CN117403279A - Rare earth modified metal ceramic inert anode composite material for aluminum electrolysis and preparation method thereof - Google Patents
Rare earth modified metal ceramic inert anode composite material for aluminum electrolysis and preparation method thereof Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
Abstract
The invention provides a rare earth modified metal ceramic inert anode composite material for aluminum electrolysis and a preparation method thereof, wherein the rare earth modified metal ceramic inert anode composite material for aluminum electrolysis consists of a high-entropy alloy phase and a metal oxide ceramic phase; the invention dopes the high entropy alloy containing five or more rare earth metal elements in Co, cr, fe, ni, ti, mn, cu, al, mo and one or more rare earth metal elements in Y, la, sc, ce, pr, nd into spinel-based metal oxide ceramic, so that the conductivity of the metal ceramic material is greatly improved while the corrosion resistance of the metal ceramic material is maintained at the same level as that of the oxide ceramic, the development bottleneck that the high corrosion resistance and the high conductivity are difficult to meet at the same time at present is broken through, and the use of industrial electrolytic aluminum inert anode can be met.
Description
Technical Field
The invention relates to the technical field of preparation of metal ceramic composite materials, in particular to a novel high-performance metal ceramic inert anode composite material for aluminum electrolysis and a preparation method thereof.
Background
Aluminum is the second largest metal material, china is the largest aluminum product producing country and consuming country in the world, electrolytic aluminum is the important focus field of national double carbon targets, at present, the Hall-Heroult method is adopted in industry to electrolyze aluminum oxide to generate raw aluminum, and the method adopts consumed carbon as an anode to reduce aluminum oxide into raw aluminum in high-temperature molten salt. The method has the problems of high carbon consumption, high production investment cost, complex process and the like, and if the carbon anode is replaced by an inert anode, the anode does not react with oxygen anions, so that a large amount of CO is reduced 2 The discharge of the gas can also generate O 2 Recycling, the cost can be greatly saved, the electrode consumption can be reduced, the yield of the electrolytic tank can be increased, and technical support can be provided for zero-carbon electrolytic aluminum.
Currently inert anodes are mainly divided into three main categories: alloy systems, oxide ceramic systems, and cermet systems. Although the alloy system has high conductivity, the corrosion resistance is poor, and long-time electrolysis in a high-temperature molten salt system cannot be realized; although the oxide ceramic system has stronger corrosion resistance, the conductivity of the oxide ceramic system can not meet the industrial production requirement; the metal ceramic system is a composite material of metal and ceramic, has the two properties of high conductivity of metal and strong corrosion resistance of ceramic, and the ceramic phase matrix material commonly used at present is ZnFe 2 O 4 And NiFe 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The metal phase of the cermet is more Cu-Ni and Fe-Ni based alloy, but the metal phase can be preferentially corroded in the use process, so that the corrosion rate of an anode is accelerated, the conductivity, the compactness, the corrosion resistance, the thermal shock resistance and the like of the cermet are difficult to improve, in the currently reported literature, the conductivity of a cermet inert anode material of patent application CN 106488998A only reaches 100S/cm at most, and the conductivity requirement of industrial electrolytic aluminum is far from (200S/cm), so that the research and development of the inert anode material which can meet the strong corrosion resistance and simultaneously ensure the high conductivity of the material is a key technology to overcome in the field, and if the technical bottleneck can be broken through, the technical route of the inert anode modified Hall-H method electrolytic molten aluminum oxide can be realized industrially.
It can be seen that on the cermet substrate, how to control the alloying element composition is of great importance. The high-entropy alloy is a novel alloy material system developed in recent years, is a solid solution alloy containing at least 5 elements, has high entropy effect, slow diffusion effect, serious lattice distortion effect and cocktail effect, and has high strength, yield stress and other excellent mechanical properties through gradual improvement of addition design and preparation process of the high-entropy alloy elements by researchers: the internal elements of the alloy are not easy to diffuse to the surface, so that the corrosion of the alloy is delayed, and the corrosion resistance and high-temperature oxidation resistance of the metal ceramic are improved; the high-entropy alloy has strong solid solution oxidation caused by serious lattice distortion phenomenon, and has good performances in wear resistance, hardness, bending strength, yield strength and compression fracture strength. The high-entropy alloy has difficult cooperative diffusion of atoms among different elements in cryolite molten salt corrosion, and nucleation and growth of a new phase are inhibited. Therefore, the high-entropy alloy has more excellent heat stability and high-temperature softening resistance than the traditional alloy, and can replace the common alloy with poor alloy phase stability, poor high-temperature oxidation resistance and poor cryolite molten salt corrosion resistance. The metal ceramic inert anode composite material synthesized by adopting the high-entropy alloy to replace the common alloy has great advantages in aluminum electrolysis.
CN 115679384The A discloses a preparation method of a micro-consumption anode material for co-production of aluminum oxide, wherein the anode material is a composite material formed by a metal phase and a ceramic phase, wherein the metal phase is AlCoCrFeNi high-entropy alloy, the content is 25-95%, and the content of the ceramic phase is 5-75%; the ceramic phase is AB 2 O 4 Wherein A is one or more of Ni, co, sn, zn and B is one or more of Fe, al, cr, sn; the invention creatively combines high-entropy alloy with ceramic phase to be used as micro-consumption anode material for co-production of alumina; thereby avoiding the anode material failure caused by preferential corrosion of individual elements in the metal phase in the long-term electrolysis process; meanwhile, the problem of high impurity content of electrolytic aluminum is solved.
Rare earth metals, known as industrial vitamins, are widely used as dopants to improve the properties of materials, which provide excellent sustainability, selectivity, reactivity and durability for target reactions during electrocatalytic reactions, and by doping rare earth metal elements in cermet materials, the point catalysis performance, corrosion resistance of inert anode materials can be improved, while improving the energy conversion and storage properties of electrolytic molten alumina processes. Therefore, the invention dopes the high entropy alloy containing four or more rare earth metal elements in Co, cr, fe, ni, ti, mn, cu, al, mo and one or more rare earth metal elements in Y, la, sc, ce, pr, nd into spinel-based metal oxide ceramic, which not only maintains the same level of corrosion resistance as oxide ceramic, but also greatly improves the conductivity of the metal ceramic material, breaks through the development bottleneck that the high corrosion resistance and the high conductivity are difficult to meet at the same time at present, and can meet the use of industrial electrolytic aluminum inert anodes.
The prior metal ceramic has the corrosion resistance problems that the metal phase is preferentially corroded in the electrolytic corrosion process, so that the metal ceramic material is immersed into electrolyte to be corroded rapidly, the metal phase overflows and the structure is unevenly distributed, and the metal phase content is correspondingly regulated to achieve the balance between the conductivity and the corrosion resistance of the material, so that the main challenges are faced by researchers. Under the current preparation and electrolysis process conditions, the contradiction between the conductivity and corrosion resistance of the metal ceramic inert anode can not be reconciled, and the conductivity of the metal ceramic inert anode is difficult to break through on the premise of keeping a low corrosion rate. Thus, there is a great need for new concepts and methods for improving the conductivity of cermet inert anodes. The application applies the rare earth modified high-entropy alloy to the ceramic matrix, and the conductivity of the synthesized composite material reaches 484S/cm in a crossing way.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a rare earth modified metal ceramic inert anode composite material for aluminum electrolysis and a preparation method thereof, which can simultaneously achieve the high-performance metal ceramic inert anode composite material meeting the requirements of conductivity and corrosion resistance of industrial electrolytic aluminum, wherein the material consists of a high-entropy alloy containing four or more than four rare earth elements in Co, cr, fe, ni, ti, mn, cu, al, mo and one or more than one rare earth element in Y, la, sc, ce, pr, nd and AB 2 O 4 And the ceramic matrix is formed.
The invention aims at solving the problem that the metal ceramic inert anode material cannot meet the requirements of high conductivity and strong corrosion resistance, and provides a high-performance metal ceramic inert anode composite material for aluminum electrolysis and a preparation method thereof. The invention aims to solve the bottleneck problem of the development of the current inert anode, namely the problem that the high conductivity and the corrosion resistance cannot be simultaneously met, and the conductivity of the material is greatly improved while the corrosion resistance is improved by doping the high-entropy alloy with excellent mechanical property and corrosion resistance and the rare earth metal element and the oxide thereof which can provide beneficial catalytic reaction activity, selectivity and durability.
In order to solve the technical problems, the invention adopts the following technical proposal
A rare earth modified metal ceramic inert anode composite material for aluminum electrolysis comprises a high-entropy alloy phase and a ceramic phase, wherein the high-entropy alloy phase comprises Co, cr and FeFive or more metal elements of Ni, ti, mn, cu, al, mo, wherein one or more rare earth metal elements of Y, la, sc, ce, pr, nd are added in the high-entropy alloy phase; the ceramic phase comprises rare earth metal oxide RMeO, common metal oxide MeO and AB 2 O 4 Spinel oxide ceramics.
Further, the rare earth metal oxide RMeO is selected from Y 2 O 3 、CeO 2 、La 2 O 3 Or Nd 2 O 3 At least one of (a) and (b); the common metal oxide MeO is selected from V 2 O 5 、Cr 2 O 3 、MnO 2 One or more of BaO; the AB 2 O 4 Spinel oxide ceramics are synthesized from single-phase metal oxides selected from NiO, fe 2 O 3 、Cu 2 O, znO at least two of the powders; fe (Fe) 2 O 3 The average particle size of the NiO powder is 1-25 μm. .
Further, the rare earth metal element accounts for 1% -40% of the total mass of the high-entropy alloy phase, and more preferably 15% -30%.
Further, in the ceramic phase, rare earth metal oxide RMeO accounts for 1 to 6 percent of the total mass of the ceramic phase, common metal oxide MeO accounts for 1 to 3 percent of the total mass of the ceramic phase, and the balance is AB 2 O 4 Spinel oxide ceramics.
Further, the high-entropy alloy phase accounts for 10-50% of the total mass of the metal ceramic inert composite anode material, and the grain size of the high-entropy alloy is 1-53 mu m.
The invention relates to a preparation method of rare earth modified metal ceramic inert anode composite material for aluminum electrolysis, which comprises the following steps:
A. mixing rare earth metal oxide RMeO, common metal oxide MeO and single-phase metal oxide in proportion, ball milling to obtain a ceramic matrix raw material, drying, cold press molding and pre-sintering to obtain a ceramic matrix block;
B. crushing and screening the ceramic matrix blocks to obtain ceramic matrix powder, adding high-entropy alloy doped with rare earth metal elements, ball-milling and mixing in a dispersing agent to obtain metal ceramic slurry, and drying to obtain metal ceramic powder;
C. adding a binder, ball milling, mixing, drying, ball milling and sieving in a vacuum ball milling tank, and cold press molding to obtain a green body;
D. sintering under inert atmosphere to obtain the metal ceramic inert anode material.
Further, the cold pressure in the step A is 60-500 Mpa, and the pressure maintaining time is 3-20 min; the presintering temperature is 1000-1450 ℃, and the heat preservation time is 4-12 h.
In the step B, the dispersing agent is ethanol or deionized water, the mass ratio of the dispersing agent to the raw materials is 2:1-6:1, and the raw materials are high-entropy alloy and ceramic matrix powder.
Further, in the step C, the binder is at least one selected from polyvinyl alcohol, nano-binder, paraffin and rubber, and the addition amount of the binder is 1-10% of the mass of the metal ceramic powder; the pressure of cold press molding is 60-500 Mpa, and the pressure maintaining time is 3-20 min.
And in the step D, the inert atmosphere is argon or nitrogen, the sintering temperature is 1000-1450 ℃, and the heat preservation time is 4-12 h.
Compared with the prior art, the invention has the following characteristics and positive effects:
(1) The method of doping high-entropy alloy with heat shock resistance, corrosion resistance and high conductivity in spinel ceramic matrix to replace common alloy can ensure the annual corrosion rate index required by aluminum electrolysis and simultaneously obviously improve the conductivity of inert anode materials. The high-entropy alloy has good corrosion resistance and high-temperature oxidation resistance and also has higher conductivity. Therefore, compared with common metals, the doped high-entropy alloy can not only keep the corrosion resistance of the material, but also improve the conductivity, improve the electrolysis efficiency and ensure the purity of the electrolytic aluminum product, and in the current report, the conductivity performance of the doped high-entropy alloy still does not reach the industrial electrolysis requirement (200S/cm).
(2) As industrial vitamins, rare earth metals have more abundant mechanical functions, electronic structures, activities and spatial arrangements, so that the surface reaction kinetics can be controlled well, and the reaction activity is improved; in addition, rare earth alloys can also introduce and enhance new properties such as the formation of intermetallic electron compounds, adsorption/desorption of reactive species, reaction selectivity, surface and internal electron interactions, and the like. Therefore, rare earth metal elements are doped in the metal ceramic inert anode, so that the aluminum electrolysis efficiency can be improved, the impurity content of product aluminum is reduced, the purity of the product aluminum is ensured, and the transformation of industrial electrolytic aluminum with low energy consumption is facilitated.
Drawings
FIG. 1 is a microstructure of the high entropy cermet inert anode composite obtained in example 1.
FIG. 2 is a profile and energy spectrum point scan of the high density cermet inert anode material obtained in example 1 after polishing.
FIG. 3 is a spectral surface scan of the high density cermet inert anode material obtained in example 1.
Detailed Description
The invention is further illustrated in detail below with reference to examples, but embodiments of the invention are not limited thereto.
The invention is suitable for the field of high-temperature aluminum electrolysis at 960 ℃ and below, and the spinel is used as a matrix material to be added with high-entropy alloy to prepare the metal ceramic inert anode composite material with high conductivity, strong corrosion resistance and thermal shock resistance.
The metal oxide powder, the high-entropy alloy powder and the like adopted in the embodiment of the invention are all commercial products.
The device used in the embodiment of the invention for observing the microscopic morphology and the energy spectrum result is Czech TESCAN MIRALMS.
Example 1
The preparation method of the rare earth modified metal ceramic inert anode composite material for aluminum electrolysis in the embodiment comprises the following steps:
(1) And respectively weighing Fe according to the mass ratio of 57.11:41.39:1:0.5 2 O 3 、NiO、MnO 2 And V 2 O 5 Raw materials, and 3.6wt% of Y was added 2 O 3 Rare earth metal oxide in which Fe 2 O 3 、NiO、MnO 2 、V 2 O 5 And Y 2 O 3 Particle size is less than or equal to 30 mu m; ball milling and mixing are carried out through a planetary ball mill, the ball-material ratio is 5:1, deionized water is selected as a dispersing agent, ball milling and mixing are carried out for 8 hours, and after ball milling, the mixed material liquid is placed in a 110+/-2 ℃ blast drying oven for drying for 48 hours; cold press molding is carried out on the dried material under 75MPa, and the pressure is maintained for 3 minutes; sintering the formed raw materials in a box furnace, heating to 1000 ℃ at the heating rate of i/n of 10 mdeg.C, preserving heat for 6h, cooling to 500 ℃ and naturally cooling with the furnace to obtain 85NiFe 2 O 4 The 15NiO ceramic matrix material is prepared by adopting stainless steel balls with the diameter of 15mm to obtain 85NiFe 2 O 4 Ball milling and crushing the 15NiO ceramic matrix material, and grinding the material and sieving the ground material with a 200-mesh screen to obtain 85NiFe 2 O 4 -15NiO ceramic matrix powder particles;
(2) Based on the total mass of the metal ceramic inert anode composite material, adding 19.5 weight percent of CoCrFeNiTi high-entropy alloy and 0.5 weight percent of Y, hf powder with equal mass ratio, wherein the particle size of the high-entropy alloy and Y, hf metal is 15-53 mu m; mixing and ball milling for 8 hours by taking ethanol as a dispersing agent to obtain mixed slurry, and drying at 80+/-2 ℃; adding PVA solution with the mass fraction of 2% into the dried mixed material, wherein the organic binder PVA solution accounts for 2% of the mass of the dried mixed powder, ball milling and mixing, drying the mixed material in a vacuum drying oven at 80+/-2 ℃ for 24 hours, ball milling the dried powder block body by using a vacuum ball milling tank, and filtering the mixed material by using a 65-mesh screen for 4 hours according to the mass ratio of 3:1 of the ball material to obtain a uniformly mixed high-entropy metal ceramic composite material;
(3) And (3) adopting a cold press molding mode, maintaining the pressure of the obtained metal ceramic composite powder at 300MPa for 5min to obtain a secondary green body, and sintering and preserving heat for 6h in a 1300 ℃ tubular furnace under the condition of introducing Ar gas to obtain the metal ceramic inert anode composite material doped with the high-entropy alloy, namely the high-performance metal ceramic composite inert anode block.
And (3) sequentially polishing the obtained inert anode block material by using water abrasive paper of No. 220, no. 400, no. 600, no. 1000 and No. 2000, polishing by using polishing cloth and diamond polishing liquid, cleaning the treated sample, and drying by using a vacuum drying oven to obtain the final inert anode material to be detected.
And carrying out X-ray diffraction scanning electron microscope and EDS (electron discharge spectrometry) energy spectrum analysis on the obtained sample, wherein the microscopic morphology is shown in figure 1: from the figure, it can be seen that the ceramic grains are uniform and the sample is compact; the scanning results in fig. 2 show that the inner part of the high-performance metal ceramic composite anode material doped with the high-entropy alloy is two phases, namely an iron-nickel spinel phase and a nickel oxide phase; the surface scanning result of fig. 3 shows that the high-entropy alloy is not agglomerated into an independent alloy phase, but is uniformly distributed in two phases, so that the rapid falling-off caused by weak corrosion resistance of the common alloy phase can be effectively avoided. The volume density of the synthesized high-performance metal ceramic composite material is 5.683g/cm 3 The porosity was 0.024%. At 960 ℃ from 90wt% cryolite, 5wt% Al 2 O 3 And 5wt% CaF 2 After corrosion for 10 hours in the composed molten salt system, the surface of the inert anode has no obvious phenomena of falling, fracture, layering, swelling and the like, and is subjected to 30wt% AlCl 3 The solution and boiling water are washed in turn and dried, and then the static corrosion rate of the high-performance metal ceramic inert anode material is measured and calculated to be 0.002799 g/(cm) 2 H) annual corrosion rate as low as 1.08cm/a. Its normal temperature conductivity is up to 484.26S/cm. The cermet composite thus obtained was subjected to 0.5A/cm in an electrolyte system at 960 ℃ 2 The average cell voltage is 2.97V, compared with the common cell voltage, the electrolysis application experiment of (a) is reduced; the cooled material has no obvious phenomena of fracture, peeling, swelling and the like, which indicates that the material has good dynamic electrolytic corrosion resistance, conductivity and comprehensive mechanical property.
Example 2
The preparation method of the rare earth modified metal ceramic inert anode composite material for aluminum electrolysis in the embodiment comprises the following steps:
(1) And respectively weighing Fe according to the mass ratio of 57.11:41.39:1:0.5 2 O 3 、NiO、MnO 2 And V 2 O 5 Raw materials, and 3.6wt% of Y was added 2 O 3 Rare earth metal oxide in which Fe 2 O 3 、NiO、MnO 2 、V 2 O 5 And Y 2 O 3 Particle size is less than or equal to 30 mu m; ball milling and mixing are carried out through a planetary ball mill, and the ball-material ratio is as followsDeionized water is selected as a dispersing agent in a ratio of 5:1, ball milling and mixing are carried out for 4 hours, and after ball milling, the mixed material liquid is placed in a blast drying oven at 110+/-2 ℃ and dried for 48 hours; and (3) carrying out cold press molding on the dried material under 75MPa, and maintaining the pressure for 3 minutes. Sintering the formed raw materials in a box furnace, heating to 1000 ℃ at the heating rate of i/n of 10 mdeg.C, preserving heat for 6h, cooling to 500 ℃ and naturally cooling with the furnace to obtain 85NiFe 2 O 4 -15NiO ceramic matrix material; the obtained 85NiFe is obtained by adopting stainless steel balls with the diameter of 15mm 2 O 4 Ball milling and crushing the 15NiO ceramic matrix material, drying and grinding the material and sieving the material with a 200-mesh sieve to obtain 85NiFe 2 O 4 -15NiO ceramic matrix powder particles;
(2) Based on the total mass of the metal ceramic inert anode composite material, 85NiFe is added 2 O 4 20wt% of CoCrFeNiMn high-entropy alloy and 1wt% of La powder are added into 15NiO ceramic matrix powder particles, and the particle sizes of the high-entropy alloy and the La powder are 1-25 nm; mixing and ball milling for 8 hours by taking ethanol as a solvent to obtain mixed slurry, and drying at 80+/-2 ℃; adding PVA solution with the mass fraction of 2% into the dried mixture, wherein an organic binder (PVA solution) accounts for 2% of the mass of the dried mixture, ball milling and mixing, drying for 24 hours in a vacuum drying oven at 100+/-2 ℃, ball milling the dried powder block by using a vacuum ball milling tank, ball milling for 4 hours, and filtering by using a 65-mesh screen to obtain a high-entropy metal ceramic composite material which meets the requirement of particle size and is uniformly mixed;
(3) And (3) maintaining the pressure of the obtained high-entropy metal ceramic composite material at 200-400 MPa for 5min by adopting a cold press molding mode to obtain a secondary green body, and sintering and preserving heat for 6h in a 1300 ℃ tubular furnace under the condition of introducing Ar gas to obtain the metal ceramic inert anode composite material doped with the high-entropy alloy, namely a high-performance metal ceramic composite inert anode block.
And (3) sequentially polishing the obtained inert anode block material by using water abrasive paper of No. 220, no. 400, no. 600, no. 1000 and No. 2000, polishing by using polishing cloth and diamond polishing liquid, and cleaning, drying, analyzing and detecting the treated sample. 0.5A/cm in an electrolyte system at 960 ℃ 2 The average cell voltage was 3.12V during electrolysis.
Example 3
The preparation method of the rare earth modified metal ceramic inert anode composite material for aluminum electrolysis in the embodiment comprises the following steps:
(1) And respectively weighing Fe according to the mass ratio of 57.11:41.39:1:0.5 2 O 3 、NiO、MnO 2 And V 2 O 5 Raw materials, and 0.5wt% CeO was added 2 Rare earth metal oxide in which Fe 2 O 3 、NiO、MnO 2 、V 2 O 5 And CeO 2 Particle size is less than or equal to 30 mu m; ball milling and mixing are carried out through a planetary ball mill, the ball-material ratio is 5:1, deionized water is selected as a dispersing agent, ball milling and mixing are carried out for 8 hours, and after ball milling, the mixed material liquid is placed in a 110+/-2 ℃ blast drying oven for drying for 48 hours; and (3) carrying out cold press molding on the dried material under 75MPa, and maintaining the pressure for 3 minutes. Sintering the formed raw materials in a box furnace, heating to 1000 ℃ at the heating rate of i/n of 10 mdeg.C, preserving heat for 4h, cooling to 500 ℃ and naturally cooling with the furnace to obtain 85NiFe 2 O 4 -15NiO ceramic matrix material; the obtained 85NiFe is obtained by adopting stainless steel balls with the diameter of 15mm 2 O 4 Ball milling and crushing the 15NiO ceramic matrix material, drying and grinding the material and sieving the material with a 200-mesh sieve to obtain 85NiFe 2 O 4 -15NiO matrix powder particles;
(2) Based on the total mass of the metal ceramic inert anode composite material, 85NiFe is added 2 O 4 19.5wt% of CoCrFeNiCu particles and 0.5wt% of Nd powder are added into the 15NiO matrix powder particles, wherein the particle size of the CoCrFeNiCu is less than or equal to 1 mu m. Mixing and ball milling for 8 hours by taking ethanol as a solvent to obtain mixed slurry, and drying at 80+/-2 ℃; adding PVA solution with the mass fraction of 2% into the dried mixture, wherein an organic binder accounts for 4% of the mass of the dried mixture, ball milling and mixing, drying the mixture in a vacuum drying oven at 110+/-2 ℃ for 24 hours, ball milling the dried powder block by using a vacuum ball milling tank, and filtering the mixture by using a 65-mesh screen for 4 hours according to the mass ratio of 3:1 to obtain a uniformly mixed high-entropy metal ceramic composite material;
(3) Adopting a cold press molding mode, maintaining the pressure of the obtained high-entropy metal ceramic composite material for 5min at 350MPa to obtain a secondary green body, and introducing Ar gasSintering and preserving heat for 6 hours in a 1300 ℃ tube furnace to obtain the NiFe doped with 19.5CoCrFeNiCu-0.5Nd 2 O 4 Base ceramic composite inert anode block.
For the obtained NiFe doped with 19.5CoCrFeNiCu-0.5Nd 2 O 4 The base ceramic composite inert anode block is sequentially polished by water abrasive paper of No. 220, no. 400, no. 600, no. 1000 and No. 2000, then polished by polishing cloth and diamond polishing liquid, and the treated sample is cleaned and dried.
Comparative example 1
(1) Fe was weighed according to the mass ratio of example 1 2 O 3 、NiO、MnO 2 、V 2 O 5 And Y 2 O 3 Raw materials, wherein Fe 2 O 3 、NiO、MnO 2 、V 2 O 5 And Y 2 O 3 All are less than or equal to 30 mu m; ball milling and mixing are carried out through a planetary ball mill, and the ball-material ratio is 5:1, selecting deionized water as a dispersing agent, ball-milling and mixing for 8 hours, and placing the mixed material liquid into a 110+/-2 ℃ blast drying oven to be dried for 48 hours after ball-milling; and (3) carrying out cold press molding on the dried material under 75MPa, and maintaining the pressure for 3 minutes. Sintering the formed raw materials in a box furnace, heating to 1000 ℃ at the heating rate of 10 ℃/min, preserving heat for 6 hours, cooling to 500 ℃, and naturally cooling along with the furnace to obtain 85NiFe 2 O 4 -15NiO ceramic matrix material; the obtained 85NiFe is obtained by adopting stainless steel balls with the diameter of 15mm 2 O 4 Ball milling and crushing the 15NiO ceramic matrix material, drying and grinding the material and sieving the material with a 200-mesh sieve to obtain 85NiFe 2 O 4 -15NiO matrix powder particles;
(2) Based on the total mass of the metal ceramic inert anode composite material, adding 20wt% of CoCrFeNiTi high-entropy alloy, wherein the grain size of the high-entropy alloy is 15-53 mu m. Mixing and ball milling for 8 hours by taking ethanol as a solvent to obtain mixed slurry, and drying at 80+/-2 ℃; adding PVA solution with the mass fraction of 2% into the dried mixed material, wherein the organic binder accounts for 2% of the mass of the dried mixed powder, ball milling and mixing, drying the mixed powder in a vacuum drying oven at 80+/-2 ℃ for 24 hours, ball milling the dried powder block by using a vacuum ball milling tank, and filtering the mixed powder block by using a 65-mesh screen for 4 hours, wherein the mass ratio of the ball material is 3:1, so that the high-entropy metal ceramic composite material which meets the requirement of particle size and is uniformly mixed is obtained.
(3) And (3) maintaining the pressure of the obtained high-entropy metal ceramic composite material at 300MPa for 5min by adopting a cold press molding mode to obtain a secondary green body, and sintering and preserving heat for 6h in a 1300 ℃ tubular furnace under the condition of introducing Ar gas to obtain the metal ceramic composite inert anode block doped with the high-entropy alloy.
And (3) sequentially polishing the obtained inert anode material by using 220# water abrasive paper, 400# water abrasive paper, 600# water abrasive paper, 1000# water abrasive paper and 2000# water abrasive paper, polishing by using polishing cloth and diamond polishing liquid, cleaning the treated sample, and drying by using a vacuum drying oven to obtain the final inert anode material to be detected.
0.5A/cm in an electrolyte system at 960 ℃ 2 The average cell voltage was 3.05V during electrolysis.
Comparative example 2
(1) Fe was weighed according to the mass ratio of example 2 2 O 3 、NiO、MnO 2 、V 2 O 5 And Y 2 O 3 Raw materials, wherein Fe 2 O 3 、NiO、MnO 2 、V 2 O 5 And Y 2 O 3 All are less than or equal to 30 mu m; ball milling and mixing are carried out through a planetary ball mill, the ball-material ratio is 5:1, deionized water is selected as a dispersing agent, ball milling and mixing are carried out for 4 hours, and after ball milling, the mixed material liquid is placed in a 110+/-2 ℃ blast drying oven for drying for 48 hours; and (3) carrying out cold press molding on the dried material under 75MPa, and maintaining the pressure for 3 minutes. Sintering the formed raw materials in a box furnace, heating to 1000 ℃ at the heating rate of i/n of 10 mdeg.C, preserving heat for 6h, cooling to 500 ℃ and naturally cooling with the furnace to obtain 85NiFe 2 O 4 -15NiO ceramic matrix material; the obtained NiFe was subjected to a stainless steel ball with a diameter of 15mm 2 O 4 Ball milling and crushing the ceramic material, drying and grinding the ceramic material, and sieving the ceramic material with a 200-mesh screen to obtain 85NiFe 2 O 4 -15NiO matrix powder particles;
(2) Based on the total mass of the metal ceramic inert anode composite material, adding 21wt% of CoCrFeNiMn high-entropy alloy, wherein the grain size of the high-entropy alloy is 1-25 nm. Mixing and ball milling for 8 hours by taking ethanol as a solvent to obtain mixed slurry, and drying at 80+/-2 ℃; adding PVA solution with the mass fraction of 2% into the dried mixed material, wherein the organic binder accounts for 2% of the mass of the dried mixed powder, ball milling and mixing, and drying for 24 hours in a vacuum drying oven at 100+/-2 ℃; and ball-milling the dried powder blocks by using a vacuum ball-milling tank, wherein the ball-material mass ratio is 3:1, ball-milling is carried out for 4 hours, and filtering by using a 65-mesh screen to obtain the high-entropy metal ceramic composite material which meets the requirement of particle size and is uniformly mixed.
(3) And (3) maintaining the pressure of the obtained high-entropy metal ceramic composite material at 200-400 MPa for 5min by adopting a cold press molding mode to obtain a secondary green body, and sintering and preserving heat for 6h in a 1300 ℃ tubular furnace under the condition of introducing Ar gas to obtain the metal ceramic composite inert anode block doped with the high-entropy alloy.
And (3) sequentially polishing the obtained inert anode material by using 220# water abrasive paper, 400# water abrasive paper, 600# water abrasive paper, 1000# water abrasive paper and 2000# water abrasive paper, polishing by using polishing cloth and diamond polishing liquid, and cleaning, drying, analyzing and detecting the treated sample. 0.5A/cm in an electrolyte system at 960 ℃ 2 The average cell voltage was 3.32V during electrolysis.
Comparative example 3
(1) Fe was weighed according to the mass ratio of example 3 2 O 3 、NiO、MnO 2 、V 2 O 5 And CeO 2 Wherein Fe is 2 O 3 The particle sizes of other powders such as NiO and the like are all less than or equal to 30 mu m; ball milling and mixing are carried out through a planetary ball mill, the ball-material ratio is 5:1, deionized water is selected as a dispersing agent, ball milling and mixing are carried out for 8 hours, and after ball milling, the mixed material liquid is placed in a 110+/-2 ℃ blast drying oven for drying for 48 hours; and (3) carrying out cold press molding on the dried material under 75MPa, and maintaining the pressure for 3 minutes. Sintering the formed raw materials in a box furnace, heating to 1000 ℃ at the heating rate of i/n of 10 mdeg.C, preserving heat for 4h, cooling to 500 ℃ and naturally cooling with the furnace to obtain 85NiFe 2 O 4 -15NiO ceramic matrix material; the obtained NiFe was subjected to a stainless steel ball with a diameter of 15mm 2 O 4 Ball milling and crushing the ceramic material, drying and grinding the ceramic material, and sieving the ceramic material with a 200-mesh screen to obtain 85NiFe 2 O 4 -15NiO matrix powder particles;
(2) With cermet inert anode compositeBased on the total mass, 85NiFe 2 O 4 20wt% of CoCrFeNiCu particles are added into the 15NiO matrix powder particles, wherein the particle size of the CoCrFeNiCu particles is less than or equal to 1 mu m. Mixing and ball milling for 8 hours by taking ethanol as a solvent to obtain mixed slurry, and drying at 80+/-2 ℃; adding PVA solution with the mass fraction of 2% into the dried mixed material, wherein the organic binder accounts for 4% of the mass of the dried mixed powder, ball milling and mixing, and drying for 24 hours in a vacuum drying oven at 110+/-2 ℃; ball-milling the dried powder blocks by using a vacuum ball-milling tank, wherein the mass ratio of the balls to the materials is 3:1, ball-milling for 4 hours, and filtering by using a 65-mesh screen to obtain the powder with the particle size according with the particle size
High entropy metal ceramic composite material is required and uniformly mixed.
(3) Adopting a cold press molding mode, maintaining the pressure of the obtained metal ceramic composite powder for 5min under 350MPa to obtain a secondary green compact, sintering and preserving heat for 6h in a 1300 ℃ tubular furnace under the condition of introducing Ar gas to obtain NiFe doped with CoCrFeNiCu 2 O 4 Base ceramic composite inert anode block.
And (3) sequentially polishing the obtained inert anode material by using 220# water abrasive paper, 400# water abrasive paper, 600# water abrasive paper, 1000# water abrasive paper and 2000# water abrasive paper, polishing by using polishing cloth and diamond polishing liquid, and cleaning and drying the treated sample.
The test results of examples 1-3 and comparative examples 1-3 are shown in the following table:
the table above lists the basic physicochemical properties of the inert anode materials synthesized in each example and comparative example, and it can be seen from the table above that the rare earth doped material has lower porosity, higher density, better corrosion resistance and conductivity than the high entropy alloy ceramic inert anode material without the rare earth doped material, which provides a basis for good dynamic electrolysis efficiency and performance. The invention dopes the high entropy alloy containing four or more rare earth metal elements in Co, cr, fe, ni, ti, mn, cu, al, mo and one or more rare earth metal elements in Y, la, sc, ce, pr, nd into spinel-based metal oxide ceramic, so that the conductivity of the metal ceramic material is greatly improved while the corrosion resistance of the metal ceramic material is kept at the same level as that of the oxide ceramic, the development bottleneck that the high corrosion resistance and the high conductivity are difficult to meet at the same time at present is broken through, and the use of industrial electrolytic aluminum inert anode can be met.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. The composition and physical and chemical properties are shown in the following table; it will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The rare earth modified metal ceramic inert anode composite material for aluminum electrolysis is characterized by comprising a high-entropy alloy phase and a ceramic phase, wherein the high-entropy alloy phase comprises five or more metal elements in Co, cr, fe, ni, ti, mn, cu, al, mo, and one or more rare earth metal elements in Y, la, sc, ce, pr, nd are added in the high-entropy alloy phase; the ceramic phase comprises rare earth metal oxide RMeO, common metal oxide MeO and AB 2 O 4 Spinel oxide ceramics.
2. Rare earth modified cermet inert anode composite for aluminium electrolysis according to claim 1, wherein the rare earth metal oxide RMeO is selected from Y 2 O 3 、CeO 2 、La 2 O 3 Or Nd 2 O 3 At least one of (a) and (b); the common metal oxide MeO is selected from V 2 O 5 、Cr 2 O 3 、MnO 2 One or more of BaO; the AB 2 O 4 Spinel oxide ceramics are synthesized from single-phase metal oxides selected from NiO, fe 2 O 3 、Cu 2 O, znO at least two of the powders; fe (Fe) 2 O 3 The average particle diameter of the NiO powder is 1-25 μm.
3. The rare earth modified cermet inert anode composite for aluminum electrolysis according to claim 1, wherein the rare earth metal element accounts for 1% -40% of the total mass of the high-entropy alloy phase.
4. The rare earth modified metal ceramic inert anode composite material for aluminum electrolysis according to claim 1, wherein the rare earth metal oxide RMeO in the ceramic phase accounts for 1% -6% of the total mass of the ceramic phase, the common metal oxide MeO accounts for 1% -3% of the total mass of the ceramic phase, and the balance AB 2 O 4 Spinel oxide ceramics.
5. The rare earth modified metal ceramic inert anode composite material for aluminum electrolysis according to claim 1, wherein the high-entropy alloy phase accounts for 10-50% of the total mass of the metal ceramic inert anode composite material, and the grain size of the high-entropy alloy is 1-53 μm.
6. The method for preparing a rare earth modified cermet inert anode composite for aluminum electrolysis according to any of claims 1-5, comprising the steps of:
A. mixing rare earth metal oxide RMeO, common metal oxide MeO and single-phase metal oxide in proportion, ball milling to obtain a ceramic matrix raw material, drying, cold press molding and pre-sintering to obtain a ceramic matrix block;
B. crushing and screening the ceramic matrix blocks to obtain ceramic matrix powder, adding high-entropy alloy doped with rare earth metal elements, ball-milling and mixing in a dispersing agent to obtain metal ceramic slurry, and drying to obtain metal ceramic powder;
C. adding a binder, ball milling, mixing, drying, ball milling and sieving in a vacuum ball milling tank, and cold press molding to obtain a green body;
D. sintering under inert atmosphere to obtain the metal ceramic inert anode material.
7. The method for preparing the rare earth modified metal ceramic inert anode composite material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: the cold pressure in the step A is 60-500 mpa, and the pressure maintaining time is 3-20 min; the presintering temperature is 1000-1450 ℃, and the heat preservation time is 4-12 h.
8. The method for preparing the rare earth modified metal ceramic inert anode composite material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: in the step B, the dispersing agent is ethanol or deionized water, the mass ratio of the dispersing agent to the raw materials is 2:1-6:1, and the raw materials are high-entropy alloy and ceramic matrix powder.
9. The method for preparing the rare earth modified metal ceramic inert anode composite material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: in the step C, the binder is at least one selected from polyvinyl alcohol, nano binder, paraffin and rubber, and the addition amount of the binder is 1-10% of the mass of the metal ceramic powder; the pressure of cold press molding is 60-500 mpa, and the pressure maintaining time is 3-20 min.
10. The method for preparing the rare earth modified metal ceramic inert anode composite material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: and in the step D, the inert atmosphere is argon and nitrogen, the sintering temperature is 1000-1450 ℃, and the heat preservation time is 4-12 h.
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