Fused product comprising niobium and in particular intended for an electrode

Abstract

The invention relates to a fused polycrystalline product consisting of constituent elements M, niobium Nb, oxygen O, and optionally nitrogen N, together representing more than 90% of the weight of the product, and, optionally, an additional constituent element making up the remaining weight to 100%, wherein the constituent element M is selected from among titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), germanium (Ge), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminium (Al), tin (Sn), cerium (Ce), tellurium (Te), selenium (Se), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), rhenium (Re), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na), barium (Ba), and mixtures thereof, wherein the atomic proportions of the elements M, niobium Nb, oxygen O, and optionally nitrogen N are defined by the formula MmNb[O(1-y)Ny]n, and wherein the atomic number subscripts are such that: 0.019 ≤ m ≤ 7.692 and 0 ≤ y ≤ 0.210 and 0.060 ≤ n ≤ 953.850.

Description

[0001] Description

[0002] Title: Molten product containing niobium and in particular intended for an electrode

[0003] Technical field

[0004] The invention relates to a method for manufacturing a product consisting of elementary constituents M, niobium Nb, oxygen O and optionally nitrogen N, together representing more than 90% of the mass of the product, and, optionally, of a complementary elementary constituent, different from M, Nb, O and N, constituting the mass complement to 100%, the elementary constituent M being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), germanium (Ge), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), manganese (Mn), cerium (Ce), tellurium (Te), selenium (Se), silicon (Si), antimony (Sb), yttrium (Y), lanthanum (La), hafnium (Hf), tantalum (Ta), rhenium (Re), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi),sodium (Na) and their mixtures, and the contents of said elementary constituents being defined by the formula M, m Nb[O(iy)N y ]n, in which the atomic indices are such that 0.019 < m < 7.692 and 0 < y < 0.210 and 0.060 < n < 953.850.

[0005] In the remainder of the description, such a product is called an “MNbO product”.

[0006] The invention also relates to such a product when obtained by fusion.

[0007] In a most preferred embodiment, the elemental constituent M is selected from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), germanium (Ge), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), tellurium (Te), selenium (Se), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), rhenium (Re), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na), barium (Ba) and their mixtures.

[0008] In a preferred embodiment, and in particular the most preferred embodiment, y = 0 and 0.019 < m < 7.500 and 2.454 < n < 25.000.

[0009] State of the art

[0010] MNbO products are used in particular as electrode material, in particular anodes, for batteries, in particular lithium-ion batteries and sodium-ion batteries, as described for example in WO2021245411, W02022043705 or EP2448054. These electrodes are generally manufactured by a process comprising a step of coating a current collector with an ink, said ink containing, among other things, a powder of MNbO product, followed by a calendering step and a cutting step. MNbO product powders are generally produced by solid-phase sintering processes, as described for example in EP2448054 and WO2021245411. These processes are complex and expensive to implement.

[0011] There is therefore a continuing need to reduce the complexity and cost of manufacturing an MNbO product.

[0012] An object of the invention is to satisfy, at least partially, this need.

[0013] Summary of the invention

[0014] According to the invention, this aim is achieved by means of a polycrystalline fused MNbO product.

[0015] Surprisingly, such a fused MNbO product has a lower surface porosity, in %, than a product of the same composition manufactured by solid-phase sintering. Despite this difference, a fused MNbO product has proven to be well suited to constitute an electrode, in particular an anode of a battery, in particular a lithium-ion battery or a sodium-ion battery.

[0016] Unexpectedly, the inventors discovered that it was not necessary to implement a complex process to produce a powder suitable for the manufacture of an electrode, as in the prior art. A simple melting process is sufficient.

[0017] Preferably, a molten product according to the invention also comprises one and preferably several of the following optional characteristics:

[0018] - y < 0.150, preferably y < 0.053;

[0019] - the quantity of the additional elementary constituent is less than 1.0%, as a percentage by mass based on the mass of the product;

[0020] - the additional elementary constituent is made up of more than 80%, in mass percentage based on the additional elementary constituent, lithium Li;

[0021] - one of the following four variants 1. to 4. applies:

[0022] 1. the elemental constituent M consists of at least one chemical element chosen from Ti, Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B, Hf and Zr, and 0.019 < m < 1.000 and y = 0 and 2.538 < n < 7.300;

[0023] 2. the elementary constituent M is W, does not replace, even partially, Nb, and 0.083 < m < 7.500 and y = 0 and 2.750 < n < 25.000;

[0024] 3. the elementary constituent M does not replace, even partially, Nb, and is made up of a first elementary constituent M' made up of at least one first chemical element chosen from W, V, Zr, Hf and Mo on the one hand and a second elementary constituent M” made up of at least one second chemical element chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, with M' different from M”, and 0.042 < m < 1.754 and y = 0 and

[0025] 2,454 < n < 7,772 ;

[0026] 4. the elemental constituent M is selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi, Na, Ba and mixtures thereof, and 0.020 < m < 7.692 and 0 < y < 0.210, preferably 0 < y < 0.150, preferably 0 < y < 0.100, preferably 0 < y < 0.053 and 0.060 < n < 953.850;

[0027] - variant 1. applies and

[0028] 1.1. in the crystal structure of the melt, M partially substitutes for Nb, Ml and M2 denoting the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the melt can thus be expressed by the formula Ml( m-Z )M2 z Nb[O(iy)Ny] n , the elementary constituent Ml being Ti, the elementary constituent M2 being Ta and 0.500 < m < 0.923 and

[0029] 0 < z < 0.282 provided that z / m < 0.306 and y = 0 and 3.350 < n < 4.683, or

[0030] 1.2. the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and optionally at least one chemical element chosen from Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B, Hf and Zr, on the other hand, and 0.019 < m < 1.000 and y = 0 and 2.538 < n < 7.300, or

[0031] - variant 3. applies and

[0032] 3.1. the elementary constituent M consists of W on the one hand and at least one chemical element chosen from Ti, Mg, V, Hf, Cr, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and 0.083 < m < 1.754, the elementary atomic index of W being greater than 0.042 and less than 1.754 and y = 0 and 2.613 < n < 7.772, or

[0033] 3.2. the elementary constituent M consists of V on the one hand and at least one chemical element chosen from Ti, Mg, Hf, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.111, the elementary atomic index of V being greater than 0.056 and less than 0.111 and y = 0 and 2.639 < n < 2.778, or

[0034] 3.3. the elementary constituent M consists of Zr on the one hand and at least one chemical element chosen from Ti, Mg, V, Hf, Cr, W, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.042, the elementary atomic index of Zr being greater than 0.021 and less than 0.042 and y = 0 and 2.454 < n < 2.583, or

[0035] 3.4. the elementary constituent M consists of Mo on the one hand and at least one chemical element chosen from Ti, Mg, V, Hf, Cr, W, Zr, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.083, the elementary atomic index of Mo being greater than 0.042 and less than 0.083 and y = 0 and 2.613 < n < 2.750.- variant 4. applies and

[0036] 4.1. the elementary constituent M consists of at least two chemical elements chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi, Ba and Na, or

[0037] 4.2. the elementary constituent M does not replace, even partially, Nb, and is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, P, Ba and their mixtures, and 0.020 < m < 7.690 and y = 0 and 0.060 < n < 953.850, or

[0038] 4.3. in the crystal structure of the melt, M partially substitutes for Nb, Ml and M2 denoting the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the melt can thus be expressed by the formula Ml( m.Z )M2 z Nb[O(iy)Ny] n , and the elemental constituent Ml is selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, and the elemental constituent M2 is selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, and

[0039] 0.020 < m < 0.765 and 0 < z < 0.286 provided that z / m < 0.800 and 0 < y < 0.210 and 2.404 < n < 19.706;

[0040] - the melted product is such that:

[0041] - variant 1. applies and the elementary constituent M is Ti and 0.019 < m < 0.526 and y = 0 and 2.538 < n < 4.000, or

[0042] - variant 1. applies and the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and at least one chemical element chosen from Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B, Hf and Zr on the other hand, and 0.374 < m < 1.000 and y = 0 and 2.913 < n < 7.300, or

[0043] - variant 3 applies and, if m' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from W, V, Zr, Hf and Mo and constituting the first elementary constituent M', and m'' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from Ti, Mg, V, Hf, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd, and constituting the second elementary constituent M”, with M' different from M”, m being equal to m' + m”, then 0.021 < m' < 1.754, or

[0044] - variant 4 applies and the elementary constituent M consists of at least two chemical elements chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, Ba and P, and 0.020 < m < 7.690 and y = 0 and 0.060 < n < 953.850, or

[0045] - variant 4 applies, and in the crystal structure of the molten product, M partially substitutes for Nb, Ml and M2 designating the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the molten product can thus be expressed by the formula Ml( m . z)M2 z Nb[O(iy)Ny]n, and the elemental constituent Ml is selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, and the elemental constituent M2 is selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, and the elemental constituents Ml and M2 do not have a common chemical element, and 0.020 < m < 0.765 and 0 < z < 0.286 provided that z / m < 0.800 and 0 < y < 0.210 and 2.404 < n < 19.706;

[0046] - in the crystal structure, M partially substitutes for Nb, Ml and M2 designating the elementary constituent M not substituted for Nb and substituted for Nb, respectively, Ml and M2 being able to be identical or different, the composition of the molten product thus being able to be expressed by the formula Ml( m.Z )M2 z Nb[O(i- y)Ny] n, the elemental constituent Ml being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), germanium (Ge), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na), barium (Ba) and mixtures thereof, the elemental constituent M2 being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), germanium (Ge), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si),antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na), Barium (Ba) and mixtures thereof, the elemental constituents Ml and M2 preferably not comprising a common chemical element, the atomic indices being such that 0.020 < m < 0.923 and 0 < z < 0.286 provided that z / m < 0.800 and 0 < y,

[0047] < 0.210 and 2.400 < n < 19.710;

[0048] - the molten product is in the form of an object whose dimensions are all greater than 3 pm.

[0049] Unless technically incompatibility exists, the optional features described above are applicable, optionally, to the said most preferred embodiment.

[0050] Preferably, in particular in said most preferred embodiment, a molten product according to the invention further comprises one and preferably several of the following optional characteristics: y = 0 and 0.019 < m < 7.500 and 2.454 < n < 25.000;

[0051] - the quantity of the additional elementary constituent is less than 1.0%, as a percentage by mass based on the mass of the product;

[0052] - the additional elementary constituent is made up of more than 80%, in mass percentage based on the additional elementary constituent, lithium Li;

[0053] - one of the following three variants 1. to 3. applies:

[0054] 1. the elemental constituent M consists of at least one chemical element chosen from Ti, Mg, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ga, Al, Ce, Si, Y, Hf, Ta, Zn, B, Sr, P, Na and Ba, and 0.019 < m < 1.000 and 2.538 < n

[0055] < 7,300 ;

[0056] 2. the elementary constituent M is W, does not replace, even partially, Nb, and 0.083 < m < 7.500 and 2.750 < n < 25.000;

[0057] 3. the elementary constituent M does not replace, even partially, Nb, and consists of a first elementary constituent M' consisting of at least one first chemical element chosen from W, V, Zr, Hf and Mo on the one hand and a second elementary constituent M” consisting of at least one second chemical element chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, with M' different from M”, and 0.042 < m < 1.754 and 2.454 < n < 7.772;

[0058] - variant 1. applies and

[0059] 1.1. in the crystal structure of the melt, M partially substitutes for Nb, Ml and M2 denoting the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the melt can thus be expressed by the formula Ml(mz)M2 z Nb[0(iy)N y ]n, the elementary constituent Ml being Ti, the elementary constituent M2 being Ta and 0.500 < m < 0.923 and 0 < z

[0060] < 0.282 provided that z / m < 0.306 and 3.350 < n < 4.683, or

[0061] 1.2. the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and optionally at least one chemical element chosen from Mg, Fe, W, Ta, Mo, Ga, Al, B Hf and Zr, and, on the other hand, or variant 3. applies and

[0062] 3.1. the elementary constituent M consists of W on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, and 0.083 < m < 1.754, the elementary atomic index of W being greater than 0.042 and less than 1.754 and 2.613 < n < 7.772, or

[0063] 3.2. the elementary constituent M consists of V on the one hand and at least one chemical element chosen from Ti, Mg, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, and m = 0.111, the elementary atomic index of V being greater than 0.056 and less than 0.111 and 2.639

[0064] < n < 2.778, or

[0065] 3.3. the elementary constituent M consists of Zr on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.042, the elementary atomic index of Zr being greater than 0.021 and less than 0.042 and 2.454 < n < 2.583, or

[0066] 3.4. the elementary constituent M consists of Mo on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Zr, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, and m = 0.083, the elementary atomic index of Mo being greater than 0.042 and less than 0.083 and 2.613 < n < 2.750, or

[0067] - the melted product is such that:

[0068] - variant 1. applies and the elementary constituent M is Ti and 0.019 < m < 0.526 and 2.538 < n

[0069] < 4,000, or

[0070] - variant 1. applies and the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and at least one chemical element chosen from Mg, Fe, W, Ta, Mo, Ga, Al, B, Hf and Zr on the other hand, and 0.374 < m < 1.000 and 2.913 < n < 7.300 or

[0071] - variant 3 applies and, if m' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from W, V, Zr, Hf and Mo and constituting the first elementary constituent M', and m'' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from Ti, Mg, V, Hf, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd, and constituting the second elementary constituent M”, with M' different from M”, m being equal to m' + m”, then 0.021 < m' < 1.754, and the elementary constituent Ml is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, Cd, Sr, B, Ba and their mixtures, and the elemental constituent M2 is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, Cd, Sr, B, Ba and mixtures thereof, and the elemental constituents Ml and M2 do not have a common chemical element, and 0.020 < m < 0.765 and 0 < z < 0,286 provided that z / m < 0.800 and 2.404 < n < 19.706; - in the crystal structure, M partially substitutes for Nb, Ml and M2 designating the elementary constituent M not substituted for Nb and substituted for Nb, respectively, Ml and M2 being able to be identical or different, the composition of the molten product being able to be expressed by the formula Ml(, m.Z )M2 z Nb[O(i- y)Ny] n, the elementary constituent Ml being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), cadmium (Cd), strontium (Sr), boron (B), phosphorus (P), sodium (Na), barium (B a) and mixtures thereof, the elementary constituent M2 being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn),cadmium (Cd), strontium (Sr), boron (B), phosphorus (P), sodium (Na), barium (B a) and mixtures thereof, the elementary constituents Ml and M2 preferably not comprising a common chemical element, the atomic indices being such that 0.020 < m < 0.923 and 0 < z < 0.286 provided that z / m < 0.800 and 2.454 < n < 19.710;,

[0072] - the molten product is in the form of an object all of whose dimensions are greater than 3 μm. The invention also relates to a powder comprising more than 90%, preferably 100% by mass of particles in a molten product according to the invention.

[0073] The invention also relates to a manufacturing process, called "general process", of a product according to the invention, said process comprising the following steps: a) mixing raw materials so as to form a starting charge suitable for obtaining, at the end of step c) and / or at the end of step f), a molten product according to the invention, b) melting the starting charge until a molten material is obtained, c) cooling until complete solidification of said molten material, so as to obtain a molten product, d) optionally, grinding said molten product, preferably until a powder is obtained, e) optionally, particle size selection of said molten product, f) before or after step d), optionally, annealing heat treatment of said molten product.

[0074] Preferably, if the molten product contains nitrogen, the nitrogen is supplied by blowing a nitrogen gas into the molten material, in step b), and / or by the presence of more than 21% of nitrogen, in mass percentage, in the gas surrounding the molten material, in step b), and / or by a heat treatment under a nitrogen atmosphere, in step f). Preferably, in step a), the starting charge supplies all or part of the oxygen, preferably all of the oxygen.

[0075] The invention also relates to a molten product obtained or capable of having been obtained by a process according to the invention.

[0076] The invention also relates to an electrode, in particular an anode, comprising a melted product according to the invention or obtained or capable of having been obtained by a process according to the invention.

[0077] The invention finally relates to a battery, in particular a lithium-ion battery and a sodium-ion battery comprising an electrode, in particular an anode, comprising a melted product according to the invention or obtained or capable of having been obtained by a method according to the invention.

[0078] Definitions and measurement protocols

[0079] A "molten product" is a product directly obtained by solidification of a molten material resulting from the melting of a starting charge. The molten product may be in the form of molten grains. "Directly obtained" means that the molten product is obtained immediately after said solidification.

[0080] A "molten material" is a mass made liquid by heating a starting charge, which may contain some solid particles, but not enough to structure the mass. To retain its shape, a molten material must be contained in a container.

[0081] A solid material consisting of a multitude of crystallites of varying size and orientation is called a "polycrystalline" material, as opposed to a monocrystalline material consisting of a single crystal. The polycrystalline nature of a material can, for example, be demonstrated by X-ray diffraction and / or by observations made using a scanning electron microscope. Such observations can reveal grain boundaries. Unless special precautions are taken, a molten product is polycrystalline.

[0082] For the sake of clarity, a distinction is made between “elementary constituents” and “chemical elements”. “Elementary constituents” means M, M', M”, Ml, M2, Nb, O and N and, optionally, a “complementary elemental constituent” which is M, M', M”, Ml, M2, Nb, O and N and which constitutes the 100% complement of the product. The elemental constituents M, M', M”, Ml, M2 and the complementary elemental constituent may consist of one or more “chemical elements” which are the elements listed in the periodic table of elements. When reference is made to the “sum of the elementary atomic numbers of the chemical element(s)” constituting an elementary constituent and this elementary constituent consists of a single chemical element, said sum is equal to the elementary atomic number of said chemical element.

[0083] In an elementary constituent formed by several chemical elements, the chemical elements are not necessarily chemically associated with each other, for example in the form of an alloy. They can be independent of each other and dispersed in the melt. For example, when the elementary constituent M is a mixture of Ti and Ta (the elementary constituent is TitiTa ta in the formula, with m = ti + ta), this does not imply the existence of a possible chemical relationship between these chemical elements. If the elementary constituent M is a mixture of Ml and M2 (the elementary constituent M is Ml( m.Z )M2 z in the formula), this does not imply the existence of a possible chemical relationship between Ml and M2. If the elementary constituent M is a mixture of M' and M” (the elementary constituent M is M' m M” m” in the formula), this does not imply the existence of a possible chemical relationship between M' and M”. If the elementary constituent M' is made up of several chemical elements, this does not imply the existence of a possible chemical relationship between said chemical elements. If the elementary constituent M” is made up of several chemical elements, this does not imply the existence of a possible chemical relationship between said chemical elements.

[0084] With the exception of nitrogen and oxygen, the content of the various chemical elements in a product melted according to the invention or manufactured according to the invention is determined by inductively coupled plasma (ICP) technology, after dissolution by attack with an acid of a ground sample having a maximum size of less than 160 μm. The nitrogen and oxygen contents are determined using an oxygen-nitrogen analyzer model ON836 marketed by the company LECO.

[0085] The amorphous phase content can be conventionally determined by Rietveld refinement of a sample to which a known quantity of a fully crystallized standard has been added, the diffraction peaks of said standard not being confused with those of the crystallized phases present in the sample.

[0086] A "particle" means a solid object with all dimensions less than 10 mm.

[0087] The sphericity of a particle is the ratio of its smallest dimension to its largest dimension.

[0088] By "block" we mean a solid object that is not a particle.

[0089] The “surface porosity” of a product is measured on a plurality of images of a powder of the product having a median size between 3 u ni and 8 pin, considering only the grains of the powder having a surface area greater than 3 u ni 2 Surface porosity is the ratio of the sum of the pore surfaces, considering more than 2000 said grains, to the sum of the observed surfaces of said grains, in percentage.

[0090] The percentiles or "percentiles" 10 (Dio), 50 (D50), 99.5 (099.5) are the particle sizes corresponding to the percentages, by mass, of 10%, 50% and 99.5% respectively, on the cumulative particle size distribution curve of the powder particles, the particle sizes being ranked in ascending order. For example, 10%, by mass, of the particles in the powder have a size smaller than Dio and 90% of the particles by mass have a size larger than Dio- The percentiles can be determined using a particle size distribution carried out using a laser particle size analyzer, for example, a Partica LA-950 from HORIBA.

[0091] The minimum size of a powder is the 10th percentile (Dio) of the powder. The median size of a powder is the 50th percentile (D50).

[0092] The "maximum size of a powder" is called the 99.5 percentile (099.5) of said powder.

[0093] By “precursor” of a compound or element is meant a constituent capable of providing said compound or element, respectively, during the implementation of a manufacturing process according to the invention.

[0094] Unless otherwise indicated, all contents of the constituents of a product according to the invention are mass percentages expressed on the basis of the product.

[0095] In the M formulas m Nb[O(iy)Ny] n and Ml( m.Z )M2 z Nb[O(iy)Ny] n , the indices m, y, z and n are atomic indices, that is to say they relate to quantities, in number of atoms, relative to the quantities of other elementary constituents.

[0096] For the indices m, z and n, these quantities are relative to the molar quantity of Nb. For example, in the formula M m Nb[O(iy)Ny] n, if m = 0.5, the product has 0.5 moles of M for each mole of Nb. For example, in the formula M m Nb[O(iy)Ny] n , if n = 3, the product contains 3 moles of [O(iy)N y ] for each mole of Nb.

[0097] The subscript y indicates a substitution rate of O by N. For example, if y = 0.1, this means that 10% of the oxygen chemical elements O have each been replaced by one nitrogen chemical element N.

[0098] When the elementary constituent M, M', M”, Ml or M2 comprises several chemical elements, the atomic indices m, m', m” and z refer to the total quantity of atoms of these chemical elements. For example, if the elementary constituent M consists of a combination of Ti and Mg, in a ratio of 2 Ti atoms for one Mg atom, M mis read [Ti^Mgmlm, or Tii.n / îMg,,, / !. An "elementary atomic index" is an index specific to a chemical element in M, M', M”, Ml or M2, in this case 2m / 3 for the elementary atomic index of Ti and m / 3 for the elementary atomic index of Mg. The sum of the elementary atomic indices of M is equal to m, the sum of the elementary atomic indices of M' is equal to m', the sum of the elementary atomic indices of M” is equal to m”, the sum of the elementary atomic indices of Ml is equal to mz and the sum of the elementary atomic indices of M2 is equal to z.

[0099] The verbs "to understand", "to comprise" and "to present" should be interpreted in a non-restrictive manner, unless otherwise indicated.

[0100] Detailed description

[0101] Other characteristics and advantages of the present invention will become apparent upon reading the detailed description which follows, provided for illustrative and non-limiting purposes.

[0102] Molten product A molten product according to the invention is of formula M m Nb[O(iy)N y ] n .

[0103] Preferably, y < 0.150, preferably y < 0.100, preferably y < 0.053.

[0104] In one embodiment, in the crystal structure, M partially substitutes for Nb, Ml and M2 denoting the elemental constituent M not substituted for Nb and substituted for Nb, respectively, Ml and M2 may be the same or different, the composition of the molten product thus being able to be expressed by the formula Ml (m-Z )M2 z Nb[O(iy)Ny] n, the elemental constituent Ml being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), germanium (Ge), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na), barium (Ba) and mixtures thereof, the elemental constituent M2 being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), germanium (Ge), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si),antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na), barium (Ba) and mixtures thereof, the atomic indices being such that 0.020 < m < 0.923 and 0 < z < 0.286 provided that z / m < 0.800 and 0 < y < 0.210 and 2.400 < n < 19.710.,

[0105] In said embodiment, the molten product has one or more of the following preferred characteristics: y < 0.150, preferably y < 0.100, preferably y < 0.053;

[0106] - the elemental constituent Ml is chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), germanium (Ge), calcium (Ca), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), barium (Ba) and mixtures thereof;

[0107] - the elemental constituent M2 is chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), germanium (Ge), calcium (Ca), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), barium (Ba) and mixtures thereof.

[0108] In a variant of said embodiment, the elementary constituents M1 and M2 do not comprise a common chemical element, i.e. one which would be present in both M1 and M2. The mass quantity of complementary element is less than 2.0%, preferably less than 1.5%, preferably less than 1.0%, preferably less than 0.5%, based on the mass of the product. Preferably, the complementary elementary constituent consists of unavoidable constituents, introduced unintentionally and necessarily with the raw materials, or "impurities". The elementary constituents M, N, and where appropriate M1 and M2 may be introduced into the starting charge to be melted as traces in one or more raw materials. The atomic indices m, y, and where appropriate mz and z respectively, take this into account.

[0109] In one embodiment, the complementary elementary constituent (complement to 100% of the elementary constituents M, Nb, O, N, and where appropriate Ml and M2) consists of more than 80%, preferably more than 85%, preferably more than 90%, preferably more than 95%, in mass percentage based on the complementary elementary constituent, lithium (Li).

[0110] Preferably, the molten product is an oxide.

[0111] The molten product is electrically neutral.

[0112] In a first variant of the molten product, the elementary constituent M consists of at least one chemical element chosen from Ti, Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B, Hf, and Zr, and 0.019 < m < 1.000 and y = 0 and 2.538 < n < 7.300.

[0113] In a first particular embodiment of the first variant of the molten product of the invention, in the crystalline structure of said molten product, M is partially substituted for Nb, Ml and M2 designating the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the molten product thus being able to be expressed by the formula Ml( m.Z )M2 z Nb[O(iy)Ny] n , the elementary constituent Ml being Ti, the elementary constituent M2 being Ta and 0.500 < m < 0.923 and 0 < z < 0.282 provided that z / m < 0.306 and y = 0 and 3.350 < n < 4.683.

[0114] In a second particular embodiment of the first variant of the molten product of the invention, the elementary constituent M consists of Ti on the one hand and optionally of at least one chemical element chosen from Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B, Hf and Zr, on the other hand, and 0.019 < m < 1.000 and y = 0 and 2.538 < n < 7.300. In this second particular embodiment of the first variant of the molten product of the invention, the elementary constituent M does not comprise an elementary constituent M2 replacing the element Nb.

[0115] In a first particular sub-mode of the second particular embodiment of the first variant of the molten product of the invention, the elementary constituent M is Ti and 0.019 < m < 0.526 and y = 0 and 2.538 < n < 4.000. In said first particular sub-mode, the molten product according to the invention may for example be presented under the formula Tio.5Nb03.5, or TiNbiO?. or under the formula Tio.33NbO3.i67, or TizNbôO .

[0116] In a second particular sub-mode of the second particular embodiment of the first variant of the molten product of the invention, the elementary constituent M consists of Ti on the one hand and at least one chemical element chosen from Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B, Hf and Zr on the other hand, and 0.374 < m < 1.000 and y = 0 and 2.913 < n < 7.300.

[0117] In a second variant of the molten product of the invention, the elementary constituent M is W, and 0.083 < m < 7.500 and y = 0 and 2.750 < n < 25.000. In this second variant of the molten product of the invention, the elementary constituent W is not substituted, even partially, for the element Nb. In said second variant, the molten product according to the invention may for example be presented under the formula W0.21NbO3.143, or WsNbuO-M, or under the formula Wo,5Nb04, or WNlvOx. or under the formula W1.75NbO7.75, or W7Nb4O3i-

[0118] In a third variant of the molten product of the invention, the elementary constituent M consists of a first elementary constituent M' consisting of at least one first chemical element chosen from W, V, Zr, Hf and Mo on the one hand and a second elementary constituent M” consisting of at least one second chemical element chosen from Ti, Mg, V, Cr, W, Hf, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, with M' different from M”, and 0.042 < m < 1.754 and y = 0 and 2.454 < n < 7.772. In this third variant of the molten product of the invention, the elementary constituent M does not comprise an elementary constituent M2 replacing the element Nb.

[0119] Preferably, in this third variant of the molten product of the invention, if m' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from W, V, Zr, Hf and Mo and constituting the first elementary constituent M', and m'' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from Ti, Mg, V, Cr, W, Zr, Hf, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd, and constituting the second elementary constituent M”, with M' different from M”, m being equal to m' + m”, then 0.021 < m' < 1.754.

[0120] In a first particular embodiment of the third variant of the molten product of the invention, the elementary constituent M is made up of W on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, Zr, Hf, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and

[0121] 0.083 < m < 1.754, the elementary atomic index of W being greater than 0.042 and less than 1.754 and y = O and 2.613 < n < 7.772.

[0122] In a second particular embodiment of the third variant of the molten product of the invention, the elementary constituent M consists of V on the one hand and at least one chemical element chosen from Ti, Mg, Cr, W, Zr, Hf, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.111, the elementary atomic index of V being greater than 0.056 and less than 0.111 and y = 0 and 2.639 < n < 2.778.

[0123] In a third particular embodiment of the third variant of the molten product of the invention, the elementary constituent M consists of Zr on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.042, the elementary atomic index of Zr being greater than 0.021 and less than 0.042 and y = 0 and 2.454 < n < 2.583.

[0124] In a fourth particular embodiment of the third variant of the molten product of the invention, the elementary constituent M consists of Mo on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Zr, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.083, the elementary atomic index of Mo being greater than 0.042 and less than 0.083 and y = 0 and 2.613 < n < 2.750.

[0125] In a fourth variant of the product of the invention, the elementary constituent M is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi, Na, Ba and mixtures thereof, and 0.020 < m < 7.692 and 0 < y < 0.210, preferably 0 < y < 0.150, preferably 0 < y < 0.100, preferably 0 < y < 0.053 and 0.060 < n < 953.850.

[0126] Preferably, the elementary constituent M is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Hf, Ta, Zn, In, Cd, Sr, B, Pb, P, Bi, Ba and mixtures thereof, preferably chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Hf, Ta, Zn, In, Cd, B, P, Ba and mixtures thereof, preferably chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, Ni, Co, Al, Sn, Sb, Y, Hf, Ta, Zn, B, Ba and mixtures thereof.

[0127] In a first particular embodiment of the fourth variant of the molten product of the invention, the elementary constituent M consists of at least two chemical elements chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi, Ba and Na. In said first particular embodiment, the molten product according to the invention may for example be presented under the formula Tio,oo4i7Moo,o79i7Nb02,75, or Tio,o5Moo,9sNbi2033, or under the formula Mo0.0021Zr0.0396NbO2.5833, or Moo,o5Zro,95Nb24062.

[0128] In a second particular embodiment of the fourth variant of the molten product of the invention, the elementary constituent M is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, P, Ba and mixtures thereof, and 0.020 < m < 7.690 and y = 0 and 0.060 < n < 953.850. In this second particular embodiment of the fourth variant of the molten product of the invention, the elementary constituent M does not comprise an elementary constituent M2 replacing the element Nb. In said second particular embodiment, the molten product according to the invention may for example be presented under the formula Moo.0056Vo.1056Nb02.7778, i.e. Moo,05Vo,95Nb9025-

[0129] Preferably, in this second particular embodiment of the fourth variant of the molten product of the invention, the elementary constituent M consists of at least two chemical elements chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, Ba and P. In a third particular embodiment of the fourth variant of the molten product of the invention, in the crystal structure, M partially substitutes for Nb, Ml and M2 designating the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the molten product thus being able to be expressed by the formula Ml( m-Z )M2 z Nb[O(iy)Ny] n, the elementary constituent Ml is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, preferably from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Hf, Ta, Zn, In, Cd, Sr, B, Pb, Bi, P, Ba and mixtures thereof, the elementary constituent M2 is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, preference from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Hf, Ta, Zn, In, Cd, Sr, B, Pb, Bi, P, B a and mixtures thereof, and

[0130] 0.020 < m < 0.765 and 0 < z < 0.286 provided that z / m < 0.800 and 0 < y < 0.210 and 2.404 < n < 19.706.

[0131] Preferably, in this third particular embodiment of the fourth variant of the product of the invention, the elementary constituents Ml and M2 do not comprise a common chemical element. In said third particular embodiment, the fused product according to the invention may for example be presented under the formula Moo,o627Wo,o209Zro,oo42Nb02,7594, or MoojsWo^sNbn^sZro, 05032,975, Ml being Mo and W, M2 being Zr.

[0132] In the most preferred embodiment, y = 0 and 0.019 < m < 7.500 and 2.454 < n < 25.000.

[0133] In the crystal structure, M partially substitutes for Nb, Ml and M2 denoting the elemental constituent M not substituted for Nb and substituted for Nb, respectively, Ml and M2 being able to be identical or different, the composition of the molten product can thus be expressed by the formula Ml( m.Z )M2 z Nb[O(i- y)Ny] n, the elementary constituent Ml being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), cadmium (Cd), strontium (Sr), boron (B), phosphorus (P), sodium (Na), barium (B a) and mixtures thereof, the elementary constituent M2 being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn),cadmium (Cd), strontium (Sr), boron (B), phosphorus (P), sodium (Na), barium (B a) and mixtures thereof, the atomic indices being such that 0.020 < m < 0.923 and 0 < z < 0.286 provided that z / m < 0.800 and 2.454 < n < 19.710.,

[0134] In said most preferred embodiment, the molten product has one or more of the following preferred characteristics:

[0135] - the elemental constituent Ml is chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), calcium (Ca), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), cadmium (Cd), strontium (Sr), boron (B), phosphorus (P), barium (Ba) and mixtures thereof;

[0136] - the elemental constituent M2 is chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), calcium (Ca), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), cadmium (Cd), strontium (Sr), boron (B), phosphorus (P), barium (Ba) and mixtures thereof.

[0137] In a variant of said most preferred embodiment, the elemental constituents Ml and M2 do not comprise a common chemical element, i.e. which would be present in both Ml and M2.

[0138] In the most preferred embodiment, the mass quantity of complementary element is less than 2.0%, preferably less than 1.5%, preferably less than 1.0%, preferably less than 0.5%, based on the mass of the product. Preferably, the complementary elemental constituent consists of unavoidable constituents, introduced unintentionally and necessarily with the raw materials, or "impurities". The elemental constituents M, N, and optionally M1 and M2 may be introduced into the feedstock to be melted as traces in one or more raw materials. The atomic indices m, y, and optionally mz and z respectively, take this into account.

[0139] Optionally, in the most preferred embodiment, the complementary elemental constituent (complement to 100% of the elemental constituents M, Nb, O, N, and where appropriate Ml and M2) consists of more than 80%, preferably more than 85%, preferably more than 90%, preferably more than 95%, in mass percentage based on the complementary elemental constituent, lithium (Li).

[0140] Preferably, in the most preferred embodiment, the molten product is an oxide.

[0141] The molten product, in the most preferred embodiment, is electrically neutral.

[0142] In a first variant of the molten product in the most preferred embodiment, the elemental constituent M consists of at least one chemical element selected from Ti, Mg, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ga, Al, Ce, Si, Y, Hf, Ta, Zn, B, Sr, P, Na and Ba.

[0143] In a first particular embodiment of the first variant of the molten product of the invention in the most preferred embodiment, in the crystal structure of said molten product, M is partially substituted for Nb, Ml and M2 designating the elemental constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the molten product thus being able to be expressed by the formula Ml (mz)M2 z Nb[O(iy)N y ]n, the elementary constituent Ml being Ti, the elementary constituent M2 being Ta and 0.500 < m < 0.923 and 0 < z < 0.282 provided that z / m < 0.306 and 3.350 < n < 4.683.

[0144] In a second particular embodiment of the first variant of the molten product of the invention in the most preferred embodiment, the elementary constituent M consists of Ti on the one hand and optionally of at least one chemical element chosen from Mg, Fe, W, Ta, Mo, Ga, Al, B, Hf and Zr, on the other hand. In this second particular embodiment of the first variant of the molten product of the invention, the elementary constituent M does not comprise an elementary constituent M2 replacing the element Nb.

[0145] In a first particular sub-mode of the second particular embodiment of the first variant of the molten product of the invention in the most preferred embodiment, the elementary constituent M is Ti and 0.019 < m < 0.526 and 2.538 < n < 4.000. In said first particular sub-mode, the molten product according to the invention may for example be presented under the formula Tio,5Nb03,5, or TiNbiC)?. or under the formula Tio,33Nb03,i67, or TiiNbeOiu.

[0146] In a second particular sub-mode of the second particular embodiment of the first variant of the molten product of the invention in the most preferred embodiment, the elemental constituent M consists of Ti on the one hand and at least one chemical element chosen from Mg, Fe, W, Ta, Mo, Ga, Al, B, Hf and Zr on the other hand, and 0.374 < m < 1.000 and 2.913 < n < 7.300.

[0147] In a second variant of the molten product of the invention in the most preferred embodiment, the elemental constituent M is W, and 0.083 < m < 7.500 and 2.750 < n < 25.000. In this second variant of the molten product of the invention, the elemental constituent W is not substituted, even partially, for the element Nb. In said second variant, the molten product according to the invention may for example be in the formula Wo,2iNb03,i43, or WsNbuO-M, or in the formula Wo,5Nb04, or WNbiOx. or in the formula W1.75NbO7.75, or W7Nb4O3i-

[0148] In a third variant of the molten product of the invention in the most preferred embodiment, the elemental constituent M consists of a first elemental constituent M' consisting of at least one first chemical element selected from W, V, Zr, Hf and Mo on the one hand and a second elemental constituent M” consisting of at least one second chemical element selected from Ti, Mg, V, Cr, W, Hf, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, with M' different from M”, and 0.042 < m < 1.754 and 2.454 < n < 7.772. In this third variant of the molten product of the invention, the elemental constituent M does not comprise an elemental constituent M2 replacing the element Nb.Preferably, in this third variant of the molten product of the invention in the most preferred embodiment, if m' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from W, V, Zr, Hf and Mo and constituting the first elementary constituent M', and m” denotes the sum of the elementary atomic indices of the chemical element(s) chosen from Ti, Mg, V, Cr, W, Zr, Hf, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd, and constituting the second elementary constituent M”, with M' different from M”, m being equal to m' + m”, then 0.021 < m' < 1.754.

[0149] In a first particular embodiment of the third variant of the molten product of the invention in the most preferred embodiment, the elementary constituent M consists of W on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, Zr, Hf, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and

[0150] 0.083 < m < 1.754, the elementary atomic index of W being greater than 0.042 and less than 1.754 and 2.613 < n < 7.772.

[0151] In a second particular embodiment of the third variant of the molten product of the invention in the most preferred embodiment, the elementary constituent M consists of V on the one hand and at least one chemical element chosen from Ti, Mg, Cr, W, Zr, Hf, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.111, the elementary atomic index of V being greater than 0.056 and less than 0.111 and 2.639 < n < 2.778.

[0152] In a third particular embodiment of the third variant of the molten product of the invention in the most preferred embodiment, the elemental constituent M consists of Zr on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.042, the elemental atomic index of Zr being greater than 0.021 and less than 0.042 and 2.454 < n < 2.583.

[0153] In a fourth particular embodiment of the third variant of the molten product of the invention in the most preferred embodiment, the elemental constituent M consists of Mo on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Zr, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.083, the elemental atomic index of Mo being greater than 0.042 and less than 0.083 and 2.613 < n < 2.750.

[0154] Microstructure

[0155] Preferably, the amorphous phase content, expressed in mass percentages based on the mass of the molten product, is less than 20%, preferably less than 15%, preferably less than 10%, preferably less than 5%.

[0156] Preferably, the crystallized phases not containing niobium represent, in total, less than 10%, preferably less than 5%, in mass percentages based on the crystallized phases.

[0157] Shape of the melted product

[0158] In a preferred embodiment, the molten product according to the invention is in the form of a particle. Preferably, the minimum size of the powder is greater than 0.01 μm, preferably greater than 0.1 μm, preferably greater than 0.5 μm, or even greater than 1 μm and / or the maximum size of the powder is less than 10 mm, preferably less than 5 mm, preferably less than 1 mm, preferably less than 500 μm, preferably less than 250 μm, preferably less than 100 μm.

[0159] In one embodiment, the sphericity of more than 80% by number of the particles of the powder is greater than 0.5, preferably 0.6, preferably greater than 0.7, or even greater than 0.8.

[0160] The invention also relates to a powder comprising more than 90% by mass, or even more than 95%, or even substantially 100% of particles in a molten product according to the invention.

[0161] Preferably, the median size of the powder is greater than 0.2 pm, preferably greater than 0.5 pm and / or, preferably less than 70 pm, preferably less than 50 pm, preferably less than 40 pm, preferably less than 30 pm, preferably less than 20 pm.

[0162] In one embodiment, a powder according to the invention is sintered to form an electrode, preferably an anode of a battery, in particular a lithium ion battery or a sodium ion battery.

[0163] In one embodiment, the product is in the form of an object whose dimensions are all greater than 1 μm, preferably greater than 3 μm, preferably greater than 5 μm. With these dimensions, it is advantageously easy to detect the specific microstructure of the molten product according to the invention.

[0164] Process

[0165] The invention also relates to a so-called “general method” comprising steps a) to c) and optionally d) to f).

[0166] In one embodiment, the method according to the invention comprises a step d) and a step e).

[0167] In one embodiment, the method according to the invention comprises a step d), a step e) and a step f)-

[0168] Step f) can in particular be implemented when the molten product according to the invention contains nitrogen.

[0169] In step a), a starting charge for manufacturing a molten product according to the invention is formed from raw materials providing the chemical elements necessary for manufacturing the product according to the invention, in suitable proportions. The starting charge may in particular be formed from metals and / or compounds of one or more of the chemical elements of element M and / or niobium and / or optionally nitrogen and / or oxygen. Preferably, the starting charge is formed from metals and / or compounds of one or more of the chemical elements of element M and / or niobium and / or oxygen and optionally nitrogen. These compounds may in particular be in the form of oxides and / or carbonates and / or hydroxides and / or oxalates and / or nitrates.The adjustment of the composition of the starting charge can be done by adding pure oxides or mixtures of oxides and / or carbonates and / or hydroxides and / or oxalates and / or nitrates and / or metals, in particular NbiCE. of NbCL. of NbO, of Nb, of oxide(s) of one or more of the chemical elements of the elemental constituent M, of carbonate(s) of one or more of the chemical elements of the elemental constituent M, of hydroxide(s) of one or more of the chemical elements of the elemental constituent M, of oxalate(s) of one or more of the chemical elements of the elemental constituent M, of nitrate(s) of one or more of the chemical elements of the elemental constituent M, of metal / metals of one or more of the chemical elements of the elemental constituent M. The use of oxide(s) and / or carbonate(s) and / or hydroxide(s) and / or nitrate(s) and / or oxalate(s) improves the availability of oxygen necessary for the formation of the fused product MnbO and its electroneutrality.

[0170] Oxygen is not necessarily, partially or exclusively, introduced by the raw materials. In particular, it may be introduced, partially or entirely, by blowing gas into the bath of molten raw materials. Preferably, however, it is exclusively introduced by the raw materials.

[0171] In one embodiment, particularly when a particular oxygen substoichiometry or redox state is desired, oxalates and / or metals and / or oxides of Nb, and / or one or more of the chemical elements of the elemental constituent M are preferably used. For example, in said embodiment, the oxides of the elemental constituent Nb such as NbO and NbCL and / or the metal Nb may be used. In this embodiment, the starting charge may also comprise a carbon source. The carbon source may be chosen from carbon, petroleum coke, pitch, coal and mixtures thereof, preferably petroleum coke.

[0172] Preferably, at least one elemental constituent among M and niobium is introduced into the starting charge in the form of one or more oxides.

[0173] In one embodiment, the compounds and / or metals providing the constituent chemical elements of M, niobium and optionally nitrogen together represent more than 90%, or even more than 95%, in mass percentages, of the constituents of the starting charge.

[0174] Approximately all of the niobium is found in the molten product produced. Some of the starting charge, such as nitrogen and chemical elements of M such as silicon, chromium, molybdenum, antimony, boron, bismuth, phosphorus, copper, may volatilize during the melting stage, depending on the melting conditions. Through general knowledge, or through simple routine tests, the skilled person knows how to adapt the quantity of raw materials in the starting charge according to the content he wishes to find in the molten products and the melting conditions used.

[0175] In a first variant of the general process of the invention, the starting charge is a mixture of raw materials providing, or even consisting of niobium, preferably oxygen, and an elementary constituent M consisting of at least one chemical element chosen from Ti, Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B and Zr, and such that the molten product obtained is such that 0.019 < m < 1.000 and y = 0 and 2.538 < n < 7.300.

[0176] In a first particular embodiment of the first variant of the general process of the invention, the starting charge is a mixture of raw materials providing, or even consisting of niobium, preferably oxygen, Ti as elemental constituent Ml, Ta as elemental constituent M2, and in such a way that the molten product obtained is such that 0.500 < m < 0.923 and 0 < z < 0.282 provided that z / m < 0.306 and y = 0 and 3.350 < n < 4.683.

[0177] In a second particular embodiment of the first variant of the general process of the invention, the starting charge is a mixture of raw materials providing or even consisting of niobium, preferably oxygen, and as elemental constituent M, Ti on the one hand and optionally at least one chemical element chosen from Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B and Zr, on the other hand, and in such a way that the molten product obtained is such that 0.019 < m < 1.000 and y = 0 and 2.538 < n < 7.300. In this second particular embodiment of the first variant of the general process of the invention, the elemental constituent M of the starting charge does not contain an elemental constituent M2 replacing the element Nb in the molten product obtained.

[0178] In a first particular sub-mode of the second particular embodiment of the first variant of the general process of the invention, the starting charge is a mixture of raw materials providing, or even consisting of niobium, preferably oxygen, Ti as elemental constituent M, and in such a way that the molten product obtained is such that 0.019 < m < 0.526 and y = 0 and 2.538 < n < 4.000.

[0179] In a second particular sub-mode of the second particular embodiment of the first variant of the general method of the invention, the starting charge is a mixture of raw materials providing, or even consisting of niobium, preferably oxygen, an elementary constituent M chosen from Ti on the one hand and at least one chemical element chosen from Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B and Zr on the other hand, and in such a way that the molten product obtained is such that 0.374 < m < 1.000 and y = 0 and 2.913 < n < 7.300.

[0180] In a second variant of the general process of the invention, the starting charge is a mixture of raw materials providing, or even consisting of W as element M, niobium, preferably oxygen, so that the molten product obtained is such that 0.083 < m < 7.500 and y = 0 and 2.750 < n < 25.000. In this second variant of the general process of the invention, the element W present in the starting charge does not replace, even partially, the element Nb in the molten product obtained.

[0181] In a third variant of the general process of the invention, the starting charge is a mixture of raw materials providing, or even consisting of

[0182] - an elementary constituent M consisting of a first elementary constituent M' consisting of at least one first chemical element chosen from W, V, Zr and Mo on the one hand and a second elementary constituent M' ' consisting of at least one second chemical element chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, with M' different from M”, and

[0183] - niobium, and

[0184] - preferably oxygen, so that the molten product obtained is such that 0.042 < m < 1.754 and y = 0 and 2.454 < n < 7.772.

[0185] In this third variant of the general process of the invention, the elementary constituent M of the starting charge does not contain an elementary constituent M2 replacing the element Nb in the molten product obtained.

[0186] Preferably, in this third variant of the general method of the invention, if m' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from W, V, Zr, Mo and constituting the first elementary constituent M' and m'' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd, and constituting the second elementary constituent M”, with M' different from M”, m being equal to m' + m”, then 0.021 < m' < 1.754.

[0187] In a first particular embodiment of the third variant of the general process of the invention, the starting charge is a mixture of raw materials providing:

[0188] - an elementary constituent M consisting of W on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and

[0189] - niobium, and

[0190] - preferably oxygen, so that the molten product obtained is such that 0.083 < m < 1.754, the elementary atomic index of W being greater than 0.042 and less than 1.754 and y = 0 and 2.613 < n < 7.772.

[0191] In a second particular embodiment of the fourth variant of the general process of the invention, the starting charge is a mixture of raw materials providing:

[0192] - an elementary constituent M consisting of V on the one hand and at least one chemical element chosen from Ti, Mg, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and

[0193] - niobium and

[0194] - preferably oxygen, so that the molten product obtained is such that m = 0.111, the elementary atomic index of V being greater than 0.056 and less than 0.111, and y = 0 and 2.639 < n < 2.778.

[0195] In a third particular embodiment of the third variant of the general process of the invention, the starting charge is a mixture of raw materials providing:

[0196] - an elementary constituent M consisting of Zr on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and

[0197] - niobium, and

[0198] - preferably oxygen, so that the molten product obtained is such that m = 0.042, the elementary atomic index of Zr being greater than 0.021 and less than 0.042, and y = 0 and 2.454 < n < 2.583.

[0199] In a fourth particular embodiment of the third variant of the general process of the invention, the starting charge is a mixture of raw materials providing:

[0200] - an elementary constituent M consisting of Mo on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Zr, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and

[0201] - niobium, and

[0202] - preferably oxygen, so that the molten product obtained is such that m = 0.083, the elementary atomic index of Mo being greater than 0.042 and less than 0.083, and y = 0 and 2.613 < n < 2.750.

[0203] In a fourth variant of the general process of the invention, the starting charge is a mixture of raw materials providing:

[0204] - an elementary constituent M consisting of at least one chemical element chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi and Na, and

[0205] - niobium, and

[0206] - preferably oxygen, and

[0207] - optionally nitrogen, so that the molten product obtained is such that 0.020 < m < 7.692, and 0 < y < 0.210, preferably 0 < y < 0.150, preferably 0 < y < 0.100, preferably 0 < y < 0.053 and 0.06 < n < 953.85.

[0208] In a first particular embodiment of the fourth variant of the general method of the invention, the elementary constituent M is constituted by at least two chemical elements chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi and Na.

[0209] In a second particular embodiment of the fourth variant of the general process of the invention, the starting charge is a mixture of raw materials providing:

[0210] - an elementary constituent M chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, P and their mixtures, and

[0211] - niobium, and

[0212] - preferably oxygen, so that the molten product obtained is such that 0.020 < m < 7.690, and y = 0 and 0.060 < n < 953.850.

[0213] In this second particular embodiment of the fourth variant of the general process of the invention, the elementary constituent M of the starting charge does not contain an elementary constituent M2 replacing the element Nb in the molten product obtained.

[0214] Preferably, in this second particular embodiment of the fourth variant of the general method of the invention, the elementary constituent M is constituted by at least two chemical elements chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi and P.

[0215] In a third particular embodiment of the fourth variant of the general process of the invention, the starting charge is a mixture of raw materials providing:

[0216] - an elementary constituent Ml chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi and mixtures thereof, preferably from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Hf, Ta, Zn, In, Cd, Sr, B, Pb, Bi, P and mixtures thereof, and

[0217] - niobium, and

[0218] - an elementary constituent M2 chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi and mixtures thereof, preferably from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Hf, Ta, Zn, In, Cd, Sr, B, Pb, Bi, P and mixtures thereof, and

[0219] - preferably oxygen and

[0220] - optionally nitrogen, so that the molten product obtained is such that in the crystal structure, M partially substitutes for Nb, Ml and M2 designating the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the molten product can thus be expressed by the formula Ml( m . z)M2 z Nb[O(iy)N y ]n, with 0.020 < m < 0.765 and 0 < z < 0.286 provided that z / m < 0.800 and 0 < y < 0.210 and 2.404 < n < 19.706.

[0221] Preferably, in this third particular embodiment of the fourth variant of the general process of the invention, the elementary constituents M1 and M2 do not comprise a common chemical element.

[0222] In the most preferred embodiment, the starting charge is a mixture of raw materials providing, as elemental constituent M, a constituent selected from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), cadmium (Cd), strontium (Sr), boron (B), phosphorus (P), sodium (Na), barium (B a) and mixtures thereof.

[0223] In the most preferred embodiment, in the starting charge, the amounts of the constituents are such that y = 0 and 0.019 < m < 7.500 and 2.454 < n < 25.000.

[0224] More preferably, said starting charge has one or more of the preferred characteristics below:

[0225] - the quantity of the additional elementary constituent is less than 1.0%, as a percentage by mass based on the mass of the product; - the additional elementary constituent consists of more than 80%, as a percentage by mass based on the additional elementary constituent, lithium Li;

[0226] - one of the following three variants 1. to 3. applies:

[0227] 1. the elemental constituent M consists of at least one chemical element chosen from Ti, Mg, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ga, Al, Ce, Si, Y, Hf, Ta, Zn, B, Sr, P, Na and Ba, and 0.019 < m < 1.000 and 2.538 < n

[0228] < 7,300 ;

[0229] 2. the elementary constituent M is W, does not replace, even partially, Nb, and 0.083 < m < 7.500 and 2.750 < n < 25.000;

[0230] 3. the elementary constituent M does not replace, even partially, Nb, and consists of a first elementary constituent M' consisting of at least one first chemical element chosen from W, V, Zr, Hf and Mo on the one hand and a second elementary constituent M” consisting of at least one second chemical element chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, with M' different from M”, and 0.042 < m < 1.754 and 2.454 < n < 7.772;

[0231] - variant 1. applies and

[0232] 1.1. in the crystal structure of the melt, M partially substitutes for Nb, Ml and M2 denoting the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the melt can thus be expressed by the formula Ml( m.Z )M2 z Nb[O(iy)Ny] n , the elementary constituent Ml being Ti, the elementary constituent M2 being Ta and 0.500 < m < 0.923 and 0 < z

[0233] < 0.282 provided that z / m < 0.306 and 3.350 < n < 4.683, or

[0234] 1.2. the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and optionally at least one chemical element chosen from Mg, Fe, W, Ta, Mo, Ga, Al, B, Hf and Zr, on the other hand, or variant 3. applies and

[0235] 3.1. the elementary constituent M consists of W on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, and 0.083 < m < 1.754, the elementary atomic index of W being greater than 0.042 and less than 1.754 and 2.613 < n < 7.772, or

[0236] 3.2. the elementary constituent M consists of V on the one hand and at least one chemical element chosen from Ti, Mg, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, and m = 0.111, the elementary atomic index of V being greater than 0.056 and less than 0.111 and 2.639

[0237] < n < 2.778, or

[0238] 3.3. the elementary constituent M consists of Zr on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.042, the elementary atomic index of Zr being greater than 0.021 and less than 0.042 and 2.454 < n < 2.583, or

[0239] 3.4. the elementary constituent M consists of Mo on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Zr, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, and m = 0.083, the elementary atomic index of Mo being greater than 0.042 and less than 0.083 and 2.613 < n < 2.750, or

[0240] - the melted product is such that:

[0241] - variant 1. applies and the elementary constituent M is Ti and 0.019 < m < 0.526 and 2.538 < n < 4.000, or

[0242] - variant 1. applies and the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and at least one chemical element chosen from Mg, Fe, W, Ta, Mo, Ga, Al, B, Hf and Zr on the other hand, and 0.374 < m < 1.000 and 2.913 < n < 7.300 or

[0243] - variant 3 applies and, if m' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from W, V, Zr, Hf and Mo and constituting the first elementary constituent M', and m'' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from Ti, Mg, V, Hf, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd, and constituting the second elementary constituent M”, with M' different from M”, m being equal to m' + m”, then 0.021 < m' < 1.754, and the elementary constituent Ml is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, Cd, Sr, B, Ba and their mixtures, and the elemental constituent M2 is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, Cd, Sr, B, Ba and mixtures thereof, and the elemental constituents Ml and M2 do not have a common chemical element, and 0.020 < m < 0.765 and 0 < z < 0,286 provided that z / m < 0.800 and 2.404 < n < 19.706;,

[0244] - in the crystal structure, M partially substitutes for Nb, Ml and M2 designating the elementary constituent M not substituted for Nb and substituted for Nb, respectively, Ml and M2 being able to be identical or different, the composition of the molten product thus being able to be expressed by the formula Ml( m.Z )M2 z Nb[O(i- y)Ny] n, the elementary constituent Ml being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn), cadmium (Cd), strontium (Sr), boron (B), phosphorus (P), sodium (Na), barium (B a) and mixtures thereof, the elementary constituent M2 being chosen from titanium (Ti), magnesium (Mg), vanadium (V), chromium (Cr), tungsten (W), zirconium (Zr), molybdenum (Mo), copper (Cu), iron (Fe), gallium (Ga), calcium (Ca), potassium (K), nickel (Ni), cobalt (Co), aluminum (Al), tin (Sn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), hafnium (Hf), tantalum (Ta), zinc (Zn),cadmium (Cd), strontium (Sr), boron (B), phosphorus (P), sodium (Na), barium (B a) and mixtures thereof, the elementary constituents Ml and M2 preferably not comprising a common chemical element, the atomic indices being such that 0.020 < m < 0.923 and 0 < z < 0.286 provided that z / m < 0.800 and 2.454 < n < 19.710;,

[0245] - the molten product is in the form of an object whose dimensions are all greater than 3 pm.

[0246] Generally, the feedstock is adapted for manufacturing a molten product according to the most preferred embodiment, preferably adapted so that the manufactured molten product has one or more of the optional characteristics of the molten product according to the most preferred embodiment.

[0247] The particle sizes of the powders used can be those commonly encountered in melting processes.

[0248] A thorough mixing of the raw materials can be carried out in a mixer. This mixture is then poured into a melting furnace.

[0249] In step b), the starting charge is melted.

[0250] All known furnaces are possible, such as an induction furnace, a plasma furnace, a Héroult-type electric arc furnace, provided that they allow the starting charge to be melted. Crucible melting in a heat treatment furnace, preferably an electric furnace, is also possible. Electrofusion advantageously allows the production of large quantities of molten product with interesting yields. Preferably, the starting charge is melted in a Héroult-type arc furnace. For example, a Héroult-type arc furnace with two electrodes and a tank with a diameter of approximately 0.8 m and capable of containing approximately 180 kg of molten liquid can be used.

[0251] In step b), the energy supplied is preferably greater than 800 kWh / T of starting load, preferably greater than 900 kWh / T. Preferably, the energy supplied is between 800 kWh / T and 1800 kWh / T. The voltage is for example 90 Volts and the power 220 kW.

[0252] After melting, the starting charge is in the form of a molten material, which may possibly contain some solid particles, but in insufficient quantity for them to structure the said mass. By definition, to retain its shape, a molten material must be contained in a container.

[0253] It is possible to improve the quality of the mixing of the molten material by bubbling a gas, as mentioned in FR 1 208 577.

[0254] Said bubbling gas may be air or oxygen, in particular when the molten product to be manufactured is a product not exhibiting oxygen substoichiometry.

[0255] Said bubbling gas may also be a nitrogen gas, preferably nitrogen (N2), in particular if the molten product to be manufactured contains the element nitrogen (N).

[0256] Said bubbling gas may also be chosen from argon, helium, hydrogen, CO2, CO and their mixtures, preferably a mixture of a first gas chosen from argon, helium, CO2 and their mixtures on the one hand and CO on the other hand, in particular if the molten product to be manufactured must have oxygen substoichiometry or a particular oxidation-reduction state.

[0257] By his general knowledge, or by simple routine tests, the person skilled in the art knows how to adapt the quantity of nitrogen gas, preferably nitrogen, to be blown into the molten material according to the quantity of nitrogen element that he wishes to find in the molten product.

[0258] The gaseous environment of the molten material may be neutral, reducing or oxidizing. In one embodiment, the gaseous environment of the molten material is a gas comprising more than 21% dinitrogen, preferably more than 30% dinitrogen, preferably more than 50% dinitrogen, preferably more than 90% dinitrogen, in mass percentages.

[0259] The temperature of the molten liquid, for example measured from the stream of said molten liquid before step c) of dispersion or casting, is preferably higher than the melting temperature of the product according to the invention, preferably higher than 1300°C and preferably lower than 1700°C, preferably lower than 1600°C, preferably lower than 1550°C, preferably lower than 1500°C.

[0260] In step c), the cooling rate is preferably greater than 50°C / s, preferably greater than 100°C / s, preferably greater than 200°C / s.

[0261] In one embodiment, the cooling rate is greater than 200°C / s and preferably less than 10,000°C / s, preferably less than 1,000°C / s, preferably less than 800°C / s, preferably less than 600°C / s.

[0262] In a first embodiment of step c), step c) comprises the following steps: cl) dispersion of the molten material in the form of liquid droplets, c2) solidification of these liquid droplets by contact with a fluid, preferably a gas, so as to obtain particles of molten product.

[0263] The molten product according to the invention, in particular manufactured according to this first embodiment, may be presented, at the end of step c), in the form of a powder of particles whose minimum size is greater than 0.005 mm and whose maximum size is less than 5 mm.

[0264] In step cl), a stream of molten liquid is dispersed into liquid droplets.

[0265] Dispersion may result from blowing through the stream of molten material.

[0266] The molten particles may be spherical or not, hollow or solid, depending in particular on the blowing conditions and / or the composition of the molten material.

[0267] Any other method of atomizing a molten material, known to those skilled in the art, is conceivable.

[0268] In step cl), the stream of said molten material is brought into contact with a “dispersion” fluid, preferably a “dispersion” gas. In one embodiment, the dispersion fluid is a gas having an oxygen volume content greater than 20%, preferably air and / or water vapor, more preferably air, in particular when the molten product to be manufactured is a product not having oxygen substoichiometry.

[0269] In one embodiment, the dispersing fluid is a nitrogen gas, preferably nitrogen, particularly if the molten product to be manufactured contains the element nitrogen.

[0270] In one embodiment, the dispersion fluid is a dispersion gas chosen from argon, helium, hydrogen, CO2, CO and their mixtures, preferably a mixture comprising a first gas chosen from argon, helium, CO2 and their mixtures on the one hand and a second gas chosen from hydrogen, CO and their mixtures on the other hand, in particular if the molten product to be manufactured must have a sub-stoichiometry in oxygen or a particular oxidation-reduction state.

[0271] In one embodiment, the dispersion fluid is a dispersion gas chosen from argon, helium and mixtures thereof, in particular if the molten product to be manufactured must contain the chemical element nitrogen (N) and if in step a), compounds providing nitrogen have been used and / or if in step b), bubbling of nitrogen gas, preferably dinitrogen, into the molten material has been carried out and / or if in step b), the gaseous environment of the molten material was a gas comprising more than 21% dinitrogen, in molar percentage.

[0272] In step c2), the liquid droplets are transformed into solid particles by contact with a “solidification” fluid, preferably a solidification gas, which may be chosen from those described for step c1). Preferably, the method is adapted so that, as soon as it is formed, the droplet of molten liquid is in contact with the solidification fluid, which may be identical or different to the dispersion fluid used for step c1) and which, preferably, is identical to the dispersion fluid used for step c1).

[0273] In one embodiment, steps c1) and c2) comprise cooling the droplets by blowing air at room temperature.

[0274] In one embodiment, step c2) comprises cooling the droplets by immersion in water.

[0275] Preferably, no other means of solidification than cooling by contact with the fluid is used.

[0276] More preferably, the dispersion (step c1)) and the solidification (step c2)) are substantially simultaneous, the molten material being dispersed by a fluid, preferably gaseous, capable of cooling and solidifying this liquid. Preferably, contact with the fluid is maintained at least until the droplets have completely solidified. At the end of step c2), a set of solid particles is obtained which has a minimum size of at least 0.01 in and a maximum size of at most 3 mm, or even at most 5 mm, depending on the dispersion conditions.

[0277] In a second embodiment, step c) comprises the following steps: cl') pouring the molten material into a mold; c2') solidification by cooling of the molten material poured into the mold until an at least partially solidified block is obtained; c3') demolding of the block.

[0278] In step cl'), the molten material is poured into a mold capable of withstanding the molten liquid bath. Preferably, molds made of graphite, cast iron, or as defined in US 3,993,119 are used. In the case of an induction furnace, the coil is considered to constitute a mold.

[0279] In one embodiment, the casting is carried out under a “casting” gas having an oxygen volume content greater than 20%, preferably under air, in particular when the molten product to be manufactured is a product not having oxygen substoichiometry.

[0280] In one embodiment, the casting is carried out under a nitrogen gas, preferably nitrogen, in particular if the molten product to be manufactured contains the chemical element nitrogen (N).

[0281] In one embodiment, the casting is carried out under a casting gas chosen from argon, helium, hydrogen, CO2, CO and their mixtures, preferably under a casting gas consisting of a first gas chosen from argon, helium, CO2 and their mixtures on the one hand and a second gas chosen from hydrogen, CO and their mixtures on the other hand, in particular if the molten product to be manufactured has oxygen substoichiometry or a particular oxidation-reduction state.

[0282] In one embodiment, the casting is carried out under a casting gas chosen from argon, helium and their mixtures, in particular if the molten product to be manufactured contains the element nitrogen and if, in step a), compounds providing nitrogen have been used and / or if in step b), bubbling of nitrogen gas, preferably dinitrogen, into the molten material has been carried out, and / or if in step b), the gaseous environment of the molten material was a gas comprising more than 21% dinitrogen, in mass percentage.

[0283] In step c2'), the molten material poured into the mold is cooled until an at least partially solidified block is obtained.

[0284] In step c3'), the block is removed from the mold. Preferably, the block is removed from the mold as soon as it has sufficient rigidity to substantially retain its shape.

[0285] Preferably, in step c1') and / or in step c2') and / or after step c3'), said molten material in the process of solidification is brought into contact, directly or indirectly, with a "solidification" fluid, preferably a "solidification" gas, which may be identical or different from that described for step c1'). This contacting can be carried out immediately upon casting. To facilitate the contacting of the molten material with the solidification fluid, preferably the solidification gas, it is preferable to remove the block from the mold as quickly as possible, if possible before complete solidification, and then immediately begin contacting with the solidification fluid, preferably the solidification gas. Solidification therefore continues in step c3').

[0286] Preferably, contact with the solidifying fluid, preferably the solidifying gas, is maintained until the block has completely solidified.

[0287] After complete solidification, a block is obtained which is capable of giving, after steps d) and optionally e) and f), a powder of particles of the molten product according to the invention.

[0288] In a third embodiment, step c) comprises the following steps: cl”) casting of the molten material, in the form of a jet, between two rollers, preferably both rotating and / or cooled; c2”) solidification by cooling of the molten material cast in contact with the rollers until an at least partially solidified block is obtained.

[0289] In step cl”), the molten material is poured in the form of a jet between two rollers capable of resisting the molten liquid, so as to roll the jet of molten liquid. Preferably, the rollers are made of steel. Preferably, they are driven by a counter-rotating movement so as to roll the jet of liquid. Preferably, said rollers are cooled, preferably by means of a circulation of fluid, preferably a liquid, preferably water, preferably without said liquid being in contact with the jet of molten liquid.

[0290] In step c2' '), the jet of liquid poured between the rollers is cooled until a block is obtained that is at least partially solidified.

[0291] Preferably, in step c1”) and / or in step c2”), said molten material is brought into contact, directly or indirectly, with a “cooling” fluid, preferably a “cooling” gas.

[0292] In one embodiment, the cooling fluid is a cooling gas having an oxygen volume content greater than 20%, preferably air and / or water vapor, more preferably air, in particular when the molten product to be manufactured is a product not having oxygen substoichiometry.

[0293] In one embodiment, the cooling fluid is a nitrogen gas, preferably nitrogen, particularly if the molten product to be manufactured contains the chemical element nitrogen (N).

[0294] In one embodiment, the cooling fluid is a cooling gas chosen from argon, helium, hydrogen, CO2, CO and their mixtures, preferably a mixture consisting of a first gas chosen from argon, helium, CO2 and their mixtures on the one hand and a second gas chosen from hydrogen, CO and their mixtures on the other hand, in particular if the molten product to be manufactured has oxygen substoichiometry or a particular oxidation-reduction state.In one embodiment, the cooling fluid is a cooling gas chosen from argon, helium and their mixtures, in particular if the molten product to be manufactured contains the element nitrogen and if in step a), compounds providing nitrogen have been used and / or if in step b), bubbling of nitrogen gas, preferably dinitrogen in the molten material has been carried out, and / or if in step b), the gaseous environment of the molten material was a gas comprising more than 21% of dinitrogen, in molar percentage.

[0295] Preferably, contact with the cooling fluid, preferably the cooling gas, is maintained until the block has completely solidified.

[0296] In one embodiment, in step c), the molten material is extracted from the melting furnace continuously or semi-continuously.

[0297] In optional step d), the molten product obtained is crushed and / or ground so as to reduce the size of the pieces, preferably until a powder of molten particles having a median size D50 preferably greater than 0.2 pm, preferably greater than 0.5 pm and / or, preferably, less than 70 pm, preferably less than 50 pm, preferably less than 40 pm, preferably less than 30 pm, preferably less than 20 pm is obtained.

[0298] All types of crushers and grinders can be used to reduce the size of pieces, with grinding preferably carried out dry and / or in a solvent, preferably water. An attrition mill, an air jet mill or a ball mill are well suited.

[0299] The molten particle powder may also undergo, in particular after step d), an additional step intended to form atomized particles, agglomerates or aggregates. All techniques known to those skilled in the art may be used, in particular atomization of a slip or granulation.

[0300] In step e), optional, a particle size selection is then carried out, depending on the intended application, for example by sieving or cycloning, in particular so that the particle powder obtained has a median size D50 preferably greater than 0.2 pm, preferably greater than 0.5 pm and / or, preferably, less than 70 pm, preferably less than 50 pm, preferably less than 40 pm, preferably less than 30 pm, preferably less than 20 pm.

[0301] In one embodiment, the method according to the invention comprises steps d) and e).

[0302] In step f), optional, a heat treatment of annealing of said molten product is then carried out.

[0303] Advantageously, step f) makes it possible to provide the nitrogen element and / or to modify the oxygen stoichiometry and / or to modify the oxidation-reduction state of at least one chemical element in the molten product.

[0304] The molten product, preferably in the form of particles, is introduced into a furnace. The annealing temperature is lower than the melting temperature of the molten product and preferably higher than 800°C, preferably higher than 900°C and lower than 1300°C, preferably lower than 1200°C. The duration of the hold at the annealing temperature is preferably higher than 2 hours and / or preferably lower than 24 hours.

[0305] In one embodiment, the molten product is annealed under a nitrogen atmosphere, preferably containing nitrogen, preferably at atmospheric pressure. This annealing heat treatment makes it possible in particular to introduce the nitrogen element into the molten product. By means of general knowledge, or by simple routine tests, a person skilled in the art knows how to adapt the parameters of said heat treatment according to the content of the chemical element nitrogen targeted in the molten product.

[0306] In one embodiment, the molten product is annealed under an atmosphere containing a gas having an oxygen volume content greater than 20%, preferably air, in particular to modify the oxygen stoichiometry of the molten product, in particular to increase the amount of oxygen in the molten product.

[0307] In one embodiment, the molten product is annealed under an atmosphere containing an "annealing" gas chosen from argon, helium, hydrogen, CO2, CO and their mixtures, preferably consisting of a first gas chosen from argon, helium, CO2 and their mixtures on the one hand and by a second gas chosen from hydrogen, CO and their mixtures on the other hand, in particular to reduce the quantity of oxygen in the molten product and / or modify the redox state of at least one of the elements of the molten product.

[0308] In one embodiment, the molten product is annealed under an atmosphere containing an annealing gas chosen from argon, helium and mixtures thereof, in particular to promote the development of a crystalline phase while preserving the oxygen stoichiometry of the molten product and / or the redox state of at least one of the elements of the molten product and / or the quantity of the elementary constituent nitrogen of the molten product. When the method comprises a step f), the molten product according to the invention may be ground and / or undergo a particle size selection step, before and / or after said step f), preferably at least before said step f).

[0309] In one embodiment, the method according to the invention comprises steps d), e) and f), said steps being able to be carried out in any order, step f) being for example before step d). Preferably, in said embodiment, a step d) is carried out, then a step e), then a step f).

[0310] Examples

[0311] Characterization protocol

[0312] The characterization methods below, described in the context of the examples, can also be used to characterize the invention more generally. The particle size distribution of the powders of the examples and in particular the determination of the percentile or "percentile" 50 (D50), is determined using a laser granulometer, for example, a Partica LA-950 from the company HORIBA.

[0313] The measurement of the surface porosity of the grains of a powder, as a percentage of the surface area of ​​said grains, is measured using the following method.

[0314] Each powder of Examples 1 to 3 is vacuum coated in an epoxy resin. The coated samples obtained are then polished conventionally on a polishing machine with abrasives of decreasing size, the last polishing operation being carried out with an abrasive disc of size equal to 1 μm.

[0315] The polished coated samples are then metallized using a platinum target for 12 seconds before being observed using a Zeiss Gemini SEM 560 electron microscope, equipped with a BSD4 detector, with a voltage of 15 kV and a diaphragm of 20 pm. For each sample, a square area with a side length equal to 921.6 pm is selected. This area is then observed in 400 square images with a side length equal to 46.08 pm, without overlap between the images, an image corresponding to 1024 pixels x 1024 pixels with a pixel size equal to 45 nm. The images are obtained using ATLAS software.

[0316] Each image i is then analyzed using the Fiji software, available on the site https: / / imagej.net / software / fiji / according to the following method:

[0317] 1) open the image in Fiji;

[0318] 2) delete any previous results with the “Analysis>Clear Results” function;

[0319] 3) Eliminate the noise using the function “Plugins>ImageJ on GPU (CEIJx)>Filter>Non-local mean on GPU” by indicating in the “radiusX” box a value equal to 2, in the “radiusY” box a value equal to 2, in the “radiusZ” box a value equal to 0, in the “sigma” box a value equal to 1, then confirming with “OK”;

[0320] 4) binarize the image with the “Autothreshold> Intermode” function, with the “Ignore black”, “While object on black background” and “Show threshold value in log windows” boxes checked;

[0321] 5) Note the value of the intermode L of the modified image i obtained in the previous step 4);

[0322] 6) After having carried out all of steps 3) to 5) on each image i, calculate the value of the average intermode I m which is the average of the intermodes L;

[0323] 7) Then on each image obtained at the end of step 4), apply the function “Image>Adjust>Threshold” by entering the value I m as the minimum value and the value 255 as the maximum value;

[0324] 8) Then, on each image obtained at the end of the previous step 7), apply the function “Plugins>morphological filters” by selecting “closing” for the “operation” section, “square” for the “Element” section and 3 for the “Radius (in pixels)” section; 9) Then apply on each image obtained at the end of step 8) the function “Process>binary>Fill holes”;

[0325] 10) For each image obtained at the end of step 9) above, calculate the surface covered by objects made up of white pixels with a surface area greater than 3 pm 2 (in other words grains with a surface area greater than 3 p in 2 ). Sgi, using the "Analyze> analyze particles" function, indicating 0.00-1.00 in the "Circularity" box and "Overlay" in the "Show" box. Access the Sgi value using the "summarize" function;

[0326] 11) Then calculate the total surface area covered by objects made up of white pixels with a surface area greater than 3 pm 2 , Sgt, equal to the sum of the Sgi of each image;

[0327] 12) Then on each image obtained at the end of step 4), apply the function “Image>Adjust>Threshold” by entering the value 0 as the minimum value and the value 5+I m as maximum value;

[0328] 13) Then, on each image obtained at the end of the previous step 12), apply the “Plugins>morphological filters” function by selecting “closing” for the “operation” section, “square” for the “Element” section and 3 for the “Radius (in pixels)” section;

[0329] 14) Then on each image obtained at the end of the previous step 13), apply the function “Plugins>MorphoLibJ>Filtering>Kill Border;

[0330] 15) Then on each image obtained at the end of the previous step 14), calculate the surface covered by the objects made up of white pixels (in other words the porosity present on the surface of the grains), Spi, using the “Analyze> analyze particles” function, indicating “0.00-1.00” in the “Circularity” box and “Overlay” in the “Show” box. Access the Spi value using the “summarize” function;

[0331] 16) Then calculate the total area covered by objects made up of white pixels, Spt , equal to the sum of the Spi of each image;

[0332] 17) calculate the ratio 100 x (Sp t / Sgt). This ratio characterizes the surface porosity of the grains, as a percentage of the surface area of ​​said grains.

[0333] Manufacturing protocol

[0334] The following examples are provided for illustrative purposes and do not limit the invention.

[0335] The following raw materials were used for Example 1, outside the invention, and Examples 2 and 3 according to the invention:

[0336] - a niobium oxide powder, comprising more than 99.9% by mass of niobium oxide NbtOi, the median size of which is equal to 0.9 pm, and comprising the elements Fe and Si in trace amounts;

[0337] - a molybdenum oxide powder, comprising more than 99.9% by mass of molybdenum oxide MoO3, the median size of which is equal to 1.4 pm, and comprising in trace amounts the elements Ca and Na; - a tungsten oxide powder, comprising more than 99.7% by mass of tungsten oxide WO3, the median size of which is equal to 0.5 pm, and comprising in trace amounts the elements Al and Si;

[0338] - a zirconia powder, comprising more than 98.7% by mass of zirconium oxide and hafnium oxide, the median size of which is greater than 3.4 pm, and comprising the elements Al, Si and Na in trace amounts;

[0339] - a titanium oxide powder in the anatase form, comprising more than 99.5% by mass of titanium oxide TiCL, the median size of which is greater than 0.15 pm, and comprising the elements Al and Fe in trace amounts.

[0340] In the products of Examples 1, 2 and 3, the elements Al, Fe, Si, Ca and Na result from the presence of these elements, in trace amounts, in the raw materials used.

[0341] The product of example 1 outside the invention was manufactured in accordance with the teaching of WO2021074593.

[0342] 50 grams of a starting charge whose composition appears in the following table 1, in mass percentages, were obtained by intimate mixing of the raw materials at a speed equal to 550 revolutions per minute for 3 hours in a planetary mill.

[0343] [Table 1]

[0344] Then this starting charge underwent the following heat treatment, in an electric furnace under air, at atmospheric pressure, in an alumina crucible:

[0345] - rise up to 900°C at a speed equal to 300°C / h,

[0346] - maintained at 900°C for 12 hours,

[0347] - free cooling.

[0348] After treatment, the product was deagglomerated using an impact mill. The powder obtained after deagglomeration has a median size of 4.8 pm.

[0349] The molten product of Example 2, according to the invention, was manufactured according to the following method of the invention.

[0350] In step a), the raw materials were thoroughly mixed, in the mass percentages indicated in Table 2, so as to obtain a starting charge of mass equal to 25 kg. The molybdenum oxide powder was added in an excess quantity compared to the quantity of molybdenum to be obtained in the final product in order to take into account losses by vaporization during melting.

[0351] [Table 2]

[0352] The starting charge, with a mass of 25 kg, was poured into a Héroult-type arc melting furnace. It was then melted in step b) following a melting with a voltage of 80 Volts and an applied energy substantially equal to 1000 kWh / T, in order to melt the starting charge completely and homogeneously.

[0353] In step c), when the melting was complete, the molten liquid was poured in such a way as to form a stream. The temperature of the molten liquid measured during pouring was approximately 1650°C.

[0354] A blast of compressed dry air, at room temperature and an overpressure of 2 bars, broke the net and dispersed the molten liquid into droplets.

[0355] Blowing cooled these droplets and froze them into molten particles ranging in size from 50 pm to 4 mm.

[0356] The molten particles were received in a stainless steel box whose walls were cooled with water.

[0357] In step d), the molten particles were then ground in an opposed air jet mill to obtain a powder with a median size of 4 pm.

[0358] The powder of Example 3, according to the invention, was manufactured according to the same process as the powder of Example 2, this process further comprising a step f) of heat treatment of annealing in an electric furnace, in air, at atmospheric pressure, in an alumina crucible, according to the following cycle:

[0359] - rise up to 900°C at a speed equal to 300°C / h,

[0360] - maintained at 900°C for 2 hours,

[0361] - free cooling.

[0362] Tables 3 and 4 below summarize the results obtained.

[0363] [Table 3]

[0364] (*): excluding invention

[0365] The quantity of complementary elementary constituent of the powders of examples 1, 2 and 3 is less than 0.5%.

[0366] The X-ray diffraction diagrams carried out on the powders of examples 1, 2 and 3 do not show a crystallized phase containing no niobium. [Table 4]

[0367] (*): excluding invention

[0368] Surface porosity of surface grains greater than 3 pm 2 of the powders of examples 2 and 3 according to the invention is lower than that of the grains with a surface area greater than 3 pm 2 of the powder of example 1, outside the invention. For a given composition, this difference in surface porosity is considered by the inventors as a signature of the manufacturing process according to the invention.

[0369] These examples also make it possible to demonstrate the effectiveness of the method according to the invention.

[0370] As is now clearly apparent, the process according to the invention makes it possible to manufacture MNbO products in a simple and economical manner in industrial quantities.

[0371] Of course, the present invention is not limited to the embodiments described, provided as illustrative and non-limiting examples.

[0372] In particular, the products according to the invention are not limited to particular shapes or dimensions.

Claims

CLAIMS 1. Polycrystalline fused product consisting of elementary constituents M, niobium Nb, oxygen O and optionally nitrogen N, together representing more than 90% of the mass of the product, and, optionally, of a complementary elementary constituent constituting the mass balance to 100%, the elementary constituent M being chosen from titanium Ti, magnesium Mg, vanadium V, chromium Cr, tungsten W, zirconium Zr, molybdenum Mo, copper Cu, iron Fe, gallium Ga, germanium Ge, calcium Ca, potassium K, nickel Ni, cobalt Co, aluminum Al, tin Sn, cerium Ce, tellurium Te, selenium Se, silicon Si, antimony Sb, yttrium Y, hafnium Hf, tantalum Ta, rhenium Re, zinc Zn, indium In, cadmium Cd, strontium Sr, boron B, lead Pb, phosphorus P, bismuth Bi, sodium Na, barium (Ba) and their mixtures, and the atomic proportions of said elements M, niobium Nb,oxygen O and optionally nitrogen N being defined by the formula M, m Nb[O(iy)N y ]n, in which the atomic indices are such that: 0.019 < m < 7.692 and 0 < y < 0.210 and 0.060 < n < 953.850; the amount of the complementary elementary constituent is less than 2.0%, as a mass percentage based on the mass of the product.

2. Molten product according to the immediately preceding claim, in which y < 0.

150.

3. Molten product according to the immediately preceding claim, in which y < 0.

053.

4. A molten product according to any preceding claim, wherein the amount of the additional elemental constituent is less than 1.0%, as a mass percentage based on the mass of the product.

5. Molten product according to any one of the preceding claims, in which the additional elementary constituent consists of more than 80%, in mass percentage based on the additional elementary constituent, lithium Li.

6. Molten product according to any one of the preceding claims, in which one of the following four variants 1. to 4. applies:

1. The elemental constituent M consists of at least one chemical element selected from Ti, Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B, Hf and Zr, and 0.019 < m < 1.000 and y = 0 and 2.538 < n < 7.300; 2. The elementary constituent M is W, does not replace, even partially, Nb, and 0.083 < m < 7.500 and y = 0 and 2.750 < n < 25.000; 3. The elementary constituent M does not replace, even partially, Nb, and consists of a first elementary constituent M' consisting of at least one first chemical element chosen from W, V, Zr, Hf and Mo on the one hand and a second elementary constituent M” consisting of at least one second chemical element chosen from Ti, Mg, V, Cr, W, Zr, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, with M' different from M”, and 0.042 < m < 1.754 and y = 0 and 2.454 < n < 7.772; 4. The elemental constituent M is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi, Na, Ba and mixtures thereof, and 0.020 < m < 7.692 and 0 < y < 0.210, preferably 0 < y < 0.150, preferably 0 < y < 0.100, preferably 0 < y < 0.053 and 0.060 < n < 953.

850.

7. A melted product according to the immediately preceding claim, wherein variant 1. applies and LL in the crystal structure of the melt, M partially substitutes for Nb, Ml and M2 denoting the elemental constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the melt can thus be expressed by the formula Ml( m . z)M2 z Nb[O(iy)N y ]n, the elementary constituent Ml being Ti, the elementary constituent M2 being Ta and 0.500 < m < 0.923 and 0 < z < 0.282 provided that z / m < 0.306 and y = 0 and 3.350 < n < 4.683, or 1.

2. the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and optionally at least one chemical element chosen from Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B, Hf and Zr, on the other hand, and 0.019 < m < 1.000 and y = 0 and 2.538 < n < 7.300, or variant 3. Applies and 3.

1. the elementary constituent M consists of W on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, Zr, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and 0.083 < m < 1.754, the elementary atomic index of W being greater than 0.042 and less than 1.754 and y = 0 and 2.613 < n < 7.772, or 3.

2. the elementary constituent M consists of V on the one hand and at least one chemical element chosen from Ti, Mg, Cr, W, Zr, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.111, the elementary atomic index of V being greater than 0.056 and less than 0.111 and y = 0 and 2.639 < n < 2.778, or 3.

3. the elementary constituent M consists of Zr on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.042, the elementary atomic index of Zr being greater than 0.021 and less than 0.042 and y = 0 and 2.454 < n < 2.583, or 3.

4. the elementary constituent M is made up of Mo on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Zr, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.083, the elementary atomic index of Mo being greater than 0.042 and less than 0.083 and y = 0 and 2.613 < n < 2.750, or variant 4. applies and 4.

1. the elementary constituent M consists of at least two chemical elements chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi, Ba and Na, or 4.

2. the elementary constituent M does not replace, even partially, Nb, and is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, P, Ba and their mixtures, and 0.020 < m < 7.690 and y = 0 and 0.060 < n < 953.850, or 4.

3. in the crystal structure of the molten product, M partially substitutes for Nb, Ml and M2 denoting the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the molten product can thus be expressed by the formula Ml( m . z)M2 zNb[O(iy)Ny]n, and the elemental constituent Ml is selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, and the elemental constituent M2 is selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, and 0.020 < m < 0.765 and 0 < z < 0.286 provided that z / m < 0.800 and 0 < y < 0.210 and 2.404 < n < 19.

706.

8. A molten product according to any one of the two immediately preceding claims, wherein - variant 1. applies and the elementary constituent M is Ti and 0.019 < m < 0.526 and y = 0 and 2.538 < n < 4.000, or - variant 1. applies and the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and at least one chemical element chosen from Mg, Fe, Ni, Co, W, Ta, Mo, Ga, Al, B, Hf and Zr on the other hand, and 0.374 < m < 1.000 and y = 0 and 2.913 < n < 7.300, or - variant 3 applies and, if m' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from W, V, Zr and Mo and constituting the first elementary constituent M', and m” denotes the sum of the elementary atomic indices of the chemical element(s) chosen from Ti, Mg, V, Cr, W, Zr, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd, and constituting the second elementary constituent M”, with M' different from M”, m being equal to m' + m”, then 0.021 < m' < 1.754, or - variant 4 applies and the elementary constituent M consists of at least two chemical elements chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Te, Se, Si, Sb, Y, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, Ba and P, and 0.020 < m < 7.690 and y = 0 and 0.060 < n < 953.850, or - variant 4 applies, and in the crystal structure of the molten product, M partially substitutes for Nb, Ml and M2 designating the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the molten product can thus be expressed by the formula Ml( m.Z )M2 z Nb[O(iy)Ny] n, and the elemental constituent Ml is selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, and the elemental constituent M2 is selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, P, Y, Hf, Ta, Zn, In, Cd, Sr, B, Bi, Ba and mixtures thereof, and the elemental constituents Ml and M2 do not have a common chemical element, and 0.020 < m < 0.765 and 0 < z < 0.286 provided that z / m < 0.800 and 0 < y < 0.210 and 2,404 < n < 19,706.

9. A molten product according to claim 1, wherein in the crystal structure, M partially substitutes for Nb, Ml and M2 denoting the elemental constituent M not substituted for Nb and substituted for Nb, respectively, Ml and M2 being able to be the same or different, the composition of the molten product thus being able to be expressed by the formula Ml( m.Z )M2 z Nb[O(iy)Ny] n, the elementary constituent Ml being chosen from titanium Ti, magnesium Mg, vanadium V, chromium Cr, tungsten W, zirconium Zr, molybdenum Mo, copper Cu, iron Fe, gallium Ga, germanium Ge, calcium Ca, potassium K, nickel Ni, cobalt Co, aluminum Al, tin Sn, cerium Ce, silicon Si, antimony Sb, yttrium Y, hafnium Hf, tantalum Ta, zinc Zn, indium In, cadmium Cd, strontium Sr, boron B, lead Pb, phosphorus P, bismuth Bi, sodium Na, barium (Ba) and mixtures thereof, the elementary constituent M2 being chosen from titanium Ti, magnesium Mg, vanadium V, chromium Cr, tungsten W, zirconium Zr, molybdenum Mo, copper Cu, iron Fe, gallium Ga, germanium Ge, calcium Ca, potassium K, nickel Ni, cobalt Co, aluminum Al, tin Sn, cerium Ce, silicon Si, antimony Sb, yttrium Y, hafnium Hf, tantalum Ta, zinc Zn, indium In, cadmium Cd,strontium Sr, boron B, lead Pb, phosphorus P, bismuth Bi, sodium Na, barium (Ba) and mixtures thereof, the atomic indices being such that 0.020 < m < 0.923 and 0 < z < 0.286 provided that z / m < 0.800 and 0 < y < 0.210 and 2.400 < n < 19.710., 10. Fused product according to the immediately preceding claim, in which the elementary constituents M1 and M2 do not comprise a common chemical element.

11. A molten product according to any one of the immediately preceding claims, in the form of an object all of whose dimensions are greater than 3 μm.

12. Molten product according to claims 1 to 11, in which y = 0.

13. A melted product according to claim 12, claims 2, 3, 6, 7 and 8 not applying, wherein one of the following three variants 1. to 3. applies:

1. the elemental constituent M consists of at least one chemical element selected from Ti, Mg, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ga, Al, Ce, Si, Y, Hf, Ta, Zn, B, Sr, P, Na and Ba, and 0.019 < m < 1.000 and 2.538 < n < 7.300; 2. the elementary constituent M is W, does not replace, even partially, Nb, and 0.083 < m < 7.500 and 2.750 < n < 25.000; 3. the elementary constituent M does not replace, even partially, Nb, and is made up of a first elementary constituent M' made up of at least one first chemical element chosen from W, V, Zr, Hf and Mo on the one hand and a second elementary constituent M” made up of at least one second chemical element chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn, Hf and Cd on the other hand, with M' different from M”, and 0.042 < m < 1.754 and 2.454 < n < 7.

772.

14. Melted product according to the preceding claim, in which variant 1. applies and 1.

1. in the crystal structure of the molten product, M partially substitutes for Nb, Ml and M2 denoting the elementary constituent M not substituted for Nb and substituted for Nb, respectively, the composition of the molten product can thus be expressed by the formula Ml( m . z)M2 z Nb[O(iy)N y ]n, the elementary constituent Ml being Ti, the elementary constituent M2 being Ta and 0.500 < m < 0.923 and 0 < z < 0.282 provided that z / m < 0.306 and y = 0 and 3.350 < n < 4.683, or 1.

2. the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and optionally at least one chemical element chosen from Mg, Fe, W, Ta, Mo, Ga, Al, B, Hf and Zr, on the other hand, and, or variant 3. Applies and 3.

1. the elementary constituent M consists of W on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, Zr, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and 0.083 < m < 1.754, the elementary atomic index of W being greater than 0.042 and less than 1.754 and 2.613 < n < 7.772, or 3.

2. the elementary constituent M consists of V on the one hand and at least one chemical element chosen from Ti, Mg, Cr, W, Zr, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.111, the elementary atomic index of V being greater than 0.056 and less than 0.111 and 2.639 < n < 2.778, or 3.

3. the elementary constituent M consists of Zr on the one hand and at least one chemical element chosen from Ti, Mg, V, Cr, W, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.042, the elementary atomic index of Zr being greater than 0.021 and less than 0.042 and 2.454 < n < 2.583, or 3.

4. the elementary constituent M is made up of Mo on the one hand and at least one element chemical chosen from Ti, Mg, V, Cr, W, Zr, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd on the other hand, and m = 0.083, the elemental atomic number of Mo being greater than 0.042 and less than 0.083 and 2.613 < n < 2.

750.

15. A molten product according to any one of the two immediately preceding claims, wherein - variant 1. applies and the elementary constituent M is Ti, or - variant 1. applies and the elementary constituent M does not replace, even partially, Nb, and is made up of Ti on the one hand and at least one chemical element chosen from Mg, Fe, W, Ta, Mo, Ga, Al, B, Hf and Zr on the other hand, or - variant 3 applies and, if m' denotes the sum of the elementary atomic indices of the chemical element(s) chosen from W, V, Zr and Mo and constituting the first elementary constituent M', and m” denotes the sum of the elementary atomic indices of the chemical element(s) chosen from Ti, Mg, V, Cr, W, Zr, Mo, Hf, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Ce, Si, Sb, Y, Ta, Zn and Cd, and constituting the second elementary constituent M”, with M' different from M”, m being equal to m' + m”, then 0.021 < m' < 1.

754.

16. A molten product according to any one of claims 12 to 15, wherein 0.019 < m < 7.500 and 2.454 < n < 25.

000.

17. Powder comprising more than 90% by mass of particles in a molten product according to any one of the preceding claims.

18. A method of manufacturing a molten product according to any one of claims 1 to 16, said method comprising the following steps: a) mixing raw materials so as to form a starting charge suitable for obtaining, at the end of step c) and / or at the end of step f), said molten product, b) melting the starting charge until a molten material is obtained, c) cooling until complete solidification of said molten material, so as to obtain a molten product, d) optionally, grinding said molten product, preferably until a powder is obtained, e) optionally, particle size selection of said molten product, f) before or after step d), optionally, annealing heat treatment of said molten product.

19. Method according to the immediately preceding claim, in which nitrogen is supplied by blowing a nitrogen gas into the molten material, in step b), and / or by the presence of more than 21% of nitrogen, in mass percentage, in the gas of the gaseous environment of the molten material in step b), and / or by a heat treatment under a nitrogen atmosphere, in step f).

20. Method according to any one of the two immediately preceding claims, in which in step a), the starting charge provides all or part of the oxygen, preferably all of the oxygen.

21. Molten product obtained or capable of having been obtained by a process according to any one of claims 18 to 20.

22. Electrode, comprising a molten product according to any one of claims 1 to 16.

23. Battery, preferably chosen from a lithium-ion battery and a sodium-ion battery, comprising an electrode, preferably an anode, according to the immediately preceding claim.

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