An electrically conductive component, a method of making the same, and an energy conversion and storage device

Abstract

The present application relates to the technical field of energy conversion and storage, and particularly relates to a conductive component, a preparation method thereof and an energy conversion and storage device. The preparation method provided by the present application comprises the following steps: providing a conductive base material and a nitrogen source compound, and placing the conductive base material and the nitrogen source compound in a reaction environment; heating the nitrogen source compound and the conductive base material under an inert atmosphere, and making pyrolysis products of the nitrogen source compound carried by the inert atmosphere to flow through the surface of the conductive base material to perform a nitriding reaction; and performing post-treatment on the conductive base material after the nitriding reaction, so as to obtain a conductive component with a nitride protective layer formed on the surface. The present application can have the advantages of safety, economy and process simplification, so as to promote the popularization and practical application effect of the nitride protective layer technology in the energy conversion and storage device.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of energy conversion and storage, and in particular to a conductive component, a preparation method thereof and an energy conversion and storage device. BACKGROUND

[0002] Energy conversion and storage devices (such as electrolytic cells, fuel cells) can realize mutual conversion between electrical energy and chemical energy as key energy conversion equipment. Key conductive components such as electrodes, bipolar plates and porous transport layers in energy conversion and storage devices are usually made of metal or alloy materials. When exposed to air or in a high potential and strong corrosive operating environment, an oxide layer is easily formed on the surface of these conductive components or further corrosion occurs, which significantly increases the contact resistance and seriously restricts the overall performance and service life of the device.

[0003] To improve the oxidation resistance and corrosion resistance of the conductive component, a nitride protective layer with high conductivity can be constructed on the surface thereof, thereby effectively reducing the contact resistance and prolonging the service life of the component. At present, the preparation of the nitride protective layer mainly relies on the following three technical paths:

[0004] 1) Magnetron sputtering method: a nitride coating is deposited on the surface of the conductive substrate by using a magnetron sputtering device. This method has strict requirements on the surface state of the substrate, which needs to be free of oil stains, impurities and have appropriate roughness. The whole process needs to be carried out in a vacuum environment to prevent defects in the coating.

[0005] 2) Ammonia nitriding method: high-purity ammonia gas is used as a nitrogen source and a reducing agent, which is decomposed to generate active nitrogen species at high temperature, and then reacts with the surface of the conductive substrate to form a nitride protective layer.

[0006] 3) Nitrogen nitriding method: high-purity nitrogen gas is used as the reaction atmosphere, and the nitrogen gas reacts with the surface of the substrate under high temperature and vacuum conditions to form a nitride protective layer.

[0007] However, the above methods have obvious limitations: the magnetron sputtering process is complex, and the substrate pretreatment and equipment vacuum degree are required to be high; the ammonia nitriding method uses ammonia gas with high cost, which is toxic and explosive, and has safety hazards, which is not conducive to large-scale application; the nitrogen nitriding method relies on high temperature and high vacuum environment, which requires strict equipment and high energy consumption, and the utilization rate of nitrogen gas is low, resulting in high production cost.

[0008] These defects seriously restrict the promotion and practical application effect of the nitride protective layer technology in energy conversion and storage devices. Therefore, it is urgent to develop a new alternative scheme that is safer, more economical and simpler in process. SUMMARY

[0009] In order to solve the above problems, the present invention proposes a conductive component, a method for its preparation, and an energy conversion and storage device.

[0010] The first aspect of this invention provides a method for preparing a conductive component, comprising:

[0011] A conductive substrate and a nitrogen source compound are provided, and the conductive substrate and the nitrogen source compound are placed in a reaction environment;

[0012] A nitrogen source compound and a conductive substrate are heated under an inert atmosphere, and the pyrolysis products of the nitrogen source compound are carried by the inert atmosphere to flow over the surface of the conductive substrate to carry out a nitriding reaction.

[0013] The conductive substrate after nitriding reaction is post-treated to obtain a conductive component with a nitride protective layer formed on its surface.

[0014] Furthermore, the heat treatment includes heating the nitrogen source compound and / or the conductive substrate in stages.

[0015] Furthermore, the phased heating process includes:

[0016] First temperature control stage: The temperature of the reaction environment is controlled to rise from 0-25℃ to 280-320℃ at a heating rate of 1~30℃ / min, and the heating time is controlled to be 10~300 minutes;

[0017] Second temperature control stage: Maintain the reaction environment temperature at 280-320℃ for heating, and control the heating time to 1-50 minutes;

[0018] The third temperature control stage: The temperature of the reaction environment is controlled to rise from 280-320℃ to 880-920℃ at a heating rate of 1~30℃ / min, and the heating time is controlled to be 20~600 minutes.

[0019] Fourth temperature control stage: Maintain the reaction environment temperature at 880-920℃, and control the heating time to 1-50 minutes;

[0020] Fifth temperature control stage: The temperature of the reaction environment is controlled to drop from 880-920℃ to 80-120℃ at a heating rate of 1~40℃ / min, and the heating time is controlled to be 20~800min.

[0021] Furthermore, at least one of the following conditions must be met:

[0022] (1) The nitrogen mass percentage of the nitrogen source compound is 15-50%;

[0023] (2) The mass ratio of nitrogen source compound to conductive substrate is 0.01~10:1;

[0024] (3) Nitrogen source compounds include nitrogen fertilizers;

[0025] (4) The nitrogen source compound includes at least one of ammonium bicarbonate, calcium nitrate, urea, ammonium nitrate, glycine, thiourea or ammonium nitrite;

[0026] (5) The material of the conductive substrate includes at least one of metal, alloy or metal oxide;

[0027] (6) The conductive substrate contains at least one metallic element selected from titanium, copper, nickel, aluminum, niobium, iron, or cobalt;

[0028] (7) The nitride protective layer includes at least one of titanium nitride, copper nitride, nickel nitride, aluminum nitride, niobium nitride, iron nitride, or cobalt nitride;

[0029] (8) The inert atmosphere includes at least one of helium, krypton or neon;

[0030] (9) During the heat treatment and nitriding reaction, the pressure of the reaction environment is controlled at 3~8×10. 2 mmHg.

[0031] Furthermore, before heating the nitrogen source compound and the conductive substrate under an inert atmosphere, the process further includes: replacing the reaction environment with an inert atmosphere; after the reaction environment is filled with an inert atmosphere, continuously introducing an inert atmosphere into the reaction environment and allowing the inert atmosphere to flow sequentially through the nitrogen source compound and the conductive substrate.

[0032] Furthermore, the displacement gas operation includes: evacuating the reaction environment pressure to 1~8×10⁻⁶. -1 mmHg, then an inert gas is introduced until the reaction environment pressure is 3~8×10. 2 mmHg, repeat until the reaction environment is filled with an inert atmosphere; when continuously introducing an inert atmosphere into the reaction environment, the inert atmosphere is continuously introduced into the reaction environment at a flow rate of 1~80ccm.

[0033] Furthermore, the reaction apparatus providing the reaction environment includes any one of a vacuum tube furnace, a vacuum atmosphere furnace, or a box furnace; wherein, when the reaction apparatus is a vacuum tube furnace, the reaction environment includes a first temperature zone and a second temperature zone connected to the first temperature zone, the nitrogen source compound is placed in the first temperature zone, and the conductive substrate is placed in the second temperature zone; during the heating process, the temperatures of the first temperature zone and the second temperature zone can be controlled independently; an inert atmosphere is introduced from the first temperature zone, flows sequentially through the nitrogen source compound and the conductive substrate, and then flows out through the second temperature zone.

[0034] Furthermore, the post-treatment of the conductive substrate after nitriding includes: cooling the conductive substrate after nitriding to room temperature under an inert atmosphere with a flow rate of 1~80ccm; and / or, before the heat treatment, the conductive substrate is further cleaned, including: ultrasonically cleaning the conductive substrate with acetone, deionized water and ethanol respectively.

[0035] A second aspect of the present invention also provides a conductive component, which is prepared by the conductive component preparation method described above.

[0036] A third aspect of the present invention also provides an energy conversion and storage device, including the conductive component as described above.

[0037] The beneficial effects of this invention are as follows:

[0038] In this invention, nitrogen source compounds such as nitrogen fertilizers can be used as nitrogen sources and placed together with conductive substrates in a reaction environment. The pyrolysis products formed by the pyrolysis of nitrogen source compounds can directly react with the nitridation surface of conductive substrates to form a nitride protective layer, thereby improving the conductivity, corrosion resistance, and oxidation resistance of conductive components and effectively improving the performance and lifespan of energy conversion and storage devices.

[0039] Compared to magnetron sputtering and traditional ammonia and nitrogen nitriding methods, the nitriding reaction process on the conductive substrate surface of this invention can be carried out under normal pressure without maintaining vacuum conditions, and does not require high-end equipment. Furthermore, by using the pyrolysis products generated from the pyrolysis of nitrogen source compounds as the nitrogen source, high-purity atmospheric nitrogen source conditions are not required, avoiding waste of nitrogen source and improving the economic efficiency of the preparation process. In particular, it has high safety compared to the ammonia nitriding method, as the nitrogen source compounds are less hazardous and are superior to highly hazardous ammonia in terms of storage and use. In addition, the size of the conductive substrate processed by this invention is not limited and the preparation process is simple. The surface nitriding reaction time can be shortened to the range of 1 to 50 minutes, which is faster and more efficient.

[0040] In summary, this invention combines advantages such as safety, economy, and process simplification, thereby promoting the application and practical effectiveness of nitride protective layer technology in energy conversion and storage devices.

[0041] The summary section is provided to present the chosen concepts in a simplified form, which will be further described in the detailed description below. The summary section is not intended to identify essential or necessary features of this disclosure, nor is it intended to limit the scope of this disclosure. Attached Figure Description

[0042] The above and other objects, features and advantages of this disclosure will become more apparent from the accompanying drawings, in which like reference numerals generally denote like parts.

[0043] Figure 1 A schematic diagram of the nitriding process of a conductive substrate according to an embodiment of the present invention is shown;

[0044] Figure 2 The diagram shows the morphology of the conductive substrate before and after nitriding according to an embodiment of the present invention; the left side shows the morphology of the conductive substrate after nitriding, and the right side shows the morphology of the conductive substrate before nitriding.

[0045] Figure 3 The energy dispersive spectrum of the conductive component obtained according to an embodiment of the present invention is shown;

[0046] Figure 4 A schematic diagram comparing the hydrogen production performance of an electrolyzer using an unnitrided conductive substrate and a nitrided conductive component obtained according to embodiments of the present invention is shown.

[0047] Figure 5 A schematic diagram comparing the durability of an electrolytic cell with an unnitrided conductive substrate and a nitrided conductive component obtained by applying embodiments of the present invention is shown.

[0048] Figure 6 A schematic diagram showing the comparison of interfacial contact resistance before and after nitriding of the conductive substrate according to an embodiment of the present invention is provided.

[0049] The accompanying figure is labeled as follows:

[0050] 1. Reaction apparatus; 2. First temperature zone; 3. Second temperature zone; 4. Inert atmosphere; 5. Mixed gas; 6. Reactor dish; 7. Stand; 8. Nitrogen source compound; 9. Conductive substrate. Detailed Implementation

[0051] Embodiments of the present disclosure will now be described in more detail with reference to the accompanying drawings. While embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the present disclosure will be thorough and complete, and will fully convey the scope of the present disclosure to those skilled in the art.

[0052] The term "comprising" and its variations as used herein signify open inclusion, i.e., "including but not limited to". Unless otherwise stated, the term "or" means "and / or". The term "based on" means "at least partially based on". The terms "one example embodiment" and "one embodiment" mean "at least one example embodiment". The term "another embodiment" means "at least one additional embodiment". The terms "first", "second", etc., may refer to different or the same objects. Other explicit and implicit definitions may also be included below.

[0053] It should be noted that the reference Figure 1 As shown, Figure 1 The assembly process of the magnetic block and magnetic pole clamping structure in the embodiment of the present invention is illustrated.

[0054] As for the foregoing, the general inventive concept of this invention is to use nitrogen source compounds such as nitrogen fertilizers as the nitrogen source. The nitrogen source compounds are heated and decomposed to generate pyrolysis products, which then undergo a nitriding reaction with the surface of a conductive substrate. Compared to magnetron sputtering and traditional ammonia or nitrogen nitriding methods, this invention uses nitrogen source compounds as the nitrogen source to nitrid the conductive substrate, eliminating the need to control the surface roughness of the conductive substrate, and requiring neither expensive equipment nor complex processes. Furthermore, this method can be carried out under normal pressure conditions. The nitrogen source compounds are safe and reliable nitrogen sources, posing no safety hazards and are superior to highly hazardous ammonia in terms of storage and use. This significantly reduces the difficulty and cost of nitriding and increases safety. In addition, the nitriding process is relatively gentle and stable, and the prepared nitride protective layer exhibits good uniformity and controllable thickness.

[0055] Based on the above general inventive concept, embodiments of the present invention provide a method for preparing a conductive component, comprising:

[0056] A conductive substrate and a nitrogen source compound are provided, and the conductive substrate and the nitrogen source compound are placed in a reaction environment;

[0057] A nitrogen source compound and a conductive substrate are heated under an inert atmosphere, and the pyrolysis products of the nitrogen source compound are carried by the inert atmosphere to flow over the surface of the conductive substrate to carry out a nitriding reaction.

[0058] The conductive substrate after nitriding reaction is post-treated to obtain a conductive component with a nitride protective layer formed on its surface.

[0059] It is understandable that when the conductive substrate and the nitrogen source compound are placed together in the reaction environment, under the protection of an inert atmosphere, the nitrogen source compound can generate gaseous pyrolysis products (such as ammonia) by heating. The inert atmosphere, as a carrier gas, can carry the nitrogen source compound to the surface of the conductive substrate, thereby reacting with the surface of the conductive substrate to generate a nitride protective layer. The resulting conductive component, due to the presence of the nitride protective layer, has higher conductivity, corrosion resistance, and oxidation resistance compared to the conductive substrate that has not undergone nitriding.

[0060] Furthermore, since a non-atmospheric nitrogen source compound is used as the nitrogen source, it is safer to store and use compared to the more dangerous ammonia gas. As a common and readily available nitride, the nitrogen source compound can undergo a pyrolysis reaction at a certain temperature to generate ammonia gas. By controlling the pyrolysis heating time of the nitrogen source compound, the required amount of nitrogen source can be obtained, avoiding waste of nitrogen source and greatly improving economic efficiency. The nitriding process of the conductive substrate of this invention can be carried out under normal pressure conditions, avoiding reliance on vacuum equipment and reducing equipment investment and maintenance costs. In addition, the conductive substrate is not limited by size, does not need to control its surface roughness, and the preparation process is simple. The nitriding treatment time can be only 10~50 minutes, which is short and efficient, making it more conducive to large-scale production. The formed titanium nitride protective layer does not change the original structure of the conductive substrate, the degree of nitriding has good uniformity, and the thickness of the nitrided layer is controllable.

[0061] In some embodiments, the nitrogen source compound can be nitrogen fertilizer, which refers to a unit fertilizer with nitrogen (N) as its main component, a specified N content, and which provides nitrogen nutrition to plants when applied to the soil. By using nitrogen fertilizer as the nitrogen source, nitrogen fertilizer can generate atmospheric pyrolysis products such as ammonia during the heating process. By controlling parameters such as the temperature and time of the heating process, the required amount of atmospheric nitrogen source can be obtained. Compared with directly using nitrogen or ammonia as the nitrogen source, nitrogen fertilizer is non-toxic and inexpensive, which can reduce the difficulty and cost of nitrification treatment and increase safety.

[0062] In some embodiments, when the nitrogen source compound is a nitrogen fertilizer, it includes at least one of ammonium bicarbonate, calcium nitrate, urea, and ammonium nitrate. These compounds, as inexpensive and safe nitrogen sources, can replace hazardous ammonia, reducing costs and safety hazards. Moreover, these compounds, as nitrogen sources, exhibit mild pyrolysis characteristics during heat treatment, making it easier to control the reaction rate of the nitriding reaction.

[0063] It should be understood that, in some embodiments, the nitrogen source compound may also be other nitrogen-containing compounds other than nitrogen fertilizers, including at least one of glycine, thiourea or ammonium nitrite, which can also provide pure nitrogen species to improve the quality of the nitride protective layer.

[0064] In some embodiments, the nitrogen mass percentage of the nitrogen source compound is 15-50%. Within this range, it is more conducive to the participation of sufficient nitrogen in the reaction and to avoid resource waste. A nitrogen mass percentage of less than 15% is not conducive to the integrity of the nitride protective layer, while a percentage higher than 50% is not conducive to cost control and is prone to over-reaction.

[0065] In some embodiments, the mass ratio of nitrogen source compound to conductive substrate is 0.01 to 10:1. Within this mass ratio range, it is more conducive to ensuring economy and nitriding reaction efficiency. It should be understood that excessive nitrogen source compound will not significantly improve the effect, but will increase the burden of exhaust gas treatment, which is not conducive to process simplification and improving economy.

[0066] In some embodiments, the material of the conductive substrate includes at least one of metal, alloy, or metal oxide; for example, the material of the conductive substrate can be titanium metal to obtain a titanium metal conductive component with a titanium nitride protective layer. However, the material treated by the nitriding reaction in the embodiments of this application is not limited to metal, but can also be an alloy or metal oxide (e.g., titanium alloy or titanium oxide), as long as it can ensure that a nitriding reaction occurs with the nitrogen source compound and that it is conductive.

[0067] In some embodiments, the conductive substrate contains at least one metallic element selected from titanium, copper, nickel, aluminum, niobium, iron, or cobalt. These metallic elements can ensure that the conductive substrate has high conductivity and is easy to form stable nitrides to meet the requirements of different electrochemical devices.

[0068] In some embodiments, the nitride protective layer includes at least one of titanium nitride, copper nitride, nickel nitride, aluminum nitride, niobium nitride, iron nitride, or cobalt nitride. It is understood that, depending on the selection of the conductive substrate, the nitride protective layer may be titanium nitride, copper nitride, nickel nitride, aluminum nitride, niobium nitride, iron nitride, or cobalt nitride. For example, when the conductive substrate is titanium, the nitride protective layer may be titanium nitride; when the conductive substrate is niobium, the nitride protective layer may be niobium nitride.

[0069] In some embodiments, the inert atmosphere includes at least one of helium, krypton, or neon. These gases have high chemical stability as inert atmospheres and can effectively prevent oxidation reactions on the surface of the conductive substrate. Among them, helium has high thermal conductivity, which is beneficial for temperature uniformity, while krypton and neon have high density, which helps to stabilize the atmosphere.

[0070] In some embodiments, both the heat treatment and the nitriding reaction of the conductive substrate are carried out at atmospheric pressure, eliminating the need for a vacuum environment and thus saving equipment costs. For example, during the heat treatment and nitriding reaction, the pressure of the reaction environment is controlled at 3~8×10⁻⁶. 2 Within the mmHg range, this facilitates process simplification and improves economic efficiency, promoting the application of nitride protective layer technology in energy conversion and storage devices.

[0071] In some embodiments, the heat treatment includes staged heating of the nitrogen source compound and / or the conductive substrate. Staged heating optimizes the nitriding reaction kinetics by precisely controlling the rate of temperature change and the holding time, ensuring a smooth release of nitrogen fertilizer pyrolysis products and avoiding unevenness of the protective layer or damage to the substrate caused by sudden temperature changes. This improves the density and bonding strength of the protective layer. In other words, it facilitates a smoother and more stable nitriding process, resulting in a titanium nitride protective layer with good uniformity and controllable thickness.

[0072] It should be understood that the heat treatment of the nitrogen source compound and the conductive substrate can be the same or different. For example, the heat treatment time and temperature of the nitrogen source compound can be exactly the same or similar to the heat treatment time and temperature of the conductive substrate, or the heat treatment time and temperature of the nitrogen source compound can be both less than the heat treatment time and temperature of the conductive substrate.

[0073] Furthermore, the above-mentioned staged heating process includes:

[0074] First temperature control stage: The temperature of the reaction environment is controlled to rise from 0-25℃ to 280-320℃ at a heating rate of 1~30℃ / min, and the heating time is controlled to be 10~300 minutes;

[0075] Second temperature control stage: Maintain the reaction environment temperature at 280-320℃ for heating, and control the heating time to 1-50 minutes;

[0076] The third temperature control stage: The temperature of the reaction environment is controlled to rise from 280-320℃ to 880-920℃ at a heating rate of 1~30℃ / min, and the heating time is controlled to be 20~600 minutes.

[0077] Fourth temperature control stage: Maintain the reaction environment temperature at 880-920℃, and control the heating time to 1-50 minutes;

[0078] Fifth temperature control stage: The temperature of the reaction environment is controlled to drop from 880-920℃ to 80-120℃ at a heating rate of 1~40℃ / min, and the heating time is controlled to be 20~800min.

[0079] It should be noted that the first temperature control stage involves slow heating to remove adsorbed moisture and impurities from the conductive substrate surface, avoiding thermal shock, and simultaneously initiating the initial pyrolysis of nitrogen source compounds, laying the foundation for subsequent high-temperature reactions. In the second temperature control stage, the heat preservation phase stabilizes the pyrolysis process, ensuring uniform distribution of nitrogen source compound pyrolysis products, promoting the formation of initial nitride nuclei on the conductive substrate surface, and improving the uniformity of the protective layer. The third temperature control stage is the main nitride reaction zone, where the reactivity of metals and nitrogen species is enhanced at high temperatures, forming a dense nitride layer. Controlling the heating rate during this process prevents excessively rapid crystal growth, ensuring controllable nitride protective layer thickness. The high-temperature heat preservation in the fourth temperature control stage ensures complete nitride reaction, eliminating unreacted areas, while simultaneously promoting crystal structure stabilization, releasing thermal stress, and improving the mechanical properties of the nitride protective layer. The fifth temperature control stage involves slow cooling to reduce thermal stress accumulation, preventing cracking or peeling of the nitride protective layer, thereby optimizing interfacial bonding strength and ensuring long-term reliability.

[0080] In some embodiments, before heating the nitrogen source compound and the conductive substrate under an inert atmosphere, the method further includes: purging the reaction environment with an inert atmosphere; after the reaction environment is filled with an inert atmosphere, continuously introducing an inert atmosphere into the reaction environment and allowing the inert atmosphere to flow sequentially through the nitrogen source compound and the conductive substrate.

[0081] During the displacement gas operation, an inert atmosphere is injected into the reaction environment to remove moisture and oxygen. After the displacement gas operation is completed, the moisture and oxygen content in the reaction environment is significantly reduced, preventing oxidation of the conductive substrate and waste of the nitrogen source compound. Once the reaction environment is filled with an inert atmosphere, an inert atmosphere is continuously introduced into the reaction environment, flowing sequentially through the nitrogen source compound and the conductive substrate. This facilitates the efficient transport of the pyrolysis products of the nitrogen source compound to the surface of the conductive substrate for nitriding reaction. Those skilled in the art can adjust the pressure and inert gas flow rate involved in the displacement gas process according to the specific application requirements.

[0082] In some embodiments, the displacement gas operation includes: evacuating the reaction environment pressure to 1~8×10⁻⁶. -1 mmHg, then an inert gas is introduced until the reaction environment pressure is 3~8×10. 2 mmHg, repeat until the reaction environment is filled with an inert atmosphere; for example, evacuate the reaction environment pressure to a negative pressure of 2 × 10⁻⁶ mmHg. -1 mmHg, then argon gas is introduced into the reaction environment until the pressure of the reaction environment is 3~8×10. 2 mmHg, then the reaction environment pressure is evacuated to a negative pressure of 2×10 -1 mmHg, then argon gas is introduced into the reaction environment until the pressure of the reaction environment is 3~8×10. 2 mmHg, complete the gas replacement operation.

[0083] In some embodiments, when an inert atmosphere is continuously introduced into the reaction environment, the inert atmosphere is continuously introduced into the reaction environment at a flow rate of 1-80 ccm. After the purging gas operation is completed, the conductive substrate and the nitrogen source compound are purged with an inert atmosphere (e.g., argon) at a flow rate of 1-80 ccm. This facilitates the efficient transport of the pyrolysis products of the nitrogen source compound to the surface of the conductive substrate for nitriding reaction by the inert atmosphere. Introducing an inert atmosphere in the flow rate range of 1-80 ccm is also beneficial for optimizing mass transfer efficiency and avoiding uneven reaction caused by excessively fast gas flow.

[0084] In some embodiments, the reaction apparatus providing the reaction environment includes any one of a vacuum tube furnace, a vacuum atmosphere furnace, or a box furnace, all of which can perform pyrolysis treatment of nitrogen source compounds and conductive substrates.

[0085] In some embodiments, when the reaction apparatus is a vacuum tube furnace, the reaction environment includes a first temperature zone and a second temperature zone connected to the first temperature zone. The nitrogen source compound is placed in the first temperature zone, and the conductive substrate is placed in the second temperature zone. During the heating process, the temperatures of the first and second temperature zones can be controlled independently to facilitate precise management of the pyrolysis reaction of the nitrogen source compound and the nitriding reaction of the conductive substrate. An inert atmosphere is introduced from the first temperature zone, flows sequentially through the nitrogen source compound and the conductive substrate, and then flows out through the second temperature zone to facilitate the efficient transport of the pyrolysis products of the nitrogen source compound to the surface of the conductive substrate for nitriding reaction by the inert atmosphere.

[0086] In some embodiments, post-treatment of the conductive substrate after nitriding includes cooling the conductive substrate after nitriding to room temperature under an inert atmosphere and a flow rate of 1-80 ccm to prevent deformation and cracking of the nitride protective layer.

[0087] In some embodiments, prior to the heat treatment, the conductive substrate is further cleaned, including ultrasonic cleaning of the conductive substrate with acetone, deionized water and ethanol respectively, to remove oil and impurities from the surface of the conductive substrate, improve the adhesion of the nitride protective layer and ensure performance stability.

[0088] Another embodiment of the present invention also provides a conductive component, which is prepared by the conductive component preparation method described above.

[0089] The conductive component in this embodiment of the invention has a uniform and dense nitride protective layer on its surface, which significantly reduces the interfacial contact resistance compared to the non-nitride conductive substrate, significantly improves oxidation and corrosion resistance, and extends service life.

[0090] Another embodiment of the present invention provides an energy conversion and storage device, including the conductive components described above.

[0091] The energy conversion and storage device in the embodiments of the present invention can be an electrochemical energy storage device and can have the above-mentioned conductive components, wherein the conductive components can be other conductive components such as bipolar plates (BP), porous transport layers (PTL) or electrodes.

[0092] To demonstrate the advantages of the method provided by this invention, a specific embodiment is described below. (Reference) Figure 1 As shown, Figure 1 A schematic diagram of the nitriding process of the conductive substrate 1 according to an embodiment of the present invention is shown. The reaction device 1 providing the reaction environment is a vacuum tube furnace. This vacuum tube furnace is a dual-temperature zone high-temperature vacuum tube furnace, that is, the heating chamber of the vacuum tube furnace has two independent heating zones to precisely control the temperature of different zones. The left side of the vacuum tube furnace is the first temperature zone 2, and the right side is the second temperature zone 3. The left temperature zone 1 is used to place the nitrogen source compound 8, and the right temperature zone is used to place the conductive substrate 9. Argon gas is introduced into the left side of the vacuum tube furnace through the gas inlet to provide an inert atmosphere 4 and prevent oxidation. At the outlet valve pipe on the right side of the vacuum tube furnace, an external anti-backflow and exhaust gas treatment device is installed.

[0093] During the preparation process, the titanium metal conductive substrate 9 was ultrasonically cleaned for 5 minutes with acetone, deionized water and ethanol respectively to ensure the surface cleanliness of the titanium metal conductive substrate 9. Nitrogen fertilizer with a nitrogen content of 35% was used as nitrogen source compound 8. The mass ratio of nitrogen fertilizer to cleaned titanium metal conductive substrate 9 was 0.01~10:1. The nitrogen fertilizer was placed in the reactor dish 6 and the prepared titanium metal conductive substrate 7 was placed on the built platform 7 and placed together in the two temperature zones of the high temperature vacuum tube furnace.

[0094] Then, the gas purging operation is performed in the heating chamber of the tubular furnace: the pressure in the heating chamber of the high-temperature vacuum tubular furnace is evacuated to a negative pressure of 1×10⁻⁶. -1 mmHg, then argon gas is introduced into the heating chamber until the pressure inside the heating chamber is 3×10. 2 mmHg, complete the first gas replacement, and pump the pressure in the heating chamber back up to 1×10. -1 After reaching a pressure of 3 × 10 mmHg, argon gas is introduced into the heating chamber until the pressure reaches 3 × 10 mmHg. 2 mmHg, complete the second purging operation. After the purging operation, ensure that argon gas flows into the heating chamber at a flow rate of 1~80ccm for purging, and open the valve connecting the anti-backflow device to ensure that the pressure in the heating chamber is stable at 3×10. 2 mmHg; The valve of the anti-backflow device allows the pyrolysis products of nitrogen fertilizer to be discharged through the valve after forming a mixed gas 5 with argon during the subsequent heating process, thus avoiding backflow;

[0095] Next, the nitrogen fertilizer and the titanium metal conductive substrate 9 were simultaneously heated in stages: the same multi-stage heating program was set for the two temperature zones of the vacuum tube furnace. In the first temperature control stage, the heating program was set at 0℃-300℃ at a heating rate of 15℃ / min for 20 minutes; in the second temperature control stage, the heating temperature was maintained at 300℃ for 25 minutes; in the third temperature control stage, the heating program was set at 300℃-900℃ at a heating rate of 15℃ / min for 40 minutes; in the fourth temperature control stage, the heating temperature was maintained at 900℃ for 25 minutes; in the fifth temperature control stage, the heating program was set at 900℃-100℃ at a heating rate of 20℃ / min for 40 minutes. After the heating program ended, the nitriding reaction was completed. Finally, the two temperature zones of the high-temperature vacuum tube furnace were cooled to room temperature while maintaining argon gas purging at a flow rate of 40ccm to obtain a titanium metal conductive component with a titanium nitride protective layer.

[0096] It should be noted that in this embodiment, the nitrogen fertilizer is ammonium bicarbonate, and the titanium metal conductive substrate is titanium felt (i.e., a felt-like porous material made from pure titanium as raw material through felting and ultra-high temperature vacuum sintering process). The reactor dish 6 and the stand 7 for placing the nitrogen fertilizer and the titanium metal conductive substrate can be made of alumina. In other embodiments not shown, the reactor dish 6 and the stand 7 can also be replaced by other materials that are resistant to high temperature and do not participate in the nitriding reaction, such as quartz, yttrium oxide, silicon carbide, zirconium oxide, etc.

[0097] To verify the advantages of this embodiment, refer to Figure 2 As shown, images were acquired of the titanium metal conductive component with the titanium nitride protective layer prepared in this embodiment and the unnitrided titanium metal conductive substrate, respectively, to obtain schematic diagrams of the morphology of the conductive substrate before and after nitriding. It can be found that a titanium nitride protective layer is formed on the surface of the nitrided titanium metal conductive substrate.

[0098] Furthermore, the titanium metal conductive component with a titanium nitride protective layer prepared in this embodiment was subjected to EDS characterization tests, and the results were as follows: Figure 3 The energy dispersive spectrum shown; combined with Figure 3 It can be observed that the surface of the titanium metal conductive component has a dense and uniform distribution of N and Ti elements, indicating that a titanium nitride protective layer has been formed.

[0099] To verify the performance improvement of the energy conversion and storage device by the titanium conductive component with a titanium nitride protective layer prepared in this embodiment, the surface-nitride-treated titanium conductive component and the untreated titanium conductive substrate prepared in this embodiment were respectively assembled as electrodes in an electrolyzer for hydrogen production performance testing and durability testing. Figure 4 The diagram showing the comparison of hydrogen production performance and Figure 5 The diagram shows a comparison of durability performance. Combined with... Figure 4It can be observed that, under the same current density, the electrolysis voltage of the surface-nitrided titanium conductive component is significantly lower than that of the untreated titanium conductive substrate, indicating that the titanium conductive component prepared in this embodiment effectively reduces the overpotential during electrolysis and improves hydrogen production efficiency. Combined with... Figure 5 It can be observed that titanium metal conductive components with titanium nitride protective layers exhibit lower electrolytic voltage fluctuations after 10K cycles. This indicates that the titanium nitride protective layer effectively isolates the substrate from direct contact with the corrosive environment. The titanium nitride protective layer grows in situ on the substrate surface and remains intact during long-term operation. The high conductivity of the titanium nitride protective layer itself does not significantly decrease during long-term use.

[0100] To verify the improved interfacial contact resistance of the titanium conductive component with a titanium nitride protective layer prepared in this embodiment, the interfacial contact resistance values ​​of the titanium conductive component with a titanium nitride protective layer prepared in this embodiment and the untreated titanium conductive substrate were tested under different pressures. The comparison chart is shown below. Figure 6 As shown, it can be observed that throughout the entire pressure test range, the contact resistance of the titanium conductive component with a titanium nitride protective layer is significantly lower than that of the untreated titanium conductive substrate.

[0101] The various embodiments of this disclosure have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A method for preparing a conductive component, characterized in that, include: A conductive substrate and a nitrogen source compound are provided, and the conductive substrate and the nitrogen source compound are placed in a reaction environment; The nitrogen source compound and the conductive substrate are heated under an inert atmosphere, and the pyrolysis products of the nitrogen source compound are carried by the inert atmosphere and flow through the surface of the conductive substrate to carry out a nitriding reaction. The conductive substrate after the nitriding reaction is post-treated to obtain a conductive component with a nitride protective layer formed on its surface; The heating treatment includes heating the nitrogen source compound and / or the conductive substrate in stages, and the staged heating includes: a first temperature control stage: controlling the temperature of the reaction environment to rise from 0-25℃ to 280-320℃ at a heating rate of 1~30℃ / min, with the heating time controlled to be 10~300 minutes; a second temperature control stage: maintaining the temperature of the reaction environment at 280-320℃ for heating, with the heating time controlled to be 1~50 minutes; a third temperature control stage: heating at a rate of 1~3... The temperature of the reaction environment is controlled to rise from 280-320℃ to 880-920℃ at a heating rate of 0℃ / min, and the heating time is controlled to be 20-600 minutes; the fourth temperature control stage: the temperature of the reaction environment is maintained at 880-920℃, and the heating time is controlled to be 1-50 minutes; the fifth temperature control stage: the temperature of the reaction environment is controlled to drop from 880-920℃ to 80-120℃ at a heating rate of 1-40℃ / min, and the heating time is controlled to be 20-800 minutes; The reaction apparatus is a vacuum tube furnace. The reaction environment includes a first temperature zone and a second temperature zone connected to the first temperature zone. The nitrogen source compound is placed in the first temperature zone, and the conductive substrate is placed in the second temperature zone. During the heating process, the temperatures of the first temperature zone and the second temperature zone can be controlled independently. The inert atmosphere is introduced through the first temperature zone, flows sequentially through the nitrogen source compound and the conductive substrate, and then flows out through the second temperature zone.

2. The method for preparing the conductive component according to claim 1, characterized in that, At least one of the following conditions must be met: (1) The nitrogen mass percentage of the nitrogen source compound is 15-50%; (2) The mass ratio of the nitrogen source compound to the conductive substrate is 0.01~10:1; (3) The nitrogen source compounds include nitrogen fertilizers; (4) The nitrogen source compound includes at least one of ammonium bicarbonate, calcium nitrate, urea, ammonium nitrate, glycine, thiourea or ammonium nitrite; (5) The material of the conductive substrate includes at least one of metal, alloy or metal oxide; (6) The conductive substrate contains at least one metallic element selected from titanium, copper, nickel, aluminum, niobium, iron, or cobalt; (7) The nitride protective layer includes at least one of titanium nitride, copper nitride, nickel nitride, aluminum nitride, niobium nitride, iron nitride, or cobalt nitride; (8) The inert atmosphere includes at least one of helium, krypton or neon; (9) During the heat treatment and nitriding reaction, the pressure of the reaction environment is controlled at 3~8×10. 2 mmHg.

3. The method for preparing the conductive component according to any one of claims 1 to 2, characterized in that, Before heat treatment of the nitrogen source compound and the conductive substrate under an inert atmosphere, the process further includes: The reaction environment is purged with an inert atmosphere. After the reaction environment is filled with the inert atmosphere, the inert atmosphere is continuously introduced into the reaction environment, and the inert atmosphere flows sequentially through the nitrogen source compound and the conductive substrate.

4. The method for preparing the conductive component according to claim 3, characterized in that, The displacement gas operation includes: evacuating the reaction environment pressure to 1~8×10⁻⁶. -1 mmHg, then an inert gas is introduced until the reaction environment pressure is 3~8×10. 2 mmHg, repeat until the reaction environment is filled with the inert atmosphere; When the inert atmosphere is continuously introduced into the reaction environment, the inert atmosphere is continuously introduced into the reaction environment at a flow rate of 1~80ccm.

5. The method for preparing a conductive component according to any one of claims 1 to 2, characterized in that, Post-treatment of the conductive substrate after nitriding includes: cooling the conductive substrate to room temperature under an inert atmosphere and a flow rate of 1-80 ccm; and / or, Prior to the heat treatment, the conductive substrate is further cleaned by ultrasonic cleaning with acetone, deionized water and ethanol respectively.

6. A conductive component, characterized in that, It is prepared by the method for preparing conductive components as described in any one of claims 1 to 5.

7. An energy conversion and storage device, characterized in that, Includes the conductive component as described in claim 6.

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