• 专利附录
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    • 专利摘要:
    The invention relates to an electrode material, preferably an inert anode material, comprising at least a metal core and a cermet material, characterized in that: - said metal core comprises at least one nickel alloy (Ni) and of iron (Fe), said cermet material comprises at least in percentages by weight: • 45 to 80% of a phase (2) of nickel ferrite oxide of composition NixFeyMzO4 with 0.605 x 0 0.90; 1.90 ≤ y ≤ 2.40; 0.00 ≤ z ≤ 0.20 and M being a metal selected from aluminum (Al), cobalt (Co), chromium (Cr), manganese (Mn), titanium (Ti), zirconium ( Zr), tin (Sn), vanadium (V), niobium (Nb), tantalum (Ta) and hafnium (Hf) or a combination of these metals, • 15 to 45% of a metal phase (1) comprising at least one alloy of nickel and copper, • optionally up to 10% of a phase (3) monoxide composition NixFe1-xO with 0.705 x'≤ 1.00.
    公开号:FR3022917A1
    申请号:FR1401435
    申请日:2014-06-26
    公开日:2016-01-01
    发明作者:Christian Barthelemy；Sylvie Bouvet；Armand Gabriel；Veronique Laurent；Ariane Marmottant
    申请人:Rio Tinto Alcan International Ltd；
    IPC主号:
    专利说明:

    [0001] The invention relates to electrode materials, and more particularly to anodes for the production of aluminum by electrolysis. It relates more specifically anodes called "inert" or "non-consumable", and their preparation and use. The following description refers more specifically to the use of the electrode material object of the present invention as an inert anode for the manufacture of aluminum by an igneous electrolysis process. However, mention of this industrial application in the description does not limit the scope of the invention. The present invention may relate to other industrial applications of the electrode material described hereinafter. Aluminum metal is produced industrially by igneous electrolysis, namely by electrolytic reduction of alumina in solution in a bath based on molten cryolite, called an electrolysis bath, according to the Hall-Héroult process. The electrolytic reduction is performed in electrolysis cells comprising an electrolytic cell, provided with carbon cathode elements, and one or more anodes. The electrolysis bath is contained in the vessel and the anodes are partially immersed in the electrolysis bath. The electrolysis current makes it possible to maintain the electrolysis bath at the temperature required by the Joule effect. The electrolysis cell is regularly supplied with alumina so as to compensate for the consumption of alumina produced by the electrolysis reaction. In standard technology, the anodes are of carbonaceous material and the electrolysis is carried out at a temperature typically of the order of 950 ° C. The anodes of carbonaceous material being gradually consumed during the electrolysis, it is necessary to continuously readjust the height of the portion of the anodes which is immersed in the bath and intervene on the cell to perform the replacement of the anodes. In addition, the consumption of anodes: - produces carbon dioxide (more than two tons of carbon dioxide per tonne of aluminum produced), which contributes to the greenhouse effect, and - releases sulfur dioxide from the fact that the presence of sulfur in the raw materials used for the manufacture of the anode. The development of an alumina electrolysis technology using "inert" or "non-consumable" anodes seeking to overcome these drawbacks inevitably runs up against the difficulty of producing anodes meeting various different quality criteria.
    [0002] Indeed, the anodes must be sufficiently conductive to the temperature of use so as not to increase inappropriately the power consumption associated with this technology. Furthermore, the anodes must resist corrosion in aggressive cryolithic baths so as to have a sufficient life and in order to avoid contamination of the electrolyte and aluminum in undesirable elements. Finally the anodes must be manipulable. This imposes certain mechanical properties: fragile anodes would be unusable in industrial processes. In order to satisfy these criteria set out above, namely of conductivity, corrosion resistance, as well as strength, it has been proposed to use monolithic ceramic pieces for the manufacture of these inert anodes. For example, the patent applications W002 / 066710, W002 / 083992 and US2004 / 089558 describe various oxide compositions capable of enabling the production of ceramic inert anodes, for which the amount of metal phase is generally less than 10% by weight. weight. However, the electrical conductivity of this type of anode and their mechanical properties are insufficient. Furthermore, it has also been proposed to use all-metal parts for the manufacture of these inert anodes. For example, patent applications WO99 / 36591 and W000 / 06803 describe such inert anodes which are entirely metallic. However, the corrosion resistance of these anodes in cryolithic baths remains insufficient. Finally, it has been proposed to use, as electrode materials, ceramic matrix composite materials containing one or more metal phases, so as to combine the respective advantages of the metal phase and the ceramic phase. Such composite materials, which contain at least one ceramic phase and at least one metal phase, are known under the name "cermet material". The metallic phases of these cermet materials make it possible to improve the mechanical properties of the electrodes as well as their conductivity, while the ceramic phases make it possible to improve the resistance to corrosion in the cryolitic baths.
    [0003] However, the lack of stability of the various metallic and ceramic phases during a prolonged passage of such cermet material anodes in the cryolitic baths tends to limit their life and cause the contamination of the electrolyte and aluminum . Many patent applications concern this type of anode made of cermet material.
    [0004] For example, mention may be made of international application WO2004 / 082355, which describes a process for manufacturing an inert anode made of NiO-NiFe2O4-M type cermet comprising at least one N nickel monoxide phase, a nickel S spinel phase containing iron and nickel, and a metallic phase M containing copper and nickel, said process being characterized in that it comprises: the preparation of an initial mixture including at least one precursor of said N monoxide and S spinel phases, a precursor of the metal phase M and an organic binder, the proportion of organic binder in the initial mixture being less than 2.0% by weight and the precursor of the metal phase comprising a metal powder containing copper and nickel, a setting operation in the form of the mixture, so as to form a green anode of determined shape, a sintering operation of the green anode at a temperature above 900 ° C. in a controlled atmosphere c enclosing at least one inert gas and oxygen.
    [0005] This method, which improves the production of the anode by reducing the amount of binder, does not entirely solve the problem of stability of the anode in the cryolithic bath. In particular, it was found that the electrical conductivity of the nickel NiFe2O4 spinel phase decreased during electrolysis, which conditioned the life of the anode.
    [0006] International application WO2005 / 035813 describes an anode manufacturing process containing a cermet in which one of the constituents of the oxide is a metallic element that can be reduced in whole or in part during a reduction operation during the manufacturing process. This method, which improves the anode fabrication by reducing the metal exudation, does not fully solve the problem of anode stability in the cryolithic bath. International Application W001 / 31090 discloses an inert cermet anode comprising a ceramic phase represented by the formula NixFe2yMzO (3y + x + z) ± 6, where M represents at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mb, Hf and rare earths, preferably Zn and / or Co, x is between 0.1 and 0.99, y is between 0.0001 and 0.9, z is from 0.0001 to 0.5, and b is from 0 to about 0.03. This inert cermet anode also contains a metal phase, such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and / or Os. A service life compatible with industrial conditions of use is not demonstrated for this type of anode. Thus, it is noted that the electrode materials known from the state of the art are not fully satisfactory for producing inert anodes for the production of aluminum which function optimally (i.e. lower power consumption) and with an acceptable service life from an industrial point of view. The present invention aims to overcome the disadvantages detailed above that present electrode materials known from the state of the art.
    [0007] Indeed, the inventors of the present invention have quite surprisingly developed a new electrode material, in particular a new inert anode material for the use of said inert anode in the production of aluminum which combines the following antagonistic parameters: satisfactory conductivity at the usual temperature conditions of igneous electrolysis processes, and this to not increase the power consumption associated with this technology; resistance to corrosion in the cryolithic baths usually used for this electrolysis and which are therefore aggressive; appropriate mechanical properties of the inert anode for industrial handling; an inert life of the inert anode satisfactory from an industrial point of view (therefore essentially economic), and improved compared to the inert anodes known from the state of the art; the reduction of the contamination of aluminum produced by electrolysis, as well as the electrolysis bath based on molten cryolite. The invention firstly relates to an electrode material, preferably an inert anode material, comprising at least one metal core and one cermet material, said metal core being at least covered with said cermet material and said cermet material forming a layer. external of said electrode material which is intended to be in contact with an electrolysis bath, more particularly a cryolithic bath, said electrode material is characterized in that: said metal core comprises at least one nickel alloy (Ni) and iron (Fe), the mass proportions of Ni and Fe being the following: - 40% 5 Ni 5. 85%, preferably 55% 5 Ni 5 80%, - 15% 5 Fe 5 60%, preferably 20% 5 Fe 5. 45%, said cermet material comprises at least in percentages by weight: - 45 to 80% of a nickel ferrite oxide phase of composition Ni, FeyMZO4 with 0.605 x5 0.90; 1.90 to 5.40; 0.00 5 z5 0.20 and M being a metal selected from aluminum (AI), cobalt (Co), chromium (Cr), manganese (Mn), titanium (Ti), zirconium (Zr ), tin (Sn), vanadium (V), niobium (Nb), tantalum (Ta) and hafnium (Hf) or being a combination of these metals, - 15 to 45 ') / 0 d a metal phase comprising at least one alloy of nickel and copper, the mass proportions of Ni and Cu being the following: - 20% s Ni 5 90%, - 10% 5 Cu 5 80%, and - optionally up to at 10% of a monoxide phase of composition Nixfel_x, 0 with 0.705 x'.5 1.00.
    [0008] Thus, in the context of the present invention, if x 'is equal to 1, said monoxide phase which may optionally comprise the cermet material is NiO (namely nickel monoxide). The inventors of the present invention have indeed found quite surprisingly that the composition of the electrode material described above is particularly suitable for the use of this material as an inert anode in cryolithic baths during the manufacture of aluminum by igneous electrolysis. The electrode material according to the invention has the essential characteristics of having at least one metal core and an outer layer formed of a cermet material, said outer layer of cermet material is intended to be in contact with an electrolysis bath, more particularly a cryolithic bath, namely when the inert anode made from this electrode material is immersed in a cryolite-based electrolysis bath during electrolysis. The various constituents of the electrode material according to the invention and their respective amounts have been optimally chosen so that the metal core and the cermet material exert synergistic effects between them so that, from this point of view, it is possible to obtain electrode material, an inert anode fully satisfying the aforementioned requirements of conductivity, corrosion resistance and strength expected of inert anodes used in the production of aluminum, for example by igneous electrolysis.
    [0009] In particular, it should be noted that when the electrode material according to the invention is used as an inert anode for producing aluminum in a cryolithic bath, said material has the remarkable and very advantageous feature that its resistance to corrosion occurs and is maintained during electrolysis. Synergistic effects between the metal core and the cermet material are described below.
    [0010] In the electrode material according to the invention, the following interactions occur: on the one hand, the metallic core: acts as a reservoir which supplies the cermet material with iron and nickel, said cermet material having a tendency to and - protects the cermet material so that it does not undergo chemical or structural modification that would make it less conductive and less resistant to corrosion. on the other hand, the cermet material acts as a chemical buffer which prevents dissolution of the electrode material in a cryolithic bath, while ensuring high electrical conductivity. The cermet material protects the metal core against corrosion induced by the presence of fluorine and oxygen in the cryolithic bath. In other words, the cermet material prevents the anode from dissolving or becoming passive. Hereinafter, the multiple advantages provided by the constituents of the electrode material according to the invention, as well as the interactions between these constituents which produce synergistic effects which are appropriate for the industrial applications of this electrode material, which are notably aluminum production. Firstly, thanks to the composition of the metal core detailed above, the metal core provides good electrical conductivity of the electrode material according to the invention.
    [0011] Ni-Fe based alloys are known to be good alloys for use as anode at high temperatures, for example at igneous electrolysis temperatures. The iron mass percentage of between 15% and 60% included in the metal core is particularly suitable for the metal core to supply the cermet material with iron. Indeed, during electrolysis, the cermet material can lose iron if corrosion occurs on the surface of the anode. In the electrode material according to the invention, this loss of iron of the cermet material is compensated by the fact that iron will move from the metal core to the cermet material, in particular via cationic defects in the structures of the oxides that comprise said material. cermet (and this because of oxidation phenomena). The iron of the metallic core will then enter the phase of nickel ferrite oxide of the cermet material and thus ensure the maintenance of the composition of this phase, therefore the corrosion resistance and the electrical conductivity of this phase of nickel ferrite oxide. In other words, thanks to this supply, the iron of the metal core maintains the zone "chemical buffer" that constitutes the cermet material. Thus, the iron of the metal core is essential for the regeneration of the cermet material. Also, the lower limit of 15% and the upper limit of 60% of the mass percentage of iron in the metal core have been chosen to avoid degrading: the metal core during the movement of iron out of the metallic core, the cermet material during the manufacture of the electrode material (that is, to avoid an excessive redox reaction reaction during the sintering step during the manufacturing process) and / or during the electrolysis which could have the effect of Consequently, the composition of the cermet material no longer has the technical characteristics detailed above. If the iron moves too quickly out of the metal core, it can lead to heterogeneities or even iron-free zones in the Ni-Fe alloy of the metal core. The movement of iron occurs mainly at the grain boundaries of the metal core. This results in a loosening of grains over long periods, leaving areas very depleted of iron. This is why it is essential to regulate the flow of iron correctly in order to: - avoid a too fast recovery of the metallic iron core which could create these zones apprauvries in iron thus weakening the metal core and, consequently consequently anode, and - regenerate the cermet material as electrolysis. Thus, in addition to the appropriate selection of the amount of iron in the metal core, it has also been necessary to optimize the amount of nickel it contains. Nickel confers refractoriness on the Ni-Fe alloy (ie mechanical temperature maintenance) and its resistance to oxidation. Indeed, the resistance to oxidation of the metal core increases with the nickel content. It has been found that a nickel mass percentage of between 40% and 85% is particularly advantageous and perfectly in line with the aforementioned range of mass percentage of iron in order to: avoid that the metal core of the electrode material according to FIG. The invention depletes too much iron over time, resulting in a high nickel concentration on the surface of the metal core, and thus the formation of NiO, or even NiF2 in the presence of oxygen and fluorine. NiO and NiF2 are poor conductors. optimally regulate the flow of iron out of the metal core so as to feed the cermet material into this metal, considering that if there is not enough nickel, the iron may leave the metal core too quickly . But, on the contrary, if there is too much nickel, the iron will not sufficiently feed the cermet material so as to regenerate it in iron. The metal core of the electrode material according to the invention has the advantage of locally maintaining a reducing potential which counteracts the oxidizing potential of the cermet material on the cryolithic bath side, said oxidizing potential being linked to the electrolysis reaction in the bath cryolithic in which is immersed an inert anode manufactured from the electrode material according to the invention. The composition of the metal core has been carefully selected so that the deterioration of the metal core of the electrode material according to the invention is avoided by oxidation and / or fluorination. In other words, if the electrode material did not comprise an iron-containing metal core, an internal oxidation would occur which would allow fluorine diffusion to alter the micro-structure of said material as well as its electrical conductivity. This would result, if the material is used as an inert anode, to destroy it completely during electrolysis. In addition, the metal core guarantees a good mechanical stability (in other words a strength) of the electrode material according to the invention which is suitable for handling it in the industrial applications for which it is intended. In one embodiment of the invention, the metal core of the electrode material further comprises copper (Cu) in the following proportions by weight: 5% Cu 40%.
    [0012] Preferably, in this embodiment of the invention, the mass proportions of the metal core are as follows: 40 40) / É Ni Ni 70 70%;; - 20% s Fe 5 45%; - 7% Cu Cu 5 20`) / 0.
    [0013] Copper is a more noble metal than nickel, so it will oxidize after nickel. Thus, the presence of copper in the composition of the metal core contributes to maintaining the aforementioned chemical buffer zone in the cermet material.
    [0014] However, the amount of copper will be appropriately selected and, to this end, will not exceed 40%, in order to avoid any risk of diffusion of the copper out of the metallic core too quickly and consequently out of the electrode material. . In fact, the copper can react with the alumina dissolved in the cryolithic bath so as to form copper aluminates which are highly soluble in this bath and which will therefore contaminate it. In another embodiment of the invention, the metal core of the electrode material further comprises at least one metal A, said metal A being selected from chromium (Cr), cobalt (Co), manganese (Mn ) and molybdenum (Mo), the mass proportion of metal A in the metal core being 0.5% to 30%. Advantageously, when the metal core further comprises at least one metal A, the mass proportions are the following: - 40% É Ni É 80 ° X,; 15% Fe 40%; - 0% C u 20%; - 0.5% 5 to 5. 15%. Preferably, when the metal A is Mo, the mass proportion in Mo is as follows: 0.5% Mo 10% 10%. Preferably, when the metal A is Cr or Mn, the mass proportion of Cr or Mn is as follows: 5% Cr or Mn 15%. The presence of the metal A in the composition of the metal core has the advantage of being at the origin of the formation of mixed oxide layers in said metal core which contribute to regulate the movement of the iron from the metallic core to the cermet material. . However, as explained above, the regulation of the flow of iron within the electrode material according to the invention is important for the optimization of the use of the inert anode manufactured from such anode. material. If the amount of metal A in the metal core exceeds 30%, soluble fluorides or oxyfluorides may form which could contaminate the cryolithic bath. Thus, the amount of metal A will be adapted to avoid the formation of soluble fluorides and oxyfluorides. In another embodiment of the invention, the metal core further comprises at least one metal M 'chosen from the same metals M listed above in the description of the composition of the nickel ferrite oxide phase of the cermet material, namely said metal M 'is chosen from aluminum (AI), cobalt (Co), chromium (Cr), manganese (Mn), titanium (Ti), zirconium (Zr), tin (Sn), vanadium (V), niobium (Nb), tantalum (Ta) and hafnium (Hf) or is a combination of these metals, the mass proportion of the metal M 'in the metal core being the following: 0.5% 5 M '5 10%.
    [0015] Advantageously, when the metal core further comprises at least one metal M ', the mass proportions are as follows: 40% Ni 80%; - 15% Fe 5 40%; - 0% 5 Cu 5 20%; - 05A20%; - 0.5% <_ M'S5%. The presence of the metal M 'in the composition of the metal core has the advantage of being able to supply this metal M' with the phase of nickel ferrite oxide which can lose, during the electrolysis, a part of the metals M such as as described above that it includes in its composition. In other words, the metal M 'can move from the metal core to the cermet material to compensate for losses of the metal M nickel ferrite oxide phase. This regeneration during the electrolysis of the nickel ferrite oxide phase thus improves the resistance to high temperature oxidation of the cermet material.
    [0016] Advantageously, the metal core comprises at least one metal M 'which is identical to the metal M of the ferrite oxide phase of the cermet material. In a most advantageous manner, the metal metal M 'or metals are identical to the metals M of the nickel ferrite oxide phase of the cermet material.
    [0017] Then, in this embodiment, the presence of the metal M 'in the composition of the metal core has the advantage of being able to supply this metal with the phase of nickel ferrite oxide which can lose, during the electrolysis, a part of this metal that it understands its composition. In other words, during the electrolysis, the metal M 'present initially in the composition of the metal core will be transported in the nickel ferrite oxide phase of the cermet material in order to compensate for the losses in the metal M said nickel ferrite oxide phase comprises. As explained above, the regeneration during the electrolysis of the nickel ferrite oxide phase thus improves the high temperature oxidation resistance of the cermet material.
    [0018] Like the metal A, the amount of the metal M 'should be appropriately selected to avoid the risk of formation of soluble fluorides or oxyfluorides in the cryolithic bath. Therefore, in order to avoid this problem of the formation of fluorides or oxyfluorides, the mass percentage of the metal M 'will not exceed 10%.
    [0019] In view of the respective lists of metals A and M 'detailed above, it should be noted that cobalt (Co), chromium (Cr) and manganese (Mn) can be part of both metals A and metals M '. Indeed, according to their amount in the metal core and according to the initial composition of the nickel ferrite oxide phase of the cermet material, these metals Co, Cr and Mn can: - be at the origin of the formation of layers of mixed oxides in the metal core, that is to say exert the function of the metals A described above and / or - supply or refill the ferrite oxide phase of nickel in this metal M 'is that is, to perform the function of the metals M 'described above. In one embodiment of the invention, the metal core may further comprise at least one rare earth, preferably a rare earth selected from yttrium (Y), cerium (Ce), lanthanum (La) and neodymium (Nd). The rare earth can represent up to 5% of the mass of the metallic core. More preferably, this mass percentage of rare earth is less than or equal to 3%. The rare earths present in the metal core of the electrode material according to the invention contribute to increasing the resistance to oxidation of the Ni-Fe alloy. The technical characteristics of the cermet material that comprises the electrode material according to the invention are now more detailed.
    [0020] By selecting a composition of the cermet material as detailed above, said cermet material is particularly resistant to corrosion under polarization. In addition, the cermet material protects the metal core and, because of this protection, it contributes to the maintenance of the electrical conductivity of the electrode material according to the invention. Indeed, in the electrode material according to the invention, the electrical conductivity of the anode is due in large part to the metal core that said electrode material comprises. Furthermore, the composition of the cermet material as described above has been carefully selected to avoid the problems of degradation at the grain boundaries of this material and the infiltration of the cryolithic bath to the metal core, as well as to maintain good conductivity electrical (ie greater than 80 Siemens (S) / cm). Preferably, the thickness of the cermet material which forms the outer layer of the electrode material according to the invention (and of which the metal core is at least covered) is greater than or equal to 1 mm, more preferably between 2 and 8 mm. . Such a thickness is advantageous for imparting to the cermet material a role of chemical buffer already mentioned above, that is to say a protection function of the metal core combined with good resistance to corrosion, as well as to a conductivity electrical power during the life of the inert anode. Thus, in the electrode material according to the invention, the cermet material is not a simple coating layer of the metal core but represents an essential element of this electrode material and has a certain thickness for optimizing its properties. different functions.
    [0021] Therefore, the cermet material is thick enough to: 1) exhibit an effective retention power: namely, firstly to preserve the iron within the electrode material and secondly to prevent oxygen or fluorine present in the cryolithic bath does not degrade the metal core, 2) to remain in the state during the use of the electrode material, for example for its use as an inert anode during the manufacture of 'aluminum. In other words, it is advisable to provide a thickness of the cermet material such that its slow (and inevitable) dissolution over time does not fundamentally modify its properties detailed above, namely in particular slowing down and limiting the infiltration of the cryolithic bath into the metallic core.
    [0022] In addition, the cermet material is also relatively thin so that it can be regenerated to iron uniformly throughout its thickness so as to ensure optimum use of the inert anode made from the electrode material according to the invention. , ie during the manufacture of aluminum. The different constituents of the cermet material and their respective amounts have been appropriately selected so that the cermet material and, consequently, the electrode material according to the invention can have the advantages which are detailed below. Non-stoichiometric nickel ferrite oxide (ie, iron to nickel atomic ratio greater than 2) is known to be one of the oxides which combines corrosion resistance in a cryolithic bath and electrical conductivity, the latter being a function of said ratio. atomic iron on nickel and varying between 10 and 100 S.cm-1 at 960 ° C. Therefore, the composition of the nickel ferrite oxide phase selected in the context of the invention and described above constitutes a good compromise between the electrical conductivity and the corrosion resistance. The above-described composition of the electrode material thus selected is particularly suitable for preventing the composition of the nickel ferrite oxide phase from changing during use of the inert anode and tending toward the NiFe 2 O 4 composition. (ie a weakly conductive composition). In fact, during the igneous electrolysis and at the surface of the inert anode, iron leaves the nickel ferrite oxide phase by oxidation of Fe2 + ions in Fe3 + and can give rise to the formation of Fe2O3 or of iron aluminate or iron fluorides which dissolve in the cryolithic bath. The movement of iron from the metal core to the cermet material aims to overcome this iron loss of nickel ferrite oxide phase.
    [0023] The nickel ferrite oxide phase of the cermet material has a spinel structure. By spinel structure is meant a crystalline structure of AB204 type composition where A is a tetrahedral site cation (surrounded by 4 oxygens) and B are two octahedral site cations (surrounded by 6 oxygens). This type of compact cubic structure is particularly advantageous under aggressive conditions such as a cryolithic bath for the production of aluminum. The iron of the nickel ferrite oxide phase electrically condenses the nickel ferrite by electron jumps between Fe2 + and Fe3 + ions at the octahedral sites of the spinel structure. In addition, under the electrolysis conditions, this phase of nickel ferrite oxide within the selected cermet material gives rise to the surface formation of the cermet material of a layer of nickel ferrite which is adhesive and coherent. Indeed, when the inert anode is immersed in a cryolithic bath, the nickel ferrite oxide phase tends to dissolve slightly so that an aluminate layer is formed on the surface of the cermet material ( NiA1204) which is very slightly soluble in the cryolithic bath. The presence of this aluminate layer slows down the insertion of oxygen and fluorine present in the cryolithic bath into the cermet material and, therefore, reduces the rate of oxidation of said cermet material, and thus contributes to preserving the integrity electrode material according to the invention. It should be noted that the nickel ferrite oxide composition as described above (i.e. NixFeyMzO4 with 0.605 x 0.590, 1.90 5. y.5 2.40, 0.005 z5 0, 20) which comprises the electrode material according to the invention, is particularly suitable for the use of this material as an inert anode for igneous electrolysis. Indeed, during electrolysis, the composition of this phase of nickel ferrite oxide will vary slightly within the cermet material depending on whether it is a part of said ferrite oxide phase of nickel which is: 1) near the cryolithic bath (ie almost on the surface of the inert anode): x will then tend towards the value of 0.9; which is favorable for the corrosion resistance of the nickel ferrite oxide phase. 2) near the metal core: x will then tend towards the value of 0.6; which is favorable for the conductivity of the nickel ferrite oxide phase; at the heart of the cermet material: the value x of the nickel ferrite oxide phase will be between 0.7 and 0.8; This is particularly advantageous since it represents a good compromise between the corrosion resistance and the conductivity of the nickel ferrite oxide phase, and hence consequently of the cermet material. The conductivity and the corrosion resistance of the nickel ferrite oxide phase change according to the stoichiometry of said nickel ferrite oxide phase, namely for values of x between 0.6 and 1: the conductivity decreases to become almost zero for x equal to 1, whereas conversely, the resistance to corrosion tends to increase with the increase of x. Therefore, it is essential to achieve a chemical balance of this nickel ferrite oxide phase which is a good compromise in which the electrical conductivity and corrosion resistance are satisfactory. As explained above, the nickel ferrite oxide phase then acts as a chemical buffer. The core of the cermet material constitutes the active zone of said cermet material, namely that it imposes the local equilibrium conditions of the cermet material which must slow down and condition the transport of materials detailed above. Furthermore, the weight percentage of the nickel ferrite oxide phase in the cermet material between 45 and 80% is particularly suitable for this phase to be percolating, that is to say, it completely surrounds the grains. of the metallic phase of the cermet material. In this way, this phase of nickel ferrite oxide contributes to slowing the oxidation of the metal phase of the cermet material, and therefore consequently of the electrode material according to the invention.
    [0024] Preferably, the nickel ferrite oxide phase of the cermet material is between 60% and 80% of the mass of the cermet material. Preferably, the nickel ferrite oxide phase of the cermet material has the composition NixFeyM, 04, with 0.705. x5 0.85; 2.00 5 y, 2.20; 0.005 z5 0.10.
    [0025] The choice of the metal M that comprises the nickel ferrite oxide phase of the cermet material is now more fully detailed. If the metal M is aluminum or chromium, this has the advantage of reducing or slowing down the solubilization of the nickel ferrite oxide phase in the cryolithic bath. The amount of aluminum or chromium will be appropriately selected to prevent the element from introducing heterogeneities into the composition of the cermet material oxides in the case of powder metallurgical fabrication of the anode material, with respect to the fact that this element diffuses little during sintering during the manufacture of the cermet material. The other metals M envisaged, for example of valencies 2 + / 3 + (such as Co, Mn), of valence 4+ (such as Ti, Zr, Sn, V, Nb, Hf), or of valence 5+ (such that Ta) have the advantage of increasing the electrical conductivity of the nickel ferrite oxide phase. The metal phase containing at least one Ni-Cu alloy that comprises the cermet material participates in: the electrical conductivity of the "initial" cermet material (ie the cermet material as it is at the beginning of the use of the anode inert), and the maintenance of the electrical conductivity of the cermet material, when it changes during the electrolysis as has been explained above. This metal phase comprising at least one Ni-Cu alloy is advantageously finely distributed (ie with a particle size of this metal phase of between about 10pm and 50pm on average) and homogeneously in the ferrite oxide phase of nickel. Obtaining such a fine and homogeneous distribution of the metal phase comprising at least one Ni-Cu alloy in the nickel ferrite oxide phase is perfectly within the reach of a person skilled in the art of powder metallurgy. .
    [0026] In other words, this metal phase comprising at least one Ni-Cu alloy is advantageously surrounded by the nickel ferrite oxide phase, which, under polarization, prevents it from oxidizing rapidly and thus lead to the formation of soluble species in the cryolithic bath such as NiO which is also less conductive.
    [0027] Thus, this fine and homogeneous distribution of the Ni-Cu alloy in the nickel ferrite oxide phase has the advantage of maintaining reducing conditions that oppose the oxidative conditions of the cryolithic bath. A mass percentage of the metal phase (said metal phase comprising at least one Ni-Cu alloy) of the cermet material which is between 15% and 45% is particularly suitable for maintaining a reducing potential allowing the durable coexistence of the phases of the cermet material. detailed above, namely the phase of nickel ferrite oxide, the metal phase of Ni-Cu alloy, and if appropriate the monoxide phase of composition Nixfei.x0 with 0.70E x'E 1.00 .
    [0028] Preferably, said metal phase comprising at least one Ni-Cu alloy represents between 25% and 35% of the mass of the cermet material. Preferably, in the Ni-Cu alloy that comprises at least said metal phase of the cermet material, the mass proportions of Ni and Cu are as follows: 50% Ni 90% and 10% Cu 50%.
    [0029] The nickel of the Ni-Cu alloy of the metal phase will oxidize first and thus protect the copper from this phase of oxidation. The oxidation of this metal phase comprising at least one Ni-Cu alloy which is rich in nickel causes the formation of a NiO phase or the insertion of nickel into the nickel ferrite oxide phase, which fixes it locally, then on the other hand, if copper is oxidized, it diffuses rapidly what is of course to be avoided. This justifies why in the metal phase comprising at least one Ni-Cu alloy of the cermet material, it is advantageous for nickel to be the majority, and for it to oxidize over long periods of time compatible with the lifetime of a nickel. inert anode used in the manufacture of aluminum. In this way, it avoids the oxidation of the copper of this Ni-Cu metal phase which would have the drawbacks detailed above. It should be noted that nickel is very slightly soluble in a cryolithic bath rich in alumina. The nickel present on the surface of the cermet material (thus on the surface of the electrode material according to the invention) combines with the alumina of the cryolithic bath and thus forms by precipitation nickel aluminate NixFeyA13_x_y04 very little soluble. The presence of this phase of nickel aluminate thus formed contributes to limiting the entry of fluorine and oxygen into the electrode material. Thus, the copper (noble element) of this Ni-Cu metal phase will remain in the cermet material for long periods. This has the advantage of having reducing conditions which make it possible to maintain the composition of the nickel ferrite oxide phase, and thus to benefit from the appropriate compromise between the resistance to corrosion in the cryolithic bath and the electrical conductivity which has has been mentioned above and should be satisfied for optimization of the use of an inert anode during the manufacture of aluminum. The weight percentage of copper comprised between 10% and 80%, and preferably between 10% and 50%, in the Ni-Cu alloy of the metal phase of the cermet material is particularly suitable for copper to be present throughout the process. electrolysis but also in a quantity small enough to avoid exudation when the anode is prepared by powder metallurgy, in view of the fact that the sintering temperature that can be used for the production of the inert anode is greater than the melting temperature of copper. When balancing the phases of the cermet material during manufacture of the inert anode and / or electrolysis, the metal phase of the cermet material which contains at least one Ni-Cu alloy may further comprise low amount of iron, for example a mass percentage of between 1% and 2% relative to the total mass of this metal phase. However, it is preferable not initially to introduce iron in metallic form as a starting component used for the manufacture of the cermet material, in order to prevent its oxidation during the elaboration of the electrode material and / or during the preparation of the electrode material. electrolysis which would cause its dissolution in the cryolithic bath, thereby creating porosities in the electrode material.
    [0030] In one embodiment of the invention, the metallic phase of the cermet material further comprises gold (Au) and / or silver (Ag), the mass percentage of these Au and / or Ag metals does not exceed 5% of the mass of said metal phase of the cermet material. Preferably, said mass percentage of these Au and / or Ag metals represents between 2% and 3% of the mass of said metallic phase of the cermet material.
    [0031] As explained above, in one embodiment of the invention, the cermet material further comprises a monoxide phase of composition Nix, Fel_x, 0 with 0.70. 1.00, preferably with 0.75 xS. 0.85. As explained above, the mass percentage of this monoxide phase relative to the mass of the cermet material is at most 10%.
    [0032] This monoxide phase of the cermet material also makes it possible to avoid, following the oxidation of nickel ferrite, the formation of Fe 2 O 3 which is very soluble in a cryolithic bath. On the other hand, when the inert anode is prepared by powder metallurgy, if NiO 2 is used as a starting component in the composition of the cermet material during the preparation of the electrode material according to the invention, it will be advantageous to to adapt the amount used so that this monoxide phase which, remember, is likely to be present in the cermet material contributes to the densification of the electrode material. In addition, this monoxide phase as detailed above is likely to contain iron which can come from, for example, the ferrite used during sintering during the manufacture of the cermet material. The presence of iron will essentially result from chemical interactions between the different phases of the cermet material of the electrode material according to the invention during its preparation. It should be noted that nickel monoxide (NiO) can form in the cermet material by internal oxidation during electrolysis during the production of aluminum because the cermet material comprises at least one oxide phase. nickel ferrite and a metal phase comprising at least one Ni-Cu alloy as described above. Nickel monoxide is much less conductive (1 to 2 S.cm-1 at 960 ° C) than nickel ferrite oxide phase, hence the need to limit the amount. In other words, during the electrolysis, the cermet material is likely to contain NiO, even if this monoxide was not part of the starting constituents used for the manufacture of the cermet material (in other words even if the NiO was not present in the initial composition of the cermet material of the electrode material according to the invention). In one embodiment of the invention, the cermet material further comprises at least one rare earth oxide phase. The rare earth oxide of this phase is advantageously chosen from Y 2 O 3, CeO 2, La 2 O 3 and Nd 2 O 3. This phase of rare earth oxides can represent at most 5% of the mass of the cermet material. Preferably, the mass percentage of this phase of rare earth oxide (s) is less than or equal to 3% of the mass of cermet material.
    [0033] The presence of a rare earth oxide phase in the composition of the cermet material contributes to improving the quality of the grain boundaries. In addition, this phase of earth oxide blocks the fluorine of the cryolithic bath by forming fluorides and thus avoids the deep insertion of fluorine within the inert anode during the electrolysis which would contribute to degrade it.
    [0034] The electrode material according to the present invention may also comprise one or more accommodation layers or also called "intermediate layers" which are arranged between the metal core and the cermet material. In other words, in this embodiment of the invention, the metal core of the electrode material is covered with intermediate layer (s), as well as a cermet material. And, as explained above, the cermet material forms the outer layer of the electrode material which is intended to be in contact with a cryolithic bath, namely when the inert anode made from this electrode material is immersed. in a cryolithic bath during electrolysis. It is indeed advantageous that the electrode material according to the invention comprises between the metal core and the material cermet at least one intermediate layer. Preferably, the intermediate layer comprises at least nickel and is predominantly metallic. Thus, in one embodiment of the invention, the electrode material further comprises at least one intermediate layer disposed between the metal core and the cermet material, said intermediate layer comprising at least nickel and being predominantly metallic. The intermediate layer helps to accommodate the mechanical stresses due to the differences in expansion coefficients of the metal core and the cermet material that comprises the electrode material according to the invention.
    [0035] In addition, the intermediate layer contributes to maintaining the composition of the nickel ferrite oxide phase of the cermet material described above. Indeed, the intermediate layer will regulate the transport of iron from the metal core to the cermet material, because it includes nickel which limits the movement of iron. The thickness of the intermediate layer may be between a hundred microns and about one millimeter. In one embodiment, the intermediate layer is a layer of nickel having a thickness of between 200 and 300 μm which has, for example, been deposited by electrodeposition on the metal core of the electrode material according to the invention. According to another variant of the invention, this intermediate layer is a layer of a cermet material (that is to say a material which comprises at least one ceramic phase and at least one metallic phase) which comprises in volume more than 50% of a metal phase comprising at least nickel. For example, this metal phase is a Ni-Cu alloy. The intermediate layer may act together with the cermet material in its "buffer zone" function detailed above. That is why, advantageously, when the electrode material according to the invention comprises at least one intermediate layer, the total thickness of the cermet material and of the intermediate layer is greater than or equal to 1 mm, said cermet material having a thickness of at least 0.5mm.
    [0036] The compositions of the different phases of the electrode material can be calculated using a thermodynamic software and verified experimentally via measurements using the Castaing microprobe or by EDX (Energy Dispersive X-ray spectrometry) on SEM photographs. know the abbreviation of "scanning electron microscope").
    [0037] The invention also relates to a method of manufacturing the electrode material according to the invention which has been described above. The method for manufacturing the electrode material described above comprises at least the following steps: the metal core of the electrode material described above is prepared, for example, according to a method chosen from casting, molding ( preferably, lost wax molding or sand molding), or a hot-forming technique such as rolling, extrusion or powder metallurgy. Optionally, the deposition of at least one intermediate layer as described above is carried out on the metal core.
    [0038] The deposition of the cermet material as described above is carried out on the metal core, as the case may be on the last deposited intermediate layer, said deposition of cermet material being able to be produced by a method chosen from: - the projection methods, by Example: ^ plasma projection, - supersonic flame projection (HVOF, acronym for "High Velocity Oxy-Fuel"), ^ supersonic flame high pressure projection (HPVOF, acronym for "High-Pressure High Velocity Oxi-Fuel"), ^ supersonic air projection (HVAF), detonation gun, cold spraying, or powder metallurgy methods. By powder metallurgy method is meant a process which comprises a succession of steps of uniaxial or isostatic compaction (cold or hot) of a mixture of powders which are followed by a heat treatment (sintering) under a controlled atmosphere .
    [0039] The deposition of the intermediate layer can be performed by any deposition technique perfectly within the reach of the skilled person. For example, there may be mentioned immersion, spraying, painting, brushing, projection (including all the thermal spraying techniques which have been detailed above for the deposition of the cermet material), the electrodeposition, the deposit chemical vapor phase, the physical vapor deposition. The present list of deposition techniques of the intermediate layer is in no way limiting. Any technique perfectly equivalent to the scope of the skilled person can be considered. Advantageously, before the deposition of the cermet material or, where appropriate, of a first intermediate layer, a pre-treatment is carried out (for example blasting or sanding) on the surface of the metal core so as to eliminate any impurities. for example, those resulting from the casting process and to increase the adhesion of the deposit which follows (namely the deposition of the cermet material or of a first intermediate layer).
    [0040] In a conceivable embodiment of the invention, the metal core, any intermediate layers and the cermet material are made by co-sintering or by additive manufacturing. Laser processes (for example, laser welding or laser sintering) can also be used to manufacture the electrode material according to the invention.
    [0041] Of course, the method of manufacturing the electrode material will be adapted according to the use of said material, for example if it is used as an inert anode in a cryolithic bath during the production of aluminum. In particular, the choice of its shape, its dimensions, the composition of the metal metallic core, as well as the cermet material and its possible intermediate layers will be made according to the use for which the electrode material is intended according to the invention. The preparation of the metal core, as well as the technique of the deposition of any intermediate layers and cermet material are perfectly within the reach of the skilled person because they implement techniques well known therein.
    [0042] In addition, it should be noted that the various techniques mentioned above both for the preparation of the metal core and the deposition of any intermediate layers and cermet material can be implemented separately or in combination.
    [0043] It is important that, after manufacture of the electrode material according to the invention, the outer surface of said electrode material is uniformly covered with a dense layer (ie which advantageously has a porosity less than or equal to 5%) and adherent of the cermet material as described above.
    [0044] The invention also relates to an inert anode made from the electrode material according to the invention which has been described above. The inert anode made from the electrode material according to the invention is particularly suitable for use in the manufacture of aluminum, for example by an igneous electrolysis process.
    [0045] More specifically, the inert anode according to the invention is designed to withstand the cryolithic baths conventionally used in the field of aluminum production, namely cryolithic baths which may have current densities of between about 0.5 and about 1.2 A / cm 2 in a temperature range of about 880 ° C to 980 ° C.
    [0046] Indeed, the inert anode has a very good conductivity (greater than 80 S / cm) and is particularly resistant to corrosion in cryolithic baths as detailed above. The inert anode according to the invention has the advantage of having a lifetime of more than 10,000 hours. This is particularly advantageous from an industrial point of view for both maintenance and economic reasons. It should be noted that the inert anode according to the invention has a longer life than inert anodes made exclusively of a cermet material. The present invention also relates to an electrolysis cell which comprises at least one inert anode as described above.
    [0047] The present invention also relates to a method of manufacturing aluminum by electrolysis in an electrolysis cell as described above. DESCRIPTION OF THE SINGLE FIGURE FIG. 1 is a photograph of a SEM observation in backscattered electrons of a portion of the inert anode of Example 3 according to the invention.
    [0048] EXPERIMENTAL PART Examples of electrode materials on the one hand comparative with the invention and on the other hand according to the invention, as well as their use as an inert anode during electrolysis, are described below. below.
    [0049] For all the experiments described below, the electrolysis conditions were as follows: a cryolitic bath with a cryothelial ratio equal to 2, the cryolitic ratio being the ratio in molar percentages of NaF over AIF3, with saturation at A1203 and 5% CaF2 at a temperature of 960 ° C and a current of 0.8 A / cm 2.
    [0050] COMPARATIVE EXAMPLES Example A: Comparative Example of an Anode: An Anode in the Form of a Cylinder having a Diameter of 20 mm in Diameter and Made from a Cermet Material the Composition of Which Was an Oxide Phase Nio nickel ferrite, 9Fe2, 304, ie pure nickel ferrite oxide, was manufactured.
    [0051] This anode was subjected for 96 hours to electrolysis under the conditions as described above. At the end of the electrolysis, it was found that the anode had been deformed and had a general shape similar to that of a "diabolo" indicating that the working zone of this anode had been the interface between the bath cryolithic and gaseous atmosphere.
    [0052] This deformation of the anode can be explained by the fact that the pure nickel ferrite oxide oxidizes rapidly and becomes less conductive than the cryolithic bath. Thus, it is found in this example A that pure nickel ferrite oxide is not a suitable material for the manufacture of an inert anode for use in igneous electrolysis for the production of aluminum.
    [0053] Example B: Comparative Example 2 of an Anode: An anode formed solely from a cermet material which contained in mass percentages: 67% of a nickel ferrite oxide phase of composition: Ni0.77Fe2.19A10, 0404; 2% of a Ni0 phase; 2% Y 2 O 3; - 29% of a metal phase of a Ni-Cu alloy comprising, in percentages by weight, 85% of nickel and 15% of copper. was tested for 360 hours under the electrolysis conditions detailed above. It should be noted that in this example B, the cermet material of this anode corresponds to a cermet material as described above, namely a cermet material that can comprise the electrode material according to the invention. At the end of the 360 hours, it was noted by scanning electron microscopy analysis that the anode then had a very porous microstructure. In addition, on the surface of the anode, the metal phase had completely disappeared, and this to a thickness of 2.9 mm. Only the phases of nickel ferrite oxide and nickel monoxide were present at the surface of the anode and were distributed in the form of a superposition of layers parallel to each other extending towards the surface of the anode. The nickel ferrite oxide layer closest to the surface of the anode had the following composition: NiFe204, namely a non-conductive composition. After a while, the anode of this example B was no longer conductive enough. Indeed, this anode did not include a means of regeneration of iron nickel ferrite oxide phase which disappeared as electrolysis. Thus, it is found in this example B that an anode which comprises only a cermet material as described above is not satisfactory for use during electrolysis for the production of aluminum. II - EXAMPLES ACCORDING TO THE INVENTION For all the electrode materials of examples 1 to 5 according to the invention which follow, the manufacturing method was as follows: The manufacture of the cermet material that comprises the electrode material according to the The invention was carried out as follows: 1) A nickel ferrite oxide of composition NixFe3-x04 was first prepared with a slight excess of NiO by carrying out the following steps: - a mixture was prepared which comprised 65 8% of Fe 2 O 3 powder and 34.2% of NiO powder; then, the mixture thus obtained was subjected to a heat treatment for 5 hours in air at 1150 ° C. so as to obtain a nickel ferrite oxide powder. 2) Then, in order to obtain a cermet material which is in the form of a powder, this nickel ferrite oxide powder as obtained in step 1) above was mixed with powders nickel, copper, alumina and optionally yttrium oxide (according to the compositions detailed in the examples below), and added 1 to 5% of organic binder to the mixture. Then, for the manufacture of the inert anode, the following steps were carried out: The powder of cermet material thus obtained was pressed onto a metal core composition (said composition of the metal core is detailed in each of the examples according to the invention below); It was sintered (by heat treatment) under controlled atmosphere to a maximum temperature of between 1100 ° C and about 1350 ° C.
    [0054] After sintering, the cermet material of the anode contained the following phases: a phase of nickel ferrite oxide of composition Ni0.75Fe2.20A10.0504, a monoxide phase of composition Ni0.85Fe0.150, - a phase Ni-Cu alloy metal alloy comprising a mixture, in percentages by weight, of 85% of Ni and 15% of Cu, where appropriate, one to two phases of yttrium oxide (according to the compositions - see in the examples according to the invention below); Example 1: Example 11 of an Anode According to the Invention An inert anode was made from an electrode material according to the present invention which comprised: a metal core comprising a mixture of nickel, iron and molybdenum in the mass proportions: 80% nickel, 15% iron and 5% molybdenum; a cermet material with a thickness of 8 mm, said cermet material contained in mass percentages: - 67% of a nickel ferrite oxide phase of Ni0,75Fe2,20A10,0504 composition; 1.5% of a monoxide phase of composition Ni 0.85 Fe 0.150 - 31% of a metal phase of Ni-Cu alloy comprising a mixture, in percentages by weight, of 85% nickel and 15% of copper. - and 0.5% of a Y203 phase. It should be noted that this cermet material corresponds to a cermet material of the same type as that of the anode of Comparative Example B, and therefore comparable in terms of its physicochemical properties. After 96 hours of electrolysis under the conditions as detailed above, no wear damage was detected on the anode of this Example 1. A layer of pure nickel ferrite oxide is present at the surface of the anode.
    [0055] Under this layer, the three phases of the cermet material (namely a phase of nickel ferrite oxide, a monoxide phase and a metal phase) are always present. These results of Example 1 are quite different from the results obtained with the anode of Example B (an anode which, for memory only included a cermet material of the same type).
    [0056] Thus, this example 1 demonstrates the effectiveness of the electrode material according to the invention. Indeed, from the electrode material according to the invention, there is obtained an inert anode perfectly suitable for use in igneous electrolysis for the production of aluminum. In addition, in view of the different results obtained between Example B and Example 1, this Example 1 demonstrates the interest that the electrode material comprises not only a cermet material but also a metal core. Example 2: 2nd Example of an Anode According to the Invention An anode with an external diameter of 34.4 mm was manufactured from an electrode material according to the invention, said electrode material comprised: a metal core comprising a mixture of nickel, iron and copper in the following proportions: 65% nickel, 25% iron and 10% copper; a cermet material covering the lateral wall of the metal core to a thickness of 7 mm and to a thickness of 16 mm the bottom wall of the metal core.
    [0057] Said cermet material contained, in mass percentages: 66%, a nickel ferrite oxide phase of composition: Ni0.75Fe2.20A10.0504; - 1.5% a monoxide phase of composition Nio, 85 Fe0.150 - 31% a metal phase of Ni-Cu alloy comprising a mixture, in percentages by weight, of 85% of nickel and 15% of copper. - and 1.5% of a Y203 phase. As for example 1, it should be noted that this cermet material corresponds to a cermet material of the same type as that of the anode of Comparative Example B. This anode of Example 2 was subjected to electrolysis for a period of 96 hours under the conditions of electrolysis as described above. The anode of Example 2 showed a stable potential during these 96 hours of testing. In addition, after 96 hours of electrolysis, it was found that the anode was intact. It has furthermore been found that the three phases of the cermet material (namely a phase of nickel ferrite oxide, a monoxide phase and a metal phase) were always present. These results of Example 2 are very different from the results obtained with the anode of Example B (an anode which, for memory only included a cermet material of the same type). Thus, this example 2 demonstrates the effectiveness of the electrode material according to the invention. Indeed, from the electrode material according to the invention, there is obtained an inert anode perfectly suitable for use in igneous electrolysis for the production of aluminum.
    [0058] In addition, in view of the different results obtained between Example B and Example 2, this example 2 demonstrates the interest that the electrode material comprises not only a cermet material but also a metal core. In other words, this example 2 shows the beneficial interactions between the metal core and the cermet material in the electrode material according to the invention.
    [0059] Example 3: 3rd Example of an Anode According to the Invention A third anode according to the present invention of the same composition as that of Example 2 was manufactured and therefore very similar to this one. Specifically, the anode of Example 3 was distinguished from that of Example 2 only by certain differences in size, namely: the thickness of the cermet material on the side wall of the metal core was 8 mm; the thickness of the cermet material on the bottom wall of the metal core was 1.2 mm; the outer diameter of the anode was 34.4 mm. After 96 hours of electrolysis, the cermet material was still present on the anode.
    [0060] In addition, there was no wear damage of the anode. The three initial phases of the cermet material (ie nickel ferrite oxide, monoxide and metal phases) were still present. A thin layer of nickel ferrite oxide of composition Ni0.9Fe2.104 very close to the composition of pure nickel ferrite oxide had formed on the surface of the anode and the cermet material below this thin layer had the following compositions: nickel ferrite oxide phase of composition Ni Fe Al 0.82-2.212-0.05-0 4 monoxide phase of composition Ni0.8Fe0.20 The metallic phase of the cermet material always contained nickel and copper. With regard to the inert anode of this example 3 according to the invention, FIG. 1 is a photograph of a SEM observation in backscattered electrons of a part of this inert anode taken after 96 hours of electrolysis and after have resin coated, cut and polished. More precisely, the photographed part is the cermet material that this anode comprises. The characteristics of this observation by SEM were as follows: micrograph representing an area of 460 microns by 1.2 millimeters, at the level of the wall of the bottom of the anode. In the photograph of FIG. 1, the different phases are visualized in the presence of the cermet material that are: the Ni-Cu alloy metal phase 1 (the white dots), the NixFeyA1 nickel ferrite oxide phase 2, 04 (dark gray dots), phase 3 Nixfel_x0 monoxide (light gray dots), and porosities 4 (black dots). In addition, in FIG. 1, the various limitations are indicated: "interface": the interface between the cermet material and the metal core of the inert anode; "Reduced area": The area of the cermet material located between the core of the cermet material and the metal core of the inert anode; "Buffer zone": The chemical buffer zone of the cermet material, that is, the core of the cermet material; "Nickel ferrite oxide layer": The outer side of the cermet material, ie the layer of cermet material that was in contact with the cryolithic bath during electrolysis. It is observed that the cermet material part which has been in contact with the cryolithic bath during the electrolysis has been transformed into a thin layer of dense nickel ferrite oxide of about forty microns (dark gray color of the dots in the figure 1). The part of the material cermet in contact with the metal core of the inert anode has a large proportion of metal (white color points in Figure 1), showing the reduction of cermet material by the metal core during electrolysis .
    [0061] Finally, given the importance of the "buffer zone" in Figure 1, we note that the majority of the cermet material has been only slightly transformed: despite the presence of porosities, the three phases present are still visible and therefore always present after 96 hours of electrolysis.
    [0062] Example 4: 4th Example of an Anode According to the Invention An anode 24.2 mm in external diameter was made from an electrode material according to the invention, said electrode material comprised: a metal core comprising a mixture of nickel, iron and copper in the following proportions: 65% nickel, 25% iron and 10% copper; a cermet material having a thickness of 2 mm, said cermet material contained in mass percentages: said cermet material contained, in mass percentages: 67% of a nickel ferrite oxide phase of composition: Ni0.75Fe2.20A1 0, 0.5-10%, 1% of a monoxide phase of composition N 0, 85 Fe 0 · 150; - 32% of a metal phase of Ni-Cu alloy comprising a mixture, in percentages by weight, of 85% of nickel and 15% of copper.
    [0063] After 213 hours of electrolysis under the conditions as described above, the anode according to Example 4 was intact. Example 5: Fifth Example of an Anode According to the Invention A fifth anode according to the present invention of the same composition as that of Example 4 was manufactured and therefore very similar to this one. More specifically, the anode of Example 5 differed from that of Example 4 only by certain differences in dimensions, namely: the external diameter of the anode was 34 mm; the thickness of the cermet material was 8 mm; After 404 hours of electrolysis under the conditions which have been detailed above, it can be seen that the anode exhibits only slight wear damage. In addition, the cermet material is always present on the anode and contains three phases (namely a phase of nickel ferrite oxide, a monoxide phase and a metal phase). These results of Example 5 are very different from the results. obtained with the anode of Example B (an anode which, for memory only included a cermet material of the same type). Thus, this example demonstrates the effectiveness of the electrode material according to the invention. Indeed, from the electrode material according to the invention, there is obtained an inert anode perfectly suitable for use in igneous electrolysis for the production of aluminum. Furthermore, in view of the different results obtained between Example B and Example 5, this example demonstrates the interest that the electrode material comprises not only a cermet material but also a metal core.
    权利要求:
    Claims (24)
    [0001]
    REVENDICATIONS1. An electrode material, preferably an inert anode material, comprising at least one metal core and a cermet material, said metal core being at least covered with said cermet material and said cermet material forming an outer layer of said electrode material which is intended to be in contact with an electrolysis bath, characterized in that: said metal core comprises at least one alloy of nickel (Ni) and iron (Fe), the mass proportions of Ni and Fe being as follows: % E Ni 5. 85%, preferably 55% 5 Ni .E 80%, - 15% Fe 60%, preferably 20% Fe 45%, said cermet material comprises at least percentages by weight: - 45 at 80% of a phase (2) of nickel ferrite oxide of composition NixFeyM, 04 with 0.605 x 0.90; 1.90 EI 2.40; 0.00% 0.20 and M being a metal selected from aluminum (AI), cobalt (Co), chromium (Cr), manganese (Mn), titanium (Ti), zirconium (Zr) ), tin (Sn), vanadium (V), niobium (Nb), tantalum (Ta) and hafnium (Hf) or being a combination of these metals, - 15 to 45% of a phase (1) metal comprising at least one alloy of nickel and copper, the mass proportions of Ni and Cu being the following: - 20`) / 0 É Ni É 90`) / 0, - 10% Cu 5 80%, and optionally up to 10% of a (3) monoxide phase of composition Nixfel_x0 with 0.70E x'E 1.00.
    [0002]
    2. Electrode material according to claim 1, characterized in that the metal core of the electrode material further comprises copper (Cu) in the following proportions by weight: 5% Cu 4% 40%.
    [0003]
    3. Electrode material according to claim 2, characterized in that the mass proportions of the metal core are as follows: 40% Ni 5. 70% 20% Fe 45%; - 7% 5 Cu 5 20%.
    [0004]
    An electrode material according to any of claims 1 to 3, characterized in that the metal core of the electrode material further comprises at least one metal A, said metal A being selected from chromium (Cr), manganese (Mn), cobalt (Co) and molybdenum (Mo), the mass proportion of metal A in the metal core being as follows: 0.5% 5 to 30%.
    [0005]
    5. Electrode material according to claim 4, characterized in that the mass proportions of the metal core are as follows: 40% Ni 80%; - 15% Fe 5 40%; 0% 5 Cu 5 20%; 0.5% to 515%.
    [0006]
    6. Electrode material according to any one of claims 1 to 5, characterized in that the metal core further comprises at least one metal M 'selected from aluminum (AI), cobalt (Co), chromium (Cr), manganese (Mn), titanium (Ti), zirconium (Zr), tin (Sn), vanadium (V), niobium (Nb), tantalum (Ta) and hafnium (Hf) or is a combination of these metals, the mass proportion of the metal M 'in the metal core being as follows: 0.5% 5 M' 5 10%.
    [0007]
    7. Electrode material according to claim 6, characterized in that the mass proportions of the metal core are as follows: 40% Ni 5 80%); 15% Fe 5 40%; 0% 5 Cu 5 20%; 05 to 520%; 0.5% M 5 5%.
    [0008]
    8. electrode material according to any one of claims 1 to 7, characterized in that the metal core further comprises at least one rare earth, preferably a rare earth selected from yttrium (Y), cerium (Ce) ), lanthanum (La) and neodymium (Nd).
    [0009]
    9. Electrode material according to claim 8, characterized in that the rare earth represents up to 5% of the mass of the metal core.
    [0010]
    An electrode material according to any one of claims 1 to 9, characterized in that the nickel ferrite oxide phase (2) of the cermet material has the composition NixFeyM, 04, with 0.705 x 0.85; 2.00 $ 2.20; 0.00 E Z5 0.10.
    [0011]
    11. Electrode material according to any one of claims 1 to 10, characterized in that the phase (1) metal comprising at least one Ni-Cu alloy is between 25% and 35% of the mass of the cermet material.
    [0012]
    12. Electrode material according to any one of claims 1 to 11, characterized in that in the Ni-Cu alloy that comprises at least said metallic phase (1) of the cermet material, the mass proportions of Ni and Cu are the following: 50% Ni 90% and 10% 50%) / 0.
    [0013]
    13. Electrode material according to any one of claims 1 to 12, characterized in that the cermet material comprises a phase (3) monoxide composition Nixfe1, 0 with 0.755 x'E 0.85.
    [0014]
    An electrode material according to any one of claims 1 to 13, characterized in that the cermet material further comprises at least one rare earth oxide phase.
    [0015]
    Electrode material according to claim 14, characterized in that the rare earth oxide is selected from Y 2 O 3, CeO 2, La 2 O 3 and Nd 2 O 3.
    [0016]
    16. Electrode material according to claim 14 or 15, characterized in that the rare earth oxide phase represents at most 5% of the mass of the cermet material.
    [0017]
    An electrode material according to any one of claims 1 to 16, characterized in that the metal phase of the cermet material further comprises gold (Au) and / or silver (Ag), the percentage mass of these Au and / or Ag metals not exceeding 5% of the mass of said metallic phase of the cermet material.
    [0018]
    18. Electrode material according to any one of claims 1 to 17, characterized in that the thickness of the cermet material is greater than or equal to 1 mm.
    [0019]
    19. An electrode material according to claim 18, characterized in that the thickness of the cermet material is between 2 and 8 mm.
    [0020]
    20. An electrode material according to any one of claims 1 to 17, characterized in that it further comprises at least one intermediate layer disposed between the metal core and the cermet material, said intermediate layer comprising at least nickel and being predominantly metallic.
    [0021]
    Electrode material according to claim 20, characterized in that the total thickness of the cermet material and the intermediate layer is greater than or equal to 1 mm, said cermet material having a thickness of at least 0.5 mm.
    [0022]
    22. Electrode material according to claim 20 or 21, characterized in that the intermediate layer is a layer of nickel having a thickness of between 200 and 300 μm.
    [0023]
    23. Electrode material according to claim 20 or 21, characterized in that the intermediate layer is a layer of a cermet material which comprises in volume more than 50% of a metal phase comprising at least nickel.
    [0024]
    24. A method of manufacturing an electrode material according to any one of claims 1 to 19, or one of claims 20 to 23 when the electrode material further comprises at least one intermediate layer, characterized in that the manufacturing process comprises at least the following steps: the metal core of said electrode material is prepared according to a method chosen from casting, molding, rolling, hot forming such as rolling, extrusion, metallurgy of powders. Optionally, the deposition of at least one intermediate layer is carried out on the metal core. The deposition of the cermet material is carried out on the metal core, where appropriate on the last deposited intermediate layer, said deposition being carried out by a method chosen from the spraying or metallurgy methods of the powders. Inert anode made from an electrode material according to any one of claims 1 to 23. 26. Electrolytic cell comprising at least one inert anode according to claim 25. 27. Process for the production of aluminum by electrolysis in an electrolysis cell according to claim 26.
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    同族专利:
    公开号 | 公开日
    AU2015278874B2|2020-02-06|
    EP3161187A1|2017-05-03|
    WO2015198128A1|2015-12-30|
    CA2952263A1|2015-12-30|
    EP3161187B1|2019-09-11|
    AR101822A1|2017-01-18|
    RU2691290C2|2019-06-13|
    AU2015278874A1|2016-12-22|
    EP3161187A4|2018-04-04|
    US20170130351A1|2017-05-11|
    CN106488998A|2017-03-08|
    FR3022917B1|2016-06-24|
    RU2017102320A3|2019-01-28|
    CN106488998B|2018-12-21|
    RU2017102320A|2018-07-26|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1401435A|FR3022917B1|2014-06-26|2014-06-26|ELECTRODE MATERIAL AND ITS USE IN THE MANUFACTURE OF INERT ANODE|FR1401435A| FR3022917B1|2014-06-26|2014-06-26|ELECTRODE MATERIAL AND ITS USE IN THE MANUFACTURE OF INERT ANODE|
    US15/321,795| US20170130351A1|2014-06-26|2015-06-23|Electrode Material and Use Thereof for the Manufacture of an Inert Anode|
    PCT/IB2015/001041| WO2015198128A1|2014-06-26|2015-06-23|Electrode material and use thereof for the manufacture of an inert anode|
    CA2952263A| CA2952263A1|2014-06-26|2015-06-23|Electrode material and use thereof for the manufacture of an inert anode|
    AU2015278874A| AU2015278874B2|2014-06-26|2015-06-23|Electrode material and use thereof for the manufacture of an inert anode|
    CN201580034714.7A| CN106488998B|2014-06-26|2015-06-23|It is used to prepare the electrode material and application thereof of inert anode|
    RU2017102320A| RU2691290C2|2014-06-26|2015-06-23|Electrode material and use thereof for inert anode production|
    EP15811198.9A| EP3161187B1|2014-06-26|2015-06-23|Electrode material and use thereof for the manufacture of an inert anode|
    ARP150102040A| AR101822A1|2014-06-26|2015-06-25|ELECTRODE MATERIAL AND ITS USE FOR THE MANUFACTURE OF AN INERT ANODE|
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