, transportation and application links. When hydrogen atoms enter the material structure, they will trigger hydrogen-induced cracking behavior with hydrogen embrittlement characteristics, seriously affecting the structural safety of the material. The hydrogen diffusion coefficient is extremely sensitive to temperature. In order to obtain accurate and reliable diffusion coefficient data, the entire experimental system (including two electrolytic cells and samples) needs to maintain a very precise and stable temperature. The electrochemical hydrogen permeation device currently used lacks the means to control the electrolytic cell and the sample to maintain a stable temperature. At the same time, the hydrogen diffusion coefficient varies significantly under the action of external force coupling. Therefore, an electrochemical hydrogen permeation device that can simultaneously simulate thermal-mechanical coupling conditions is needed. Summary of the Invention

[0003] The technical problem addressed by the present invention is that the hydrogen diffusion coefficient is extremely sensitive to temperature. To obtain accurate and reliable diffusion coefficient data, the entire experimental system (including the two electrolytic cells and the sample) must maintain a very precise and stable temperature. Currently used electrochemical hydrogen permeation devices lack a means to maintain stable temperatures for the electrolytic cells and the sample. Furthermore, the hydrogen diffusion coefficient exhibits significant variations under external force coupling. Therefore, a thermomechanically coupled electrochemical hydrogen permeation device and its use method are provided.

[0004] The technical solution adopted by the present invention to solve the technical problem is: a thermomechanically coupled electrochemical hydrogen permeation device, comprising a device body, a sample, an electrochemical workstation, a constant current meter and a data collection unit, wherein one side of the sample is nickel-plated;

[0005] The device body has a cavity, the sample is detachably mounted on the device body, the sample divides the cavity into two horizontally opposed and mutually sealed cathode chambers and anode chambers, the cathode chamber contains a 0.1 mol / L hydrogen chloride solution, the anode chamber contains a 0.2 mol / L sodium hydroxide solution, the nickel plating on one side of the sample is immersed in the solution in the anode chamber, and the other side of the sample is immersed in the solution in the cathode chamber, the electrochemical workstation calomel electrode and the electrochemical workstation platinum electrode on the electrochemical workstation are inserted into the anode chamber of the device body and immersed In the solution, the cathode electrolytic hydrogen-charging platinum electrode of the galvanometer is inserted into the cathode chamber of the device body and immersed in the solution. The cathode of the electrochemical workstation is set on the side of the sample located in the anode chamber, and the anode of the galvanometer is on the side of the sample located in the cathode chamber. The cathode chamber is provided with a pressurizing mechanism for pressurizing the solution. The anode chamber is provided with a constant temperature water circulation system. The constant temperature water circulation system is used to circulate and heat the solution and exchange heat with the solution in the anode chamber to achieve a constant temperature state of the solution in the anode chamber. The data collection unit is connected to the electrochemical workstation. Compared with the existing technology, this solution sets the sample between the cathode chamber and the anode chamber, and under the action of the constant temperature water circulation system, circulates and heats the solution in the anode chamber, and then pressurizes the solution in the cathode chamber to achieve a constant temperature state of the solution in the anode chamber. The sample data is measured by the electrochemical workstation and the galvanometer to achieve metal hydrogen permeation testing under high temperature and high pressure.

[0006] In order to realize a constant temperature water circulation system, some embodiments are preferred, in which the constant temperature water circulation system includes a circulating water pump, a hydrogen filling liquid tank, a circulating water coil and a heater. The circulating water coil is arranged in the anode chamber of the device body and immersed in the solution. One end of the hydrogen filling liquid tank is connected to one end of the circulating water coil, and the other end of the circulating water coil is connected to the input end of the circulating water pump 4, and the output end of the circulating water pump 4 is connected to the other end of the hydrogen filling liquid tank. The hydrogen filling liquid tank is provided with a heater for heating the solution.

[0007] In some preferred embodiments, water inlet valves are provided at both ends of the circulating water coil.

[0008] In some preferred embodiments, the heater is a ceramic heater.

[0009] In some preferred embodiments, the boosting mechanism includes a high-pressure water pump, and the device body is located on the cathode chamber and is provided with a water inlet and a water outlet, the water inlet is connected to the output end of the high-pressure water pump, and the input end of the high-pressure water pump is connected to the water outlet.

[0010] In some preferred embodiments, the device body includes a left chamber and a right chamber, one end of the left chamber has a first connection port, one end of the right chamber has a second connection port, the first connection port and the second connection port are relatively fixedly connected, a sample slot for placing the sample is formed between the first connection port and the second connection port, and the sample is arranged in the sample slot.

[0011] In some preferred embodiments, a first flange is provided on the first connection port, and a second flange is provided on the second connection port, and the first flange and the second flange are arranged opposite to each other and fixedly connected to each other.

[0012] In some preferred embodiments, a first sealing gasket is provided between the first connection port and the sample, and a second sealing gasket is provided between the second connection port and the sample.

[0013] In some preferred embodiments, the first sealing gasket and the second sealing gasket each include a ceramic gasket and a polytetrafluoroethylene lining disposed on the ceramic gasket.

[0014] A method for using the above-mentioned thermomechanically coupled electrochemical hydrogen permeation device comprises the following steps:

[0015] S1. Pre-treat and nickel-plate the sample on one side, and then measure the kinetic parameters;

[0016] S2. Before the test, the cathode chamber and hydrogen liquid tank on the device body must be inspected for tightness;

[0017] S3. The metal sample to be tested is fixedly installed between the anode chamber and the cathode chamber, and the sample is connected to an electrochemical workstation and a constant current instrument, respectively. A 0.2 mol / L sodium hydroxide solution is delivered to the anode chamber as an electrolyte, and a 0.1 mol / L hydrogen chloride solution is delivered to the cathode chamber as an electrolyte, and a polarization potential of 300 mV is applied to passivate the nickel-plated layer on the surface of the sample;

[0018] S4, start the constant temperature water circulation system, adjust the set temperature of the external constant temperature water circulation system, set the electrochemical workstation to constant potential mode, and when the background current value is less than 1×10 -6 After A, the solution in the anode chamber is filled with hydrogen and circulated for heating, and then the solution in the cathode chamber is pressurized to heat the solution in the anode chamber to achieve a constant temperature state, and the temperature is controlled throughout the test;

[0019] S5. After the residual current stabilizes, the electrochemical workstation records the change of hydrogen release current over time. When the steady state of hydrogen atomic diffusion is established and the hydrogen release current reaches the maximum value I∞, stop recording data and the experiment ends.

[0020] The beneficial effects of the present invention are as follows: when using the thermomechanically coupled electrochemical hydrogen permeation device and the method for using the device, a sample is placed between a cathode chamber and an anode chamber, and under the action of a constant temperature water circulation system, the solution in the anode chamber is circulated and heated, and then the solution in the cathode chamber is pressurized to achieve a constant temperature state of the solution in the anode chamber, and the sample data is measured by an electrochemical workstation and a constant current meter to achieve metal hydrogen permeation testing under high temperature and high pressure, avoiding parameter changes in the hydrogen permeation curve measured by the prior art due to temperature differences occurring during the experiment, and reducing the influence of temperature on the parameters of the experimental results. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The present invention will be further described below with reference to the accompanying drawings and examples.

[0022] Figure 1 It is a schematic diagram of the device of the present invention.

[0023] Figure 2 It is a system diagram of a constant temperature water circulation system.

[0024] In the figure: 1-anode chamber, 2-cathode chamber, 3-constant temperature water circulation system, 4-circulating water pump, 5-electrochemical workstation, 6-galvanometer, 7-data collection unit, 8-sample tank, 9-first sealing gasket, second sealing gasket, 10-cathode electrolysis hydrogen charging platinum electrode, 11-electrochemical workstation platinum electrode, 12-electrochemical workstation calomel electrode, 13-heater, 14-high pressure water pump, 15-temperature sensor, 16-temperature controller, 17-circulating water coil, 18-water inlet valve. DETAILED DESCRIPTION

[0025] The present invention is further described in detail below in conjunction with the embodiments:

[0026] The present invention is not limited to the following specific embodiments. Based on the disclosure of the present invention, a person skilled in the art may adopt a variety of other specific embodiments to implement the present invention. Any simple changes or modifications made to the design structure and concept of the present invention fall within the scope of protection of the present invention. It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other unless they conflict.

[0027] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, features defined as "first", "second", etc. may explicitly or implicitly include one or more of the features. In the description of the present invention, unless otherwise specified, "multiple" means two or more.

[0028] In the description of the present invention, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood in a broad sense. For example, they may refer to fixed connections, detachable connections, or integral connections; mechanical connections or electrical connections; direct connections or indirect connections through an intermediate medium; and internal communication between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention based on specific circumstances.

[0029] Example 1

[0030] like Figure 1-2 As shown, a thermomechanically coupled electrochemical hydrogen permeation device includes a device body, a sample, an electrochemical workstation 5, a constant current meter 6 and a data collection unit 7, and one side of the sample is nickel-plated;

[0031] The device body has a cavity, and the sample is detachably mounted on the device body. The sample divides the cavity into two horizontally opposed and mutually sealed cathode chambers 2 and anode chambers 1. The cathode chamber 2 contains a 0.1 mol / L hydrogen chloride solution, and the anode chamber 1 contains a 0.2 mol / L sodium hydroxide solution. The nickel plating on one side of the sample is immersed in the solution in the anode chamber 1, and the other side of the sample is immersed in the solution in the cathode chamber 2. The electrochemical workstation calomel electrode 12 and the electrochemical workstation platinum electrode 11 on the electrochemical workstation 5 are inserted into the anode chamber 1 of the device body and immersed in the solution. The cathode electrolysis hydrogen charging platinum electrode 10 of the constant current meter 6 is inserted into the cathode chamber 2 of the device body and immersed in the solution. The cathode of the electrochemical workstation 5 is arranged on the side of the sample located in the anode chamber 1. The anode of the constant current meter 6 is on the side of the sample located in the cathode chamber 2. The cathode chamber 2 is provided with a pressurizing mechanism for pressurizing the solution. The anode chamber 1 is provided with a constant temperature water circulation system 3. The constant temperature water circulation system 3 is used to circulate and heat the solution and exchange heat with the solution in the anode chamber 1 to achieve a constant temperature state of the solution in the anode chamber 1. The data collection unit 7 is connected to the electrochemical workstation 5.

[0032] The constant temperature water circulation system 3 includes a circulating water pump 4, a hydrogen filling liquid tank, a circulating water coil 17 and a heater 13. The circulating water coil 17 is arranged in the anode chamber 1 of the device body and immersed in the solution. One end of the hydrogen filling liquid tank is connected to one end of the circulating water coil 17, and the other end of the circulating water coil 17 is connected to the input end of the circulating water pump 4. The output end of the circulating water pump 4 is connected to the other end of the hydrogen filling liquid tank. A heater 13 for heating the solution is provided on the hydrogen filling liquid tank. In this embodiment, the heater 13 is a ceramic heater 13. Water inlet valves 18 are provided at both ends of the circulating water coil 17. A temperature sensor 15 is provided on the hydrogen filling liquid tank, and the temperature sensor 15 is connected to the temperature controller 16.

[0033] The boosting mechanism includes a high-pressure water pump 14. The device body is located on the cathode chamber 2 and is provided with a water inlet and a water outlet. The water inlet is connected to the output end of the high-pressure water pump 14, and the input end of the high-pressure water pump 14 is connected to the water outlet.

[0034] The device body includes a left chamber and a right chamber, one end of the left chamber has a first connection port, one end of the right chamber has a second connection port, the first connection port and the second connection port are relatively fixedly connected, a sample slot 8 for placing the sample is formed between the first connection port and the second connection port, the sample is arranged in the sample slot 8, a first flange is provided on the first connection port, and a second flange is provided on the second connection port, the first flange and the second flange are arranged opposite to each other and fixedly connected to each other, a first sealing gasket is provided between the first connection port and the sample, and a second sealing gasket 9 is provided between the second connection port and the sample, the first sealing gasket and the second sealing gasket 9 include both ceramic gaskets and polytetrafluoroethylene linings arranged on the ceramic gaskets.

[0035] Example 2 uses a method for using the device in Example 1, specifically: a method for using a thermodynamically coupled electrochemical hydrogen permeation device as described above, including the following steps:

[0036] S1. Pre-treat and nickel-plate the sample on one side, and then measure the kinetic parameters;

[0037] S2. Before the test, the cathode chamber 2 and the hydrogen liquid tank on the device body must be pressurized to 1.5 times the atmospheric pressure for sealing inspection;

[0038] S3, the metal sample to be tested is fixedly installed between the anode chamber 1 and the cathode chamber 2, and the sample is respectively connected to the electrochemical workstation 5 and the constant current meter 6, and a 0.2 mol / L sodium hydroxide solution is respectively delivered to the anode chamber 1 as an electrolyte and a 0.1 mol / L hydrogen chloride solution is delivered to the cathode chamber 2 as an electrolyte, and a 300 mV polarization potential is applied to passivate the nickel plating layer on the surface of the sample, that is, the sample is located on one side of the cathode chamber 2 in contact with the 0.1 mol / L hydrogen chloride solution, and the sample is located on one side of the anode chamber 1 in contact with the 0.2 mol / L sodium hydroxide solution;

[0039] S4, start the constant temperature water circulation system 3, adjust the set temperature of the external constant temperature water circulation system 3 to 25℃±1℃, set the electrochemical workstation 5 to constant potential mode, and when the background current value is less than 1×10 -6 After A, turn on the switch of the hydrogen filling tank to start building pressure. At the same time, start the circulating water pump 4 and the high-pressure water pump 14. Let the high-pressure water pump 14 run at no load with the water inlet valve 18 closed. Slowly open the water inlet valve 18 to ensure that the hydrochloric acid solution in the cathode chamber 2 enters the high-pressure water pump 14. Continue to observe the pressure and flow to ensure that the values ​​are within a safe range. Then turn on the heater 13 to heat the solution in the anode chamber 1. The temperature is controlled throughout the test at 40°C ± 1°C to achieve circulating heating of the solution in the anode chamber 1. The solution in the anode chamber 1 is in a constant temperature state and the temperature is controlled throughout the test.

[0040] S5. After the residual current stabilizes, the electrochemical workstation 5 records the change of the hydrogen release current with time. When the steady state of hydrogen atom diffusion is established and the hydrogen release current reaches the maximum value I∞, the data recording stops and the experiment ends.

[0041] The above description of the preferred embodiments of the present invention is intended to serve as a guide. Based on the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. A thermomechanically coupled electrochemical hydrogen permeation device, characterized in that: The device comprises a device body, a sample, an electrochemical workstation (5), a constant current meter (6) and a data collection unit (7), wherein one side of the sample is nickel-plated; The device body has a cavity, the sample is detachably mounted on the device body, the sample divides the cavity into two horizontally opposed and mutually sealed cathode chambers (2) and anode chambers (1), the cathode chamber (2) has a 0.1 mol / L hydrogen chloride solution, the anode chamber (1) has a 0.2 mol / L sodium hydroxide solution, the nickel plating on one side of the sample is immersed in the solution in the anode chamber (1), and the other side of the sample is immersed in the solution in the cathode chamber (2), the electrochemical workstation (5) calomel electrode (12) and the electrochemical workstation (5) platinum electrode (11) on the electrochemical workstation (5) are inserted into the anode chamber (1) of the device body and immersed in the solution The cathode electrolytic hydrogen charging platinum electrode (10) of the constant current meter (6) is inserted into the cathode chamber (2) of the device body and immersed in the solution. The cathode of the electrochemical workstation (5) is arranged on the side of the sample located in the anode chamber (1). The anode of the constant current meter (6) is on the side of the sample located in the cathode chamber (2). The anode chamber (1) is provided with a pressurizing mechanism for pressurizing the solution. The cathode chamber (2) is provided with a constant temperature water circulation system (3). The constant temperature water circulation system (3) is used to circulate and heat the solution and exchange heat with the solution in the cathode chamber (2) to achieve a constant temperature state of the solution in the anode chamber (1). The data collection unit (7) is connected to the electrochemical workstation (5).

2. A thermomechanically coupled electrochemical hydrogen permeation device according to claim 1, characterized in that: The constant temperature water circulation system (3) comprises a circulating water pump (4), a hydrogen filling liquid tank, a circulating water coil (17) and a heater (13). The circulating water coil (17) is arranged in the anode chamber (1) of the device body and immersed in the solution. One end of the hydrogen filling liquid tank is connected to one end of the circulating water coil (17), the other end of the circulating water coil (17) is connected to the input end of the circulating water pump 4, and the output end of the circulating water pump 4 is connected to the other end of the hydrogen filling liquid tank. The hydrogen filling liquid tank is provided with a heater (13) for heating the solution.

3. A thermomechanically coupled electrochemical hydrogen permeation device according to claim 2, characterized in that: Both ends of the circulating water coil (17) are connected to water inlet valves (18).

4. A thermomechanically coupled electrochemical hydrogen permeation device according to claim 2 or 3, characterized in that: The heater (13) is a ceramic heater (13).

5. A thermomechanically coupled electrochemical hydrogen permeation device according to claim 4, characterized in that: The boosting mechanism comprises a high-pressure water pump (14); the device body is located on the cathode chamber (2) and is provided with a water inlet and a water outlet; the water inlet is connected to the output end of the high-pressure water pump (14); and the input end of the high-pressure water pump (14) is connected to the water outlet.

6. The thermomechanically coupled electrochemical hydrogen permeation device according to claim 1, characterized in that: The device body comprises a left chamber and a right chamber, one end of the left chamber has a first connection port, one end of the right chamber has a second connection port, the first connection port and the second connection port are relatively fixedly connected, a sample slot (8) for placing a sample is formed between the first connection port and the second connection port, and the sample is arranged in the sample slot (8).

7. The thermomechanically coupled electrochemical hydrogen permeation device according to claim 6, characterized in that: The first connection port is provided with a first flange, and the second connection port is provided with a second flange. The first flange and the second flange are arranged opposite to each other and fixedly connected to each other.

8. The thermomechanically coupled electrochemical hydrogen permeation device according to claim 7, characterized in that: A first sealing gasket is provided between the first connection port and the sample, and a second sealing gasket (9) is provided between the second connection port and the sample.

9. The thermomechanically coupled electrochemical hydrogen permeation device according to claim 8, characterized in that: The first sealing gasket and the second sealing gasket (9) comprise a ceramic gasket and a polytetrafluoroethylene lining arranged on the ceramic gasket.

10. A method for using a thermomechanically coupled electrochemical hydrogen permeation device according to any one of claims 1 to 9, characterized in that: The steps are as follows: S1. Pre-treat and nickel-plate the sample on one side, and then measure the kinetic parameters; S2. Before the test, the cathode chamber (2) and the hydrogen liquid tank on the device body must be inspected for tightness; S3, the metal sample to be tested is fixedly installed between the anode chamber (1) and the cathode chamber (2), and the sample is connected to the electrochemical workstation (5) and the constant current meter (6), respectively, and 0.2 mol / L sodium hydroxide solution is delivered to the anode chamber (1) as an electrolyte and 0.1 mol / L hydrogen chloride solution is delivered to the cathode chamber (2) as an electrolyte, and a polarization potential of 300 mV is applied to passivate the nickel plating layer on the surface of the sample; S4, start the constant temperature water circulation system (3), adjust the set temperature of the external constant temperature water circulation system (3), set the electrochemical workstation (5) to constant potential mode, and when the background current value is less than 1×10 -6 After A, the solution in the anode chamber (1) is circulated and heated, and the solution in the cathode chamber (2) is pressurized to heat the solution, so that the solution in the anode chamber (1) is kept at a constant temperature, and the temperature is controlled throughout the test; S5. After the residual current stabilizes, the electrochemical workstation (5) records the change of hydrogen release current over time. When the steady state of hydrogen atom diffusion is established and the hydrogen release current reaches the maximum value I∞, the data recording stops and the experiment ends.

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