CN113308713A - Metal ceramic anode and preparation method and application thereof - Google Patents

Metal ceramic anode and preparation method and application thereof Download PDF

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CN113308713A
CN113308713A CN202110569744.5A CN202110569744A CN113308713A CN 113308713 A CN113308713 A CN 113308713A CN 202110569744 A CN202110569744 A CN 202110569744A CN 113308713 A CN113308713 A CN 113308713A
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ceramic
nife
nio
powder
foam metal
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席锦会
葛鹏
亢宁宁
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Western Metal Material Co ltd
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Western Metal Material Co ltd
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    • 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
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2666—Other ferrites containing nickel, copper or cobalt
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2

Abstract

The invention belongs to the technical field of electrode materials, and particularly relates to a metal ceramic anode and a preparation method and application thereof. The invention provides a metal ceramic anode, which comprises a through-hole foam metal matrix and ceramic, wherein the ceramic comprises filled ceramic filled in pores of the through-hole foam metal matrix and a ceramic outer layer positioned on the outer surface of the through-hole foam metal matrix; the through-hole foam metal matrix is made of copper or nickel; the ceramic is made of doped NiO-NiFe2O4Ceramic, said doped NiO-NiFe2O4The ceramic comprises NiO-NiFe2O4Ceramic matrix and doped oxide. The through-hole foam metal matrix forms a communication net in the inventionThe metal phase with the shape structure and the filling ceramic filled in the pores of the through-hole foam metal matrix also form a ceramic phase with a communicated net structure, which is beneficial to improving the electrical conductivity, the thermal shock resistance and the mechanical strength of the metal ceramic anode.

Description

Metal ceramic anode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a metal ceramic anode and a preparation method and application thereof.
Background
At present, the aluminum electrolysis industry usually adopts a molten salt electrolysis method, the used anode is a carbon anode, a large amount of carbon and energy are needed to be consumed in the aluminum electrolysis production process, and the anode needs to be continuously replaced due to continuous consumption of the anode in the electrolysis production process, so that the production is difficult to be stably carried out. The consumption of the anode can be greatly reduced by replacing the carbon anode with a non-consumable cermet inert anode. The prior technical conception generally adopts ceramic powder and metal powder to mix and then sinter to obtain the metal ceramic, but in the conception, the metal phase in the metal ceramic has poor wettability relative to the ceramic phase, and the metal phase in the inert anode is often agglomerated after sintering and can not form a communicated net structure, so that the requirements of the existing aluminum electrolysis industry on the performances of high conductivity, corrosion resistance, high mechanical strength and high thermal shock resistance of the anode can not be met.
In order to improve the wettability of the metal with respect to the ceramic phase, the Chinese patent CN103556184B and the article NiFe2O4Inert anode preparation and metal/NiFe2O4Wettability study (Yaoyun. NiFe2O4Inert anode preparation and metal/NiFe2O4Wettability study [ D]University of Kunming science, 2019.) by introducing polyvinylpyrrolidone as surfactant, obtaining nanopowder by ball milling technology, doping Ti powder to make Cu and NiFe in sintering process2O4Titanium is used as intermediate metal to form reaction wetting, so that Cu and NiFe are improved2O4Wettability of the ceramic. However, the distribution of the metal phase in the method still does not reach a communicated three-dimensional net structure, the wettability of the metal phase to the ceramic phase is still to be improved, and the obtained cermet anode has low conductivity, thermal shock resistance and poor corrosion resistance.
Disclosure of Invention
In view of the above, the present invention provides a cermet anode, which has a connected metal phase, has the characteristics of high electrical conductivity, good thermal shock resistance and excellent corrosion resistance, and meets the use requirements of the aluminum electrolysis industry.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a metal ceramic anode, which comprises a through-hole foam metal matrix and ceramic, wherein the ceramic comprises filled ceramic filled in pores of the through-hole foam metal matrix and a ceramic outer layer positioned on the outer surface of the through-hole foam metal matrix;
the through-hole foam metal matrix is made of copper or nickel;
the ceramic is made of doped NiO-NiFe2O4Ceramic, said doped NiO-NiFe2O4The ceramic comprises NiO-NiFe2O4Ceramic matrix and doped oxide.
Preferably, the mass of the through-hole foam metal matrix is 10-27% of the mass of the metal ceramic anode.
Preferably, the aperture of the through-hole foam metal matrix is 3-5 mm, and the porosity is 60-80%.
Preferably, the doped NiO-NiFe2O4In the ceramic, NiO and NiFe2O4The mass ratio of (10-15): (85-90);
the doped oxide is TiO2、MnO2And V2O5One or more of;
the total mass of the doped oxide is less than or equal to 5 percent of the total mass of the ceramic.
Preferably, the thickness of the ceramic outer layer is 5-10 mm.
The invention also provides a preparation method of the metal ceramic anode in the technical scheme, which comprises the following steps:
doped NiO-NiFe2O4Crushing the ceramic to obtain ceramic powder;
mixing and granulating the ceramic powder and a binder to obtain granulated powder;
filling the granulation powder in the pores of the through-hole foam metal matrix and coating the outer surface of the through-hole foam metal matrix, and sequentially pressing and sintering to obtain the metal ceramic anode; the through-hole foam metal matrix is made of copper or nickel.
Preferably, the doped NiO-NiFe2O4The preparation method of the ceramic comprises the following steps:
NiO and Fe2O3Mixing with the doped oxide, and performing ball milling to obtain ball milled powder;
mixing the ball milling powder and the bonding substance, and sequentially molding and calcining to obtain the doped NiO-NiFe2O4A ceramic.
Preferably, the calcining temperature is 1000-1250 ℃, and the time is 6-8 h.
Preferably, the sintering time is 6-10 h;
when the through-hole foam metal substrate is made of copper, the sintering temperature is 1050-1080 ℃;
and when the through-hole foam metal substrate is made of nickel, the sintering temperature is 1050-1300 ℃.
The invention also provides the application of the metal ceramic anode in the technical scheme or the metal ceramic anode prepared by the preparation method in the technical scheme in aluminum electrolysis.
The invention provides a metal ceramic anode, which comprises a through-hole foam metal matrix and ceramic, so the ceramic comprises filled ceramic filled in the pores of the through-hole foam metal matrix and a ceramic outer layer positioned on the outer surface of the through-hole foam metal matrix; the through-hole foam metal matrix is made of copper or nickel; the ceramic is made of doped NiO-NiFe2O4Ceramic, said doped NiO-NiFe2O4The ceramic comprises NiO-NiFe2O4Ceramic matrix and doped oxide. In the invention, the filling ceramic and the ceramic outer layer are doped NiO-NiFe with the same material2O4The ceramic is beneficial to improving the corrosion resistance of the metal ceramic anode; the through-hole foam metal matrix is a continuous metal phase, and the use of the through-hole foam metal matrix is beneficial to avoiding the agglomeration of the metal phase in the preparation process of the metal ceramic anode and improving the conductivity and the supporting performance of the metal ceramic anode; at the same time, the through-hole bubbleThe metal foam matrix forms a metal phase with a communicated net structure, and the filling ceramic filled in the pores of the through-hole metal foam matrix also forms a ceramic phase with a communicated net structure, so that the wetting condition of the metal phase and the ceramic phase is greatly improved, and the thermal shock resistance and the mechanical strength of the metal ceramic anode are favorably improved.
The test result of the embodiment shows that the room-temperature bending strength of the cermet anode provided by the invention is 274-360 MPa, and the mechanical property is excellent; the conductivity at 960 ℃ is 130-180 omega-1·cm-1The conductivity is high; the cycle times of the thermal shock resistance test at room temperature and 960 ℃ are 19-25 times, and the thermal shock resistance is excellent; the static corrosion rate of 20h in the cryolite fused salt at 960 ℃ is 0.8 multiplied by 10-4～1.2×10-4g·cm-2·h-1And the corrosion resistance is excellent.
Drawings
FIG. 1 is a macroscopic view of the copper foam used in example 1.
FIG. 2 is a macroscopic cross-sectional view of the cermet anode obtained in example 1;
FIG. 3 shows NiFe obtained in comparative example 22O4SEM image of the base inert anode.
Detailed Description
The invention provides a metal ceramic anode, which comprises a through-hole foam metal matrix and ceramic, wherein the ceramic comprises filled ceramic filled in pores of the through-hole foam metal matrix and a ceramic outer layer positioned on the outer surface of the through-hole foam metal matrix;
the through-hole foam metal matrix is made of copper or nickel;
the ceramic is made of doped NiO-NiFe2O4Ceramic, said doped NiO-NiFe2O4The ceramic comprises NiO-NiFe2O4Ceramic matrix and doped oxide.
The cermet anode provided by the invention comprises a through-hole foam metal matrix. In the invention, the material of the through-hole foam metal matrix is copper or nickel. In the invention, the aperture of the through-hole foam metal matrix is preferably 3-5 mm, more preferably 3.2-4.8 mm, and still more preferably 3.5-4.5 mm; the porosity is preferably 60 to 80%, more preferably 63 to 78%, and still more preferably 65 to 75%. In the invention, the mass of the through-hole foam metal matrix is preferably 10-27%, more preferably 12-25%, and even more preferably 14-23% of the mass of the metal ceramic anode.
The cermet anode provided by the invention comprises ceramics, wherein the ceramics comprise filled ceramics filled in pores of the through-hole foam metal matrix and a ceramic outer layer positioned on the outer surface of the through-hole foam metal matrix.
In the invention, the material of the filled ceramic is consistent with that of the ceramic outer layer. In the invention, the ceramic material is doped NiO-NiFe2O4Ceramic, said doped NiO-NiFe2O4The ceramic comprises NiO-NiFe2O4Ceramic matrix and doped oxide.
In the present invention, the doped NiO-NiFe2O4In the ceramic, NiO and NiFe2O4The mass ratio of (A) to (B) is preferably (10-15): (85-90), more preferably (11-15): (85-89), and more preferably (12-15): (85-88), most preferably 15: 85. in the present invention, the doped NiO-NiFe2O4In the ceramic, the doped oxide is preferably TiO2、MnO2And V2O5One or more of (a). In the present invention, the total mass of the doped oxides is preferably 5% or less of the total mass of the ceramic. In the present invention, the doped NiO-NiFe2O4In the ceramic, the mass of the individual doped oxides is preferably 2% or less of the total mass of the ceramic. In the invention, the thickness of the ceramic outer layer is preferably 5-10 mm, and more preferably 6-9 mm.
The invention also provides a preparation method of the metal ceramic anode in the technical scheme, which comprises the following steps:
doped NiO-NiFe2O4Crushing the ceramic to obtain ceramic powder;
mixing and granulating the ceramic powder and a binder to obtain granulated powder;
filling the granulation powder in the pores of the through-hole foam metal matrix and coating the outer surface of the through-hole foam metal matrix, and sequentially pressing and sintering to obtain the metal ceramic anode; the through-hole foam metal matrix is made of copper or nickel.
In the present invention, the components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention mixes NiO-NiFe2O4And (5) crushing the ceramic to obtain ceramic powder.
In the present invention, the doped NiO-NiFe2O4The method for preparing the ceramic preferably comprises the following steps:
NiO and Fe2O3Mixing with the doped oxide, and performing ball milling to obtain ball milled powder;
mixing the ball milling powder and the bonding substance, and sequentially molding and calcining to obtain the doped NiO-NiFe2O4A ceramic.
NiO and Fe are mixed2O3And mixing the mixture with the doped oxide, and carrying out ball milling to obtain ball milled powder.
In the present invention, the NiO and Fe2O3The mass ratio of (A) to (B) is preferably (38.68-42.09): (59.91-61.32), more preferably (39-42): (60-61.1). In the present invention, the doped oxide is preferably TiO2、MnO2And V2O5One or more of (a). In the present invention, the total mass of the doped oxides is preferably equal to or less than NiO and Fe2O3And 5% of the total mass of the doped oxide. In the present invention, the mass of the single doped oxide is preferably equal to or less than NiO and Fe2O3And 2% of the total mass of the doped oxide.
In the present invention, the ball milling is preferably wet ball milling. In the present invention, the liquid medium for ball milling is preferably deionized water. In the invention, the ball-to-material ratio of the ball mill is preferably (1.5-3): 1, more preferably (1.7 to 2.7): 1. in the invention, the rotation speed of the ball mill is preferably 300-500 rpm, more preferably 350-450 rpm; the time is preferably 8 to 16 hours, and more preferably 10 to 14 hours.
After the ball milling, the invention preferably further comprises drying the obtained ball milling mixture to obtain ball milled powder. In the invention, the drying temperature is preferably 120-150 ℃, and more preferably 120-140 ℃; the time is preferably 8 to 12 hours, and more preferably 9 to 11 hours. In the present invention, the drying apparatus is preferably an oven.
After the ball milling powder is obtained, the ball milling powder and the bonding substance are mixed, and the mixture is sequentially molded and calcined to obtain the doped NiO-NiFe2O4A ceramic.
In the present invention, the binding substance is preferably polyvinyl alcohol. In the present invention, the mass ratio of the ball mill powder to the binding substance is preferably 19: 1.
in the present invention, the mixing method of the ball mill powder and the binding substance is preferably granulation; the granulation method of the present invention is not particularly limited, and granulation known to those skilled in the art may be employed.
After granulation, the mixed system obtained is preferably screened, and undersize products are taken as granules and subjected to subsequent operation. In the present invention, the mesh number of the screen is preferably 60 meshes.
After the granulated material is obtained, the granulated material is molded to obtain a molded blank.
In the invention, the molding pressure is preferably 80-120 MPa, more preferably 85-115 MPa, and still more preferably 90-110 MPa; the dwell time is preferably 40 to 80s, more preferably 50 to 70s, and still more preferably 55 to 65 s. In the present invention, the molding is preferably performed at room temperature, specifically, 18 to 40 ℃. The shape of the forming blank is not particularly limited, and any shape can be adopted.
After a forming blank is obtained, the forming blank is calcined to obtain the doped NiO-NiFe2O4A ceramic.
In the invention, the calcination temperature is preferably 1000-1250 ℃, more preferably 1050-1200 ℃, and further preferably 1080-1180 ℃; the time is preferably 6 to 8 hours, more preferably 6.3 to 7.8 hours, and still more preferably 6.5 to 7.5 hours.
Obtaining the doped NiO-NiFe2O4After the ceramic, the invention mixes NiO-NiFe2O4And (5) crushing the ceramic to obtain ceramic powder.
The present invention is not particularly limited to the above-mentioned crushing, and a crushing method known to those skilled in the art may be employed. In the present invention, the particle size of the ceramic powder is preferably 0.106mm or less.
After the ceramic powder is obtained, the ceramic powder and the binder are mixed and granulated to obtain granulated powder.
In the present invention, the binder is preferably polyvinyl alcohol. In the present invention, the mass ratio of the ceramic powder to the binder is preferably 19: 1. the present invention is not particularly limited to the above-mentioned mixing granulation, and mixing granulation known to those skilled in the art may be employed. After granulation, the mixed system obtained is preferably screened, and undersize is taken as granulated powder and is subjected to subsequent operation. In the present invention, the mesh number of the screen is preferably 30 meshes.
After the granulating powder is obtained, the granulating powder is filled in the pores of the through-hole foam metal matrix and coats the outer surface of the through-hole foam metal matrix, and the metal ceramic anode is obtained by pressing and sintering in sequence.
In the present invention, the method of filling the granulated powder in the pores of the open-cell foam metal substrate and coating the outer surface of the open-cell foam metal substrate is preferably: laying a layer of granulation powder on the bottom surface of the mould, placing the through-hole foam metal matrix in the center of the mould, filling the granulation powder on the periphery and the upper surface of the through-hole foam metal matrix, and compacting. In the present invention, the shape of the mold is preferably cylindrical. The tap density is not particularly limited in the present invention, and may be a tap density well known to those skilled in the art; the invention promotes the filling of the granulation powder into the pores of the through-hole foam metal matrix through compaction.
In the invention, the pressing pressure is preferably 120-200 MPa, more preferably 130-190 MPa, and still more preferably 140-180 MPa; the dwell time is preferably 40 to 80s, more preferably 50 to 70s, and still more preferably 55 to 65 s. In the present invention, the pressing is preferably performed at room temperature, specifically, 18 to 40 ℃.
In the invention, when the through-hole foam metal substrate is made of copper, the sintering temperature is preferably 1050-1080 ℃, more preferably 1050-1070 ℃, and further preferably 1050-1060 ℃; when the through-hole foam metal substrate is made of nickel, the sintering temperature is preferably 1050-1300 ℃, more preferably 1050-1250 ℃, and further preferably 1100-1200 ℃. In the invention, the sintering time is preferably 6-10 h, more preferably 6.5-9.5 h, and still more preferably 7-9 h. In the present invention, the degree of vacuum of the sintering is preferably 10-2～10-1Pa, more preferably 2X 10-2～9×10-2Pa. In the present invention, the sintering equipment is preferably a sintering furnace, more preferably a vacuum sintering furnace.
The invention also provides the application of the metal ceramic anode in the technical scheme or the metal ceramic anode prepared by the preparation method in the technical scheme in aluminum electrolysis.
In order to further illustrate the present invention, the following examples are provided to describe a cermet anode of the present invention and its preparation method and application in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
According to the proportion of 41.3: 56.7: 2 mass ratio of NiO to Fe2O3And doped oxide TiO2Mixing, ball milling for 12h by a wet method by taking deionized water as a liquid medium, and drying for 8h at 120 ℃ to obtain ball milled powder;
according to the following steps of 19: 1, mixing the ball milling powder and polyvinyl alcohol serving as a bonding substance, sieving by a 60-mesh sieve, taking undersize products, maintaining the pressure for 40s under the pressure of 80MPa, molding, and calcining at 1050 ℃ for 6h to obtain doped NiO-NiFe2O4A ceramic;
will mix withHetero NiO-NiFe2O4Crushing the ceramic to obtain ceramic powder with the particle size of less than or equal to 0.105 mm;
according to the following steps of 19: 1, mixing the obtained ceramic powder and a binder for granulation, sieving by a 30-mesh sieve, and taking undersize as granulated powder;
filling 338g of the obtained granulation powder into pores of foam copper with the mass of 113.9g, the size of phi 30mm multiplied by 45mm and the porosity of 60 percent and the outer surface of the coated foam copper by using a phi 41mm cylindrical die, keeping the pressure for 40s under the pressure of 120MPa for pressing, and then sintering for 6h at 1000 ℃ to obtain the metal ceramic anode with the phi 40mm multiplied by 60mm, the thickness of the upper surface ceramic layer and the peripheral ceramic layer being 5mm and the thickness of the lower surface ceramic layer being 10 mm.
FIG. 1 is a macroscopic view of a copper foam used in example 1 of the present invention, and it can be seen from FIG. 1 that the copper foam has a continuous network structure.
Example 2
According to the weight ratio of 41.7: 57.3: 1, NiO and Fe2O3And doped oxide MnO2Mixing, ball milling for 12h by a wet method by taking deionized water as a liquid medium, and drying for 10h at 120 ℃ to obtain ball milled powder;
according to the following steps of 19: 1, mixing the ball milling powder and polyvinyl alcohol serving as a bonding substance, sieving by a 60-mesh sieve, taking undersize products, maintaining the pressure for 60s under the pressure of 120MPa, forming, and calcining at 1200 ℃ for 8h to obtain doped NiO-NiFe2O4A ceramic;
doped NiO-NiFe2O4Crushing the ceramic to obtain ceramic powder with the particle size of less than or equal to 0.105 mm;
according to the following steps of 19: 1, mixing the obtained ceramic powder and a binder for granulation, sieving by a 30-mesh sieve, and taking undersize as granulated powder;
and filling 598g of the obtained granulated powder into pores of the foam copper with the mass of 63.3g, the size of phi 30mm multiplied by 40mm and the porosity of 75% and the outer surface of the coated foam copper by using a phi 51mm cylindrical die, keeping the pressure for 60s under 140MPa for pressing, and then sintering at 1050 ℃ for 6h to obtain the metal ceramic anode with the phi 50mm multiplied by 60mm, the upper surface ceramic layer, the lower surface ceramic layer and the peripheral ceramic layer with the thickness of 10 mm.
Example 3
According to the weight ratio of 41.6: 56.9: 1.5 mass ratio of NiO to Fe2O3And a doped oxide V2O5Mixing, ball milling for 12h by a wet method by taking deionized water as a liquid medium, and drying for 12h at 120 ℃ to obtain ball milled powder;
according to the following steps of 19: 1, mixing the ball milling powder and polyvinyl alcohol serving as a bonding substance, sieving by a 60-mesh sieve, taking undersize products, maintaining the pressure for 60s under the pressure of 100MPa, forming, and calcining at 1250 ℃ for 8h to obtain doped NiO-NiFe2O4A ceramic;
doped NiO-NiFe2O4Crushing the ceramic to obtain ceramic powder with the particle size of less than or equal to 0.105 mm;
according to the following steps of 19: 1, mixing the obtained ceramic powder and a binder for granulation, sieving by a 30-mesh sieve, and taking undersize as granulated powder;
and filling 1030g of the obtained granulation powder into a pore of foam nickel with the mass of 314.4g, the size of phi 50mm multiplied by 60mm and the porosity of 70% and the outer surface of the coated foam nickel by using a phi 61mm cylindrical die, keeping the pressure for 60s under the pressure of 180MPa, pressing, and sintering at 1250 ℃ for 6h to obtain the metal ceramic anode with the phi 60mm multiplied by 80mm, the thicknesses of the upper surface ceramic layer and the lower surface ceramic layer of 10mm and the thickness of the peripheral ceramic layer of 5 mm.
Example 4
According to the following steps of 40: 55: 2: 1.5: 1.5 mass ratio of NiO to Fe2O3And doped oxide TiO2、MnO2、V2O5Mixing, ball milling for 12h by a wet method by taking deionized water as a liquid medium, and drying for 12h at 120 ℃ to obtain ball milled powder;
according to the following steps of 19: 1, mixing the ball milling powder and polyvinyl alcohol serving as a bonding substance, sieving by a 60-mesh sieve, taking undersize products, maintaining the pressure for 80s under the pressure of 90MPa, molding, and calcining at 1100 ℃ for 6h to obtain doped NiO-NiFe2O4A ceramic;
doped NiO-NiFe2O4Crushing the ceramic to obtain ceramic powder with the particle size of less than or equal to 0.105 mm;
according to the following steps of 19: 1, mixing the obtained ceramic powder and a binder for granulation, sieving by a 30-mesh sieve, and taking undersize as granulated powder;
8139g of the obtained granulation powder is filled in 3018g of foamed nickel pores with the size of phi 100mm multiplied by 120mm and the porosity of 80 percent and the outer surface of the coated foamed nickel by using a phi 122mm cylindrical die, the pressure is maintained for 80s under 200MPa for pressing, and then the metal ceramic anode with the quality of phi 120mm multiplied by 150mm and the thicknesses of an upper surface ceramic layer, a lower surface ceramic layer and a peripheral ceramic layer of 5mm is obtained by sintering at 1300 ℃ for 8 h.
And (3) carrying out performance test on the cermet anodes obtained in the embodiments 1-4, wherein the test items and the test method are as follows:
1. room temperature bending strength: the bending strength of the sample was measured by a three-point bending method with a span of 30mm and a loading rate of 0.5mm/min, and the bending strength, F-breaking load, L-span, b-width, h-thickness were calculated by the formula R ═ (3F × L)/(2b × h).
2. Conductivity: the sample is put into a tube furnace filled with argon, the temperature is gradually increased to 960 ℃ from room temperature, and the electric conductivity is calculated according to ohm's law by measuring the voltage and the current of the sample at 960 ℃.
3. Thermal shock resistance: and (3) putting the sample into a 960 ℃ well-type resistance furnace, preserving heat for 5min, quickly taking out the sample, naturally cooling the sample to room temperature at room temperature, then quickly putting the sample into the well-type resistance furnace again, repeating the operation until the sample is broken, and recording the number of circulating operations.
4. Electrolytic corrosion rate: determination of samples on fused cryolite (90% Na) by mass loss method3AlF6-5％CaF2-5％Al2O3(by mass)) electrolytic corrosion rate in the electrolyte, the electrolytic temperature is 960 ℃, the electrolytic time is 24h, and the anode current density is 0.8A/cm2The pole pitch was 3 cm.
The test results are shown in Table 1.
TABLE 1 results of performance test of cermet anodes obtained in examples 1 to 4
Figure BDA0003082204910000101
As can be seen from the table 1, the room-temperature bending strength of the cermet anode provided by the invention is 274-360 MPa, and the mechanical property is excellent; the conductivity of the alloy is 130-180 omega at 960 DEG C-1·cm-1The conductivity is high; the cycle times of the thermal shock resistance test at room temperature and 960 ℃ are 19-25 times, and the thermal shock resistance is excellent; the static corrosion rate of 20h in the cryolite fused salt at 960 ℃ is 0.8 multiplied by 10-4～1.2×10-4g·cm-2·h-1And the corrosion resistance is excellent.
Comparative example 1
The preparation of the wet type nano NiFe is carried out according to the method disclosed in the document CN101713083B2O4-NiO-Cu-Ni cermet inert anode:
mixing Fe2O3And NiO or Ni2O3Mixing the raw materials according to the weight ratio of 1: 0.1-5, adding water into the mixture, performing wet ball milling and drying, and calcining at 900-1200 ℃ in a sintering furnace to prepare NiFe2O4-a NiO precursor ceramic powder;
with NiFe2O4the-NiO precursor ceramic powder is taken as a raw material, Cu powder and Ni powder are added for mixing, and Ti powder and MnO are added2、V2O5Taking the mixture of MgO and CaO as a trace dopant, adding the mixture of absolute ethyl alcohol and polyvinylpyrrolidone to carry out secondary planetary ball milling, drying, and grinding ball milling materials to obtain NiFe2O4-mixed nanopowder of NiO-Cu-Ni;
70-85 wt% of precursor ceramic powder, 14-17 wt% of Cu powder, 2-5 wt% of Ni powder, 0-2 wt% of Ti powder and 0-1 wt% of MnO2Powder, 0-1.5% V2O5Placing the powder, 0-1% of MgO powder and 0-1% of CaO powder into a rubber wrapping sleeve, compacting by vibration, vacuumizing, shaping, and performing cold isostatic pressing to obtain a cylindrical green body;
then sintering in a vacuum furnace or an atmosphere furnace, wherein the sintering temperature is 650-950 ℃, and finally obtaining NiFeO4-NiO-Cu-Ni cermet inert anode.
After the inert anode is applied to electrolytic aluminum production, the current efficiency reaches 94-95%, and the cell voltage is reduced to 385-390 mV.
Comparative example 2
According to NiFe2O4Inert anode preparation and metal/NiFe2O4Method for preparing NiFe in wettability research2O4And (3) base inert anode:
with Fe2O3And NiO is taken as a raw material, and the weight ratio of NiO: fe2O342.1 wt%: 57.9 wt%, and milling in a planetary ball mill by adopting a wet ball milling mode; drying the ball-milled precursor at a constant temperature to remove water, and calcining at 1100 ℃ to prepare ceramic powder; 17 wt% of Cu + Ni (wherein the mass ratio of Cu to Ni is 85%: 15%), and 1% of doped TiO2Powder or 1% Ti powder, 1% MnO2Powder, 1.5% V2O5Ball milling is carried out on powder, 1% of MgO powder, 1% of CaO, absolute ethyl alcohol and 3% of PVP as grinding aid, dispersing agent, film forming agent and adhesive for 24h, drying is carried out at constant temperature of 80 ℃ for 12h, CIP forming is carried out under 240MPa, and sintering is carried out at Ar atmosphere of 900-1250 ℃ for 12h to prepare NiFe2O4And (4) an inert anode.
The research of the comparative example document shows that the optimal doping amount of Ti is about 1 percent, and the thermal shock resistance of the Ti-doped wetting inert anode is 13 times; the static corrosion rate is reduced to 1.235 mm. y-1. The problems with this study are: sintering of the ultrafine powder can increase the shrinkage rate of a sintered body to a great extent, easily cause large cracks to form in the anode matrix, reduce the comprehensive performance of the material, and even cause sintering failure. In addition, for the obtained NiFe2O4Scanning electron microscopic tests are carried out on the inert anode, an obtained SEM image is shown in figure 3, as can be seen from figure 3, in the comparative example, although wettability between metal and ceramic is improved and spreading is formed, the continuous three-dimensional network structure formed by the metal is not perfect, the metal phase does not form a basically continuous integral structure like foam metal, in addition, the pore size and the metal thickness are not uniform like the foam metal, so that on the premise of containing the same content of the metal phase, the conductivity, the thermal shock resistance and the mechanical strength of the comparative example 2 are poor.
Comparative example 3
According to the following steps of 40: 55: 2: 1.5: 1.5 mass ratio of NiO to Fe2O3And doped oxide TiO2、MnO2、V2O5Mixing, ball milling for 12h by a wet method by taking deionized water as a liquid medium, and drying for 12h at 120 ℃ to obtain ball milled powder;
according to the following steps of 19: 1, mixing the ball milling powder and polyvinyl alcohol serving as a bonding substance, sieving by a 60-mesh sieve, taking undersize products, maintaining the pressure for 80s under the pressure of 90MPa, molding, and calcining at 1100 ℃ for 6h to obtain doped NiO-NiFe2O4A ceramic;
doped NiO-NiFe2O4Crushing the ceramic to obtain ceramic powder with the particle size of less than or equal to 0.105 mm;
according to the following steps of 19: 1, mixing the obtained ceramic powder and a binder for granulation, sieving by a 30-mesh sieve, and taking undersize as granulated powder;
8139g of the obtained granulation powder is filled in the pores of the foam copper with the mass of 3018g, the size of phi 100mm multiplied by 120mm and the porosity of 50 percent and the outer surface of the coated foam copper by using a phi 122mm cylindrical die, the pressure is maintained for 80s under the pressure of 200MPa for pressing, and then the metal ceramic anode with the phi 120mm multiplied by 150mm and the thicknesses of the upper surface ceramic layer, the lower surface ceramic layer and the peripheral ceramic layer of 15mm is obtained by sintering at 1350 ℃.
Observing and testing the cermet anode obtained in the comparison ratio 3, and finding out that (1) the granulated powder cannot be fully compacted and the ceramic phase is not compact when the ceramic powder is filled because the porosity of the foamed nickel is smaller and the pore diameter is reduced under the same volume; (2) the foam copper is melted, and part of copper permeates into pores of the ceramic, so that a foam body communicated with the metal copper is damaged, the metal copper cannot form a continuous three-dimensional net structure, and the conductivity is poor; (3) the outer ceramic layer is 15mm thick, local stripping of the outer ceramic layer occurs when the thermal shock resistance of the material is tested, and the thermal shock resistance and the mechanical property are poor.
As can be seen from examples 1-4 and comparative example 3, in the cermet anode provided by the invention, the porosity selection and sintering temperature selection of the foamed ceramic and the thickness of the outer ceramic layer of the cermet inert anode have synergistic effects on the conductivity, thermal shock resistance and mechanical properties of the obtained cermet anode product.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A cermet anode comprising an open-cell foam metal substrate and a ceramic, wherein the ceramic comprises a filled ceramic filled in pores of the open-cell foam metal substrate and a ceramic outer layer positioned on the outer surface of the open-cell foam metal substrate;
the through-hole foam metal matrix is made of copper or nickel;
the ceramic is doped NiO-NiFe2O4Ceramic, said doped NiO-NiFe2O4The ceramic comprises NiO-NiFe2O4Ceramic matrix and doped oxide.
2. The cermet anode of claim 1, wherein the through-hole metal foam matrix comprises 10-27% by mass of the cermet anode.
3. The cermet anode of claim 1 or 2, characterized in that the pore diameter of the through-hole foam metal matrix is 3-5 mm and the porosity is 60-80%.
4. The cermet anode of claim 1, wherein the doped NiO-NiFe2O4In the ceramic, NiO and NiFe2O4The mass ratio of (10-15): (85-90);
the doped oxide is TiO2、MnO2And V2O5One or more of;
the total mass of the doped oxide is less than or equal to 5 percent of the total mass of the ceramic.
5. The cermet anode of claim 1, wherein the ceramic outer layer has a thickness of 5 to 10 mm.
6. A method of making a cermet anode of any of claims 1 to 5 comprising the steps of:
doped NiO-NiFe2O4Crushing the ceramic to obtain ceramic powder;
mixing and granulating the ceramic powder and a binder to obtain granulated powder;
filling the granulation powder in the pores of the through-hole foam metal matrix and coating the outer surface of the through-hole foam metal matrix, and sequentially pressing and sintering to obtain the metal ceramic anode; the through-hole foam metal matrix is made of copper or nickel.
7. The method of claim 6, wherein the doped NiO-NiFe2O4The preparation method of the ceramic comprises the following steps:
NiO and Fe2O3Mixing with the doped oxide, and performing ball milling to obtain ball milled powder;
mixing the ball milling powder and the bonding substance, and sequentially molding and calcining to obtain the doped NiO-NiFe2O4A ceramic.
8. The preparation method according to claim 7, wherein the calcination is carried out at a temperature of 1000 to 1250 ℃ for 6 to 8 hours.
9. The preparation method according to claim 6, wherein the sintering time is 6-10 h;
when the through-hole foam metal substrate is made of copper, the sintering temperature is 1050-1080 ℃;
and when the through-hole foam metal substrate is made of nickel, the sintering temperature is 1050-1300 ℃.
10. Use of the cermet anode of any of claims 1 to 5 or prepared by the preparation method of any of claims 6 to 9 in aluminum electrolysis.
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CN108330508A (en) * 2018-05-16 2018-07-27 东北大学 A kind of connection method of cermet inert anode used for aluminium electrolysis and metal conducting bar
CN108484213A (en) * 2018-06-14 2018-09-04 哈尔滨工业大学 A kind of ceramet is composite porous and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BG50938A3 (en) * 1986-09-16 1992-12-15 Lanxide Technology Co Ltd Porous ceramic material and method for its production
CN103556184A (en) * 2013-11-13 2014-02-05 昆明冶金研究院 Preparation method of all-wet nano NiFe2O4-NiO-Cu-Ni metal ceramic inert anode
CN104047035A (en) * 2014-06-27 2014-09-17 中国铝业股份有限公司 Inert anode for fused salt electrolysis and preparation method thereof
CN107058844A (en) * 2017-05-22 2017-08-18 华北电力大学（保定） A kind of micropore metal ceramics and preparation method as wet electrical dust precipitator pole plate
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