阅读说明：本技术 正极组合物 (Positive electrode composition ) 是由 L·伯特里 R·阿密斯 V·比塞特 M-D·布拉伊达 S·莱斯特格斯 T·勒默希埃尔 于 2019-07-30 设计创作，主要内容包括：本申请涉及一种NVPF基组合物及其在电池领域中作为电化学活性材料的用途。本发明还涉及一种包含所述组合物的导电组合物以及一种用于获得所述组合物的方法。(The present application relates to NVPF-based compositions and their use as electrochemically active materials in the field of batteries. The invention also relates to a conductive composition comprising said composition and to a method for obtaining said composition.)

1. A composition comprising optionally partially oxidized NVPF particles and carbon in graphitized form, characterized by (1) a carbon content of between 1.0% and 3.5%, indeed even between 1.0% and 3.0%, this content being expressed by weight of elemental carbon relative to the total weight of the composition, (2) a bulk density TD greater than or equal to 0.9g/ml, indeed even greater than or equal to 1.0g/ml, indeed even greater than or equal to 1.1g/ml or 1.2g/ml, and (3) a particle size distribution by volume exhibiting the following characteristics:

■ is less than or equal to 25.0 mu m, indeed even less than or equal to 20.0 mu m Dv 90;

■ Dv50 of between 1.0 μm and 10.0 μm, indeed even between 1.0 μm and 5.0 μm;

the distribution is obtained by laser diffraction from a dispersion of the composition in ethanol, in particular absolute ethanol.

2. A composition consisting essentially of NVPF particles, optionally partially oxidized, and made of carbon in graphitized form, characterized by (1) a carbon content of between 1.0% and 3.5%, indeed even between 1.0% and 3.0%, expressed by weight of elemental carbon relative to the total weight of the composition, (2) a bulk density TD greater than or equal to 0.9g/ml, indeed even greater than or equal to 1.0g/ml, indeed even greater than or equal to 1.1g/ml or 1.2g/ml, and (3) a particle size distribution by volume exhibiting the following characteristics:

■ is less than or equal to 25.0 mu m, indeed even less than or equal to 20.0 mu m Dv 90;

■ Dv50 of between 1.0 μm and 10.0 μm, indeed even between 1.0 μm and 5.0 μm;

the distribution is obtained by laser diffraction from a dispersion of the composition in ethanol, in particular absolute ethanol.

3. The composition of claim 1 or 2, wherein the optionally partially oxidized NVPF is an essential element of the composition.

4. A composition as claimed in claims 1 to 3 wherein the proportion by weight of NVPF optionally partially oxidised is between 97.0% and 99.0% by weight, expressed relative to the total weight of the composition.

5. Composition according to one of claims 1 to 4, in which the unit cell parameter c is greater than or equal to 10.686 angstroms, indeed even greater than or equal to 10.750 angstroms.

6. Composition according to one of the preceding claims, in which the unit cell volume V is between 872.604 and 878.390 angstroms³In the meantime.

7. The composition of any one of the preceding claims, exhibiting a ratio R of less than or equal to 1.5, preferably less than or equal to 1.0, indeed even less than or equal to 0.9, wherein:

-R represents the ratio I calculated over at least 6 measurements made at different points of a sample of the composition_D/I_GThe arithmetic mean of (a);

-I_Dexpressed in about 1340cm^-1Intensity of the centered raman vibrational band;

-I_Gexpressed in about 1590cm^-1Intensity of the central raman vibration band.

8. A composition as claimed in any preceding claim, wherein:

-Dv90 is less than or equal to 25.0 μm; or

-Dv90 is less than or equal to 20.0 μm; or

-Dv90 is between 5.0 μm and 25.0 μm; or

Dv90 is between 5.0 μm and 20.0 μm.

9. The composition according to any of the preceding claims, wherein Dv50 is between 1.0 μ ι η and 5.0 μ ι η.

10. Composition in accordance with one of the preceding claims, wherein Dv10 is greater than or equal to 0.50 μ ι η, indeed even greater than or equal to 1.0 μ ι η.

11. Composition in accordance with one of the preceding claims, wherein the dispersion coefficient σ/m defined by the relation (Dv90-Dv10)/Dv50 is at most 10.0, indeed even between 2.0 and 8.0, indeed even more between 2.5 and 5.0.

12. The composition of any of the preceding claims, wherein the particle size distribution comprises two populations: a first population of particles, which is predominant, centered on a value between 1.0 μm and 4.0 μm, preferentially between 2.0 μm and 3.5 μm; and a second population, which is secondary, centered on a value between 10.0 μm and 25.0 μm, preferentially between 15.0 μm and 21.0 μm.

13. The composition of claim 12, wherein the ratio of the peak intensity of the first population to the peak intensity of the second population is greater than or equal to 3.0.

14. Composition according to one of the preceding claims, in which the proportion of particles having a size greater than 12.0 μm is greater than or equal to 5.0%, indeed even greater than or equal to 10.0%, indeed even greater than or equal to 15.0%.

15. Composition according to one of the preceding claims, exhibiting a thickness at least equal to 2m²A/g, indeed even greater than or equal to 10m²BET specific surface area in g.

16. The composition of one of claims 1 to 15, wherein the bulk density is less than or equal to 2.0g/ml, indeed even 1.8g/ml, indeed even more than 1.5 g/ml.

17. A process for preparing a composition as claimed in any one of claims 1 to 16, comprising the steps of:

a) stirring with a stirring device consisting of₂O₅And NH₄H₂PO₄And a mixture of water, both reactants being in the solid state, the initial proportion of water being between 75% and 150% with respect to the two reactants V₂O₅And NH₄H₂PO₄By weight;

b) calcining the wet paste obtained from the preceding step at a temperature of at least 700 ℃ so as to cause the formation of VPO₄；

c) Subjecting the VPO obtained in step b)₄Mixing with sodium fluoride and an oxygen-containing hydrocarbon compound which thermally degrades to produce carbon in partially graphitized form, and calcining the mixture thus obtained at a temperature of at least 700 ℃;

d) deagglomerating the product obtained in step c) to produce the composition.

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

19. A conductive composition comprising the composition of any one of claims 1 to 16, at least one electronically conductive material, and optionally a binder.

20. The conductive composition of claim 19, wherein the electronically conductive material is selected from carbon fibers, carbon black, carbon nanotubes, graphene, and the like.

21. The conductive composition according to claim 19 or 20, wherein the binder is selected from polytetrafluoroethylene, polyvinylidene fluoride or copolymers of vinylidene fluoride and at least one comonomer, such as for example hexafluoropropylene, polymers derived from carboxymethylcellulose, polysaccharides and latexes, in particular of the styrene/butadiene rubber type.

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

[ background art ]

In recent years, with the application of lithium ion batteries to various electronic devices (such as cellular phones and electric cars), the demand for lithium ion batteries has increased. In fact, lithium-based compounds are relatively expensive, and natural lithium sources are not uniformly distributed on earth and are not readily available because they are limited to a few countries. Therefore, alternatives to this element have been sought. For this reason, sodium ion batteries have been developed. This is because sodium is very abundant and uniformly distributed, and is advantageously non-toxic and economically more advantageous.

However, for a three-fold molar mass, Na⁺The reduction potential of the/Na couple is (2.71V compared to SHE) and is therefore greater than Li⁺Reduction potential of the/Li couple (-3.05V compared to SHE). These particularities make it difficult to select the host material. Recently, material Na₃V₂(PO₄)₂F₃(or NVPF) has proven to be a particularly advantageous electrochemically active material due to its quality of electrochemical performance.

FR 3042313 and WO 2017/064189 describe NVPF particles which may exhibit an average size of less than 25 μm, preferably less than 10 μm, as determined by laser particle size analysis. This document does not describe the improved Dv10, Dv50 and Dv90 characteristics of the compositions of the present invention.

CN 103594716 describes NVPF-based compositions without information on Dv10, Dv50 and Dv90 characteristics.

CN 105655565 describes that it exhibits a molecular weight that can exceed 1g/cm³The bulk density NVPF-based composition of (a). These compositions comprise compounds having the formula Na₃V₂(PO₄)₃And conductive polymers, such as Polyaniline (PANI) type. The particle size distribution is not mentioned.

[ problem ] to

The volumetric energy density of an electrode represents the amount of energy that the electrode can store per unit volume. It must be maximized to limit the volume of the battery. This is entirely more true because certain applications require a reduced volume of the battery, for example when the battery is in the form of a button cell. To ensure extraction and reinsertion of sodium ions of the electrochemically active material, the electrodes are formed from a conductive composition comprising the electrochemically active material and an appropriate proportion of an electrochemically inactive material (such as a binder or conductive additive), and the conductive composition is characterized by a certain porosity. The conductive additive ensures that electrons leak through the electrode. The binder ensures adhesion to the current collector and mechanical strength of the composite electrode. Porosity is essential for its part for ion percolation between the electrolyte and the active material. In order to maximize the volumetric capacity (expressed as Ah/l in this patent application), attempts were made to limit the amount of electrochemically inactive material and the porosity in the composite, without compromising the extraction and reinsertion of the active material sodium ions.

Electrochemically active materials that can be easily formulated with electrochemically inactive materials, as well as conductive compositions that can be easily coated and do not cause defects (such as, for example, "striped" films) are also sought.

As electrochemically active material, the composition of the present invention aims to solve this dilemma.

[ summary of the invention ]

The invention relates to a composition comprising optionally partially oxidized NVPF particles and carbon in graphitized form, characterized by (1) a carbon content of between 1.0% and 3.5%, indeed even between 1.0% and 3.0%, this content being expressed by the weight of elemental carbon relative to the total weight of the composition, (2) a bulk density TD greater than or equal to 0.9g/ml, indeed even greater than or equal to 1.0g/ml, indeed even greater than or equal to 1.1g/ml or 1.2g/ml, and (3) a particle size distribution by volume exhibiting the following characteristics:

■ is less than or equal to 25.0 mu m, indeed even less than or equal to 20.0 mu m Dv 90;

■ Dv50 of between 1.0 μm and 10.0 μm, more particularly between 1.0 μm and 7.0 μm, indeed even between 1.0 μm and 5.0 μm;

the distribution is obtained by laser diffraction from a dispersion of the composition in ethanol, in particular absolute ethanol.

Further details regarding the present invention are now given below, including in the claims.

The compositions of the present invention comprise NVPF particles, which are optionally partially oxidized. Optionally partially oxidized NVPF is a major element of the composition. The proportion by weight of which is greater than or equal to 97.0%, this proportion being expressed with respect to the total weight of the composition. This ratio may be between 97.0% and 99.0% by weight. The composition of the present invention does not contain Na₃V₂(PO₄)₃Or if it comprises it, the proportion thereof by weight in the composition is at most 1.0%, indeed even at most 0.5%.

More particularly, the composition of the invention is mainly composed of NVPF particles, optionally partially oxidized, and carbon in graphitized form, characterized by (1) a carbon content, expressed by the weight of elemental carbon relative to the total weight of the composition, of between 1.0% and 3.5%, indeed even between 1.0% and 3.0%, (2) a bulk density TD greater than or equal to 0.9g/ml, indeed even greater than or equal to 1.0g/ml, indeed even greater than or equal to 1.1g/ml or 1.2g/ml, and (3) a particle size distribution by volume exhibiting the following characteristics:

■ is less than or equal to 25.0 mu m, indeed even less than or equal to 20.0 mu m Dv 90;

■ Dv50 of between 1.0 μm and 10.0 μm, more particularly between 1.0 μm and 7.0 μm, indeed even between 1.0 μm and 5.0 μm;

the distribution is obtained by laser diffraction from a dispersion of the composition in ethanol, in particular absolute ethanol.

NVPF is of the formula Na₃V₂(PO₄)₂F₃The compound of (1). 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 also of vanadium in the oxidation state + IV and by the partial replacement of the fluorine atoms by oxygen atoms. The partially oxidized NVPF may be represented by the formula Na₃V₂(PO₄)₂F_3-xO_xMeaning, x is an integer between 0 and 0.5.

The optionally partially oxidized NVPF is crystallized in the orthogonal unit cells of the Amam space group. The unit cell parameter c may be greater than or equal to 10.686 angstroms, indeed even greater than or equal to 10.750 angstroms. It may be substantially equal to 10.750 angstroms. The unit cell parameter a may be, for its part, between 9.027 and 9.036 angstroms, preferably substantially equal to 9.029 angstroms. The unit cell parameter b may be, in itself, between 9.038 and 9.045 angstroms, preferably substantially equal to 9.044 angstroms. The unit cell volume V is, for its part, at 872.604 and 878.390 angstroms³Preferably substantially equal to 878.000 angstroms³。

For NVPF, the unit cell parameter c is between 10.741 and 10.754 angstroms. The unit cell parameter a is between 9.028 and 9.031 angstroms. The unit cell parameter b is between 9.043 and 9.045 angstroms. The unit cell volume V is in itself877.335 and 878.390 angstroms³Preferably substantially equal to 878.000 angstroms³。

The compositions of the present invention are also characterized by their carbon content. The latter is between 1.0% and 3.5%, indeed even between 1.0% and 3.0%, this content being expressed by the weight of elemental carbon relative to the total weight of the composition. The carbon content was determined by microanalysis.

The composition comprises carbon in graphitized form. The carbon in graphitized form contributes to the electronic conductivity at the surface of the NVPF particles. The presence of carbon in graphitized form in the composition can be demonstrated using raman spectroscopy. More particularly, Raman spectroscopy can be used to obtain Raman spectra at 1580 and 1600cm^-1More particularly at about 1590cm^-1The presence of a central vibrating band demonstrated carbon in its graphitized form. As described below, carbon in a graphitized form is obtained by pyrolysis of an oxygen-containing hydrocarbon compound. Thermal decomposition also results in the formation of amorphous carbon.

The composition of the invention may exhibit a ratio R of less than or equal to 1.5, preferably less than or equal to 1.0, indeed even less than or equal to 0.9, wherein:

-R represents the ratio I calculated over at least 6 measurements made at different points of a sample of the composition_D/I_GThe arithmetic mean of (a);

-I_Dexpressed in about 1340cm^-1Intensity of the centered raman vibrational band;

-I_Gexpressed in about 1590cm^-1Intensity of the central raman vibration band.

About 1340cm^-1The vibration band of (a) may be attributed to amorphous (or disordered) carbon. The tape is generally located 1330 and 1360cm^-1In the meantime. About 1590cm^-1The vibration band of (a) may be attributed to graphitized carbon. The tape is located at 1580 and 1600cm overall^-1In the meantime.

The composition of the invention further exhibits a bulk density TD greater than or equal to 0.9g/ml, indeed even greater than or equal to 1.0g/ml, indeed even greater than or equal to 1.1g/ml or 1.2 g/ml. Bulk density is measured in a known manner using powder bulk equipment.

The following method may be applied to determine the bulk density:

i) filling a graduated cylinder of 25ml, preferably grade a + according to standard ISO 6706, with a composition whose initial volume Vi is approximately 20 ml;

ii) the test specimen was subsequently subjected to a series of 3000 strokes;

iii) the final volume Vf of the composition is then measured.

The bulk density is then defined by:

TD (in g/ml) — weight/volume Vf of the composition

Thus, the invention as defined in the present patent application (including in the claims) relates in particular to a composition comprising NVPF particles, optionally partially oxidized, and carbon in graphitized form, characterized by (1) a carbon content, expressed by weight of elemental carbon relative to the total weight of the composition, of between 1.0% and 3.5%, indeed even between 1.0% and 3.0%, (2) a bulk density TD greater than or equal to 0.9g/ml, indeed even greater than or equal to 1.0g/ml, indeed even greater than or equal to 1.1g/ml or 1.2g/ml, and (3) a particle size distribution by volume exhibiting the following characteristics:

■ is less than or equal to 25.0 mu m, indeed even less than or equal to 20.0 mu m Dv 90;

■ Dv50 of between 1.0 μm and 10.0 μm, more particularly between 1.0 μm and 7.0 μm, indeed even between 1.0 μm and 5.0 μm;

the distribution is obtained by laser diffraction from a dispersion of the composition in ethanol, in particular absolute ethanol,

and determining the bulk density by a method comprising:

i) filling a graduated cylinder of 25ml, preferably grade a + according to standard ISO 6706, with a composition whose initial volume Vi is approximately 20 ml;

ii) the test specimen was subsequently subjected to a series of 3000 strokes;

iii) the final volume Vf of the composition is then measured,

the bulk density is then defined by the following relationship:

TD (in g/ml) is the weight/volume Vf of the composition.

Generally, striking involves lifting the specimen to a height and allowing it to fall. For example, this height may be 0.5 inches.

It is generally believed that after 3000 strokes, the volume of the composition no longer changes. After a series of 3000 hits, it was possible to continue subjecting the test specimen to another series of hits to verify that the absolute value of the volume difference between two successive series of hits was less than 2.0% (i.e., (| V)_{First series}-V_{The latter series}│)/V_{First series}x 100<2.0%). However, if the difference is greater than or equal to 2.0%, the program continues with other series of shots until the difference is less than 2.0%. The volume Vf to be considered is the volume Vf in which the absolute value of the difference in volume between two successive series of blows is less than 2.0%.

The method of determining bulk density can be found more particularly in the examples section.

The bulk density is generally less than or equal to 2.0g/ml, indeed even 1.8g/ml, indeed even more than 1.5 g/ml.

The compositions of the present invention also exhibit a particular particle size distribution. The latter is measured by laser diffraction from a dispersion of the composition in ethanol, in particular absolute ethanol. Laser diffraction allows the particle size distribution of particles to be determined by measuring the angular change in the intensity of light scattered as the laser beam passes through a sample of dispersed particles. Large particles scatter light at small angles relative to the laser beam and small particles scatter light at larger angles. The distribution characteristics given in the present patent application, such as Dv10, Dv50, or Dv90, are obtained from the distribution by volume rather than by number. The parameters Dv10, Dv50 and Dv90 have a general meaning in the field of measurement by laser diffraction. See, e.g., https:

//www.horiba.com/fileadmin/uploads/Scientific/Documents/PSA/PSA_Guidebook.pdf。

dvx denotes the value determined from the distribution by volume of the particle sizes, where x% of the particles have a size less than or equal to this value Dvx. Thus, for example, for Dv10, 10% of the particles have a size less than Dv 10. As another example, for Dv90, 90% of the particles have a size less than Dv 90. Dv50 corresponds to the median value of the distribution by volume.

Thus, for the compositions of the present invention, Dv90 is less than or equal to 25.0 μm, indeed even less than or equal to 20.0 μm. Dv90 may be between 5.0 μm and 25.0 μm, indeed even between 5.0 μm and 20.0 μm.

Furthermore, Dv50 is between 1.0 μm and 10.0 μm, more particularly between 1.0 μm and 7.0 μm, indeed even between 1.0 μm and 5.0 μm.

Furthermore, Dv10 may be greater than or equal to 0.50 μm, indeed even greater than or equal to 1.0 μm. Moreover, the distribution is narrow, characterized by a dispersion coefficient σ/m of at most 10.0. This coefficient is determined by: σ/m ═ (Dv90-Dv10)/Dv 50.σ/m may instead be between 2.0 and 8.0, more particularly between 2.5 and 6.0, indeed even between 2.5 and 5.0.

The particle size distribution may comprise two populations (populations): a first population of particles, which is predominant, centered on a value between 1.0 μm and 4.0 μm, preferentially between 2.0 μm and 3.5 μm; and a second population, which is secondary, centered on a value between 10.0 μm and 25.0 μm, preferentially between 15.0 μm and 21.0 μm.

The first population is primary and the second population is secondary. This can be demonstrated in particular by the fact that: the ratio of the peak intensity of the first population to the peak intensity of the second population is greater than or equal to 3.0.

The expression "population of particles centred on a given value" means that there is a peak on the deconvolution distribution, the maximum of which lies at this given value. For deconvolution, these populations can be considered gaussian. In fig. 1, it is possible to distinguish the presence of these two populations in the size distribution.

Furthermore, the proportion of particles having a size greater than or equal to 12.0 μm (denoted P)_12μm) It may more particularly be greater than or equal to 5.0%, indeed even greater than or equal to 10.0%, indeed even greater than or equal to 15.0%. P_12μmIs determined by the size distribution by volume.

The composition of the invention may exhibit a thickness at least equal to 2m²A/g, indeed even greater than or equal to 10m²BET specific surface area in g. The specific surface area may be between 2 and 15m²Between/g, indeed even between 10 and 15m²Between/g. The BET surface area refers to a specific surface area obtained by adsorption/desorption of nitrogen gas according to the well-known Brunauer-Emmett-Teller method. Methods for determining the BET specific surface area can be found in the examples.

The composition of the present invention may be prepared by a process comprising the steps of:

a) stirring with a stirring device consisting of₂O₅And NH₄H₂PO₄And a mixture of water, both reactants being in the solid state, the initial proportion of water being between 75% and 150% with respect to the two reactants V₂O₅And NH₄H₂PO₄By weight;

b) calcining the wet paste obtained from the preceding step at a temperature of at least 700 ℃ so as to cause the formation of VPO₄；

c) Subjecting the VPO obtained in step b)₄Mixing with sodium fluoride and an oxygen-containing hydrocarbon compound which thermally degrades to produce carbon in partially graphitized form, and calcining the mixture thus obtained at a temperature of at least 700 ℃;

d) deagglomerating the product obtained in step c) to produce the composition of the invention.

In step a), a composition comprising V is formed₂O₅、NH₄H₂PO₄And water. Two compounds V₂O₅And NH₄H₂PO₄Preferably in powder form. It is possible to use powders whose particles exhibit a diameter Dv50 of at most 100 μm, indeed even at most 50 μm. Dv50 is the median diameter obtained from the size distribution by volume determined by laser granulometry. It is preferred to use a mixture in which the two starting reactants have been intimately mixed.

In order to obtain a good productThe substantially NVPF is preferably used as a near stoichiometric mixture for reaction (I). It is possible to use, for example, a V comprising an initial V/P molar ratio of between 0.9 and 1.1, indeed even between 0.95 and 1.05₂O₅And NH₄H₂PO₄A mixture of (a).

The mixture also comprises water in an initial proportion by weight of between 75% and 150%, this proportion being relative to the two reactants V by weight₂O₅And NH₄H₂PO₄Is calculated by the combination of (1). This proportion is the proportion of water present in the mixture at the beginning of step a).

The preparation of the mixture is based on mixing V₂O₅、NH₄H₂PO₄And water in any order. For example, it is possible to intimately mix the two powders, add water to the mixture of the two powders thus obtained, and subsequently mix the combination. This mixing can be carried out in a mixing device suitable for the rheology of the mixture.

The reaction between the two reactants is written as:

V₂O₅+2NH₄H₂PO₄→2(NH₄)(VO₂)(HPO₄)+H₂O(I)

the above mixture is stirred in any mixing device suitable for viscous media, such as, for example, a propeller stirrer, a pitched blade stirrer or a kneader. This is because it was observed that as the reaction proceeded, the viscosity of the mixture increased, resulting in a viscous paste. On a laboratory scale, a Controlab L0031.2 kneader can be used.

The stirring can be carried out at temperatures which are not necessarily high. Thus, this temperature may be at most 100 ℃, indeed even at most 60 ℃, indeed even at most 30 ℃. When the initial temperature at which stirring starts is less than 50 ℃, indeed even less than 30 ℃, the reaction is longer, which makes it possible to better control the viscosity of the mixture (which tends to increase as the reaction progresses) and also to prevent the reaction mixture from forming solids (setting solid). The duration of the reaction depends on the amount of water initially present in the mixture, on the state of partition of the solid used at the beginning and on the physical form of the mixture. This duration is generally between 2h and 60 h. The progress of reaction (I) can be detected according to several methods. The first visual method included dispersing a 15mg sample taken during the reaction in 5ml of deionized water under ultrasound. When the starting reactants remain, the mixture thus formed is present in the form of an opaque dispersion, whereas when the progress proceeds well, the mixture thus formed is present in the form of a translucent solution which is bright yellow in color. More quantitatively, according to the second method, the chemical reaction can be detected by analyzing a sample taken during the reaction using an x-ray diffractometer (XRD).

At the end of step a), a wet paste is obtained.

In step b), the wet paste resulting from the preceding step is calcined at a temperature of at least 700 ℃, indeed even at least 800 ℃, so as to cause the formation of VPO₄. This temperature is preferably between 700 ℃ and 1000 ℃ in order to develop the crystallinity (VPO) of the product₄Exhibit orthorhombic structure) while avoiding VPO₄And (5) decomposing.

In step c), the VPO obtained in step b) is subjected to₄With stoichiometric amounts of sodium fluoride and oxygen-containing hydrocarbon compounds (the carbon source present in the composition) and calcining the mixture thus obtained at a temperature of at least 700c, indeed even at least 800 c. Advantageously, a mixture is used in which the solids are intimately mixed. To obtain a completely intimate mixture, it is possible to use VPO which has been previously ground and/or sieved₄. For example, ground and sieved VPOs exhibiting a Dv50 between 20 and 60 μm and a Dv90 between 80 and 100 μm may be used₄The distribution itself is determined from a suspension in anhydrous ethanol.

The oxygenated hydrocarbon compound produces carbon, particularly in graphitized form, present in the composition by thermal decomposition. This compound may be, for example, a sugar, such as, for example, glucose, sucrose (saccharose), sucrose (sucrose) or fructose, or a carbohydrate, such as, for example, starch or a cellulose derivative. More preferably, it is a cellulose derivative and still more particularlyMicrocrystalline cellulose. The carbon source present in the composition is important because it easily exerts an influence on the bulk density and electrochemical characteristics (see comparative example 1). Based on VPO₄The proportion of oxygenated hydrocarbon compounds in the mixture with NaF may be between 0.5% and 15.0%, indeed even between 8.0% and 12.0% by weight, relative to VPO₄And NaF mixture.

During step b) or step c), it is advisable to minimize the contact of the reaction mixture with oxygen. To this end, the calcination may be carried out in a closed environment and/or the presence of oxygen may be limited by introducing an inert gas (e.g., nitrogen or argon) into the vessel in which the calcination occurs. For this purpose, it may also be advantageous to carry out the calcination in a closed container formed from a material which is dense and not very porous. On a laboratory scale, a SiC crucible closed with a lid of the same material is thus used.

In step d), the product obtained in step c) is deagglomerated. A ball mill or an air jet mill (air jet mill) may be used for this. Ball milling involves rotating a trough partially filled with the product to be milled and grinding balls about its horizontal axis. The setting to rotate at a limited speed results in grinding the product via impact between the product and the balls set to rotate. The key parameter controlling the final particle size of the product is the degree of filling of the cell, generally less than 2/3 for the cell volume; the charge ratio by weight of the product to be ground to the balls, which may be between 1:4 and 1:15, preferably between 1:4 and 1: 10; the nature of the grinding balls, which may be made, for example, of zirconia, yttria-stabilized zirconia, or alumina reflecting the varying hardness of the grinding media; the size of the grinding balls is generally between 0.5mm and 5cm, preferably between 1 and 2 mm; the rotational speed of the tank, generally less than 100rpm, preferably less than 80 rpm; and milling times, which may vary between 15 minutes and 4 hours, preferably between 30 minutes and 2 hours.

With respect to air jet milling, it involves entraining the product to be ground in a high velocity air stream in order to create an impact between the particles, thereby making it possible to reduce their size. More details about this technique can be found at the following addresses: https:

com/powder-particle-processing/chips/jet-mills/afg-fluid dis-posed-bed-oriented-jet-mills/. The feed rate of the product to be ground into the grinding chamber is adjusted, for example by means of a metering screw, to form a steady-state fluidized bed. A selector is placed at the outlet of the grinding chamber in order to recover only sufficiently fine particles. The key parameters controlling the final particle size of the product are the air pressure entering the grinding chamber and the rotational speed of the selector. An example of an air mill is the AFG-100 mill sold by Youkawa, Inc. (Hosokawa). The conditions described in example 1 may be used.

The progress of deagglomeration can be monitored by removing product samples over time to determine the particle size distribution in anhydrous ethanol. This allows one to determine whether the conditions for de-agglomeration are suitable to obtain the desired bulk density and size distribution characteristics. It is generally desirable to initiate de-agglomeration under the mildest de-agglomeration conditions. If the characteristics of bulk density and size distribution are not obtained, it is possible to continue de-agglomeration under more severe conditions.

The compositions of the present invention can be prepared more specifically according to the procedure described in example 1.

The compositions of the present invention are useful as electrochemically active materials for electrodes of sodium batteries or sodium ion batteries. The invention also relates to an electrode comprising a conductive composition comprising the composition of the invention, at least one electronically conductive 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 ratio may be between 40.0% and 80.0%. The proportion of conductive material is generally less than 50.0% by weight, this proportion being relative to the total weight of the conductive composition. This ratio may be between 8.0% and 30.0%. More particularly, the 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 electronically conductive material may be selected from carbon fibers, carbon black, carbon nanotubes, graphene, and the like. An example of a conductive material is Super P carbon sold by Alfa Aesar, such as H30253. The binder may advantageously be a polymer. The binder may advantageously be chosen from polytetrafluoroethylene, polyvinylidene fluoride or copolymers of vinylidene fluoride and at least one comonomer (such as, for example, hexafluoropropylene), polymers derived from carboxymethylcellulose, polysaccharides and latexes (in particular of the styrene/butadiene rubber type). The binder is preferably a copolymer of vinylidene fluoride and at least one comonomer, such as, for example, hexafluoropropylene. For example, it may be Solef 5130 grade sold by Solvay.

The conductive composition can be prepared by mixing together the ingredients that make up the conductive composition in the presence of a polar solvent, such as N-methylpyrrolidone. When the viscosity of the mixture is high, a kneader suitable for the high viscosity may be used. In the case of a polymeric binder, it is possible, for example, to first dissolve the binder in NMP, then to add the conductive material with stirring, and then to add the composition according to the invention. The mixture can then be deposited on aluminum flakes, and then NMP can be evaporated, for example, using heat.

The electrode of the present invention can be used as the positive electrode of a sodium generator. Advantageously, it is advantageously used as the positive electrode of a sodium or sodium-ion accumulator.

[ examples ]

Determination of the carbon content

Carbon content was measured by microanalysis using a Horiba EMIA 320V2 brand carbon/sulfur analyzer.

Determination of particle size distribution

The particle size distribution was measured by laser diffraction on a suspension of particles in absolute ethanol. A Malvern Mastersizer 3000 instrument equipped with a Hydro SV module was used. The tank of the instrument was filled with absolute ethanol (refractive index of ethanol 1.360) and stirred at 1800 rpm. Several milligrams of powder were then introduced directly into the cell to have a degree of shading between 5% and 15%. The optical model used is Fraunhofer (Fraunhofer).

The measurement sequence will consist of 5 consecutive measurements on the sample. The acquisition period is defined as follows:

duration of background noise measurement (red): 10.00 s;

duration of sample measurement (red): 10.00 s;

-measurement in blue light: is that;

duration of background noise measurement (blue): 10.00 s;

duration of sample measurement (blue): 10.00 s.

Determination of bulk Density

A 25ml (± 0.2ml, at 20 ℃) class a + standardised graduated cylinder was used and filled with exactly about 20ml of the bulk composition. 3000 strokes were applied before reading the final volume occupied by the accumulated powder. The bulk density was then determined by the following formula:

TD (in g/ml) weight of composition/determined final volume

Determination of BET specific surface area

The BET specific surface area was measured on a Mountech Macsorb instrument according to the "single point" brunauer emmett-teller method. The instrument measures specific surface area by a gas flow method involving continuous flow of a mixture of adsorbent and inert gas over a sample at atmospheric pressure. The gas mixture used was 70% helium and 30% nitrogen, i.e. a relative pressure of 0.3.

The sample was initially degassed under a stream of nitrogen at 200 ℃ for 2 hours and then placed on the turntable of the measuring apparatus. During the analysis, an additional 5min of degassing at 200 ℃ was performed by the instrument before the analysis. During the analysis, the adsorption and desorption phases were recorded. Specific surface area measurements were then calculated from the desorption phase. For each sample, the sensor was calibrated by injecting a known volume of pure nitrogen gas. The sample weight used for this measurement corresponds to the sample weight after degassing.

Determination of powder X-ray diffraction patterns

Powder X-ray diffraction patterns were obtained with a variable slit in a Bragg-Brentano geometry. The acquisition was carried out between 2 θ 5 ° and 2 θ 90 ° at a voltage of 40kV and a current of 30mA on an X Pert Pro MPD assembly from panaxico (Panalytical) equipped with a tube X-ray source with a copper anticathode. The detector is an xcelarator linear detector with an arc length of 2.122 °. The PHD interval is a default interval of 37% -80%. A nickel filter placed in front of the detector makes it possible to attenuate the diffraction of the copper K β lines. The exposure time was 40 seconds at a step size of 0.017 °. The phase analysis was performed on High Score Plus software equipped with the latest version of ICDD PDF4+ database. The goniometer was periodically checked using a polysilicon standard.

Recording and processing of Raman spectroscopy spectra

Spectra were acquired at 50 and 2600cm with a 532nm laser (100mW nominal power), 100X objective, 1200rpm grating, 1% filter, 100 μm confocal aperture and 2X 120s acquisition time^-1Recorded on a Horiba-XploRA PLUS spectrometer. The software for the collection and treatment operation was Labspec version 6-4-4-16 from Horiba, Horiba. For collection, the sample was deposited in powder form on a calcium fluoride window, which was itself deposited on a glass slide covered with aluminum. The sample was focused with a 100X objective lens. After acquisition, the spectrum is smoothed and then deconvoluted into two gaussian-shaped contributions: one at about 1340cm^-1Centered and the other at about 1580cm^-1As the center. Is composed of a main body at 700cm^-1And 2000cm^-1The intensity is determined from a baseline drawn between two points on the spectrum.

Preparation of a Positive electrode from the composition of the invention

The conductive composition (or electrode ink) was prepared by mixing the NVPF-based composition with carbon black (Super P-carbon) and fluoropolymer (PVDF Solef 5130) in an N-methyl-2-pyrrolidone solvent at respective ratios of 80:10:10 by weight to obtain a viscous ink. This ink was then deposited on an aluminum sheet having a thickness of 20 μm using a film applicator having a thickness of 150 μm, and then dried at 90 ℃ until the solvent was completely evaporated. Electrode disks having a diameter of 14mm were cut from the dried films and then pressed at ambient temperature for 1 minute using a uniaxial press at a pressure of 1.3 metric tons/cm 2. The discs were then dried at 120 ℃ under low vacuum for 10h and then transferred to a glove box under an argon atmosphere.

It can be observed that the compositions of the present invention are easy to formulate and do not produce "streaked" films.

Assembly of electrochemical cells of the "button cell" type

NVPF electrodes were assembled into a half-cell configuration facing a metallic sodium negative electrode in a 2032 (20mm diameter by 3.2mm thickness) coin cell geometry. The electrolyte used consisted of a mixture of equal volumes of ethylene carbonate and dimethyl carbonate containing one mole per liter of dissolved sodium hexafluorophosphate salt to which 1% by weight of fluoroethylene carbonate was added. The button cell consisted of a NVPF positive electrode, a metallic sodium negative electrode, 100 μ l of electrolyte, a stainless steel current collector with a thickness of 1mm, a ring spring with a thickness of 1.4mm, a glass fiber separator with a thickness of 16mm and a rigid casing of the cell (two hollow pieces interlocked with a seal). A thin, flat layer of metallic sodium is deposited on the current collector, the weight of sodium being sufficient to be unlimited by the system. The separator is impregnated with an electrolyte and placed between two facing electrodes. These elements are held under pressure by a spring within a rigid housing, which is then crimped to ensure the tightness of the system.

Electrochemical testing

The cell assembled by NVPF electrode is connected with Na⁺The electrochemical tests were carried out under galvanostatic conditions between 3.5V and 4.3V compared to Na, starting from charging (positive current). The current used in charging and discharging is represented by C-rate. C-rate is a measure of the speed at which a battery is charged or discharged. It is defined as the applied current divided by the theoretical current required to provide the theoretical capacity of the cell in one hour. Electrochemical tests were performed at a C/10C rate, corresponding to a theoretical charge or theoretical discharge over 10 hours.

Electrochemical testing allows the reversible charge capacity of the NVPF electrode to be determined. This capacity is reported as the volume of the composition and is expressed as Ah/l (the volume of the composition is calculated on the basis of the weight of the composition used and the bulk density TD).

Example 1: preparation of NVPF-based composition according to the invention

First, a stoichiometric amount of V₂O₅And NH₄H₂PO₄In the presence of 100% by weight of water in a kneader of the type Controlab L0031.2. The proportion of water is by weight relative to the two reactants V₂O₅And NH₄H₂PO₄Is calculated by the combination of (1). After approximately 2 hours, the mixture thickened and NH was obtained₄VO₂HPO₄(presence confirmed by XRD) and water. This wet paste was placed in a well-closed environment. For this purpose, the paste is poured into a SiC crucible which is closed by a SiC lid. The paste was then calcined at 800 ℃ for 3 hours with a temperature ramp of 5.5 ℃/min.

VPO obtained by calcination₄Is brittle and consists of pieces between 1mm and 5 cm. This product was milled using a jar mill at a rotational speed of 60rpm for approximately 2 hours. Polyethylene pots with a diameter of 20cm and a slightly oval shape were used, which made it possible to load the product to be ground together with yttria-stabilized zirconia balls with a diameter of 20 mm. The charge ratio may be 1kg of VPO for a charge of 4kg of balls₄. VPO to be ground₄Extracted from the tanks, separated from the balls and sieved at 500 μm using a vibrating sieve which may have a vibration amplitude between 0.5 and 1.6. VPO sieved at 500 μm₄Indicated in the ground VPO₄A fraction between 95% and 98% of the total weight of (A). The product thus ground and sieved exhibited the following particle size: its Dv50 is between 20 and 60 μm and its Dv90 is between 80 and 100 μm.

VPO to be thus obtained₄With stoichiometric amounts of NaF and relative to VPO₄+ NaF (Sigma-Aldrich) 10% by weight of microcrystalline cellulose. The solid mixture was pre-filled with yttria-stabilized zirconia balls (5mm and 20mm balls in a ratio of 1(5mm) to 4(20mm) by weight, ratio by weightRate [ VPO ]₄+ NaF + cellulose]Mixture: pellets 1:3) was homogenized in a polyethylene tank and spun around its axis of symmetry for approximately 2-3 hours. Grinding and sieving VPO₄So as to retain only beads smaller than 500 μm in size.

The intimate mixture of powders was then calcined at 800 ℃ for 3 hours with a temperature ramp of 5.5 ℃/min. In general, the same conditions as during the first calcination were applied to obtain VPO₄. During calcination, the powder should be well-enclosed. The resulting NVPF obtained was pure according to XRD.

The NVPF obtained is finally de-agglomerated to obtain the desired particle size distribution. For example, ball milling or air jet milling is possible. For the air jet milling, an air mill of AFG-100 index sold by Yochwa corporation was used. NVPF was introduced into the milling chamber using a metering screw. The feed rate to the grinding chamber is adjusted to be placed under the "steady state" conditions of the fluidized bed thus formed. Compressed air was introduced into the grinding chamber at a pressure of 5.5 bar using a nozzle having a diameter of 2 mm. The finest particles rise to the top portion of the grinding chamber. Its rotation of the selector between 3000 and 5000rpm makes it possible to recover the deagglomerated product.

Comparative example 1:

the composition of this example was prepared according to a method similar to that of the previous example, except that:

-carrying out V₂O₅And NH₄H₂PO₄Without the addition of water;

carbon black is added during the first calcination in order to overcome the drawbacks of the limitation of the powder (use of a crucible and a lid made of alumina).

It can be observed in the microscopic image that the carbon particles are still visible in some places, even after calcination. Furthermore, the compositions thus prepared exhibit a density by volume lower than that of the compositions according to the invention.

Drawings

Fig. 1 shows the size distribution of the composition of example 1 (dashed line) and the composition of comparative example 1 (solid line).

Figure 2 shows an SEM image of the composition of example 1. It should be noted that only NVPF particles were detected in this image, and it was not possible to observe carbon-based particles.

Fig. 3 shows potentiostatic current curves for the capacity of the composition of example 1 (dashed line) and the composition of comparative example 1 (solid line).