• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The present invention relates to a method for preparing a Na3V2 (PO4) 2F3 material comprising at least the steps of: a) reducing the vanadium oxide, V2O5, in a reducing atmosphere in the absence of elemental carbon and in the presence at least one phosphate anion precursor to form vanadium phosphate, VPO4, and b) exposing, under an inert atmosphere, a mixture of the VPO4 material obtained in step a) with an effective amount of sodium fluoride, NaF, and at least one hydrocarbon and oxygenated compound, source of elemental carbon, at temperature conditions conducive to the calcination of said mixture to form said compound Na3V2 (PO4) 2F3. It also relates to an electrode material, an electrode and a sodium secondary battery implementing a material according to the invention.
    公开号:FR3042313A1
    申请号:FR1559709
    申请日:2015-10-13
    公开日:2017-04-14
    发明作者:Nikita Hall；Sylvain Boulineau；Laurence Croguennec；Sebastien Launois；Christian Masquelier；Loic Simonin
    申请人:De Picardie Jules Vernes, University of；Centre National de la Recherche Scientifique CNRS；Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    The present invention relates to the field of secondary batteries. It is more particularly intended to provide a method for preparing an active material for secondary electrodes and more particularly for cathodes of sodium-ion batteries.
    The demand for lithium-ion batteries has increased in recent years with regard to their application in a wide variety of electronic devices such as mobile phones and electric vehicles. However, lithium-based compounds are relatively expensive and natural sources of lithium are unevenly distributed on the planet and inaccessible because they are located in a small number of countries. Alternatives to this element have been sought. To this end, sodium-ion batteries have been developed. Sodium is indeed very abundant and homogeneously distributed, and is advantageously non-toxic and economically more interesting.
    However, the redox potential of the Na + / Na pair is (-2.71 V vs.ESH) and therefore higher than that of the Li + / Li pair (-3.05VV ESH), for a triple molar mass. These specificities make it difficult to choose a host material. Recently, NaVPCLF material has been proposed as a cathode material for sodium ion batteries. Similarly Na3V2 (P04) 2F3 has proved to be a particularly interesting material with regard to its electrochemical performance.
    Methods have therefore been developed to prepare the Na3V2 (PO4) 2F3 material. Conventionally, it is proceeded to the reduction of V2O5 in the presence of phosphoric acid or a precursor thereof to form VPO4, the latter being then calcined under an inert atmosphere in the presence of NaF to form Na3V2 (PO4) 2F3.
    Regarding the first step of reducing V2O5, several alternatives are currently available. However, none of them can really be extrapolated to the preparation of significant quantities and therefore suitable for implementation on an industrial scale.
    Thus, Barker et al. proposes in US Pat. No. 6,872,492 to carry out the reduction of V 2 O 5 by mixing it with NH 4 H 2 PO 4 and carbon black. This conventional process uses elemental carbon as a reducing agent. This mode of reduction is still called carbothermy reduction. The use of elemental carbon as a reducing agent is interesting for two reasons. First, elemental carbon, which is naturally a good conductor, is an effective reducer for V2O5. Furthermore its implementation in excess leads to the formation of a composite material having better conductive properties. However, the material thus obtained is in the form of aggregates of primary particles whose size is several micrometers.
    It should also be noted that a great intimacy between the precursors allows a better reactivity during the heat treatment as well as an optimization of the carbon reducing role. For these purposes, this prior process requires two compression steps: the first carried out prior to the first calcination reaction leading to the formation of VPO4 makes it possible to promote a reactivity between the precursors and a homogeneous reduction by carbon, whereas the second, previously at the second calcination reaction leading to the formation of Na3V2 (PC> 4) 2F3, promotes the reactivity and minimizes any contact with the atmosphere which could be a source of oxidation during annealing allowing the formation of Na3V2 (PC > 4) 2F3 or during cooling. It also makes it possible to avoid excessive growth of the primary particles. But these compression steps are precisely undesirable on an industrial level.
    Moreover, and as illustrated in Example 3 below, the implementation of a reduction by carbothermy without a compression step leads to a material with reduced electrochemical properties.
    An alternative to carbothermy reduction is the use of hydrogen as a reducing agent in dilute form with argon. Thus, Chihara et al. (Ref.1) consider a step of reducing V2O5 under an argon atmosphere diluted to 5% volume of hydrogen in the presence of NH4H2PO4. The VPO4 material thus formed is then mixed with NaF and the whole compacted and then calcined to form the expected Na3V2 (PO4) 2F3. However, a step of carbon enrichment of this material Na3V2 (PO4) 2F3 is then necessary to impart to it advantageous conductive properties. This variant embodiment is therefore also not suitable for use on an industrial scale.
    Consequently, there remains the need for a process for preparing Na3V2 (PO4) 2F3 that is suitable for use on an industrial scale and therefore suitable for producing this material at a production scale of at least 100 g. .
    There is also a need for a process that does not require a compression step to densify the intermediate products.
    There is also a need for a method for accessing a Na3V2 (PC> 4) 2F3 material with advantageous or even improved electrochemical performance.
    The present invention is specifically intended to meet these needs.
    Thus, according to one of its aspects, the present invention relates to a process for the preparation of a Na 3 V 2 (PO 4) 2 F 3 material comprising at least the steps of: a) reducing the vanadium oxide, V 2 O 5, under a reducing atmosphere at 1 absence of elemental carbon and in the presence of at least one phosphate anion precursor to form vanadium phosphate, VPO4 and b) exposing, under an inert atmosphere, a mixture of the VPO4 material obtained in step a) with an effective amount of sodium fluoride, NaF, and at least one hydrocarbon and oxygenated compound, a source of elemental carbon, at temperature conditions suitable for calcining said mixture to form said compound Na3V2 (PC> 4) 2F3.
    According to the process of the invention, the material Na3V2 (PC> 4) 2F3 is obtained in the pulverulent state. More precisely, the Na 3 V 2 (PO 4) 2 F 3 material is in the form of primary particles of average size less than 2 μm and which constitute aggregates.
    Advantageously, the average size of the aggregates is less than 25 micrometers, preferably less than 10 micrometers, and in particular between 3 and 10 micrometers, while the average dimension of the primary particles forming said aggregates is between 200 nm and 2000. nm, preferably between 200 and 600 nm.
    Unexpectedly, the inventors have notably found that the completion of the step of calcining VPO4 in the presence of NaF and an organic precursor of elemental carbon makes it possible precisely to satisfy all the aforementioned expectations.
    Advantageously, the material crystallizes in an orthorombic mesh of Aman space group with the following mesh parameters: a is between 9.028 and 9.030, preferably substantially equal to 9.029, b is between 9.044 and 9.046, preferably substantially equal to at 9.045, c is greater than or equal to 10.749 and preferably substantially equal to 10.751.
    First of all, the use of such an organic precursor makes it possible to consider reducing V 2 O 5 under a reducing atmosphere and in the absence of elemental carbon.
    The process according to the invention makes it possible to dispense with the conventional mechanical compression operations required and proves effective in producing quantities of Na3V2 (PO4) 2F3 exceeding 100 g per batch of production, which makes it suitable for an implementation on an industrial scale.
    The Na3V2 (PO4) 2F3 material obtained according to the invention advantageously has a significantly reduced particle size compared to a material obtained from a process requiring a carbothermal reduction at a scale of 100 g and more. This small size is particularly interesting for the diffusion of ions in the material during its use as an electrode active material.
    The Na3V2 (PC> 4) 2F3 material obtained according to the invention advantageously has a BET specific surface area at least equal to 1 m 2 / g and preferably ranging from 3 m 2 / g to 20 m 2 / g.
    Moreover, the primary particles constituting the aggregates composing the Na3V2 (PO4) 2F3 material have an elemental carbon coating which makes it possible to significantly increase the conductive properties thereof.
    Finally, the reducing atmosphere during the first step makes it possible to increase the reduction of V5 + in V3 + and the presence of a precursor of elemental carbon during the second step makes it possible to limit as much as possible the oxidation of V3 + ions in V4 + and to limit the growth of the primary particles thus to increase the electrochemical performance of the material.
    Unexpectedly, the method according to the invention therefore provides access to a Na3V2 (PO4) 2F3 material with a high content of V3 + ions or else a low V4 + content. The electrochemical performances of the material obtained according to the invention, in connection with this increased content of V3 + ions and in connection with the low V4 + content, are in particular verified in Example 3.
    Thus, according to another of its aspects, the present invention relates to a material Na3V2 (P04) 2F3 formed of primary particles whose average size is less than 2 μιη, in particular between 200 nm and 2000 nm, preferably less than 1 μηι, and even more particularly between 200 and 600 nm, and coated on the surface of conductive carbon.
    The conductive carbon is present at from 0.5 to 5% by weight and preferably from 1 to 3% by weight of the total weight of the material.
    The primary particles are present within the material in the form of aggregates.
    Such compounds are particularly advantageous as active electrode materials for secondary batteries, particularly sodium or sodium ion batteries.
    Thus, according to another of its aspects, the invention also relates to the use of a compound according to the invention as an electrode material, in particular a positive electrode material for a sodium or sodium-ion battery. It also relates to such an electrode material and the electrode thus formed. The invention finally relates to a sodium or sodium-ion battery comprising an electrode material as previously defined. The electrode comprises a Na3V2 (PO4) 2F3 material obtained according to the invention, a polymer or binder and optionally an additional conductive compound such as a carbon compound.
    The use of the compounds according to the invention as electrode material proves to be advantageous for several reasons.
    First of all, the electrodes formed according to the invention have good flexibility and lightness, particularly desirable properties for producing accumulators.
    They have a very good chemical, thermal and electrochemical stability. Other characteristics, variants and advantages of the compounds according to the invention, of their preparation and of their implementation will emerge more clearly on reading the description, examples and figures which will follow, given by way of illustration and not limitation of the invention. 'invention. PROCESS FOR THE PREPARATION ACCORDING TO THE INVENTION a) Reduction of vanadium oxide
    As stated above, the first step of the process requires the reduction of the V 2 O 5 material under a reducing atmosphere.
    For the purposes of the invention, the reducing atmosphere describes a gas or gaseous mixture capable of providing a reducing effect with respect to a reaction carried out under this atmosphere.
    This reduction is carried out according to the invention in the absence of elemental carbon. As such, the reduction step considered according to the invention is different from a reduction by carbothermy.
    It therefore does not implement as reducing agent, under the experimental conditions conducive to the reduction of vanadium oxide, elemental carbon in the image including carbon black.
    In a preferred manner, the process according to the invention uses, as reducing agent, dihydrogen.
    Thus, the reducing atmosphere considered according to the invention is advantageously formed in all or part of hydrogen. It can thus be pure dihydrogen or dihydrogen diluted with one or more other inert gases such as for example argon or nitrogen.
    For example, it may be a mixture of argon and dihydrogen in the proportion 98%: 2% by volume respectively.
    As regards the phosphate anion precursor, it is a compound capable of generating phosphate anions under the experimental conditions of the reduction. In general, these are salts or compounds associating with one or more phosphate anions, one or more cations such as an alkali metal, alkaline earth metal or transition or a cationic complex such as for example the ammonium ion or a quaternary ammonium.
    Within the meaning of the invention, the source compound in phosphate anions may in particular be chosen from H 3 PO 4, H (NH 4) 2 PC 4 and H 2 NH 4 PO 4. Preferably, it is H2NH4PO4.
    With regard to the amount of source compound in phosphate anions it is of course adjusted to obtain the expected VPO4 derivative.
    The starting materials, namely V2O5 and the precursor phosphate anions are mixed and exposed to the reducing atmosphere retained, preferably argon diluted to 2% with dihydrogen, and the whole heated to a temperature conducive to achieving the desired reduction, usually around 800 ° C. The adjustment of the experimental parameters, such as rate of rise in temperature and reaction time are clearly within the skill of those skilled in the art.
    As illustrated in Example 1 below, the mixture of starting materials can be heated with a temperature flow of 10 ° C / minute up to 800 ° C and held at this temperature for 3 hours. b) Transformation of vanadium phosphate into NaiWPCLLFy
    The vanadium phosphate obtained at the end of the reduction step is advantageously consecutively treated to form the expected product.
    As stated above, the vanadium phosphate obtained according to the invention does not need to be compacted or further compressed to increase the density of the powder prior to its conversion into Na3V2 (PO4) 2F3.
    The method according to the invention is thus advantageously devoid of mechanical compression steps, in particular a mechanical compression step between its step of reducing vanadium oxide to vanadium phosphate and the step of converting it. in expected compound. The stage of transformation of vanadium phosphate uses sodium fluoride as a source of both sodium ions and fluoride ion and at least one hydrocarbon and oxygenated compound capable of generating elemental carbon.
    As regards this hydrocarbon and oxygenated compound, it may especially be a sugar such as for example glucose, sucrose and fructose or a carbohydrate such as for example starch or a cellulose derivative.
    More preferentially it is a cellulose derivative and even more particularly microcrystalline cellulose.
    As detailed above, the decomposition of this hydrocarbon compound during the reaction of VPO4 vanadium phosphate with NaF to form Na3V2 (PC> 4) 2F3 is dedicated on the one hand to incorporate carbon in Na3V2 (PO4) 2F3 and d on the other hand to provide increased protection against V3 + vanadium ions against a V4 + oxidation phenomenon during heat treatment.
    The presence of carbon within and at the surface of the constituent aggregates of the material Na3V2 (PC> 4) 2F3 makes it possible to increase its conductive performances.
    Advantageously, the elemental carbon is at least in the form of a coating on all or part of the outer surface of the primary particles constituting the aggregates forming the material Na3V2 (P04) 2F3.
    The amount and chemical nature of the carbon precursor are adjusted to provide this coating under the experimental conditions selected for the transformation of vanadium phosphate. This adjustment is clearly within the skill of those skilled in the art.
    For example, in the case where this derivative is cellulose, it can be implemented in the appropriate proportions to obtain a carbon coating representing 0.5 to 5% by weight, the total weight of the material. In a general manner, all the raw materials including sodium fluoride, NaF, are mixed and the mixture thus formed, heated under an inert atmosphere under conditions of temperature and heating time adapted to the formation of the expected particulate material Na3 V2 (PO4) 2F3 by calcination. The adjustment of the operating parameters, such as, for example, temperature, rate of rise in temperature and temperature keeping time is clearly within the competence of those skilled in the art. As an illustration, the desired calcination can be carried out by heating, for example about 1 hour, the mixture at 800 ° C under an inert atmosphere.
    The cooling of the material Na3V2 (PO4) 2F3 can be rapid, and advantageously is carried out immediately by simply leaving the product formed out of the oven at 800 ° C. At the end of the process according to the invention, the material Na3V2 (PC> 4) 2F3 is purified. This purification step generally comprises a washing operation with water and a subsequent drying step.
    This material Na3V2 (PO4) 2F3 is suitable for use as a conductive material for forming electrodes.
    MATERIAL Na ^ Y ^ PQ4 ^ F ^ ACCORDING TO THE INVENTION
    This material according to the invention is further identified in abbreviated form NVPF-H in the following description.
    As mentioned above, the present invention also provides a Na3V2 (PO4) 2F3 material formed of primary particles of average size is less than 2 microns and coated on the surface of conductive carbon. The primary particles form aggregates, in particular of average size less than 25 micrometers, preferably less than 10 micrometers, and in particular between 3 and 10 micrometers.
    The average particle size can be measured by scanning electron microscopy (SEM).
    The Na3V2 (PO4) 2F3 material has a BET specific surface area of at least 1 m2 / g and preferably ranging from 3 m2 / g to 20 m2 / g.
    This surface may in particular be measured by means of nitrogen adsorption according to the BET technique (Brunauer, Emmett and Teller).
    Advantageously, the material Na3V2 (PC> 4) 2F3 according to the invention has from 0.5 to 5% by weight and preferably from 1 to 3% by weight of conductive carbon relative to its total weight.
    As stated above, this carbon contributes to the conductive performance of the material due to its natural conductivity.
    The Na3V2 (PO4) 2F3 material according to the invention also has an increased purity with regard to its high V3 + ion content or its low V4 + content. This purity gain is particularly verified in Example 3 through the electrochemical performance of the material obtained according to the invention.
    As stated in the publication Paula Serras et al. (Ref.2), the presence of V3 + and V4 + cations in Na3V2 (PO4) 2F3 material is conventionally illustrated using the following chemical formula Na3V20x (PO4) 2F3-x with x varying from zero to 2.
    When x is zero this formula is Na3V2 (PO4) 2F3 and the vanadium element is present in the form V3 +.
    When x is 2 this formula is Na3 (V0) 2 (PO4) 2F and the Vanadium element is present in the V4 + form.
    Since vanadium is predominantly present as V3 + in this type of material, the formula Na3 V2 (PO4) 2F3 is conventionally used to represent it.
    According to the invention, the material Na3V2 (PO4) 2F3 advantageously has an orthormbic mesh of Amam gap group with the following mesh parameters: a is between 9.028 and 9.030, preferably substantially equal to 9.029 - b is between 9.044 and 9.046, preferably substantially equal to 9.045 - c is greater than or equal to 10.749 and preferably substantially equal to 10.751
    In the context of the present invention, this proportion of V4 + cation is significantly reduced compared to the same existing materials. Thus a material according to the invention advantageously has a cation content V4 + at most equal to 1% by weight. This small proportion can in particular be represented by a y4 + / V3 + molar ratio of less than 5% and preferably less than 1%.
    Electrode active material
    As stated above, the material Na3V2 (PC> 4) 2F3 according to the invention is particularly advantageous as electrode active material.
    Thus, according to another of its aspects, the invention also relates to an electrode active material comprising at least one material Na3V2 (PC> 4) 2F3 according to the invention.
    This material may be used together with one or more additional compounds conventionally used, for example a binder or a conductive additive.
    The at least one electronic conductive additive may be chosen from carbon fibers, carbon black, carbon nanotubes, graphene and their analogues.
    The binder (s) may advantageously be chosen from fluorinated binders, in particular from polytetrafluoroethylene, polyvinylidene fluoride, polymers derived from carboxymethylcellulose, polysaccharides and latices, in particular from styrene-butadiene rubber type.
    Preferably, the electrode material is from 10% to 95% by weight of the total weight of the electrode, in particular more than 40% by weight, and more preferably from 40% to 80% by weight, based on the weight total of said electrode.
    An electrode according to the invention can be used as a positive electrode of a lithium or sodium generator.
    Advantageously, it is preferred for use as a positive electrode for a secondary battery with sodium or sodium ion.
    As mentioned above, the present invention also relates to a sodium secondary battery comprising an electrode according to the invention.
    In the text, the expressions "between ... and ..." and "ranging from ... to ..." and "ranging from ... to ..." are equivalent and mean that the terminals are included, unless otherwise stated.
    Unless otherwise indicated, the expression "comprising / including a" shall be understood as "comprising / including at least one". The invention will now be described by means of the following figures and examples given of course by way of illustration and not limitation of the invention.
    FIGURES
    Figure 1: Characterization by X-ray diffraction of Na3V2 (PO4) 2F3 synthesized in Example 1 from VPO4 (reduction by H2).
    2: SEM photo of Na3V2 (P04) 2F3 (NVPF-HC) material according to the invention obtained according to Example 1 by the ArÆL / cellulose route.
    3: SEM photo of the material Na3V2 (PO4) 2F3 (NVPF-CB) not according to the invention prepared by carbothermic reduction according to Example 2.
    FIG. 4: Electrochemical performance of the NVPF-CB materials of Example 2 (dark gray line) and NVPF-HC of Example 1 (line in light gray).
    BIBLIOGRAPHIC REFERENCES Ref. 1: Kuniko Chihara et al., Journal of Power Sources 227 (2013) 80-85 Ref. 2: Paula Serras et al., J. Mater. Chem., 2012, 22, 22301
    M A TF, R TFT, AND METHODS
    The EPR spectra are made using a Bruker EMX spectrometer equipped with an ER-4192-ST and ER-4131 VT cavity at 100 k.
    The SEM characterization is carried out using a ZEISS brand LEO 1530 scanning microscope.
    RX characterizations are performed using a PANalytical Empyrean diffractometer with a copper cathode. EXAMPLE 1 VPO4 is obtained beforehand by carrying out a premix of the precursors V2O5 (110 g) and NH4H2PO4 (140 g) in a mill. The mixture thus obtained is then heated in an oven at a heating rate of 10 ° C./minute to 800 ° C. and maintained at this temperature for 3 hours under an argon atmosphere enriched with 2% H 2. The gray powder thus obtained was characterized by X-ray diffraction.
    Na3V2 (PO4) 2F3 material (> 100g) was then prepared from a mixture of VPO4 (160g) as prepared above, with NaF (70g) under stoichiometric conditions (2: 3). and cellulose (23 g). This mixture was calcined under an argon atmosphere at 800 ° C for 1 hour. At the end of this calcination step, the material obtained is removed from the oven at 800 ° C. to cool it rapidly. The material Na3V2 (PO4) 2F3 (NVPF-HC) is then washed with water and dried at 80 ° C. for 24 hours.
    Figure 1 below shows the characterization by X-ray diffraction of this product, indexed in an orthorhombic mesh (Amam space group) of parameters a = 9.02940 (2) Å, b = 9.04483 ( 2) Â and c = 10.75145 (2) Â.
    Figure 2 shows the characterization by SEM of this material according to the invention.
    COMPARATIVE EXAMPLE 2
    Na3V2 material (PC> 4) 2F3 was also prepared according to the protocol described in Example 1 but with a focus on carbothermic reduction. It is still referred to hereafter as NVPF-CB.
    The essential difference from the protocol of Example 1 is the use of carbon black (TIMCAL super C65, 18 g) which leads to the formation of a particulate surface carbon of the product thus formed. In contrast to the invention, the surface carbon of the primary particles is in the form of a heterogeneous and sparse deposit.
    Figure 3 shows the SEM characterization of this material. EXAMPLE 3 CHARACTERIZATION OF NA3WPCM2F3 ACCORDING TO THE INVENTION (NVPF-H) VERSUS NAIPULIFE ACCORDING TO EXAMPLE 2 (NVPF-CB).
    The characterization of these two materials reveals a number of structural and morphological differences, the most significant of which are detectable by spectroscopy RPE, DRX and SEM.
    The comparison of FIGS. 2 and 3 makes it possible to highlight these differences.
    Thus, the SEM analysis reveals a clear difference in terms of the size of the primary particles and the carbon surface coating of these particles.
    The primary particles of the material synthesized using carbon black (NVPF-CB) have an average size greater than 2 μm, whereas they are less than 2 microns, preferably less than 1 micrometer, more preferably between 200 and 600 nm for the particles of the material according to the invention (NVPF-H).
    The presence of a carbonaceous coating is also noted.
    It is also observed by laser particle size analysis (measuring apparatus: MALVERN MASTERSIZER S model MS S) that the agglomerates of the NVPF-CB material have an average volume diameter d (v0.5) significantly greater than 25 μm. On the other hand, the average volume diameter d (v0.5) of the agglomerates of the material according to the invention is less than 10 μm.
    A significant difference between the two materials is also observed by comparing their respective EPR spectra.
    The NVPF-H material advantageously reveals a much higher V3 + content, and in particular greater than or equal to 99%.
    As detailed in the description, a V4 + content is attributed to the oxidized species of Na3V2 (PC> 4) 2F3 which is Na3V20x (PO4) 2F3-x.
    This oxidized species has been characterized by Seras et. al. (ref.2). The incorporation of a carbon source material in the second synthesis step, which leads to the formation of a carbonaceous coating of the primary particles, clearly protects the Na3V2 (PO4) 2F3 from the oxidation phenomenon in Na3V20x (PO4 ) 2F3-x.
    It is noted that the NVPF-CB material, on the other hand, has a V4 + content of the order of 1 to 5%.
    These results thus clearly reveal the interest of the method according to the invention which makes it possible to overcome the steps of compression that can not be envisaged at the scale of an industrial production, while guaranteeing the obtaining of a NVPF-H material of low V4 + content because at most equal to 10%.
    The electrochemical performances of the two materials were also tested in galvanostatic mode at a constant current density of 12.8 mA / g between the voltage terminals 2V and 4.3 V. Figure 4 gives an account of these measurements.
    The specific capacity and irreversibility at the first cycle of each material were determined in a button cell using a carbon electrode as the anode.
    It appears that the NVPF-CB and NVPF-H materials respectively have an initial specific capacity of 122 mAh / g and 128 mAh / g and an irreversibility of 30% and 23%.
    权利要求:
    Claims (20)
    [1" id="c-fr-0001]
    A process for the preparation of an Na 3 V 2 (PO 4) 2 F 3 material comprising at least the steps of: a) reducing the vanadium oxide, V 2 O 5, in a reducing atmosphere in the absence of elemental carbon and in the presence of at least one phosphate anion precursor to form vanadium phosphate, VPO4, and b) exposing, under an inert atmosphere, a mixture of the VPO4 material obtained in step a) with an effective amount of sodium fluoride, NaF, and at least one hydrocarbon and oxygenated compound, source of elemental carbon, at temperature conditions suitable for the calcination of said mixture to form said compound Na3V2 (PC> 4) 2F3.
    [2" id="c-fr-0002]
    2. Method according to the preceding claim wherein the reducing atmosphere uses as a reducing agent dihydrogen.
    [3" id="c-fr-0003]
    3. Process according to claim 1 or 2, wherein the phosphate anion precursor is selected from H3PO4, H (NH4) 2PC4 and H2NH4PO4 and preferably is H2NH4PO4.
    [4" id="c-fr-0004]
    4. A process according to any one of the preceding claims, wherein step a) is carried out under argon atmosphere diluted to 2% with dihydrogen, and at a temperature of about 800 ° C.
    [5" id="c-fr-0005]
    5. Process according to any one of the preceding claims, in which the hydrocarbon and oxygenated compound of step b) is chosen from sugars and carbohydrates and in particular is a cellulose derivative.
    [6" id="c-fr-0006]
    6. Process according to any one of the preceding claims, wherein the calcination of step b) is carried out at 800 ° C under an inert atmosphere.
    [7" id="c-fr-0007]
    7. Method according to any one of the preceding claims, characterized in that it is devoid of a mechanical compression step between step a) and step b).
    [8" id="c-fr-0008]
    8. Method according to any one of the preceding claims, characterized in that the material Na3V2 (PC> 4) 2F3 is in the form of primary particles of average size less than 2 pm and which are constituents of aggregates.
    [9" id="c-fr-0009]
    9. Material Na3V2 (P04) 2F3 formed of primary particles of average size less than 2 pm, in particular between 200 nm and 2000 nm, preferably less than 1 μιη, and more particularly between 200 and 600 nm and coated on the surface of conductive carbon.
    [10" id="c-fr-0010]
    10. Material according to the preceding claim, having from 0.5 to 5% by weight and preferably from 1 to 3% by weight of conductive carbon relative to its total weight.
    [11" id="c-fr-0011]
    11. Material according to one of claims 9 or 10, wherein the particles are in the form of aggregates, in particular of average size less than 25 μm, preferably less than 10 μm, and in particular between 3 and 10 μm. pm.
    [12" id="c-fr-0012]
    12. Material according to any one of claims 9 to 11, having a BET specific surface at least equal to 1 m2 / g and preferably ranging from 3 m2 / g to 20m2 / g.
    [13" id="c-fr-0013]
    13. Material according to any one of claims 9 or 12, having a cation content V4 + at most equal to 1% by weight.
    [14" id="c-fr-0014]
    14. Material according to any one of claims 9 to 13 obtained according to the process as defined according to any one of claims 1 to 8.
    [15" id="c-fr-0015]
    Material according to any one of claims 9 to 14, having an orthorombic mesh of Aman gap group with the following mesh parameters: a is between 9.028 and 9.030, preferably substantially equal to 9.029, b is between 9.044 and 9.046, preferably substantially equal to 9.045, - c is greater than or equal to 10.749 and preferably substantially equal to 10.751.
    [16" id="c-fr-0016]
    16. Use of a material as defined in any one of claims 9 to 15 as electrode active material.
    [17" id="c-fr-0017]
    An electrode active material comprising at least one material as defined in any one of claims 9 to 15.
    [18" id="c-fr-0018]
    18. An electrode formed wholly or partly of a material as defined in claims 9 to 15.
    [19" id="c-fr-0019]
    19. Electrode according to the preceding claim further comprising a polymer or binder and optionally an additional conductive compound such as a carbon compound.
    [20" id="c-fr-0020]
    20. Sodium or sodium ion secondary battery comprising an electrode according to claim 18 or 19.
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    同族专利:
    公开号 | 公开日
    CN108349738A|2018-07-31|
    JP2021185125A|2021-12-09|
    EP3484814B1|2019-11-20|
    FR3042313B1|2020-04-03|
    PL3484814T3|2020-06-01|
    JP2018531871A|2018-11-01|
    US11040881B2|2021-06-22|
    WO2017064189A1|2017-04-20|
    US20180297847A1|2018-10-18|
    KR20180072708A|2018-06-29|
    HUE047790T2|2020-05-28|
    EP3484814A1|2019-05-22|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1559709A|FR3042313B1|2015-10-13|2015-10-13|PROCESS FOR THE PREPARATION OF A PARTICULATE MATERIAL NA3V22F3|
    FR1559709|2015-10-13|FR1559709A| FR3042313B1|2015-10-13|2015-10-13|PROCESS FOR THE PREPARATION OF A PARTICULATE MATERIAL NA3V22F3|
    JP2018519448A| JP7004646B2|2015-10-13|2016-10-13|Method for Producing Na3V22F3 Particulate Matter|
    KR1020187011926A| KR20180072708A|2015-10-13|2016-10-13|Method for producing Na3V22F3 particulate material|
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    EP16781440.9A| EP3484814B1|2015-10-13|2016-10-13|Process for preparing a particulate material na3v22f3|
    US15/767,472| US11040881B2|2015-10-13|2016-10-13|Method for preparing a NA3V22F3 particulate material|
    CN201680060268.1A| CN108349738A|2015-10-13|2016-10-13|Prepare Na3V22F3The method of granular materials|
    HUE16781440A| HUE047790T2|2015-10-13|2016-10-13|Process for preparing a particulate material na3v22f3|
    PCT/EP2016/074597| WO2017064189A1|2015-10-13|2016-10-13|Method for preparing a na3v22f3 particulate material|
    JP2021133042A| JP2021185125A|2015-10-13|2021-08-17|PRODUCTION METHOD OF Na3 V22F3 PARTICULATE MATERIAL|
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