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CN-121972651-A - Multi-component high-entropy alloy nickel ferrite composite anode material and preparation method thereof

CN121972651ACN 121972651 ACN121972651 ACN 121972651ACN-121972651-A

Abstract

The invention belongs to the technical field of powder metallurgy, and particularly relates to a multi-component high-entropy alloy nickel ferrite composite anode material and a preparation method thereof. The invention obviously improves the overall performance of the anode through the cooperation of the high-entropy alloy and the nickel ferrite, the high-entropy alloy provides good conductivity and structural support, and the nickel ferrite provides excellent corrosion resistance and electrochemical inertia. In addition, the preparation method of the anode material has the advantages of controllable process and abundant raw materials, and is suitable for industrial amplification. The example results show that the anode material provided by the invention has high density and excellent corrosion resistance.

Inventors

  • YANG WENJIE
  • QIAO MU
  • HUANG YINGDE
  • SHI CHENYANG
  • ZHU GUANGLI
  • ZHAN YIYANG

Assignees

  • 郑州大学

Dates

Publication Date
20260505
Application Date
20260130

Claims (10)

  1. 1. A multi-component high-entropy alloy nickel ferrite composite anode material, which is characterized by comprising a high-entropy alloy and NiFe 2 O 4 ; the high entropy alloy includes Fe, co, ni and Cr, and any one or more of Mn, al, ti and Mo.
  2. 2. The preparation method of the multi-component high-entropy alloy nickel ferrite composite anode material is characterized by comprising the following steps of: S1, weighing metal simple substance powder according to an equal atomic ratio, ball-milling the powder, drying the powder, and performing heat treatment on the dried powder to obtain high-entropy alloy powder, wherein the heat treatment comprises the steps of placing the powder in a flash evaporation Joule furnace, introducing a reducing atmosphere, heating to 650-850 ℃ in the flash evaporation Joule furnace at 500-1000 ℃ per second under the flowing reducing atmosphere, preserving heat for 60-120S, vacuumizing and performing flash evaporation discharge at 160-180 v; S2, mixing, ball milling and drying high-entropy alloy powder and NiFe 2 O 4 powder, performing compression molding by using cold isostatic pressing equipment after ball milling, placing the pressed powder in a tubular furnace, firstly heating to 1000-1200 ℃ at a heating rate of 10 ℃ per minute, preserving heat for 60-90min in Ar atmosphere, and then heating to 1250-1450 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 90-120min in Ar-1%O 2 atmosphere to obtain the multi-component high-entropy alloy nickel ferrite composite anode material; the metal simple substance powder comprises Fe, co, ni and Cr, and also comprises any one or more of Mn, al, ti and Mo.
  3. 3. The preparation method of the alloy powder according to claim 2, wherein the ball milling in the step S1 is to put hard alloy or stainless steel balls and powder into a ball milling tank according to the mass ratio of the ball powder of 6-10:1, and to add absolute ethyl alcohol or acetone to cover the ball powder, and then to introduce inert gas as protective gas; the rotation speed of the ball mill is 360-500rpm, the ball milling time is 36-60h, and the ball milling time lasts for 5-10min every 1 h.
  4. 4. The method according to claim 2, wherein the step S1 is performed by drying the powder after ball milling in a vacuum oven at 80-100℃for 12-16 hours.
  5. 5. The method according to claim 2, wherein the flow rate of the reducing atmosphere in the step S1 is more than 100 mL/min, and the reducing atmosphere is hydrogen.
  6. 6. The method according to claim 2, wherein the NiFe 2 O 4 powder in step S2 has a particle size of 5-15 μm.
  7. 7. The preparation method according to claim 2, wherein the mass ratio of the high-entropy alloy powder to the NiFe 2 O 4 powder in the step S2 is 25-30:70-75.
  8. 8. The preparation method according to claim 2, wherein the ball milling in the step S2 is to put hard alloy balls and powder into a ball milling tank according to the mass ratio of the ball powder being 8:1, add equal volume of absolute ethyl alcohol and introduce Ar as protective gas for ball milling for 10-16 hours, and the rotating speed is 180-300 rpm.
  9. 9. The method according to claim 2, wherein the drying in step S2 is performed by placing the powder after ball milling in a vacuum drying oven and drying at 70-80 ℃ for 10-12 hours.
  10. 10. Use of the anode material of claim 1, or the anode material prepared by the method of any one of claims 2-9, in aluminum electrolysis.

Description

Multi-component high-entropy alloy nickel ferrite composite anode material and preparation method thereof Technical Field The invention belongs to the technical field of powder metallurgy, and particularly relates to a multi-component high-entropy alloy nickel ferrite composite anode material and a preparation method thereof. Background In the conventional aluminum electrolysis process, a carbon anode is widely used. The method can continuously consume and generate a large amount of carbon dioxide greenhouse gases in the electrolysis process, which not only causes the loss of raw materials, but also causes serious problems of carbon emission and environmental pollution. Therefore, developing an inert anode that is dimensionally stable, low-consumption, and even non-consumption in the electrolysis process to replace the traditional carbon anode has become a key technical goal for realizing green low-carbon transformation in the aluminum metallurgy industry. The inert anode material needs to meet multiple severe requirements in a high-temperature corrosive fluoride molten salt environment, namely, firstly, has extremely high electrochemical stability and corrosion resistance to resist corrosion of molten salt and nascent oxygen and ensure long service life, secondly, has good conductivity to ensure electric energy efficiency, and has a thermal expansion coefficient and thermal shock resistance matched with electrolysis conditions to avoid cracking in thermal cycle, and further has enough mechanical strength and toughness to bear physical stress in the production process. Finally, the preparation process of the material should be feasible and cost-controllable. Currently, many inert anode systems are being studied primarily on metal oxide ceramics (e.g., nickel ferrite, tin oxide based ceramics, etc.). Such materials, while chemically inert, are inherently brittle and have low electrical conductivity that limits their large-scale industrial use. Meanwhile, the thermal shock resistance is often insufficient, and brittle fracture is easy to occur under complex working conditions. In recent years, the High-entropy alloy (High-Entropy Alloys, HEAs) has excellent structural stability, high-temperature corrosion resistance and oxidation resistance potential due to the unique High entropy effect, serious lattice distortion effect and delayed diffusion effect, and provides a new thought for the design of inert anode materials. However, when a single high-entropy alloy is operated for a long period in an extremely high-temperature and strong-oxidizing environment such as aluminum electrolysis, continuous oxidation and even corrosion dissolution of the surface of the alloy can still occur, so that performance is attenuated. On the other hand, single ceramic phase materials are always difficult to overcome the intrinsic low conductivity and low toughness bottlenecks. Therefore, how to prepare the anode material with comprehensive performance which fully meets the requirements of the aluminum electrolysis industry through innovation of a material system is still a technical problem to be broken through in the field. Disclosure of Invention The invention aims to provide a multi-component high-entropy alloy nickel ferrite composite anode material and a preparation method thereof. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a multi-component high-entropy alloy nickel ferrite composite anode material, which comprises high-entropy alloy and NiFe 2O4; The high-entropy alloy comprises Fe, co, ni and Cr, and any one or more of Mn, al, ti and Mo. The invention also provides a preparation method of the multi-component high-entropy alloy nickel ferrite composite anode material, which comprises the following steps: S1, weighing metal simple substance powder according to an equal atomic ratio, ball-milling the powder, drying the powder, and performing heat treatment on the dried powder to obtain high-entropy alloy powder, wherein the heat treatment comprises the steps of placing the powder in a flash evaporation Joule furnace, introducing a reducing atmosphere, heating to 650-850 ℃ in the flash evaporation Joule furnace at 500-1000 ℃ per second under the flowing reducing atmosphere, preserving heat for 60-120S, vacuumizing and performing flash evaporation discharge at 160-180 v; S2, mixing, ball milling and drying high-entropy alloy powder and NiFe 2O4 powder, performing compression molding by using cold isostatic pressing equipment after ball milling, placing the pressed powder in a tubular furnace, firstly heating to 1000-1200 ℃ at a heating rate of 10 ℃ per minute, preserving heat for 60-90min in Ar atmosphere, and then heating to 1250-1450 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 90-120min in Ar-1%O 2 atmosphere to obtain the multi-component high-entropy alloy nickel ferrite composite anode material; the metal simple substance powd