POSITIVE ELECTRODE COMPOSITION

Abstract

The invention relates to an NVPF-based composition and the use thereof in the field of batteries as an electrochemically active material. The invention also relates to a conductive composition comprising said composition as well as to a method for obtaining said composition.

Description

[0001] POSITIVE ELECTRODE COMPOSITION

[0002] This application claims priority from French patent application No. 1857116 filed on July 30, 2018, the content of which is incorporated in its entirety by reference. In the event of any inconsistency between the text of this application and the text of the French patent application that would affect the clarity of a term or expression, reference shall be made to this application only.

[0003] The present invention relates to a composition based on NVPF and its use in batteries as an electrochemically active material. It also relates to a conductive composition comprising said composition, as well as to the process for obtaining said composition.

[0004] [Technical background]

[0005] Demand for lithium-ion batteries has increased in recent years due to their use in a wide variety of electronic devices, such as mobile phones and electric vehicles. However, lithium-based compounds are relatively expensive, and natural lithium sources are unevenly distributed and difficult to access, being located in only a small number of countries. Alternatives to this element have therefore been sought. To this end, sodium-ion batteries have been developed. Sodium is indeed very abundant and evenly distributed, and is advantageously non-toxic and more economical.

[0006] However, the redox potential of the Na couple +The Na3V2(PO4)2F3 (or NVPF) is -2.71 V vs. ESH and is therefore higher than that of the Li7Li couple (-3.05 V vs. ESH), for a molar mass three times greater. These characteristics make the choice of a host material difficult. Recently, the Na3V2(PO4)2F3 (or NVPF) material has proven to be a particularly interesting electrochemically active material with regard to its electrochemical performance.

[0007] FR3042313 and WO 2017 / 064189 describe NVPF particles with an average size of less than 25 µm, preferably less than 10 µm, this size being determined by laser particle size analysis. This document does not specify the improved Dv10, Dv50, and Dv90 characteristics of the composition of the invention.

[0008] CN 103594716 describes compositions based on NVPF without details on the characteristics Dv10, Dv50 and Dv90.

[0009] CN 105655565 describes NVPF-based compositions with a packed density that can exceed 1 g / cm³3 These compositions include sodium vanadium phosphate with the formula Na3V2(PO4)3 and a conductive polymer, for example, polyaniline (PANI). There is no mention of the particle size distribution.

[0010] [The technical problem]

[0011] The volumetric energy density of an electrode represents the amount of energy an electrode can store per unit volume. It must be maximized to minimize battery size. This is especially true for applications requiring a compact battery, such as button cells. To ensure the extraction and reinsertion of sodium ions from the electrochemically active material, an electrode is formed from a conductive composition comprising the electrochemically active material, as well as an appropriate proportion of electrochemically inactive materials such as a binder or conductive additive, and characterized by a certain degree of porosity. The conductive additive ensures electron percolation through the electrode. The binder ensures adhesion to the current collector and the mechanical strength of the composite electrode.Porosity is necessary for ionic percolation between the electrolyte and the active material. To maximize volumetric capacity (expressed in this application as Ah / L), the amount of electrochemically inactive material and the porosity in the composite are limited, without compromising the extraction and reabsorption of sodium ions from the active material.

[0012] It is also sought that the electrochemically active material can be easily formulated with electrochemically inactive materials and that the conductive composition can be easily coated without leading to defects such as, for example, "striated" films. As an electrochemically active material, the composition of the invention aims to resolve this compromise.

[0013] [Figures]

[0014] Fig. 1 represents the size distribution of the composition of example 1 (in dotted line) and of the composition of comparative example 1 (in solid line).

[0015] Fig. 2 represents a SEM image of the composition of example 1. We note on this image that only NVPF particles are detected and that it is not possible to observe carbonaceous particles.

[0016] Fig. 3 represents the galvanostatic potential curves versus capacitance of the composition of example 1 (dashed line) and of the composition of comparative example 1 (solid line)

[0017] [The invention]

[0018] The invention relates to a composition comprising NVPF particles, optionally partially oxidized, and carbon in graphitized form, characterized by (1) a carbon content of between 1.0% and 3.5%, or even between 1.0% and 3.0%, this content being expressed as the weight of the carbon element relative to the total weight of the composition, (2) a packed density DT greater than or equal to 0.9 g / mL, or even greater than or equal to 1.0 g / mL, or even greater than or equal to 1.1 g / mL or 1.2 g / mL, and (3) a volume distribution of particle sizes having the following characteristics:

[0019] Dv90 < 25.0 miti, or even < 20.0 pm;

[0020] Dv50 between 1.0 pm and 10.0 pm, more particularly between 1.0 pm and 7.0 pm, or even between 1.0 pm and 5.0 pm;

[0021] the distribution being obtained by laser diffraction from a dispersion of the composition in ethanol, in particular in anhydrous ethanol.

[0022] Further details of the invention are now given below, including in the claims.

[0023] The composition of the invention comprises NVPF particles, optionally partially oxidized. NVPF, optionally partially oxidized, is the major component of the composition. Its proportion by weight is greater than or equal to 97.0%, this proportion being expressed relative to the total weight of the composition. This proportion may be between 97.0% and 99.0% by weight. The composition of the invention does not comprise Na3V2(PO4)3, or if it does, its proportion by weight in the composition is at most 1.0%, or even at most 0.5%.

[0024] More particularly, the composition of the invention consists essentially of NVPF particles, possibly partially oxidized, and of carbon in graphitized form, characterized (1) by a carbon content of between 1.0% and 3.5%, or even between 1.0% and 3.0%, this content being expressed as the weight of the carbon element relative to the total weight of the composition, (2) by a packed density DT greater than or equal to 0.9 g / mL, or even greater than or equal to 1.0 g / mL, or even greater than or equal to 1.1 g / mL or 1.2 g / mL, and (3) by a volume distribution of particle sizes having the following characteristics:

[0025] Dv90 < 25.0 miti, or even < 20.0 pm;

[0026] Dv50 between 1.0 pm and 10.0 pm, more particularly between 1.0 pm and 7.0 pm, or even between 1.0 pm and 5.0 pm;

[0027] the distribution being obtained by laser diffraction from a dispersion of the composition in ethanol, in particular in anhydrous ethanol.

[0028] NVPF has the molecular formula Na3V2(PO4)2F3. In this compound, vanadium is present in the +III oxidation state. NVPF can be partially oxidized. In this case, the product is characterized by the presence of vanadium in the +IV oxidation state as well as by the partial substitution of fluorine atoms by oxygen atoms. Partially oxidized NVPF can be represented by the formula Na3V2(PO4)2F3. -x 0 x , x being an integer between 0 and 0.5.

[0029] The NVPF, possibly partially oxidized, crystallizes in an orthorhombic unit cell with space group Amam. The lattice parameter c can be greater than or equal to 10.686 angstroms, or even 10.750 angstroms. It can be approximately 10.750 angstroms. The lattice parameter a can be between 9.027 and 9.036 angstroms, preferably approximately 9.029 angstroms. The lattice parameter b can be between 9.038 and 9.045 angstroms, preferably approximately 9.044 angstroms. The lattice volume V is between 872.604 and 878.390 angstroms. 3 , preferably approximately equal to 878,000 angstroms 3 For the NVPF, the lattice parameter c is between 10.741 and 10.754 angstroms. The lattice parameter a is between 9.028 and 9.031 angstroms. The lattice parameter b is between 9.043 and 9.045 angstroms. The lattice volume V is between 877.335 and 878.390 angstroms.3 , preferably approximately equal to 878,000 angstroms 3 .

[0030] The composition of the invention is also characterized by its carbon content. This content ranges from 1.0% to 3.5%, or even from 1.0% to 3.0%, this percentage being expressed as the weight of carbon relative to the total weight of the composition. The carbon content is determined by microanalysis.

[0031] The composition includes carbon in graphitized form. Graphitized carbon contributes to the electronic conductivity at the surface of the NVPF particles. The presence of graphitized carbon in the composition can be detected using Raman spectroscopy. More specifically, graphitized carbon can be detected by Raman spectroscopy by the presence of a vibration band located between 1580 and 1600 cm⁻¹. -1 , more specifically centered around 1590 cm -1Graphitized carbon is obtained by high-temperature thermal decomposition of an oxygenated hydrocarbon compound, as described later. Thermal decomposition also leads to the formation of amorphous carbon.

[0032] The composition of the invention may have an R-r ratio less than or equal to 1.5, preferably less than or equal to 1.0, or even less than or equal to 0.9, in which:

[0033] - R denotes the arithmetic mean of the ID / IG ratio calculated on at least 6 measurements taken at various locations in a sample of the composition;

[0034] - ID designates the intensity of the Raman vibration band centered around 1340 cm 1 ;

[0035] - IG denotes the intensity of the Raman vibration band centered around 1590 cm 1 .

[0036] The vibration band is around 1340 cm -1is attributable to amorphous (or disordered) carbon. This band is generally located between 1330 and 1360 cm -1 The vibration band is around 1590 cm -1 is attributable to graphitized carbon. This band is generally located between 1580 and 1600 cm -1 The composition of the invention also has a tapped density (TD) which is greater than or equal to 0.9 g / mL, or even greater than or equal to 1.0 g / mL, or even greater than or equal to 1.1 g / mL or 1.2 g / mL. The tapped density is measured in a known manner using a powder compaction apparatus.

[0037] The following method for determining the packed density can be applied: i) fill a 25 mL graduated cylinder, preferably class A+ according to ISO 6706, with the composition, the initial volume Vi of this composition being approximately 20 mL;

[0038] ii) the test tube is then subjected to a series of 3000 blows;

[0039] ii) then, we measure the final volume Vf of the composition.

[0040] The compacted density is then defined by:

[0041] DT (in g / mL) = mass of the composition / volume Vf

[0042] Thus, the invention as defined in the present application, including in the claims, relates in particular to a composition comprising NVPF particles, possibly partially oxidized, and carbon in graphitized form, characterized by (1) a carbon content of between 1.0% and 3.5%, or even between 1.0% and 3.0%, this content being expressed as the weight of the carbon element relative to the total weight of the composition, (2) a packed density DT greater than or equal to 0.9 g / mL, or even greater than or equal to 1.0 g / mL, or even greater than or equal to 1.1 g / mL or 1.2 g / mL, and (3) a volume distribution of particle sizes having the following characteristics:

[0043] Dv90 < 25.0 miti, or even < 20.0 pm;

[0044] Dv50 between 1.0 pm and 10.0 pm, more particularly between 1.0 pm and 7.0 pm, or even between 1.0 pm and 5.0 pm; the distribution being obtained by laser diffraction from a dispersion of the composition in ethanol, particularly in anhydrous ethanol, and the packed density being determined by the following method consisting of: i) filling a 25 mL graduated cylinder, preferably of class A+ according to ISO 6706, with the composition, the initial volume Vi of this composition being about 20 mL; ii) the cylinder is then subjected to a series of 3000 blows;

[0045] ii) then, the final volume Vf of the composition is measured, the packed density then being defined by the following relation:

[0046] DT (in g / mL) = mass of the composition / volume Vf.

[0047] Generally, a blow consists of lifting the test specimen to a certain height and letting it fall back down. This height could be, for example, 0.5 inches.

[0048] It is generally considered that after 3000 blows, the volume of the composition no longer changes. After the series of 3000 blows, the specimen can be subjected to another series of blows to verify that the absolute value of the volume difference between the two consecutive series of blows is less than 2.0% (i.e., |V pre first series — Next series | )A / first series X 100 < 2.0%). If this difference is, however, greater than or equal to 2.0%, further series of strokes are continued until this difference is less than 2.0%. The volume Vf to be considered is that for which the absolute value of the volume difference between the two consecutive series of strokes is less than 2.0%.

[0049] The method for determining the packed density can be found more specifically in the examples section.

[0050] The packed density is generally less than or equal to 2.0 g / mL, or even 1.8 g / mL, or even 1.5 g / mL.

[0051] The composition of the invention also exhibits a particular particle size distribution. This is measured by laser diffraction of a dispersion of the composition in ethanol, particularly anhydrous ethanol. Laser diffraction allows the determination of particle size distributions by measuring the angular variation of the intensity of scattered light when a laser beam passes through a sample of dispersed particles. Large particles scatter light at small angles to the laser beam, and small particles scatter light at larger angles. The distribution characteristics, such as Dv10, Dv50, and Dv90, given in this application, are derived from the volume distribution, not the number distribution. The parameters Dv10, Dv50, and Dv90 have the usual meanings in the field of laser diffraction measurements. See, for example, https: / / www.horiba.com / fileadmin / uploads / Scientific / Documents / PSA / PSA Guide book.pdf.

[0052] Dvx denotes the value determined from the volume distribution of particle sizes for which x% of the particles have a size less than or equal to this value. Thus, for example, with Dv10, 10% of the particles have a size less than Dv10. For example again, with Dv90, 90% of the particles have a size less than Dv90. Dv50 corresponds to the median value of the volume distribution.

[0053] Thus, for the composition of the invention, Dv90 is less than or equal to 25.0 µm, or even less than or equal to 20.0 µm. Dv90 can be between 5.0 µm and 25.0 µm, or even between 5.0 µm and 20.0 µm.

[0054] Furthermore, Dv50 is between 1.0 pm and 10.0 pm, more specifically between 1.0 pm and 7.0 pm, or even between 1.0 pm and 5.0 pm.

[0055] Furthermore, Dv10 can be greater than or equal to 0.50 pm, or even greater than or equal to 1.0 pm. The distribution is also narrow, characterized by a dispersion coefficient s / m of at most 10.0. This coefficient is determined by the following formula: s / m = (Dv90-Dv10) / Dv50. s / m can typically be between 2.0 and 8.0, more specifically between 2.5 and 6.0, or even between 2.5 and 5.0.

[0056] The particle size distribution can include two populations: a first, majority population, centered at a value between 1.0 pm and 4.0 pm, preferentially between 2.0 pm and 3.5 pm; and a second, minority population, centered at a value between 10.0 pm and 25.0 pm, preferentially between 15.0 pm and 21.0 pm.

[0057] The first population is in the majority and the second population is in the minority. This can be demonstrated, in particular, by the fact that the ratio between the peak intensity of the first population and the peak intensity of the second population is greater than or equal to 3.0.

[0058] The expression "population centered at a given value" means the presence, on the deconvoluted distribution, of a peak whose maximum is located at that given value. For deconvolution, the populations can be considered Gaussian. In Figure 1, the presence of this dual population can be seen on the size distribution.

[0059] Furthermore, the proportion of particles with a size greater than or equal to 12.0 µm (denoted P12 m) can be more specifically greater than or equal to 5.0%, or even greater than or equal to 10.0%, or even greater than or equal to 15.0%. P12 m hiis determined from the volume size distribution.

[0060] The composition of the invention may have a specific surface area BET of at least 2 m² 2 / g, or even greater than or equal to 10 m 2 / g. This specific surface area can be between 2 and 15 m² 2 / g, or even between 10 and 15 m 2 / g. The BET surface area refers to the specific surface area obtained by nitrogen adsorption / desorption according to the well-known Brunauer-Emmett-Teller method. The method for determining the BET specific surface area can be found in the examples.

[0061] The composition of the invention can be prepared by the process comprising the following steps:

[0062] a) a mixture of V2O5 and NH4H2PO4, both of these reactants being in solid form, and water with an initial proportion between 75% and 150%, is stirred, this proportion being calculated by weight relative to the sum of the two reactants V2O5 and NH4H2PO4;

[0063] b) the wet paste from the previous step is calcined at a temperature of at least 700°C to lead to the formation of VP04;

[0064] c) the VP04 obtained in step b) is mixed with sodium fluoride and an oxygenated hydrocarbon compound, which thermally decomposes into carbon partially in graphitized form, and the mixture thus obtained is calcined at a temperature of at least 700°C;

[0065] d) the product obtained in step c) is deagglomerated to lead to the composition of the invention.

[0066] In step a), a mixture is formed comprising V₂O₅, NH₄H₂PO₄, and water. Both V₂O₅ and NH₄H₂PO₄ are preferably in powder form. Powders with a particle diameter Dv₅₀ of no more than 100 µm, or even no more than 50 µm, can be used. Dv₅₀ is the median diameter obtained from a volume size distribution determined by a laser particle size analyzer. It is preferable to use a mixture in which the two starting reagents have been thoroughly mixed.

[0067] To obtain a NVPF of good purity, it is preferable to use a mixture close to the stoichiometry of reaction (I). For example, a mixture comprising V2O5 and NH4H2PO4 can be used in an initial molar ratio V / P between 0.9 and 1.1, or even between 0.95 and 1.05.

[0068] The mixture also includes water, the initial proportion of which by weight is between 75% and 150%, this proportion being calculated by weight relative to the sum of the two reactants V2O5 and NH4H2PO4. This proportion is that of the water present in the mixture at the beginning of step a).

[0069] The preparation of the mixture involves combining V₂O₅, NH₄H₂PO₄, and water in any order. For example, the two powders can be thoroughly mixed, water added to the resulting mixture, and then the whole thing blended. This mixing can be carried out in a mixing tool adapted to the rheology of the mixture.

[0070] The reaction between the two reactants is written as:

[0071] V2O5 + 2 NH4H2P04®· 2 (NH4)(V02)(HP04) + H20 (I)

[0072] The mixture described above is stirred with any mixing tool suitable for viscous media, such as a propeller stirrer, a paddle shaker, or a mixer. Indeed, it is observed that as the reaction progresses, the viscosity of the mixture increases, resulting in a viscous paste. On a laboratory scale, the Controlab L0031.2 mixer was used.

[0073] Stirring can be carried out at a temperature that does not need to be high. Thus, this temperature can be no more than 100°C, or even no more than 60°C, or even no more than 30°C. When the initial temperature at which stirring begins is below 50°C, or even below 30°C, the reaction is longer, which allows for better control of the mixture's viscosity (which tends to increase as the reaction progresses) and also prevents the reaction mixture from solidifying. The reaction time depends on the amount of water initially present in the mixture, the degree of separation of the solids used initially, and the physical form of the mixture. This time is generally between 2 and 60 hours. It is possible to monitor the progress of the reaction (I) using several methods. A first visual method consists of dispersing 15 mg of a sample taken during the reaction in 5 mL of ultrasonically deionized water.When some of the starting reactants remain, the resulting mixture appears as an opaque dispersion, whereas when the reaction is well advanced, it appears as a translucent, bright yellow solution. More quantitatively, a second method can be used to monitor the chemical reaction by analyzing samples taken during the reaction using an X-ray diffractometer (XRD).

[0074] At the end of step a), a moist paste is obtained.

[0075] In step b), the wet paste from the previous step is calcined at a temperature of at least 700°C, or even at least 800°C, to lead to the formation of VP04. This temperature is preferably between 700°C and 1000°C to develop the crystallinity of the product (VP04 having an orthorhombic structure) while avoiding the decomposition of VP04.

[0076] In step c), the VP04 obtained in step b) is mixed with the stoichiometric amount of sodium fluoride and an oxygenated hydrocarbon compound, the source of the carbon present in the composition, and the resulting mixture is calcined at a temperature of at least 700°C, or even at least 800°C. It is advantageous to use a mixture in which the solids are intimately mixed. To obtain a well-intimate mixture, a VP04 that has been previously ground and / or sieved can be used. For example, a ground and sieved VP04 with a Dv50 between 20 and 60 pm and a Dv90 between 80 and 100 pm can be used, the distribution also being determined from a suspension in anhydrous ethanol.

[0077] The hydrocarbon and oxygenated compound, through thermal decomposition, leads to carbon, particularly in graphitized form, which is present in the composition. This compound can be, for example, a sugar such as glucose, sucrose, sucrose, or fructose, or a carbohydrate such as starch or a cellulosic derivative. Preferably, it is a cellulosic derivative, and even more specifically, microcrystalline cellulose. The carbon source in the composition is important because it can influence the packed density and electrochemical properties (see comparative example 1). The proportion of the hydrocarbon and oxygenated compound in the VP04 and NaF mixture can range from 0.5% to 15.0% by weight, or even from 8.0% to 12.0%, this proportion being calculated relative to the entire VP04 and NaF mixture.

[0078] During step b) or step c), it is necessary to minimize the contact of the reaction mixture with oxygen. This can be achieved by conducting the calcination in a confined environment and / or limiting the presence of oxygen by introducing an inert gas, such as nitrogen or argon, into the calcination vessel. Alternatively, it may be advantageous to conduct the calcination in a closed container made of a dense, low-porosity material. On a laboratory scale, a SiC crucible with a lid made of the same material has been used for this purpose.

[0079] In step d), the product obtained in step c) is deagglomerated. This can be done using a ball mill or an air jet mill. Ball milling involves rotating a partially filled container of the product to be ground and grinding balls around its horizontal axis. The rotation at a limited speed causes the product to be ground through impacts between the product and the rotating balls.The critical parameters for controlling the final particle size of the product are the filling rate of the tank, generally less than ¾ of the tank volume; the mass ratio of the product to be ground to the grinding media, which can be between 1:4 and 1:15, preferably between 1:4 and 1:10; the nature of the grinding media, which can be zirconia, yttria zirconia or alumina for example, reflecting different hardnesses of the grinding media; the size of the grinding media, generally between 0.5 mm and 5 cm, preferably between 1 and 2 mm; the rotation speed of the tank, generally less than 100 rpm, preferably less than 80 rpm; and the grinding time, which can vary between 15 minutes and 4 hours, preferably between 30 minutes and 2 hours.

[0080] Air jet milling involves propelling the product to be ground through a high-speed airflow to create collisions between particles, thus reducing their size. More details on this technique can be found at: https: / / www.hosokawa-alpine.com / Dowder-particle-processinq / machines / iet-mills / afq-fluidised-bed-opposed-iet-mill / . The feed rate of the product to be ground into the milling chamber is adjusted, for example, using a metering screw to create a fluidized bed in steady state. A selector is placed at the milling chamber outlet to recover only sufficiently fine particles. The critical parameters for controlling the final particle size of the product are the air pressure introduced into the milling chamber and the rotational speed of the selector. An example of an air mill is the AFG-100 mill marketed by Hosokawa. We can use the conditions described in example 1.

[0081] The progress of deagglomeration can be monitored by taking samples of the product over time to determine the size distribution in anhydrous ethanol. This allows us to determine if the deagglomeration conditions are adequate to obtain the desired packed density and size distribution characteristics. It is generally advisable to begin deagglomeration under the least stringent conditions. If the desired packed density and size distribution characteristics are not achieved, deagglomeration can then be continued under more stringent conditions.

[0082] The composition of the invention can be prepared more particularly according to the operating procedure described in example 1.

[0083] The composition of the invention can be used as an electrochemically active electrode material for sodium-ion or sodium-ion batteries. The invention also relates to an electrode comprising a conductive composition including the composition of the invention, at least one electron-conducting material, and optionally a binder. The proportion of the composition of the invention in the conductive composition is generally greater than 40.0% by weight, this proportion being relative to the total weight of the conductive composition. This proportion may be between 40.0% and 80.0%. The proportion of the conductive material is generally less than 50.0% by weight, this proportion being relative to the total weight of the conductive composition. This proportion may be between 8.0% and 30.0%.More specifically, a conductive composition may comprise from 75.0% to 85.0% by weight of the composition of the invention, from 5.0% to 15.0% by weight of the conductive material, and from 5.0% to 15.0% by weight of the binder. The electron-conducting material may be selected from carbon fibers, carbon black, carbon nanotubes, graphene, and their analogs. An example of a conductive material is super P carbon, for example, H 30253, marketed by Alfa Aesar. The binder may advantageously be a polymer. The binder may advantageously be selected from polytetrafluoroethylene, polyvinylidene fluoride, or a copolymer of vinylidene fluoride and at least one comonomer, such as, for example, hexafluoropropylene, carboxymethylcellulose-derived polymers, polysaccharides, and latexes, particularly styrene-butadiene rubber.The binder is preferably a copolymer of vinylidene fluoride and at least one comonomer, such as hexafluoropropylene. For example, Solef 5130 grade, marketed by Solvay, could be used. The conductive composition can be prepared by mixing its constituent ingredients together in the presence of a polar solvent such as N-methylpyrrolidone. When the viscosity of the mixture is high, a high-viscosity mixer can be used. In the case of a polymer binder, the binder can, for example, be dissolved first in the NMP, the conductive material added while stirring, followed by the composition according to the invention. The mixture can then be deposited onto an aluminum foil, and the NMP evaporated, for example, by heating.

[0084] The electrode of the invention can be used as the positive electrode of a sodium generator. Advantageously, it is preferred for use as the positive electrode for a secondary sodium or sodium-ion battery.

[0085] [Examples]

[0086] Determination of the carbon content

[0087] The carbon content is measured by microanalysis with a Horiba EMIA 320 V2 carbon / sulfur analyzer.

[0088] Determination of particle size distribution

[0089] The particle size distribution is measured by laser diffraction on a suspension of particles in anhydrous ethanol. A Malvern Mastersizer 3000 instrument equipped with the Hydro SV module is used. The instrument chamber is filled with absolute ethanol (refractive index of 1.360) and stirred at 1800 rpm. A few milligrams of powder are then introduced directly into the chamber to achieve an obscuration level of between 5 and 15%. The optical model used is Fraunhofer.

[0090] The measurement sequence will consist of 5 successive measurements on the sample. The acquisition times are defined as follows:

[0091] - duration of background noise measurement (red): 10.00 s;

[0092] - duration of sample measurement (red): 10.00 s;

[0093] - perform the measurement in blue light: yes;

[0094] - duration of background noise measurement (blue): 10.00 s;

[0095] - Sample measurement duration (blue): 10.00 s.

[0096] Determination of packed density

[0097] A standardized, class A+ graduated cylinder of 25 mL (± 0.2 mL at 20 °C) is used and filled with approximately 20 mL of the uncompacted composition. 3000 taps are applied before reading the final volume occupied by the compacted powder. The compacted density is then determined using the following formula:

[0098] DT (in g / mL) = mass of composition / final volume determined

[0099] Determination of the specific surface area BET

[0100] The BET specific surface area is measured using the Brunauer-Emmett-Teller method, also known as the "one-point" method, on a Montech Macsorb instrument. This instrument measures the specific surface area using the gas flow method, which involves the continuous flow of an adsorbent and inert gas mixture over the sample at atmospheric pressure. The gas mixture used is 70% helium and 30% nitrogen, resulting in a relative pressure of 0.3.

[0101] The samples are initially degassed for 2 hours at 200°C under a nitrogen flow before being placed on the measuring instrument's carousel. During the analysis, an additional 5-minute degassing at 200°C is performed by the instrument before analysis. During the analysis, the adsorption and desorption phases are recorded. Specific surface area measurements are then calculated for the desorption phase. For each sample, the sensor is calibrated by injecting a known volume of pure nitrogen. The sample mass used for this measurement corresponds to the sample mass after degassing. Determination of the powder X-ray diffraction pattern

[0102] Powder X-ray diffractograms were obtained in Bragg-Brentano geometry with variable slits. Acquisition was performed between 2Q = 5° and 2Q = 90° on a Panalytical Pert Pro MPD X-ray setup equipped with a copper anticathode X-ray tube source at 40 kV and 30 mA. The detector was an XCelerator linear detector with an arc length of 2.122°. The PHD range was the default range of 37–80%. A nickel filter placed in front of the detector attenuated diffraction by the copper K-beta line. The exposure time was 40 seconds in 0.017° steps. Phase analysis was performed using High Score Plus software with the latest version of the ICDD PDF4+ database. The goniometer was periodically checked using a polycrystalline silicon standard.

[0103] Recording and processing of Raman electroscopy spectra

[0104] The spectra were recorded on a Horiba XploRA PLUS spectrometer between 50 and 2600 cm⁻¹ -1 Using a 532 nm laser (100 mW nominal power), a 100X objective, a 1200 rpm grating, a 1% filter, a 100 pm confocal hole, and an acquisition time of 2 x 120 s, the Labspec version 6-4-4-16 software from Horiba was used for acquisition and processing. The sample was deposited as a powder onto a calcium fluoride window, itself placed on an aluminum-coated glass slide. Focusing was achieved on the sample with a 100X objective. After acquisition, the spectra were smoothed and then deconvolved into two Gaussian contributions: one centered around 1340 cm⁻¹. -1 and the other centered around 1580 cm -1 The intensities are determined from the baseline drawn between two points on the spectrum located 700 cm apart. -1 and at 2000 cm-1 .

[0105] Preparation of positive electrodes from the composition of the invention

[0106] The conductive compositions (or electrode inks) are prepared by mixing NVPF-based compositions with carbon black (Super P carbon) and a fluorinated polymer (PVDF Solef 5130) in respective mass proportions of 80:10:10 in N-methyl-2-pyrrolidone solvent to obtain a viscous ink. This ink is then deposited using a film applicator to a thickness of 150 µm onto a 20 µm thick aluminum foil and dried at 90°C until the solvent has completely evaporated. Electrode discs 14 mm in diameter are cut from the dried film and then pressed at room temperature using a uniaxial press with a pressure of 1.3 tonne / cm². 2for 1 minute. The discs are then dried under primary vacuum at 120 °C for 10 h before being transferred to a glove box under an argon atmosphere.

[0107] It was observed that the compositions of the invention were easily formulated and did not lead to “striated” films.

[0108] Assembly of button cell-type electrochemical cells

[0109] The NVPF electrodes are assembled in a half-cell configuration, facing a negative metallic sodium electrode, in a 2032 button cell geometry (20 mm diameter by 3.2 mm thick). The electrolyte used consists of an equivolume mixture of ethylene carbonate and dimethyl carbonate containing one mole per liter of dissolved sodium hexafluorophosphate, to which 1% by mass of fluoroethylene carbonate is added. The button cell comprises the NVPF positive electrode, the negative metallic sodium electrode, 100 pL of electrolyte, a 1 mm thick stainless steel current collector, a 1.4 mm thick coil spring, a 16 mm thick fiberglass separator, and the rigid cell casing (two hollow pieces fitting together with a gasket).A thin, flat layer of metallic sodium is deposited on the current collector, the mass of sodium being sufficient so as not to be a limiting factor in the system. The separator is soaked in electrolyte and placed between the two facing electrodes. These components are held under pressure by the spring inside the rigid casing, which is then crimped to ensure the system is leak-proof.

[0110] Electrochemical tests

[0111] The cells assembled from the NVPF electrodes are electrochemically tested under galvanic conditions, between 3.5 V and 4.3 V vs Na + / Na, starting with charging (positive current). The current used during charging and discharging is expressed as the C-rate. The C-rate is a measure of the rate at which a battery is charged or discharged. It is defined as the current drawn divided by the theoretical current required to deliver the battery's theoretical capacity in one hour. Electrochemical tests are performed at a C-rate of C / 10, corresponding to a theoretical charge or discharge over 10 hours.

[0112] Electrochemical tests allow the reversible charge capacitance of NVPF electrodes to be determined. This capacitance is reported as a volumetric capacitance of the composition and is expressed in Ah / L (the volume of the composition is calculated from the weight of the composition used and the packed density DT).

[0113] Example 1: Preparation of NVPF-based compositions according to the invention

[0114] First, stoichiometric quantities of V₂O₅ and NH₄H₂PO₄ are mixed in the presence of 100% water by weight in a Controlab L0031.2 type mixer. The water proportion is calculated by weight relative to the total of the two reactants, V₂O₅ and NH₄H₂PO₄. After approximately 2 hours, the mixture thickens, resulting in a yellow paste composed of NH₄V₂PO₄ (presence confirmed by XRD) and water. This moist paste is placed in a well-confined environment. To do this, the paste is poured into a SiC crucible closed with a SiC lid. The paste is then calcined at 800°C for 3 hours with a temperature ramp rate of 5.5°C / min.

[0115] VP04, which is produced by calcination, is friable and consists of pieces ranging from 1 mm to 5 cm in size. This product is ground using a rotary mill for approximately 2 hours at a rotation speed of 60 rpm. Slightly ovoid polyethylene jars, 20 cm in diameter, are used to load the product to be ground along with 20 mm diameter yttria-treated zirconia beads. The loading ratio can be 1 kg of VP04 to 4 kg of beads. The ground VP04 is then extracted from the jars, separated from the beads, and sieved at 500 µm using a vibrating screen with a vibration amplitude between 0.5 and 1.6. The VP04 sieved at 500 µm represents between 95% and 98% of the total mass of ground VP04. The product thus crushed and sieved has a particle size of which the Dv50 is between 20 and 60 pm and the Dv90 between 80 and 100 pm.

[0116] The resulting VP04 is mixed with a stoichiometric amount of NaF and 10% by weight of microcrystalline cellulose relative to the total weight of VP04+NaF (Sigma-Aldrich). The solids mixture is first homogenized in a polyethylene jar filled with yttria-stabilized zirconia beads (5 mm and 20 mm beads in a mass ratio of 1 (5 mm):4 (20 mm), mass ratio of mixture [VP04+NaF+cellulose]:beads = 1:3), and rotated around its axis of symmetry for approximately 2–3 hours. The VP04 was then ground and sieved to retain only grains smaller than 500 µm.

[0117] The intimate mixture of powders is then calcined at 800°C for 3 hours with a temperature ramp rate of 5.5°C / min. Generally, the same conditions are applied as during the first calcination to obtain VP04. It is essential to properly confine the powder during calcination. The final NVPF obtained is pure according to XRD.

[0118] The resulting NVPF is then deagglomerated to achieve the desired particle size distribution. This can be achieved, for example, by ball milling or air jet milling. For air jet milling, a Hosokawa AFG-100 air mill was used. The NVPF is fed into the milling chamber via a metering screw. The feed rate of the milling chamber is adjusted to maintain a steady state for the fluidized bed. Pressurized air is introduced into the milling chamber through 2 mm diameter nozzles at a pressure of 5.5 bar. The finest particles rise to the top of the milling chamber. A selector rotating between 3000 and 5000 rpm allows the deagglomerated product to be collected.

[0119] Comparative example 1:

[0120] The composition of this example was prepared using a process similar to that of the previous example, except that:

[0121] - the mixture of V2O5 and NH4H2PO4 is made without the addition of water;

[0122] - Carbon black was added during the first calcination to compensate for a lack of powder containment (an alumina crucible and lid are used).

[0123] Microscopic images showed that carbon particles were still visible in certain areas, even after calcination. Furthermore, the composition thus prepared has a lower volumetric density than the compositions according to the invention. Table

[0124]

[0125] Conditions used: the compositions of examples 1 to 3 were obtained by air jet milling (respectively with a selector speed of 3000, 4000 and 5000 rpm); the compositions of examples 4 and 5 were obtained using a ball mill

[0126] DT: The packed density of the composition of the invention was measured with an automatic VanKel 50-100 Serial #5-1582-0699 device.

Claims

DEMANDS 1. Composition comprising NVPF particles, possibly partially oxidized, and carbon in graphitized form, characterized by (1) a carbon content of between 1.0% and 3.5%, or even between 1.0% and 3.0%, this content being expressed as the weight of the carbon element relative to the total weight of the composition, (2) a packed density DT greater than or equal to 0.9 g / mL, or even greater than or equal to 1.0 g / mL, or even greater than or equal to 1.1 g / mL or 1.2 g / mL, and (3) a volume distribution of particle sizes having the following characteristics: Dv90 < 25.0 miti, or even < 20.0 pm; Dv50 between 1.0 pm and 10.0 pm, or even between 1.0 pm and 5.0 pm; the distribution being obtained by laser diffraction from a dispersion of the composition in ethanol, in particular in anhydrous ethanol.

2. Composition consisting essentially of NVPF particles, possibly partially oxidized, and of carbon in graphitized form, characterized by (1) a carbon content of between 1.0% and 3.5%, or even between 1.0% and 3.0%, this content being expressed as the weight of the carbon element relative to the total weight of the composition, (2) a packed density DT greater than or equal to 0.9 g / mL, or even greater than or equal to 1.0 g / mL, or even greater than or equal to 1.1 g / mL or 1.2 g / mL, and (3) a volume distribution of particle sizes having the following characteristics: Dv90 < 25.0 pm, or even < 20.0 pm; Dv50 between 1.0 pm and 10.0 pm, or even between 1.0 pm and 5.0 pm; the distribution being obtained by laser diffraction from a dispersion of the composition in ethanol, in particular in anhydrous ethanol.

3. Composition according to claim 1 or 2 wherein NVPF, optionally partially oxidized, is the major component of the composition.

4. Composition according to claim 1 to 3 wherein the proportion by weight of the NVPF, optionally partially oxidized, is between 97.0% and 99.0% by weight, this proportion being expressed in relation to the total weight of the composition.

5. A composition according to any one of claims 1 to 4, wherein the mesh size parameter c is greater than or equal to 10.686 angstroms, or even 10.750 angstroms.

6. A composition according to any one of the preceding claims, wherein the mesh size volume V is between 872.604 and 878.390 angstroms. 3 .

7. Composition according to any one of the preceding claims having an R-r ratio less than or equal to 1.5, preferably less than or equal to 1.0, or even less than or equal to 0.9, in which - R denotes the arithmetic mean of the ratio b / IG calculated on at least 6 measurements taken at various locations in a sample of the composition; - b denotes the intensity of the Raman vibration band centered around 1340 cm 1 ; - IG denotes the intensity of the Raman vibration band centered around 1590 cm 1 .

8. Composition according to any one of the preceding claims wherein: - Dv90 is less than or equal to 25.0 pm; or - Dv90 is less than or equal to 20.0 pm; or - Dv90 is between 5.0 pm and 25.0 pm; or - Dv90 is between 5.0 pm and 20.0 pm.

9. Composition according to any one of the preceding claims wherein Dv50 is comprised of 1.0 pm and 5.0 pm.

10. Composition according to any one of the preceding claims, wherein Dv10 is greater than or equal to 0.50 pm, or even greater than or equal to 1.0 pm.

11. Composition according to any one of the preceding claims, wherein the dispersion coefficient s / m, defined by the relation (Dv90-Dv10) / Dv50, is at most 10.0, or even is between 2.0 and 8.0, or even between 2.5 and 5.

0.

12. Composition according to any one of the preceding claims, wherein the particle size distribution comprises two populations: a first, majority population centered at a value between 1.0 pm and 4.0 pm, preferably between 2.0 pm and 3.5 pm; and a second population, minority, centered at a value between 10.0 pm and 25.0 miti, preferentially between 15.0 pm and 21.0 pm.

13. Composition according to claim 12 wherein the ratio between the peak intensity of the first population and the peak intensity of the second population is greater than or equal to 3.

0.

14. Composition according to any one of the preceding claims wherein the proportion of particles larger than 12.0 pm is greater than or equal to 5.0%, or greater than or equal to 10.0%, or even greater than or equal to 15.0%.

15. Composition according to any one of the preceding claims having a specific surface area BET of at least 2 m² 2 / g, or even greater than or equal to 10 m 2 / g.

16. Composition according to any one of claims 1 to 15 wherein the packed density is less than or equal to 2.0 g / mL, or even to 1.8 g / mL, or even to 1.5 g / mL.

17. A method for preparing the composition according to any one of claims 1 to 16 comprising the following steps: a) a mixture of V2O5 and NH4H2PO4, both of these reactants being in solid form, and water with an initial proportion between 75% and 150%, is stirred, this proportion being calculated by weight relative to the sum of the two reactants V2O5 and NH4H2PO4; b) the wet paste from the previous step is calcined at a temperature of at least 700°C to lead to the formation of VP04; c) the VP04 obtained in step b) is mixed with sodium fluoride and an oxygenated hydrocarbon compound, which thermally decomposes into carbon partially in graphitized form, and the mixture thus obtained is calcined at a temperature of at least 700°C; d) the product obtained in step c) is deagglomerated to lead to the composition.

18. Use of the composition according to any one of claims 1 to 16 as an electrochemically active electrode material for sodium-ion or sodium-ion batteries.

19. Conductive composition comprising the composition according to any one of claims 1 to 16, at least one electron-conducting material, and optionally a binder.

20. Conductive composition according to claim 19 wherein the electron-conducting material is selected from carbon fibers, carbon black, carbon nanotubes, graphene and their analogues.

21. A conductive composition according to claim 19 or 20, wherein the binder is selected from polytetrafluoroethylene, polyvinylidene fluoride, or a copolymer of vinylidene fluoride and at least one comonomer, such as, for example, hexafluoropropylene, carboxymethylcellulose-derived polymers, polysaccharides, and latexes, particularly styrene-butadiene rubber.

22. A positive electrode comprising a conductive composition according to any one of claims 19 to 21 or a composition according to any one of claims 1 to 16.