Hydrogen sulfide corrosion detection device and method for solid-state battery current collector

Abstract

The invention belongs to the field of material corrosion research, and relates to a hydrogen sulfide corrosion detection device and method for a solid-state battery current collector. The device is composed of a nitrogen supply unit, a hydrogen sulfide reaction generation unit, a detection unit, a corrosion current collector and a tail gas absorption unit. The detection method comprises the following steps: S1, enabling sulfuric acid to react with sodium sulfide nonahydrate to generate hydrogen sulfide gas; s2, the gas generation rate is adjusted through an automatic flow adjusting valve; s3, corroding the current collector by hydrogen sulfide, and recording the corrosion state and the gas concentration in real time; s4, enabling the gas to enter a tail gas absorption unit, and confirming that the hydrogen sulfide concentration of the exhausted gas is reduced to a safety threshold through a hydrogen sulfide alarm; s5, stopping supplying sulfuric acid, and filling the device with nitrogen to ensure that hydrogen sulfide is completely absorbed. The method disclosed by the invention is simple and convenient to operate, safe and environment-friendly, can stably generate hydrogen sulfide and accurately control the concentration of hydrogen sulfide, meets the corrosion detection requirements of different concentrations of hydrogen sulfide of the solid-state battery current collector, and has wide application prospects.

Description

Technical Field

[0001] This invention belongs to the field of materials corrosion research, specifically relating to a hydrogen sulfide corrosion current collector for solid-state batteries. Corrosion detection device and method. Background Technology

[0002] With the rapid development of electric vehicles and 3C electronic products, the demand for lithium batteries has increased dramatically.

[0003] Traditional lithium-ion batteries use liquid organic electrolytes, which pose flammable and explosive risks, limiting their further development. Solid-state batteries, due to their superior safety performance and high energy density, have become the focus of research and development in the lithium battery industry. The focus of research is on solid-state batteries. Sulfide-based solid-state batteries exhibit great potential due to their high ionic conductivity and excellent interfacial contact characteristics. However, sulfide electrolytes readily react with water vapor to generate corrosive hydrogen sulfide gas, which corrodes copper foil, posing a challenge to the application of copper foil in solid-state batteries. Therefore, developing novel negative electrode current collectors resistant to hydrogen sulfide corrosion is of great significance for the development of solid-state batteries.

[0004] To evaluate the hydrogen sulfide corrosion resistance of novel negative electrode current collectors, establishing an accurate evaluation system and method is crucial for developing negative electrode current collectors suitable for sulfide solid-state batteries. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention proposes a hydrogen sulfide corrosion detection device and method for solid-state battery current collectors. This invention constructs a hydrogen sulfide generation device capable of precisely controlling the concentration and flow rate of hydrogen sulfide. This device is used to evaluate the corrosion resistance of different negative electrode current collectors in a hydrogen sulfide environment. It is equipped with a gas leak alarm and a tail gas absorption device to ensure the safety and effectiveness of the entire system. The purpose of this invention is to solve the problem of evaluating the corrosion resistance of current collectors in sulfide solid-state batteries under hydrogen sulfide corrosive environments, and to provide a simple, safe, and environmentally friendly hydrogen sulfide corrosion detection device and method for solid-state battery current collectors.

[0006] This invention includes the following technical solutions: A hydrogen sulfide corrosion detection device for solid-state battery current collectors includes a nitrogen supply unit, a hydrogen sulfide reaction generation unit, a hydrogen sulfide detection unit, a hydrogen sulfide corrosion current collector unit, and a hydrogen sulfide exhaust gas absorption unit connected in series.

[0007] Furthermore, in the aforementioned detection device, the nitrogen supply unit is equipped with a nitrogen cylinder, a gas filter, and a nitrogen flow meter pressure reducing valve, and the gas outlet of the nitrogen cylinder is connected to the gas filter and the nitrogen flow meter pressure reducing valve. The hydrogen sulfide reaction generating unit is equipped with a three-necked flask and a pear-shaped separating funnel. The three-necked flask is equipped with a high liquid level sensor and a low liquid level sensor, and the pear-shaped separating funnel is equipped with an automatic flow regulating valve, a high liquid level sensor, and a low liquid level sensor. The hydrogen sulfide detection unit is equipped with a reaction monitoring camera, a hydrogen sulfide concentration and flow meter, and an online spectrometer; The hydrogen sulfide corrosion current collector is equipped with a reaction vessel and temperature and pressure detectors. The hydrogen sulfide tail gas absorption unit is equipped with a primary adsorption bottle, a secondary adsorption bottle, a gas collection bottle, a pH meter, a hydrogen sulfide alarm, and a ventilation system.

[0008] Furthermore, in the aforementioned detection device, the outlet pipe of the nitrogen cylinder is connected to one of the two ports on either side of the three-necked flask; the pear-shaped separating funnel is connected to the central port of the three-necked flask; the other port of the three-necked flask is connected to the lower port of the hydrogen sulfide concentration and flow meter; the upper port of the hydrogen sulfide concentration and flow meter is connected to the reaction vessel; and the other port of the reaction vessel is sequentially connected to the primary adsorption bottle, the secondary adsorption bottle, and the gas collecting bottle. A hydrogen sulfide alarm is placed on the outlet side of the gas collecting cylinder.

[0009] The present invention also discloses a method for detecting hydrogen sulfide corrosion using the above-mentioned detection device, comprising the following steps: S1: Add sulfuric acid dropwise from the pear-shaped separatory funnel to the three-necked flask. The sulfuric acid reacts with sodium sulfide nonahydrate to produce hydrogen sulfide gas. S2: Based on the readings of the hydrogen sulfide concentration and flow meter, the generation rate of hydrogen sulfide gas is adjusted using the automatic flow regulating valve on the pear-shaped separatory funnel; S3: Hydrogen sulfide gas enters the reaction tank to corrode the current collector, while the corrosion status and gas concentration in the current collector are recorded in real time by a reaction monitoring camera and an online spectrometer. S4: Hydrogen sulfide gas enters the hydrogen sulfide tail gas absorption unit and passes through a pH meter. The remaining sodium hydroxide in the primary and secondary adsorption bottles is fed back, and the hydrogen sulfide alarm confirms whether the concentration of hydrogen sulfide in the exhaust gas has dropped to the safe threshold. S5: Close the automatic flow regulating valve on the pear-shaped separatory funnel and open the pressure reducing valve of the nitrogen flow meter to ensure that the hydrogen sulfide gas in the device is completely absorbed.

[0010] Furthermore, in the above method, the concentration of sulfuric acid in S1 is 50-150 g / L, the concentration of sodium sulfate nonahydrate is 25-100 g / L, and the concentration ratio of sulfuric acid to sodium sulfate nonahydrate is 1.5:1-2.5:1.

[0011] Furthermore, in the above method, the hydrogen sulfide concentration in S2 is 3.5-14.0 g / L, and the hydrogen sulfide flow rate is in the range of 2.0-9.0 L / (L•h).

[0012] Furthermore, in the above method, the sodium hydroxide concentration in the first-stage adsorption bottle in S4 is 80-150 g / L, and its pH range should be controlled above 11; the sodium hydroxide concentration in the second-stage adsorption bottle is 20-40 g / L, and its pH range should be controlled above 10; and the hydrogen sulfide concentration in the exhaust gas should be below 1.0 ppm.

[0013] This invention provides a device and method for detecting hydrogen sulfide corrosion in current collectors for solid-state batteries. Compared with the prior art, this invention has the following advantages: This apparatus and method can stably generate hydrogen sulfide gas, and through precise flow rate control, achieve... Corrosion detection of the current collector under different concentrations of hydrogen sulfide. Furthermore, the corrosion was assessed by varying the hydrogen sulfide concentration and flow rate. Real-time monitoring by detectors, reaction monitoring cameras, and online spectrometers can accurately record the current collector. The corrosion state and gas concentration provide reliable data for evaluating the corrosion resistance of solid-state battery current collectors. According to support. Meanwhile, the design of the hydrogen sulfide tail gas absorption unit ensures the safety and environmental protection of the experimental process, avoiding... This avoids environmental pollution caused by hydrogen sulfide gas.

[0014] Furthermore, the apparatus and method of the present invention have broad application prospects, not only for solid-state batteries. The study of hydrogen sulfide corrosion of current collectors can be extended to the corrosion resistance of other materials in hydrogen sulfide environments. The assessment provides strong technical support for research on material corrosion. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the simulation device structure of the present invention; Wherein: 1-1 is a nitrogen cylinder, 1-2 is a gas filter, 1-3 is a nitrogen flow meter pressure reducing valve, 2-1 1-2 is a three-necked flask; 2-3 is a pear-shaped separatory funnel; 3-4 is a reaction monitoring camera; 3-5 is a hydrogen sulfide concentration and flow meter; 3-6 is an online spectrometer; 4-7 is a reaction vessel; 4-8 is a temperature and pressure detector; 5-9 is a primary adsorption bottle; 5-1 is a secondary adsorption bottle; 5-1 is a gas collecting bottle; 5-1 is a pH meter; 5-2 is a hydrogen sulfide alarm; and 5-3 is a ventilation system. Detailed Implementation

[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] Example 1 Please refer to Figure 1: A hydrogen sulfide corrosion detection device for solid-state battery current collectors includes a nitrogen supply. The system includes unit 1, hydrogen sulfide reaction generation unit 2, hydrogen sulfide detection unit 3, hydrogen sulfide corrosion current collector unit 4, and hydrogen sulfide tail gas absorption unit 5.

[0018] Nitrogen supply unit 1 is used to provide a stable flow of nitrogen to ensure that the device is emptied after testing. The nitrogen gas is hydrogen sulfide. Nitrogen cylinder 1-1 serves as a nitrogen storage device. Its outlet is connected to a three-necked flask 2-1 via a gas filter 1-2, a nitrogen flow meter, and a pressure reducing valve 1-3. The gas filter 1-2 removes impurities from the nitrogen, ensuring its purity. The nitrogen flow meter and pressure reducing valve 1-3 regulate the flow rate and pressure of the nitrogen to meet testing requirements.

[0019] Hydrogen sulfide reaction unit 2 is used to generate the required hydrogen sulfide gas. Three-necked flask 2-1 As a reaction vessel, it can accommodate the reaction solution of sulfuric acid and sodium sulfide nonahydrate, and includes a high-level sensor and a low-level sensor. Level sensors are used to monitor the high and low liquid levels of the reaction solution to ensure the safe conduct of the reaction. Pear-shaped separating funnel. 2-2 is used for adding sulfuric acid dropwise into the three-necked flask 2-1. Its automatic flow control valve, high-level sensor, and low-level sensor precisely control the dropping rate and quantity of sulfuric acid, thereby regulating the generation rate of hydrogen sulfide gas. Furthermore, the side port design of the three-necked flask 2-1 allows the generated hydrogen sulfide gas to be smoothly discharged and enter the subsequent hydrogen sulfide detection unit 3 and hydrogen sulfide corrosion collector unit 4.

[0020] The hydrogen sulfide detection unit 3 is used to detect the concentration and flow rate of hydrogen sulfide gas in real time, as well as for collection. The corrosion state of the fluid. The reaction monitoring camera 3-1 can visually monitor the current collector in the presence of hydrogen sulfide gas. The corrosion process in the specimens provides researchers with a direct view of the corrosion morphology. (Online spectrometer 3-3) This allows for the analysis of the gas composition produced during corrosion, providing further insight into the mechanism of the corrosion reaction. (Concentrated hydrogen sulfide) The 3-2 flow meter accurately measures the concentration and flow rate of hydrogen sulfide gas, ensuring the accuracy and repeatability of experimental conditions.

[0021] Hydrogen sulfide corrosion current collector unit 4 is used to place the current collector in the reaction vessel 4-1. A corrosion reaction occurs in the hydrogen sulfide gas environment. The design of reaction vessel 4-1 ensures the proper functioning of the hydrogen sulfide gas. It can make uniform contact with the current collector, thus fully simulating the corrosion conditions in the actual working environment. Meanwhile, Temperature and pressure detector 4-2 monitors the temperature and pressure inside the reaction vessel in real time to ensure safe experimental conditions. Fully stable.

[0022] Hydrogen sulfide tail gas absorption unit 5 is used to absorb and treat the hydrogen sulfide tail gas generated during the detection process. To ensure the safety and environmental friendliness of the testing, the primary adsorption bottle 5-1 and the secondary adsorption bottle 5-2 respectively... It contains high-concentration and low-concentration sodium hydroxide solutions for effective absorption of hydrogen sulfide gas. (Measured by a pH meter.) The detector 5-4 monitors the remaining sodium hydroxide in the adsorption bottle in real time, allowing for assessment of adsorption efficiency and timely replacement of the bottle to ensure optimal absorption. The hydrogen sulfide alarm 5-5 detects the concentration of hydrogen sulfide in the exhaust gas, ensuring it meets safety standards. Safe discharge is permitted only when the hydrogen sulfide concentration falls below the safety threshold. Furthermore, the exhaust system 5-6 further accelerates the absorption and treatment of exhaust gases, enhancing both the safety and environmental friendliness of the experiment.

[0023] Example 2 The method for detecting hydrogen sulfide corrosion in a solid-state battery current collector using the apparatus described in Example 1 specifically includes the following steps: S1: Add sulfuric acid dropwise from pear-shaped separatory funnel 2-2 to three-necked flask 2-1, 100 g / L Sulfuric acid reacts with 60 g / L sodium sulfide nonahydrate to produce hydrogen sulfide gas.

[0024] S2: Based on the readings of the hydrogen sulfide concentration and flow meter 3-2, use the pear-shaped separatory funnel 2-2. The automatic flow regulating valve on the device regulates the generation rate of hydrogen sulfide gas, with the hydrogen sulfide concentration controlled within the range of 7.0-8.5 g / L and the hydrogen sulfide flow rate controlled within the range of 4.0-5.5 L / (L•h).

[0025] S3: Hydrogen sulfide gas enters the reaction tank 4-1 to corrode the current collector. At the same time, the corrosion status of the current collector and the gas concentration therein are recorded in real time by the reaction monitoring camera 3-1 and the online spectrometer 3-3.

[0026] S4: Hydrogen sulfide gas enters the hydrogen sulfide tail gas absorption unit 5, and the pH meter 5-4 provides feedback on the sodium hydroxide balance in the primary adsorption bottle 5-1 and the secondary adsorption bottle 5-2, triggering a hydrogen sulfide alarm. Instrument 5-5 confirms whether the hydrogen sulfide concentration in the exhaust gas has dropped to the safe threshold, including the first-stage adsorption bottle 5-1. The sodium hydroxide concentration is 120 g / L, and its pH range should be controlled above 11. (This is from a secondary adsorption flask, part 5-2.) The sodium hydroxide concentration is 25 g / L, and its pH range should be controlled above 10. (Hydrogen sulfide alarm 5-5) The reading should be below 1.0 ppm.

[0027] S5: Close the automatic flow regulating valve on pear-shaped separatory funnel 2-2, and open the nitrogen flow meter to reduce the flow rate. Pressure valves 1-3 ensure that hydrogen sulfide gas inside the device is completely absorbed.

[0028] It should be noted that in this article, relational terms such as first and second are only used to refer to... Distinguishing one entity or operation from another does not necessarily require or imply these distinctions. There is no such actual relationship or order between entities or operations. Furthermore, the terms "including" and "package" do not apply. "Inclusion" or any other variation thereof is intended to cover non-exclusive inclusion, thereby including a range of elements. The process, method, article, or equipment includes not only those elements, but also those not explicitly listed. Other elements, or elements inherent to such a process, method, article, or apparatus.

[0029] The above are some limited preferred embodiments of the present invention, described in a relatively specific and detailed manner, but they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A hydrogen sulfide corrosion detection device for current collectors in solid-state batteries, characterized in that, It includes a nitrogen supply unit (1), a hydrogen sulfide reaction generation unit (2), a hydrogen sulfide detection unit (3), a hydrogen sulfide corrosion collector unit (4), and a hydrogen sulfide tail gas absorption unit (5) connected in series.

2. The hydrogen sulfide corrosion detection device for solid-state battery current collectors according to claim 1, Its features are, The nitrogen supply unit (1) is equipped with a nitrogen cylinder (1-1), a gas filter (1-2) and a nitrogen flow meter pressure reducing valve (1-3). The gas outlet of the nitrogen cylinder (1-1) is connected to the gas filter (1-2) and the nitrogen flow meter pressure reducing valve (1-3). The hydrogen sulfide reaction generating unit (2) is equipped with a three-necked flask (2-1) and a pear-shaped separating funnel (2-2). The three-necked flask (2-1) is equipped with a high liquid level sensor and a low liquid level sensor, and the pear-shaped separating funnel (2-2) is equipped with an automatic flow regulating valve, a high liquid level sensor and a low liquid level sensor. The hydrogen sulfide detection unit (3) is equipped with a reaction monitoring camera (3-1), a hydrogen sulfide concentration and flow meter (3-2), and an online spectrometer (3-3). The hydrogen sulfide corrosion current collector unit (4) is equipped with a reaction vessel (4-1) and a temperature and pressure detector (4-2). The hydrogen sulfide tail gas absorption unit (5) is equipped with a primary adsorption bottle (5-1), a secondary adsorption bottle (5-2), a gas collection bottle (5-3), a pH meter (5-4), a hydrogen sulfide alarm (5-5), and an exhaust system (5-6).

3. The hydrogen sulfide corrosion detection device for solid-state battery current collectors according to claim 2, Its features are, The outlet tube of the nitrogen cylinder (1-1) is connected to one of the two ports on either side of the three-necked flask (2-1), and the pear-shaped separatory funnel (2-2) is connected to the port in the middle of the three-necked flask (2-1). The other side of the bottle (2-1) is connected to the lower end of the hydrogen sulfide concentration and flow meter (3-2), and the upper end of the hydrogen sulfide concentration and flow meter (3-2) is connected to the reaction vessel (4-1). The other end of the interface is connected in sequence to the primary adsorption bottle (5-1), the secondary adsorption bottle (5-2), and the gas collecting bottle (5-3). A hydrogen sulfide alarm (5-5) is placed on the outlet side of the gas collecting cylinder (5-3).

4. A method for detecting hydrogen sulfide corrosion using the detection device as described in claim 3, characterized in that, Includes the following steps: S1: Add sulfuric acid dropwise from the pear-shaped separatory funnel (2-2) to the three-necked flask (2-1). The sulfuric acid reacts with sodium sulfide nonahydrate to produce hydrogen sulfide gas. S2: Based on the readings in the hydrogen sulfide concentration and flow meter (3-2), the generation rate of hydrogen sulfide gas is adjusted using the automatic flow regulating valve on the pear-shaped separatory funnel (2-2); S3: Hydrogen sulfide gas enters the reaction tank (4-1) to corrode the current collector. At the same time, the corrosion status of the current collector and the gas concentration therein are recorded in real time by the reaction monitoring camera (3-1) and the online spectrometer (3-3). S4: Hydrogen sulfide gas enters the hydrogen sulfide tail gas absorption unit (5) and passes through the pH meter detector (5-4). The remaining sodium hydroxide in the primary adsorption bottle (5-1) and the secondary adsorption bottle (5-2) is fed back, and the hydrogen sulfide alarm (5-5) confirms whether the concentration of hydrogen sulfide in the exhaust gas has dropped to the safe threshold. S5: Close the automatic flow regulating valve on the pear-shaped separatory funnel (2-2) and open the nitrogen flow meter pressure reducing valve (1-3) to ensure that the hydrogen sulfide gas in the device is completely absorbed.

5. The method according to claim 4, characterized in that, The concentration of sulfuric acid in S1 is 50-150 g / L, the concentration of sodium sulfate nonahydrate is 25-100 g / L, and the concentration ratio of sulfuric acid to sodium sulfate nonahydrate is 1.5:1-2.5:

1.

6. The method according to claim 4, characterized in that, The hydrogen sulfide concentration in S2 is 3.5-14.0 g / L, and the hydrogen sulfide flow rate is 2.0-9.0 L / (L•h).

7. The method according to claim 4, characterized in that, In S4, the sodium hydroxide concentration in the primary adsorption bottle (5-1) is 80-150 g / L, and its pH range should be controlled above 11. The sodium hydroxide concentration in the secondary adsorption bottle (5-2) is 20-40 g / L, and its pH range should be controlled above 10. The hydrogen sulfide concentration in the exhaust gas should be below 1.0 ppm.

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