Search

CN-121976153-A - High-entropy metal connector spinel coating and preparation method thereof

CN121976153ACN 121976153 ACN121976153 ACN 121976153ACN-121976153-A

Abstract

The invention relates to a spinel coating of a high-entropy metal connector and a preparation method thereof, belonging to the technical field of solid oxide batteries. The invention adopts in-situ preparation methods of matrix pretreatment, target material starting and pre-sputtering, sputtering deposition and thermal conversion to obtain the high-entropy metal connector spinel coating. The invention uses magnetron sputtering technology to prepare high-density multilayer metal coating, and forms spinel structure in situ through thermal conversion, and controls the thickness of the coating by controlling the number of sputtering deposition and thermal conversion cycles. By setting key technological parameters such as sputtering power, time, temperature and the like, the high-entropy oxidation coating with compact structure, strong binding force and excellent high-temperature oxidation resistance is obtained.

Inventors

  • NI HONGFEI

Assignees

  • 常州格睿克斯能源科技有限公司

Dates

Publication Date
20260505
Application Date
20251230

Claims (7)

  1. 1. A preparation method of a spinel coating of a high-entropy metal connector, which is characterized by comprising the following steps: S1, preprocessing a matrix, namely polishing the surface of ferrite stainless steel, washing with acid, respectively cleaning with ultrasonic waves in acetone and ethanol solution, and drying to obtain a preprocessed matrix; S2, starting the target, namely closing a baffle, setting the power to be 10-50W for starting under Ar atmosphere, then accelerating to be 0.5-5W/S with the pre-sputtering power, increasing the initial sputtering power to be 10-50W, maintaining for 10min, and removing pollutants and oxide layers on the surface of the target; S3, sputtering and depositing, namely setting the rotation speed of a sample disc to be 5-50 rpm, setting the distance between a target and a matrix to be 0.05-0.1 in, opening a baffle plate, starting sputtering by using a direct current magnetron sputtering process, wherein in the sputtering process, the sputtering power is 50-500W in Ar atmosphere, each target is sputtered for 30 seconds to obtain a metal layer with the thickness of about 4-6nm, repeating the sputtering for 10 times, alternately depositing metal coatings by adopting M1, M2, M3, M4 and M5 metal targets in sequence to obtain a multilayer metal coating with the structure of M1/M2/M3/M4/M5, wherein the M1, M2, M3, M4 and M5 metal targets are any five of Fe targets, co targets, ni targets, cu targets, mn targets, cr targets and Ti targets, and the five targets are different; S4, thermal conversion, namely placing the deposited multilayer metal coating sample into a muffle furnace for oxidization, and forming a (M1, M2, M3, M4, M5) 3 O 4 high-entropy spinel coating in situ; s5, repeating sputtering, namely repeating S3 and S4 on the high-entropy oxide sample with the coating to obtain the coating with the target thickness.
  2. 2. The method according to claim 1, wherein the pickling solution in the pickling process in step S1 is a 10wt.% sulfuric acid solution, and the pickling time is 30 to 50S.
  3. 3. The method according to claim 1, wherein the time for ultrasonic cleaning in acetone and ethanol solution after pickling the ferritic stainless steel in the step S1 is 10min.
  4. 4. The method according to claim 1, wherein the ferritic stainless steel in the step S1 is any one of SUS430, SUS441, SUS442, crofer22 APU, ZGM 235.
  5. 5. The method according to claim 1, wherein the oxidation temperature in the step S4 is 700 to 900 ℃ and the oxidation time is 10 to 50 h.
  6. 6. A high entropy metal connector spinel coating obtainable by the process of any one of claims 1 to 5.
  7. 7. Use of the high entropy metal connector spinel coating of claim 6 in solid oxide cells.

Description

High-entropy metal connector spinel coating and preparation method thereof Technical Field The invention belongs to the technical field of solid oxide batteries, and relates to a spinel coating of a high-entropy metal connector and a preparation method thereof. Background The solid oxide electrolytic cell (solid oxide electrolysis cells, SOECs) is used as an efficient and environment-friendly energy conversion device, and has wide application prospect in the fields of green hydrogen production and the like. The connector serves as a key component of SOECs and is responsible for connecting single cells in series and isolating electrodes. With the decrease of the working temperature of SOECs (650-800 ℃), ferritic stainless steel is an ideal material for the connector due to its good workability, low cost and thermal expansion coefficient matching with the battery assembly. However, ferritic stainless steels face significant oxidation resistance challenges in high temperature operating environments. The surface of the material is easy to form a Cr 2O3 oxide layer with poor conductivity, and the oxide layer is continuously thickened along with the extension of oxidation time, so that the Area Specific Resistance (ASR) of the connector is obviously increased. In addition, in an oxidizing atmosphere, cr element is precipitated in the form of volatile matters such as CrO 3 or CrO 2(OH)2 and diffuses to the cathode of the battery, which causes "cathode poisoning" and severely reduces the performance and service life of the battery. To inhibit the outdiffusion and volatilization of Cr element, a protective coating is often applied to the surface of the connector. The protective coating types mainly include active element oxide coatings, rare earth perovskite coatings, and spinel coatings. The high entropy spinel coating exhibits high oxidation resistance due to the high entropy effect. At present, the high-entropy oxide coating needs to be prepared into the high-entropy oxide firstly, and then the high-entropy oxide coating is coated on the surface of a substrate through traditional processes such as screen printing, thermal spraying and the like, but the coating prepared by the methods often has the problems of low density, weak binding force, multiple microscopic holes and the like, and the long-term protection effect of the coating is affected. The magnetron sputtering process can prepare a compact coating, but the sputtering is often carried out after the alloy target is smelted, so that the smelting cost of the alloy target is higher and the uniformity of components is poorer. Therefore, the development of the low-cost and high-efficiency high-entropy coating preparation method has important engineering application value for improving the oxidation resistance and service life of the SOECs metal connector. Disclosure of Invention Aiming at the problems of poor compactness, high cost of magnetron sputtering alloy targets, poor component uniformity, insufficient oxidation resistance of the coating and the like of the existing metal connector coating, the invention develops a low-cost high-entropy oxide coating in-situ preparation method, and obtains the high-entropy coating with compact structure, strong binding force and excellent high-temperature oxidation resistance. The technical scheme of the invention is as follows: a preparation method of a spinel coating of a high-entropy metal connector comprises the following steps: s1, preprocessing a matrix, namely polishing the surface of the ferrite stainless steel, washing with acid, respectively cleaning with ultrasonic waves in acetone and ethanol solution, and drying to obtain the preprocessed matrix. Preferably, the pickling solution in the pickling process is 10wt.% sulfuric acid solution, the pickling time is 30-50s, and the ultrasonic cleaning time in acetone and ethanol solutions is 10min. S2, starting the target, namely closing a baffle, setting the power to be 10-50W for starting under Ar atmosphere, then accelerating to be 0.5-5W/S with the pre-sputtering power, increasing the initial sputtering power to be 10-50W, maintaining for 10min, removing pollutants and oxide layers on the surface of the target, and improving the surface state of the target; s3, sputtering and depositing, namely setting the rotation speed of a sample disc to be 5-50 rpm, setting the distance between a target and a matrix to be 0.05-0.1 in, opening a baffle plate, starting sputtering by using a direct current magnetron sputtering process, wherein the sputtering power is 50-500W in Ar atmosphere, each target is sputtered for 30S to obtain a metal layer with the thickness of about 4-6nm, repeatedly sputtering for 10 times, alternately depositing metal coatings by adopting M1, M2, M3, M4 and M5 metal targets in sequence to obtain a multilayer metal coating with the structure of M1/M2/M3/M4/M5, wherein the M1, M2, M3, M4 and M5 metal targets are any five of Fe targets, co targets, ni t