Molten product containing niobium and particularly intended for an electrode

Abstract

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 an additional 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), 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 mixtures thereof,and the atomic proportions of said elements M, niobium Nb, oxygen O and optionally nitrogen N being defined by the formula MmNb[O(1-y)Ny]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. No abstract figure,

Description

Title of the invention: Molten product comprising niobium and in particular intended for an electrode Technical field

[0001] 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 MmNb[O(iy)Ny]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.

[0002] In the remainder of the description, such a product is called a “MNbO product”.

[0003] The invention also relates to such a product when it is obtained by fusion. State of the art

[0004] MNbO products are used in particular as electrode material, in particular anodes, batteries, in particular lithium-ion batteries and sodium-ion batteries, as for example described in WO2021245411, WO2022043705 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.

[0005] 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.

[0006] There is therefore a continuing need to reduce the complexity and cost of manufacturing an MNbO product.

[0007] An object of the invention is to satisfy, at least partially, this need. Summary of the invention

[0008] According to the invention, this aim is achieved by means of a polycrystalline fused MNbO product.

[0009] Although such a product has a specific microstructure, in particular different from a product of the same composition but obtained by solid-phase sintering, it has proven to be well suited to constituting an electrode, in particular an anode of a battery, in particular of a lithium-ion battery or a sodium-ion battery.

[0010] Unexpectedly, the inventors discovered that it was not necessary to implement a complex process to manufacture a powder suitable for the manufacture of an electrode, as according to the prior art. A simple melting process is sufficient.

[0011] Preferably, a molten product according to the invention also comprises one and preferably several of the following optional characteristics: - y < 0.150, preferably y < 0.053; - 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 is made up of more than 80%, in mass percentage based on the additional elementary constituent, lithium Li; - one of the following four variants 1. to 4. applies: 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 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 is made up of a first elementary constituent M' made up of at least one first chemical element chosen from W, V, Zr 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, Mn, Ce, Si, Sb, Y, La, 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi, Na 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; - variant 1. applies and 1.1. 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 being thus able to be expressed by the formula Ml(m_z)M2zNb[0(i_y)Ny]n, the elemental constituent Ml being Ti, the elemental 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 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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 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, Mn, Ce, Si, Sb, Y, La, 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, P 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 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)M2zNb[O(i_y)Ny]n, and the elemental constituent Ml is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, P, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Bi and mixtures thereof, and the elementary constituent M2 is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, P, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Bi and their mixtures, 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; - the melted product is such that: - 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 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi 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 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 MI (mz)M2zNb|O( iy)Ny h' ct the elemental constituent Ml is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, P, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Bi and mixtures thereof, and the elementary constituent M2 is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, P, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Bi and their mixtures, and the elementary 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; - 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)M2zNb[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), manganese (Mn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), lanthanum (La), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na) 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), manganese (Mn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), lanthanum (La), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na) 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 0 < y < 0.210 and 2.400 < n < 19.710; - the molten product is in the form of an object whose dimensions are all greater than 3 pm.

[0012] 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.

[0013] 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.

[0014] 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).

[0015] Preferably, in step a), the starting charge provides all or part of the oxygen, preferably all of the oxygen.

[0016] The invention also relates to a molten product obtained or capable of having been obtained by a process according to the invention.

[0017] 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.

[0018] 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 molten product according to the invention or obtained or capable of having been obtained by a method according to the invention. Definitions and measurement protocols

[0019] A "molten product" means a product directly obtained by solidification of a molten material resulting from the melting of a starting charge. By "directly obtained" is meant that the molten product is obtained immediately after said solidification.

[0020] A "molten material" is a mass made liquid by heating a starting charge, which may contain some solid particles, but in an insufficient quantity for them to be able to structure said mass. To retain its shape, a molten material must be contained in a container.

[0021] A "polycrystalline" material is a solid material consisting of a multitude of crystallites of varying size and orientation, 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 using observations made with a scanning electron microscope. Such observations make it possible to highlight the grain boundaries. In the absence of special precautions, a molten product is polycrystalline.

[0022] For the sake of clarity, a distinction is made between “elementary constituents” and “chemical elements”. “Elementary constituents” designate M, M', M”, Ml, M2, Nb, O and N and, optionally, a “complementary elementary constituent” other than M, M', M”, Ml, M2, Nb, O and N and constituting the complement to 100% of the product. The elemental constituents M, M', M”, Ml, M2 and the complementary elementary 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 indices 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 index of said chemical element.

[0023] 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 may be independent of each other and dispersed in the molten product. 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(mz)M2z 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.

[0024] 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 technology. or “ICP”, after dissolution by attack using an acid of a ground sample with a maximum size of less than 160 pm. The nitrogen and oxygen contents are determined using an oxygen-nitrogen analyzer model ON836 marketed by the company LECO.

[0025] 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.

[0026] By “particle” is meant a solid object all dimensions of which are less than 10 mm.

[0027] The sphericity of a particle is the ratio between its smallest dimension and its largest dimension.

[0028] By "block" we mean a solid object which is not a particle.

[0029] The percentiles or "percentiles" 10 (Di0), 50 (D50), 99.5 (D99>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 classified in ascending order. For example, 10%, by mass, of the particles of the powder have a size less than D10 and 90% of the particles by mass have a size greater than Di0. 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.

[0030] The term "minimum size of a powder" refers to the 10th percentile (Di0) of said powder.

[0031] The term "median size of a powder" refers to the 50th percentile (D50) of said powder.

[0032] The "maximum size of a powder" is called the 99.5 percentile (D995) of said powder.

[0033] By “precursor” of a compound or an element, we mean a constituent capable of providing said compound or element, respectively, during the implementation of a manufacturing method according to the invention.

[0034] Unless otherwise indicated, all the contents of the constituents of a product according to the invention are mass percentages expressed on the basis of the product.

[0035] In the formulas MmNb[O(i_y)Ny]n and Ml(m_z)M2zNb[O(i_y)Ny]n, the indices m, y, zetn are atomic indices, that is to say they relate to quantities, in number of atoms, relative to the quantities of other elementary constituents.

[0036] For the indices m, z and n, these quantities are relative to the molar quantity of Nb. For example, in the formula MmNb[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 MmNb[O(iy)Ny]n, if n = 3, the product has 3 moles of [O(iy)Ny] for each mole of Nb.

[0037] The index 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 a nitrogen chemical element N.

[0038] 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, Mm is read [Ti2 / 3Mgi / 3]m, or Ti2m / 3Mgm / 3. An "elementary atomic number" is a number specific to a chemical element in M, M', M”, Ml or M2, in this case 2m / 3 for the elementary atomic number of Ti and m / 3 for the elementary atomic number of Mg. The sum of the elementary atomic numbers of M is equal to m, the sum of the elementary atomic numbers of M' is equal to m', the sum of the elementary atomic numbers of M” is equal to m”, the sum of the elementary atomic numbers of Ml is equal to mz and the sum of the elementary atomic numbers of M2 is equal to z.

[0039] The verbs “to understand”, “to comprise” and “to present” should be interpreted in a non-restrictive manner, unless otherwise indicated. Detailed description

[0040] 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. Melted product Composition

[0041] A molten product according to the invention has the formula MmNb[O(i_y)Ny]n.

[0042] Preferably, y < 0.150, preferably y < 0.100, preferably y < 0.053.

[0043] In one embodiment, in the crystal structure, M partially substitutes for Nb, Ml and M2 designating the elemental constituent M not substituted for Nb and substituted for Nb, respectively, Ml and M2 possibly being identical or different, the composition of the molten product thus being able to be expressed by the formula Ml(mz)M2z Nb[O(1_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), manganese (Mn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), lanthanum (La), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na) and their mixtures, 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), manganese (Mn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), lanthanum (La), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi), sodium (Na) 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.

[0044] 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;- 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), manganese (Mn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), lanthanum (La), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi) and mixtures thereof;- the elementary 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), manganese (Mn), cerium (Ce), silicon (Si), antimony (Sb), yttrium (Y), lanthanum (La), hafnium (Hf), tantalum (Ta), zinc (Zn), indium (In), cadmium (Cd), strontium (Sr), boron (B), lead (Pb), phosphorus (P), bismuth (Bi) and mixtures thereof. ;

[0045] In a variant of said embodiment, the elementary constituents M1 and M2 do not comprise a common chemical element, that is to say which would be present in both M1 and M2.

[0046] The mass quantity of complementary element is preferably less than 9.0%, preferably less than 7.0%, preferably less than 5.0%, preferably less than 4.0%, preferably less than 3.0%, preferably 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 Ml 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.

[0047] 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).

[0048] Preferably, the molten product is an oxide.

[0049] The molten product is electrically neutral.

[0050] 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 and Zr, and 0.019 < m < 1.000 and y = 0 and 2.538 < n < 7.300.

[0051] 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 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)M2zNb[0(i_y)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.

[0052] In a second particular embodiment of the first variant of the molten product of the invention, the elementary constituent M is made up 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 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.

[0053] 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 Ti0^NbOs^, or TiNb2O7, or under the formula Ti0.33NbO3.i67, or Ti2 Nb6O19.

[0054] 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 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 and Zr on the other hand, and 0.374 < m < 1.000 and y = 0 and 2.913 < n < 7.300.

[0055] 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 does not replace, even partially, the element Nb. In said second variant, the molten product according to the invention may for example be presented under the formula W0>2i NbO3>i43, or W3Nbi4O44, or under the formula Wo,5Nb04, or WNb2O8, or under the formula Wi 75^07 75, or W7Nb4O3i.

[0056] In a third variant of the molten product of the invention, the elementary constituent M is constituted by a first elementary constituent M' constituted by at least one first chemical element chosen from W, V, Zr and Mo on the one hand and by a second elementary constituent M” constituted by at least one second chemical element chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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.

[0057] 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 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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.

[0058] 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, Mo, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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.

[0059] In a second particular embodiment of the third variant of the molten product of the invention, the elementary constituent M is made up 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, Mn, Ce, Si, Sb, Y, La, 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.

[0060] 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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.

[0061] 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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.

[0062] 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi, Na and their mixtures, 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.

[0063] 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, Mn, Ce, Si, Sb, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Pb, P, Bi and mixtures thereof, preferably chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, Hf, Ta, Zn, In, Cd, B, P and mixtures thereof, preferably chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, Ni, Co, Al, Sn, Mn, Sb, Y, Hf, Ta, Zn, B and mixtures thereof.

[0064] In a first particular embodiment of the fourth variant of the molten product of the invention, the elementary constituent M is constituted 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi and Na. In said first particular embodiment, the molten product according to the invention may for example be presented under the formula Ti0.004i7Mo0.079 i7NbO2.75, i.e. Ti0.05Moo.95Nbi2033, or under the formula Moo.oo2iZro.o396Nb02.5833, i.e. Mo0.05Zr0.95Nb24O62.

[0065] 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, P 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.ooseV o,io56Nb02.7778, or Moo.osVo.çsNbçOis-

[0066] Preferably, in this second particular embodiment of the fourth variant of the molten product of the invention, the elementary constituent M is made up 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi and P.

[0067] In a third particular embodiment of the fourth variant of the molten product of the invention, in the crystalline 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)M2zNb[O(i.y)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, Mn, Ce, Si, Sb, P, Y, La, 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, Mn, Ce, Si, Sb, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Pb, Bi, P 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, Mn, Ce, Si, Sb, P, Y, La, 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, Mn, Ce, Si, Sb, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Pb, Bi, P 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.

[0068] Preferably, in this third particular embodiment of the fourth variant of the product of the invention, the elementary constituents M1 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 Mo0.0627W0.0209Zr0_0042NbO2.7594, or Mo0.75W0.25Nbn.95Zr0.05O32.975, M1 being Mo and W, M2 being Zr. Microstructure

[0069] 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%.

[0070] 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. Shape of the melted product

[0071] In a preferred embodiment, the molten product according to the invention is in the form of a particle.

[0072] Preferably, the minimum size of the powder is greater than 0.01 pm, preferably greater than 0.1 pm, preferably greater than 0.5 pm, or even greater than 1 pm 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 pm, preferably less than 250 pm, preferably less than 100 pm.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] In one embodiment, a powder according to the invention is sintered to form an electrode, preferably an anode of a battery, in particular of a lithium ion battery or a sodium ion battery.

[0077] In one embodiment, the product is in the form of an object all of whose dimensions are 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. Process

[0078] The invention also relates to a so-called “general method” comprising steps a) to c) and optionally d) to f).

[0079] In one embodiment, the method according to the invention comprises a step d) and a step e).

[0080] In one embodiment, the method according to the invention comprises a step d), a step e) and a step f).

[0081] Step f) can in particular be implemented when the molten product according to the invention comprises nitrogen.

[0082] 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 Nb2O5, NbO2, NbO, Nb, oxide(s) of one or more of the chemical elements of the elementary constituent M, carbonate(s) of one or more of the chemical elements of the elementary constituent M, hydroxide(s) of one or more of the chemical elements of the elementary constituent M, oxalate(s) of one or more of the chemical elements of the elementary constituent M, nitrate(s) of one or more of the chemical elements of the elementary constituent M, metal / metals of one or more of the chemical elements of the elementary constituent M. The use of oxide(s) and / or carbonate(s) and / or hydroxide(s) and / or nitrate(s) and / or of oxalate(s) improves the availability of oxygen necessary for the formation of the molten product MnbO and its electroneutrality.

[0083] 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.

[0084] In one embodiment, in particular when a particular oxygen substoichiometry or redox state is desired, oxalates and / or metals and / or oxides of Nb, and / or of 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 NbO2 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.

[0085] Preferably, at least one elemental constituent among M and niobium is introduced into the starting charge in the form of one or more oxides.

[0086] 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.

[0087] Substantially all of the niobium is found in the manufactured molten product. Part 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 step, depending on the melting conditions. By his general knowledge, or by simple routine tests, the person skilled in the art 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.

[0088] 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.

[0089] 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.

[0090] In a 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, 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 method 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.

[0091] In a first 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, preference of oxygen, Ti as elemental constituent M, and such that the molten product obtained is such that 0.019 < m < 0.526 and y = 0 and 2.538 < n < 4.000.

[0092] 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.

[0093] 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.

[0094] 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 - 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, Mn, Ce, Si, Sb, Y, La, Ta, Zn and Cd on the other hand, with M' different from M”, and - niobium, and - 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.

[0095] 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.

[0096] 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, Mn, Ce, Si, Sb, Y, La, 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.

[0097] 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: - 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, Mn, Ce, Si, Sb, Y, La, Ta, Zn and Cd on the other hand, and - niobium, and - preferably oxygen, such 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.

[0098] 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: - 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, Mn, Ce, Si, Sb, Y, La, Ta, Zn and Cd on the other hand, and - niobium and - 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.

[0099] 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: - 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, Mn, Ce, Si, Sb, Y, La, Ta, Zn and Cd on the other hand, and - niobium, and - preferably oxygen, such 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.

[0100] 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: - 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, Mn, Ce, Si, Sb, Y, La, Ta, Zn and Cd on the other hand, and - niobium, and - 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.

[0101] In a fourth variant of the general process of the invention, the starting charge is a mixture of raw materials providing: - 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi and Na, and - niobium, and - preferably oxygen, and - optionally nitrogen, such 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.

[0102] 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi and Na.

[0103] 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: - an elementary constituent M chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, P and their mixtures, and - niobium, and - 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.

[0104] 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.

[0105] 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi and P.

[0106] 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: - an elementary constituent Ml chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Te, Se, Si, Sb, P, Y, La, 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, Mn, Ce, Si, Sb, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Pb, Bi, P and mixtures thereof, and - niobium, and - an elementary constituent M2 chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, P, Y, La, 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, Mn, Ce, Si, Sb, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Pb, Bi, P and mixtures thereof, and - preferably oxygen and - optionally nitrogen, such that the molten product obtained is such that in the crystal structure, 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 thus being able to be expressed by the formula Ml(m_z)M2zNb[O(i_y)Ny]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.

[0107] Preferably, in this third particular embodiment of the fourth variant of the general method of the invention, the elementary constituents M1 and M2 do not comprise a common chemical element.

[0108] The particle sizes of the powders used can be those commonly encountered in melting processes.

[0109] An intimate mixture of the raw materials can be carried out in a mixer. This mixture is then poured into a melting furnace.

[0110] In step b), the starting charge is melted.

[0111] All known furnaces are conceivable, such as an induction furnace, a plasma furnace, an electric arc furnace of the Héroult type, provided that they allow the starting charge to be melted. Crucible melting in a heat treatment furnace, preferably in an electric furnace, is also conceivable. Electrofusion advantageously allows the production of large quantities of molten product with interesting yields. Preferably, the starting charge is melted in an arc furnace of the Héroult type. For example, an arc furnace of the Héroult type can be used. comprising two electrodes and whose tank has a diameter of approximately 0.8 m and can contain approximately 180 kg of molten liquid.

[0112] In step b), the energy supplied is preferably greater than 800 kWh / T of starting charge, 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.

[0113] After melting, the starting charge is in the form of a molten material, which may possibly contain some solid particles, but in an insufficient quantity for them to be able to structure said mass. By definition, to retain its shape, a molten material must be contained in a container.

[0114] 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.

[0115] Said bubbling gas may be air or oxygen, in particular when the molten product to be manufactured is a product not exhibiting oxygen substoichiometry.

[0116] 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).

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] In step cl), a stream of molten liquid is dispersed into liquid droplets.

[0126] Dispersion may result from blowing through the stream of molten material.

[0127] The molten particles may be spherical or not, hollow or solid, in particular depending on the blowing conditions and / or the composition of the molten material.

[0128] Any other method of atomizing a molten material, known to those skilled in the art, is conceivable.

[0129] In step cl), the stream of said molten material is brought into contact with a “dispersion” fluid, preferably a “dispersion” gas.

[0130] 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.

[0131] In one embodiment, the dispersion fluid is a nitrogen gas, preferably dinitrogen, particularly if the molten product to be manufactured contains the element nitrogen.

[0132] 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 redox state.

[0133] In one embodiment, the dispersion fluid is a dispersion gas chosen from argon, helium and their mixtures, 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 environment The gaseous content of the molten material was a gas comprising more than 21% nitrogen, in molar percentage.

[0134] 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).

[0135] In one embodiment, steps c1) and c2) comprise cooling the droplets by blowing air at room temperature.

[0136] In one embodiment, step c2) comprises cooling the droplets by immersion in water.

[0137] Preferably, no other means of solidification than cooling by contact with the fluid is used.

[0138] 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.

[0139] At the end of step c2), a set of solid particles is obtained which has a minimum size of at least 0.01 pm and a maximum size of at most 3 mm, or even at most 5 mm, depending on the dispersion conditions.

[0140] 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 the block.

[0141] In step cl'), the molten material is poured into a mold capable of withstanding the bath of molten liquid. 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.

[0142] 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.

[0143] In one embodiment, the casting is carried out under a nitrogen gas, preferably dinitrogen, in particular if the molten product to be manufactured contains the chemical element nitrogen (N).

[0144] 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 redox state.

[0145] 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% of dinitrogen, in mass percentage.

[0146] In step c2'), the molten material poured into the mold is cooled until an at least partially solidified block is obtained.

[0147] In step c3'), the block is demolded. Preferably, the block is demolded as soon as it has sufficient rigidity to substantially retain its shape.

[0148] Preferably, in step cl') and / or in step c2') and / or after step c3'), said molten material in the process of solidifying is brought into contact, directly or indirectly, with a "solidification" fluid, preferably a "solidification" gas, which may be identical or different to that described for step cl'). This contacting may be carried out immediately upon casting.

[0149] To facilitate contacting the molten material with the solidification fluid, preferably the solidification gas, it is preferable to demould the block 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 at step c3').

[0150] Preferably, contact with the solidification fluid, preferably the solidification gas, is maintained until the block has completely solidified.

[0151] 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.

[0152] In a third embodiment, step c) comprises the following steps: cl”) pouring 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 a block is obtained which is at least partly solidified.

[0153] In step c1”), the molten material is cast 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 in a counter-rotating movement so as to roll the jet of liquid. Preferably, said rollers are cooled, preferably using a circulation of fluid, preferably a liquid, preferably water, preferably without said liquid being in contact with the jet of molten liquid.

[0154] In step c2”), the jet of liquid poured between the rollers is cooled until an at least partially solidified block is obtained.

[0155] 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.

[0156] 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.

[0157] In one embodiment, the cooling fluid is a nitrogen gas, preferably dinitrogen, particularly if the molten product to be manufactured contains the chemical element nitrogen (N).

[0158] 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 redox state.

[0159] 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.

[0160] Preferably, contact with the cooling fluid, preferably the cooling gas, is maintained until the block has completely solidified.

[0161] 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 fused 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.

[0162] All types of crushers and grinders can be used to reduce the size of the pieces, the grinding preferably being carried out dry and / or in a solvent, preferably water. An attrition mill, an air jet mill or a ball mill are well suited.

[0163] The powder of molten particles can also undergo, in particular after step d), an additional step intended to form atomized particles, agglomerates or aggregates. All the techniques known to those skilled in the art can be used, in particular atomization of a slip or granulation.

[0164] 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.

[0165] In one embodiment, the method according to the invention comprises steps d) and e).

[0166] In step f), optional, a heat treatment of annealing of said molten product is then carried out.

[0167] 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.

[0168] The molten product, preferably in the form of particles, is introduced into a furnace.

[0169] 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.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] 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).

[0174] 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).

[0175] Of course, the present invention is not limited to the embodiments described, provided as illustrative and non-limiting examples.

[0176] 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 0 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, 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 mixtures thereof, and the atomic proportions of said elements M, niobium Nb,oxygen 0 and optionally nitrogen N being defined by the formula MmNb[O(iy)Ny]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.,

2. A molten product according to the immediately preceding claim, wherein y < 0.

150.

3. A molten product according to the immediately preceding claim, wherein 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. A molten product according to any preceding claim, wherein the additional elemental constituent consists of more than 80%, by mass percentage based on the additional elemental constituent, lithium Li.

6. A molten product according to any one of the preceding claims, wherein one of the following four variants 1. to 4. applies:

7. 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 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 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, Mn, Ce, Si, Sb, Y, La, 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 selected from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi, Na 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. A molten 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 zNb[O(iy)Ny]n, the elemental constituent Ml being Ti, the elemental 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 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 is made up 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, Mn, Ce, Si, Sb, Y, La, 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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 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, Mn, Ce, Si, Sb, Y, La, 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Pb, P, Bi 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi, P 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 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)M2z Nb[O(i_y)Ny]n, and

8. the elemental constituent Ml is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, P, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Bi and mixtures thereof, and the elementary constituent M2 is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, P, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Bi and their mixtures, 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. 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 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, Cu, Fe, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, Y, La, 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, Mn, Ce, Te, Se, Si, Sb, Y, La, Hf, Ta, Re, Zn, In, Cd, Sr, B, Bi 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 denoting 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)M2zNb[O(i_y)Ny]n, and

9. the elemental constituent Ml is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, P, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Bi and mixtures thereof, and the elementary constituent M2 is chosen from Ti, Mg, V, Cr, W, Zr, Mo, Cu, Fe, Ga, Ge, Ca, K, Ni, Co, Al, Sn, Mn, Ce, Si, Sb, P, Y, La, Hf, Ta, Zn, In, Cd, Sr, B, Bi and their mixtures, and the elementary 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. The fused product of 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 fused product thus being able to be expressed by the formula Ml(m_z)M2zNb[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, manganese Mn, cerium Ce, silicon Si, antimony Sb, yttrium Y, lanthanum La, hafnium Hf, tantalum Ta, zinc Zn, indium In, cadmium Cd, strontium Sr, boron B, lead Pb, phosphorus P, bismuth Bi, sodium Na 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, manganese Mn, cerium Ce, silicon Si, antimony Sb, yttrium Y, lanthanum La, hafnium Hf, tantalum Ta, zinc Zn, indium In, cadmium Cd, strontium Sr, boron B, lead Pb, phosphorus P, bismuth Bi, sodium Na 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. A 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 dimensions of which are greater than 3 pm.

12. A powder comprising more than 90% by mass of particles in a molten product according to any one of the immediately preceding claims.

13. A method of manufacturing a molten product according to any one of claims 1 to 11, 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.

14. 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).

15. A method according to any one of the two immediately preceding claims, wherein in step a), the starting charge provides all or part of the oxygen, preferably all of the oxygen.

16. An electrode, comprising a molten product according to any one of claims 1 to 11.

17. A battery, preferably selected from a lithium-ion battery and a sodium-ion battery, comprising an electrode, preferably an anode, according to the immediately preceding claim.