CN113249755B - Inert anode material and preparation method and application thereof - Google Patents
Inert anode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an inert anode material, a preparation method and application thereof, and relates to the technical field of nonferrous metal molten salt electrolysis. The inert anode material provided by the invention comprises a metal phase and a ceramic phase; the metal phase comprises more than five elements of Al, co, cr, fe, ni, ti and Cu; the ceramic phase comprises CuAl 2 O 4 、NiAl 2 O 4 、CuCr 2 O 4 、NiCr 2 O 4 、ZnCr 2 O 4 、FeAl 2 O 4 、NiFe 2 O 4 And CuFe 2 O 4 One or more of the following. The inert anode material provided by the invention has stronger corrosion resistance, mechanical property and conductivity in a cryolite molten salt system, and can prolong the service life of the inert anode, thereby solving the problems of high energy consumption, large discharge capacity and the like in the current aluminum electrolysis industry. The inert anode material provided by the invention is suitable for an electrolyte system at 800-1000 ℃ and realizes the carbon-free aluminum electrolysis production.
Description
Technical Field
The invention relates to the technical field of nonferrous metal molten salt electrolysis, in particular to an inert anode material, a preparation method and application thereof.
Background
Aluminum is the most important basic raw material in nonferrous metal industry, and is an important support for realizing the strong country of manufacturing industry, promoting the growth of strategic emerging industry and guaranteeing the development of national defense and military industry and aerospace. The raw aluminum yield of 2020 China is 3732 ten thousand tons, which accounts for 57.18% of the world yield. At present, the production process still adopts Hall-Heroult high-temperature fused salt electrolysis method, and the ton of aluminum needs to consume 450-500 kg of carbon anode and mainly uses CO 2 、CF n The greenhouse gases escape in the form of equal greenhouse gases, and the emission of the greenhouse gases only can reach more than 5180 ten thousand tons in the annual electrolysis process. The green aluminum electrolysis technology with inert anode as core does not consume carbon anode, and oxygen evolved from ton aluminum is 800kg is more than; if the inert anode aluminum electrolysis is combined with the clean energy power generation technology, the near zero emission of the whole process of the aluminum electrolysis industry is realized.
Inert anode material is required to be at high temperature Na 3 AlF 6 -AlF 3 -Al 2 O 3 The molten salt (cryolite molten salt system) is required to have good conductivity, mechanical and corrosion resistance for long-term service. Through extensive research, alloys and cermets are considered as two materials with the most promising application prospect, wherein NiFe 2 O 4 The basic inert anode is the key point of research at home and abroad for nearly thirty years due to good electric conduction and corrosion resistance. But plague NiFe 2 O 4 The main difficulty of the metal ceramic-based inert anode is that the corrosion-resistant film layer on the surface of the anode cannot be balanced with dissolution, and the core problem is that the service life of the inert anode under the electrolysis working condition cannot be ensured due to chain reactions such as metal phase loosening and matrix phase dissociation caused by preferential dissolution of part of elements.
Although research on inert anode materials is carried out by universities and enterprises in recent years, cases of being successfully used in actual production still remain, so that the anode material with good corrosion resistance, mechanical property and conductivity in a cryolite molten salt system is provided, and the anode material becomes a problem to be solved in the prior art.
Disclosure of Invention
The invention aims to provide an inert anode material, a preparation method and application thereof, and the inert anode material provided by the invention has stronger corrosion resistance, mechanical property and conductivity in a cryolite molten salt system, can prolong the service life of an inert anode, and further solves the problems of high energy consumption, large discharge capacity and the like in the current aluminum electrolysis industry.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an inert anode material, which comprises a metal phase and a ceramic phase; the metal phase comprises more than five elements of Al, co, cr, fe, ni, ti and Cu; the ceramic phase comprises CuAl 2 O 4 、NiAl 2 O 4 、CuCr 2 O 4 、NiCr 2 O 4 、ZnCr 2 O 4 、FeAl 2 O 4 、NiFe 2 O 4 And CuFe 2 O 4 One or more of the following.
Preferably, the proportion of each single element in the metal phase is 5 to 50at%.
Preferably, the metal phase has a solid solution structure of no more than two phases.
The invention provides a preparation method of the inert anode material, which comprises the following steps:
mixing a metal phase raw material and a ceramic phase raw material to obtain a mixed material;
cold pressing the mixed material to obtain a green body;
and sintering the green body to obtain the inert anode material.
Preferably, the metal phase raw material is prepared by adopting a mechanical alloying method or an atomization method.
Preferably, the particle size of the metal phase raw material is 50 to 500 mesh.
Preferably, the mass ratio of the metal phase raw material to the ceramic phase raw material is 5-50:50-95.
Preferably, the pressure of the cold pressing is 150-350 MPa, and the pressure maintaining time is 1-10 min.
Preferably, the sintering temperature is 1000-1650 ℃ and the heat preservation time is 2-24 h.
The invention provides an application of the inert anode material prepared by the technical scheme or the preparation method of the technical scheme in electrolytic aluminum.
The invention provides an inert anode material, which comprises a metal phase and a ceramic phase; the metal phase comprises more than five elements of Al, co, cr, fe, ni, ti and Cu; the ceramic phase comprises CuAl 2 O 4 、NiAl 2 O 4 、CuCr 2 O 4 、NiCr 2 O 4 、ZnCr 2 O 4 、FeAl 2 O 4 、NiFe 2 O 4 And CuFe 2 O 4 One or more of the following. The inventionThe AlCoCrFeNiTiCu high-entropy alloy is adopted as a metal phase, elements in the high-entropy alloy are complex and various, and the sizes of atoms are different, so that atom migration is more difficult, and collaborative diffusion is difficult to carry out; meanwhile, the serious distortion of the crystal lattice can also improve the diffusion activation energy of atoms, so that the effective diffusion rate of the atoms in the high-entropy alloy is limited, and the multi-element high-entropy alloy can form stable compact oxide with a spinel phase structure after being oxidized, so that the internal diffusion of oxygen at high temperature can be effectively prevented, and the corrosion resistance and mechanical property of the material are improved. The inert anode material provided by the invention has stronger corrosion resistance, mechanical property and conductivity in a cryolite molten salt system, and can prolong the service life of the inert anode, thereby solving the problems of high energy consumption, large carbon emission and the like in the current aluminum electrolysis industry. The results of the examples show that the inert anode material provided by the invention is suitable for an electrolyte system at 800-1000 ℃ and realizes the carbon-free aluminum electrolysis production.
Detailed Description
The invention provides an inert anode material, which comprises a metal phase and a ceramic phase; the metal phase comprises more than five elements of Al, co, cr, fe, ni, ti and Cu; the ceramic phase comprises CuAl 2 O 4 、NiAl 2 O 4 、FeAl 2 O 4 、NiFe 2 O 4 And CuFe 2 O 4 One or more of the following.
The inert anode material provided by the invention comprises a metal phase. In the present invention, the metal phase includes five or more elements of Al, co, cr, fe, ni, ti and Cu, particularly preferably a metal phase composed of Al, co, cr, fe and Ni, or a metal phase composed of Al, co, cr, fe, ni, ti and Cu. In the present invention, the proportion of each single element in the metal phase is preferably 5 to 50at%, more preferably 20 to 35at%. In the present invention, the metal phase preferably has a solid solution structure of not more than two phases, more preferably has a single-phase or two-phase solid solution structure. In the present invention, when the metal phase is a single-phase solid solution structure, it specifically means an FCC crystal phase structure or a BCC crystal structure; when the metal phase is a two-phase solid solution structure, it is specifically referred to as FCC crystal phase structure and BCC crystal structure.
The inert anode material provided by the invention comprises a ceramic phase. In the present invention, the ceramic phase comprises CuAl 2 O 4 、NiAl 2 O 4 、CuCr 2 O 4 、NiCr 2 O 4 、ZnCr 2 O 4 、FeAl 2 O 4 、NiFe 2 O 4 And CuFe 2 O 4 One or more of the following.
In the present invention, the mass ratio of the metal phase to the ceramic phase is preferably 5 to 50:50 to 95, more preferably 15 to 50:50 to 85.
The invention also provides a preparation method of the inert anode material, which comprises the following steps:
mixing a metal phase raw material and a ceramic phase raw material to obtain a mixed material;
cold pressing the mixed material to obtain a green body;
and sintering the green body to obtain the inert anode material.
The invention mixes the metal phase raw material and the ceramic phase raw material to obtain the mixed material. In the present invention, the composition of the metal phase raw material is the same as that of the metal phase according to the above-described technical scheme. In the present invention, the particle size of the metal phase raw material is preferably 50 to 500 mesh, more preferably 100 to 300 mesh. In the present invention, the metal phase raw material is preferably prepared by a mechanical alloying method or an atomization method, which will be described separately below.
In the present invention, the preparation method of the metal phase raw material is preferably a mechanical alloying method, and preferably comprises the following steps:
ball milling and mixing the metal raw materials to obtain alloy powder;
and drying the alloy powder to obtain a metal phase raw material.
In the present invention, the purity of each metal raw material is independently preferably 99.9wt% or more. In the present invention, the metal raw materials preferably further comprise pretreatment before ball milling and mixing, and the pretreatment method preferably comprises: and placing the metal raw materials into ethanol for standing, and then carrying out ultrasonic cleaning and drying. In the standing process, the invention can fully immerse the metal raw material in ethanol, and the cleaning is more sufficient. In the present invention, the ethanol is preferably absolute ethanol; the standing time is preferably 1-2 hours; the power of the ultrasonic cleaning is preferably 180-300W, more preferably 200-250W; the ultrasonic cleaning time is preferably 5-30 min; the temperature of the drying is preferably 70-90 ℃, and the time of the drying is preferably 15-24 h.
In the invention, the ball milling and mixing are preferably carried out in a high-energy ball mill, and the high-energy ball mill is preferably made of a vacuum stainless steel tank; the grinding balls used for ball milling and mixing are preferably alloy balls, the alloy balls are preferably hard alloy balls or zirconia balls, and the ball-to-material ratio is preferably 4-20:1, more preferably 10:1. In the invention, the rotating speed of the ball milling and mixing is preferably 200-350 r/min, more preferably 300-350 r/min; the time of the ball-milling mixing is preferably 8 to 100 hours, more preferably 25 to 40 hours. In the present invention, a process control agent is preferably added during the ball milling mixing process, and the process control agent preferably comprises one of alcohol, stearic acid, solid paraffin, carbon tetrachloride and n-heptane; the process control agent is preferably added in an amount of 0.2 to 5wt% based on the total mass of each metal raw material. The invention adds the process control agent, which can prevent and reduce cold welding and oxidation in the ball milling process.
In the present invention, the drying temperature of the alloy powder is preferably 70 to 90 ℃, more preferably 80 ℃; the drying time is preferably 20 to 24 hours. The invention preferably sieves the dried alloy powder to obtain a metallic phase material.
In the present invention, the preparation method of the metal phase raw material is preferably an atomization method, more preferably a vacuum induction melting atomization method, and particularly preferably comprises the following steps:
carrying out induction smelting on each metal raw material to obtain an alloy melt;
spraying the alloy melt by adopting a high-pressure air nozzle or a high-pressure water nozzle, and carrying out atomization treatment to obtain a metal phase raw material.
In the present invention, the purity of each metal raw material is independently preferably 99.9wt% or more. In the present invention, the method for pretreatment of each metal raw material before induction melting is preferably the same as the pretreatment method in the mechanical alloying method described above, and will not be described here again.
In the present invention, the induction melting is preferably performed in an induction furnace, and the induction furnace is preferably subjected to a vacuum treatment before the induction melting is performed, and the vacuum degree is preferably 0.1to 1torr. In the present invention, the induction smelting is preferably performed in a protective atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere; the temperature of the induction smelting is preferably 1200-1700 ℃, more preferably 1495 ℃; the induction melting time is preferably 80 to 150 minutes.
In the invention, when the alloy melt is sprayed by a high-pressure gas nozzle, high-purity nitrogen or high-purity argon is adopted as high-pressure gas; the purity of the high-purity nitrogen and the high-purity argon is preferably 99.999 percent; the pressure of the high-pressure gas is preferably 1.7 to 4.0MPa, more preferably 2.0MPa.
In the present invention, when the alloy melt is sprayed by a high-pressure water nozzle, the pressure during water atomization is preferably 15 to 35MPa, and the cooling rate of water during atomization is controlled to be preferably 1X 10 5 ～1×10 4 K/s。
In the invention, the atomized alloy powder is preferably screened to obtain a metal phase raw material.
After the metal phase raw material is obtained, the metal phase raw material and the ceramic phase raw material are mixed to obtain a mixed material. In the present invention, the particle size of the ceramic phase raw material is preferably 50 to 500 mesh, more preferably 200 to 350 mesh. In the present invention, the ceramic phase raw material preferably includes CuAl 2 O 4 、NiAl 2 O 4 、FeAl 2 O 4 、CuCr 2 O 4 、NiCr 2 O 4 、ZnCr 2 O 4 、NiFe 2 O 4 And CuFe 2 O 4 One or more of the following. In the invention, the ceramic phase raw material has a spinel structure, and can generate a corrosion-resistant layer phase in the electrolytic process so as to enhance the corrosion resistance of the inert anode.
In the present invention, the mass ratio of the metal phase raw material to the ceramic phase raw material is preferably 5 to 50:50 to 95, more preferably 30 to 40:60 to 70.
In the invention, the mixing method of the metal phase raw material and the ceramic phase raw material is preferably ball milling, and the rotating speed of the ball milling is preferably 100-350 r/min, more preferably 150-180 r/min; the time of the ball milling is preferably 4 to 8 hours, more preferably 7 to 8 hours. In the invention, the binder and the dispersing agent are preferably added in the ball milling process; the binder is preferably polyvinyl alcohol or polyethylene glycol, and the dispersing agent is preferably deionized water or alcohol; the binder is preferably added in an amount of 0.5 to 3wt% and the dispersant is preferably added in an amount of 0.5 to 4wt% based on the total mass of the metal phase raw material and the ceramic phase raw material.
In the invention, the obtained mixed powder is preferably dried after the ball milling to obtain a mixed material. In the present invention, the drying temperature is preferably 60 to 80 ℃, more preferably 70 to 80 ℃; the drying time is preferably 24 to 30 hours.
After the mixed material is obtained, the mixed material is subjected to cold pressing to obtain a green body. In the present invention, the pressure of the cold pressing is preferably 150 to 350MPa, more preferably 200 to 310MPa; the dwell time is preferably 1to 10 minutes, more preferably 2 minutes. In the present invention, the temperature of the cold pressing is preferably 15 to 25 ℃. In the present invention, the cold pressing is preferably performed in a hydraulic press.
After the green body is obtained, the green body is sintered to obtain the inert anode material. In the present invention, the sintering is preferably performed in a sintering furnace; the sintering temperature is preferably 1000-1650 ℃, more preferably 1200-1300 ℃; the holding time is preferably 2 to 24 hours, more preferably 2 to 4 hours. In the present invention, the atmosphere for sintering is preferably a protective atmosphere, more preferably an argon or nitrogen atmosphere.
The inert anode material is prepared by adopting a cold pressing-sintering technology, and the obtained material has high density and relatively uniform, and is beneficial to improving the mechanical property of the inert anode material.
The invention also providesThe inert anode material prepared by the technical scheme or the preparation method of the technical scheme is applied to electrolytic aluminum. In the invention, the aluminum electrolyte adopted in the electrolytic aluminum is preferably a cryolite molten salt system, and particularly preferably Na 3 AlF 6 -AlF 3 -Al 2 O 3 Molten salt.
In the present invention, the temperature of the electrolytic aluminum is preferably 800 to 1000 ℃, and the time for the electrolytic aluminum is preferably 10 to 20 hours.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Al, co, cr, fe and Ni are selected as high-entropy alloy metal raw materials, all the raw materials are respectively placed in absolute ethyl alcohol for standing for 1h, then are placed in an ultrasonic cleaning machine, are subjected to ultrasonic cleaning for 10min with power of 200W, are dried after being cleaned, and are prepared according to the atomic percentage of Al: co: cr: fe: ni is 1:1:1:1:1, each metal raw material is weighed, and the purity of each metal raw material is not lower than 99.9wt%; placing the weighed metal raw materials into a high-energy ball mill for mechanical alloying reaction, wherein the ball milling adopts a vacuum stainless steel tank and a hard alloy ball, grinding ball mixing is carried out for 8 hours at 200r/min, the ball-to-material ratio is 10:1, alcohol is added as a process control agent before ball milling, and the addition amount of the alcohol is 1.0wt% based on the total mass of the metal raw materials; and after ball milling, taking out the alloy powder, placing the alloy powder in a constant-temperature drying oven, drying the alloy powder at 80 ℃ for 24 hours, and sieving the alloy powder to obtain a metal phase raw material, wherein the sieving granularity is 100-200 meshes.
200-300 mesh NiFe 2 O 4 Mixing the metal phase raw material and the ceramic phase raw material according to the mass fraction of 40wt% and 60wt%, taking polyvinyl alcohol as a binder, taking deionized water as a dispersing agent, ball-milling for 8 hours in a ball-milling tank at 150r/min, uniformly mixing, and taking a sampleDrying in an oven at 80 ℃ for 24 hours to obtain a mixed material;
pressing the mixed material into a green body by adopting a hydraulic press, wherein the pressure value is 200MPa, and maintaining the pressure at 25 ℃ for 2min;
and (3) putting the green body into a sintering furnace for sintering, wherein the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, and the sintering atmosphere is argon, so that the inert anode material is prepared.
The inert anode material prepared in this example had a density of 5.8g/cm 3 The inert anode material is used for electrolysis of an aluminum electrolysis system at 800 ℃ for 15 hours, the aluminum electrolysis system is a cryolite molten salt system, and the weight of the inert anode is increased by 4.55mg/cm 2 The impurity content of the aluminum liquid is about 0.15%; the average cell voltage is 3.431V after the 20A electrolysis experiment, and the cell voltage is reduced relative to the conventional carbon anode cell voltage (3.8-4.0V); the oxide layer has no obvious peeling, breaking and layering phenomena after cooling, and the size is almost unchanged. The inert anode material prepared by the invention has better corrosion resistance, mechanical property and conductivity.
The compressive yield strength of the inert anode material prepared in the embodiment is 1309MPa, and the mechanical property is good.
Example 2
Al, co, cr, fe, ni, ti and Cu are selected as high-entropy alloy metal raw materials, all the raw materials are respectively placed in absolute ethyl alcohol for standing for 2 hours, then are placed in an ultrasonic cleaning machine, are subjected to ultrasonic cleaning for 25 minutes at the power of 250W, are dried after being cleaned, and are prepared according to the atomic percentage of Al: co: cr: fe: ni: ti: cu is 0.6:1:1:1:1:1:1, and weighing all metal raw materials, wherein the purity of all the metal raw materials is not lower than 99.9wt%; and (3) placing the weighed metal raw materials into a copper crucible for induction smelting, vacuumizing an induction furnace before smelting, performing induction smelting under the condition that argon is used as a protective gas, wherein the working temperature is 1495 ℃, spraying a melt through a high-pressure gas nozzle after the working temperature is reached, performing atomization treatment, selecting high-purity argon with the purity of 99.999%, and the pressure of 2.0MPa, cooling and sieving the prepared alloy powder, and obtaining the metal phase raw materials with the particle size of 200-300 meshes.
200-300 meshes of CuAl 2 O 4 Mixing the metal phase raw material and the ceramic phase raw material according to the mass fraction of 30wt% and 70wt%, taking polyvinyl alcohol as a binder and deionized water as a dispersing agent, ball-milling for 7 hours at 160r/min in a ball-milling tank to uniformly mix the materials, drying the samples in a 70 ℃ oven for 30 hours to obtain a mixed material
Pressing the mixed material into a green body by adopting a hydraulic press, wherein the pressure value is 310MPa, and maintaining the pressure at 20 ℃ for 2min;
and (3) putting the green body into a sintering furnace for sintering, wherein the sintering temperature is 1300 ℃, the heat preservation time is 4 hours, and the sintering atmosphere is nitrogen, so that the inert anode material is prepared.
The inert anode material prepared in this example had a density of 5.7g/cm 3 The inert anode material is used for electrolysis of an aluminum electrolysis system at 800 ℃ for 20 hours, the aluminum electrolysis system is a cryolite molten salt system, and the weight of the inert anode is increased by 4.63mg/cm 2 The impurity content of the aluminum liquid is about 0.26%; the average cell voltage 3.479V after the 20A electrolysis experiment is reduced relative to the conventional carbon anode cell voltage (3.8-4.0V); the oxide layer has no obvious peeling, breaking and layering phenomena after cooling, and the size is almost unchanged. The inert anode prepared by the invention has better corrosion resistance, mechanical property and conductivity.
Comparative example 1
The Ni-Fe alloy inert anode is used for electrolysis of an aluminum electrolysis system at 860 ℃ for 20 hours, the aluminum electrolysis system is a cryolite molten salt system, after the electrolysis is carried out for 20 hours, anode fluorination is serious, voltage is increased from 3.426V to more than 6V, resistance of electron transmission is large, voltage is large, and conductivity is poor.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. An inert anode material comprising a metallic phase and a ceramic phase; the ceramic phase is CuAl 2 O 4 、NiAl 2 O 4 、CuCr 2 O 4 、NiCr 2 O 4 、ZnCr 2 O 4 、FeAl 2 O 4 、NiFe 2 O 4 And CuFe 2 O 4 One or more of the following; the metal phase has a high-entropy alloy solid solution structure;
the preparation method of the inert anode material comprises the following steps:
mixing a metal phase raw material and a ceramic phase raw material to obtain a mixed material; the ceramic phase raw material is CuAl 2 O 4 、NiAl 2 O 4 、CuCr 2 O 4 、NiCr 2 O 4 、ZnCr 2 O 4 、FeAl 2 O 4 、NiFe 2 O 4 And CuFe 2 O 4 One or more of the following;
cold pressing the mixed material to obtain a green body;
sintering the green body to obtain an inert anode material;
the sintering atmosphere is argon or nitrogen atmosphere;
the metal phase raw material consists of Al, co, cr, fe and Ni or Al, co, cr, fe, ni, ti and Cu, wherein when the metal phase raw material consists of Al, co, cr, fe and Ni, the atomic ratio of Al, co, cr, fe to Ni is 1:1:1:1, the sintering temperature is 1200 ℃, and the heat preservation time is 2h;
when the metal phase raw material consists of Al, co, cr, fe, ni, ti and Cu, the atomic ratio of Al, co, cr, fe, ni, ti to Cu is 0.6:1:1:1:1:1, the sintering temperature is 1300 ℃, and the heat preservation time is 4 hours;
the metal phase raw material is prepared by adopting a mechanical alloying method or an atomization method;
when the preparation method of the metal phase raw material is a mechanical alloying method, the method comprises the following steps:
ball milling and mixing the metal raw materials to obtain alloy powder;
drying the alloy powder to obtain a metal phase raw material;
when the preparation method of the metal phase raw material is an atomization method, the method comprises the following steps:
carrying out induction smelting on each metal raw material to obtain an alloy melt;
spraying the alloy melt by adopting a high-pressure air nozzle or a high-pressure water nozzle, and carrying out atomization treatment to obtain a metal phase raw material.
2. The inert anode material of claim 1 wherein said metal phase has a solid solution structure of no more than two phases.
3. A process for the preparation of an inert anode material according to any one of claims 1to 2 comprising the steps of:
mixing a metal phase raw material and a ceramic phase raw material to obtain a mixed material;
cold pressing the mixed material to obtain a green body;
and sintering the green body to obtain the inert anode material.
4. A method according to claim 3, wherein the metal phase material is prepared by mechanical alloying or atomization.
5. The method according to claim 3 or 4, wherein the metal phase raw material has a particle size of 50 to 500 mesh.
6. The method according to claim 5, wherein the mass ratio of the metal phase raw material to the ceramic phase raw material is 5 to 50:50 to 95.
7. A method according to claim 3, wherein the cold pressing pressure is 150-350 MPa and the dwell time is 1-10 min.
8. Use of an inert anode material according to any one of claims 1to 2 or an inert anode material prepared by a preparation method according to any one of claims 3 to 7 in the electrolysis of aluminium.
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| Title |
|---|
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| 罗洪杰等.铝电解用惰性阳极研究进展综述.《有色金属先进材料及其制备技术学术研讨会论文集》.东北大学出版社,2016,第175-176页. * |
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