WO2022145323A1 - Méthode de fabrication de phosphate de lithium-vanadium - Google Patents

Méthode de fabrication de phosphate de lithium-vanadium Download PDF

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WO2022145323A1
WO2022145323A1 PCT/JP2021/047758 JP2021047758W WO2022145323A1 WO 2022145323 A1 WO2022145323 A1 WO 2022145323A1 JP 2021047758 W JP2021047758 W JP 2021047758W WO 2022145323 A1 WO2022145323 A1 WO 2022145323A1
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vanadium
lithium
phosphate
carbon
particles
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PCT/JP2021/047758
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Japanese (ja)
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純也 深沢
透 畠
拓馬 加藤
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日本化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates

Definitions

  • the present invention relates to a method for producing lithium vanadium phosphate, which is useful as a positive electrode material for a lithium secondary battery or an all-solid-state battery.
  • Lithium-ion batteries are used as batteries for mobile devices and notebook computers. Lithium-ion batteries are generally considered to be excellent in capacity and energy density. It is also expected to be used as a hybrid vehicle and an electric vehicle. When the lithium ion secondary battery is used in an automobile application, the conditions of temperature and charge / discharge current become harsher than those of the conventional one.
  • Nasicon-type phosphates such as lithium vanadium phosphate (Li 3 V 2 (PO 4 ) 3 ) are highly safe even at high temperatures, so they are positive for lithium secondary batteries for automobile applications, all-solid-state batteries, etc. It is attracting attention as an active substance.
  • Li 3 V 2 (PO 4 ) 3 lithium vanadium phosphate
  • a method for producing lithium vanadium phosphate for example, a method has been proposed in which a lithium source, a vanadium compound and a phosphorus source are pulverized and mixed, the obtained homogeneous mixture is formed into pellets, and then the molded product is fired ().
  • a lithium source, a vanadium compound and a phosphorus source are pulverized and mixed, the obtained homogeneous mixture is formed into pellets, and then the molded product is fired ().
  • Patent Documents 1 and 2 vanadium oxide (V) is dissolved in an aqueous solution containing lithium hydroxide, a phosphorus source and carbon and / or a non-volatile organic compound are further added, and the obtained raw material mixed solution is dried.
  • a method has been proposed in which a precursor is obtained and the precursor is heat-treated in an inert atmosphere to obtain a composite of Li 3 V 2 (PO 4 ) 3 and a conductive carbon material.
  • Patent Document 4 mixes a lithium source, a pentavalent or tetravalent vanadium compound, a phosphorus source, and a conductive carbon material source in which carbon is generated by thermal decomposition in an aqueous solvent.
  • the third step of wet pulverizing the mixture to obtain a slurry containing the pulverized product, the fourth step of spray-drying the slurry containing the pulverized product to obtain a reaction precursor, and the reaction precursor are not used.
  • lithium vanadium phosphate when used as a positive electrode active material such as a lithium secondary battery for automobile applications and an all-solid-state battery, the specific surface area is low in order to improve battery performance or facilitate handling. Moreover, it may be desired that the particle size distribution is sharp.
  • vanadium lithium phosphate having a high specific surface area.
  • those having a sharp particle size distribution and a BET specific surface area of more than 10 m 2 / g can be obtained, but the BET specific surface area is 10 m 2 / g. It is difficult to obtain the following with a sharp particle size distribution.
  • the present invention provides a method for producing vanadium lithium phosphate, which is X-ray diffractically monophasic, has a low specific surface area of 10 m 2 / g or less, and has a sharp particle distribution. To provide.
  • the present invention (1) is a method for producing vanadium lithium phosphate having a NASICON structure.
  • the following general formula (1) in which the average particle size of the primary particles is 2.0 ⁇ m or less: LiVOPO 4 ⁇ xH 2 O (1) (X in the formula is an integer from 0 to 2)
  • Step A to prepare carbon source-adhered particles in which lithium dihydrogen phosphate (LiH 2 PO 4 ) and an organic compound that produces carbon by thermal decomposition are attached to the surface of the particles of the lithium vanadium phosphorus composite oxide represented by.
  • Step B to obtain a reaction precursor by heat-treating the carbon source-adhered particles in an oxygen-containing atmosphere.
  • Step C to obtain lithium vanadium phosphate by calcining the reaction precursor at 500 to 1300 ° C. in an inert gas atmosphere or a reducing atmosphere.
  • the present invention provides a method for producing lithium vanadium phosphate, which is characterized by having.
  • the content of the organic compound that produces carbon by the thermal decomposition in the carbon source-adhered particles is larger than 0.6 in terms of the molar ratio (C / V) of the carbon atom to the vanadium atom.
  • the present invention provides the method for producing (1) vanadium lithium phosphate, which is characterized by the above.
  • the present invention (3) is characterized in that the carbon content of the reaction precursor is 0.3 to 0.6 in terms of the molar ratio (C / V) of the carbon atom to the vanadium atom (1).
  • Or (2) for producing vanadium lithium phosphate is characterized in that the carbon content of the reaction precursor is 0.3 to 0.6 in terms of the molar ratio (C / V) of the carbon atom to the vanadium atom (1).
  • the present invention (5) is characterized in that, in the step B, the temperature at which the carbon source-adhered particles are heat-treated is 270 to 370 ° C., which is vanadium phosphate according to any one of (1) to (4). It provides a method for producing lithium.
  • the step A is A1 step of mixing vanadium pentoxide, phosphoric acid and reducing sugar in an aqueous solvent to prepare a mixed slurry (1), and A2 step of heat-treating the mixed slurry to make a solution to obtain a reduction reaction solution, and A solution containing lithium hydroxide is added to the reduction reaction solution under heating to form a lithium vanadium phosphorus composite oxide represented by the general formula (1), lithium dihydrogen phosphate (LiH 2 PO 4 ) and the above.
  • a lithium vanadium phosphorus composite oxide represented by the general formula (1), lithium dihydrogen phosphate (LiH 2 PO 4 ) and the above.
  • the present invention provides a method for producing lithium vanadium phosphate according to any one of (1) to (5), which is a step comprising the above.
  • the present invention (7) is the method for producing (6) vanadium lithium phosphate, which is characterized in that the temperature at which the mixed slurry (1) is heat-treated in the A2 step is 60 to 100 ° C. It is to provide.
  • the present invention (8) is the method for producing lithium vanadium phosphate according to (6) or (7), wherein the heating temperature of the reduction reaction solution is 40 to 100 ° C. in the A3 step. It is to provide.
  • the mixed amount of the reduced sugar is larger than 0.6 in terms of the molar ratio (C / V) of the carbon atom in terms of carbon atom to the vanadium atom of vanadium pentoxide.
  • the present invention (10) is characterized in that the average particle size of the solid content in the wet pulverized slurry (3) obtained after the A4 step is 2.0 ⁇ m or less (6) to (9). It provides a method for producing any of the vanadium lithium phosphates.
  • the present invention (11) is characterized in that the reaction precursor further contains a Me source (Me represents a metal element having an atomic number of 11 or more or a transition metal element other than V) (1).
  • Me source represents a metal element having an atomic number of 11 or more or a transition metal element other than V
  • )-(10) Provided is a method for producing any of the vanadium lithium phosphates.
  • vanadium lithium phosphate of the present invention it is possible to obtain a product having a single phase in X-ray diffraction, a BET specific surface area of 10 m 2 / g or less, a low specific surface area, and a sharp particle distribution.
  • a method for producing vanadium lithium phosphate can be provided.
  • the method for producing lithium vanadium phosphate of the present invention is: A method for producing lithium vanadium phosphate having a NASICON structure.
  • Step B to obtain a reaction precursor by heat-treating the carbon source-adhered particles in an oxygen-containing atmosphere.
  • Step C to obtain lithium vanadium phosphate by calcining the reaction precursor at 500 to 1300 ° C. in an inert gas atmosphere or a reducing atmosphere. It is a method for producing vanadium lithium phosphate, which is characterized by having.
  • the method for producing vanadium lithium phosphate of the present invention is a method for producing vanadium lithium phosphate having a NASICON structure (hereinafter, simply referred to as "vanadium lithium phosphate").
  • the vanadium lithium phosphate obtained by the method for producing lithium vanadium phosphate of the present invention is obtained by the following general formula (2) :.
  • Li x V y (PO 4 ) 3 (2) (In the formula, x indicates 2.5 or more and 3.5 or less, and y indicates 1.8 or more and 2.2 or less.)
  • the vanadium lithium phosphate represented by the above, or the vanadium lithium phosphate represented by the general formula (2) optionally represents a Me element (Me represents a metal element other than V and having an atomic number of 11 or more or a transition metal element. ) Is doped and contained in vanadium lithium phosphate.
  • X in the general formula (2) is 2.5 or more and 3.5 or less, preferably 2.8 or more and 3.2 or less.
  • y is 1.8 or more and 2.2 or less, preferably 1.9 or more and 2.1 or less.
  • the Me element to be doped is Sr, Ba, Sc, Y, Hf, Ta, W, Ru, Os, Ag, Zn, Si, Ga, Ge, Sn, Bi. , S, Se, Te, Cl, Br, I, Na, K, Mg, Ca, Al, Mn, Co, Ni, Fe, Ti, Zr, Bi, Cr, Nb, Mo and Cu. Two or more types can be mentioned. Of these, the Me element is preferably one or more selected from Mg, Ca, Al, Mn, Co, Ni, Fe, Ti, Zr, Bi, Cr, Nb, Mo and Cu. ..
  • the method for producing lithium vanadium phosphate of the present invention includes a step A, a step B, and a step C.
  • Step A In step A according to the method for producing lithium vanadium phosphate of the present invention, phosphorus is applied to the particle surface of the lithium vanadium phosphorus composite oxide represented by the general formula (1) in which the average particle size of the primary particles is 2.0 ⁇ m or less.
  • This is a step of preparing carbon source-adhered particles to which lithium dihydrogen acid (LiH 2 PO 4 ) and an organic compound that produces carbon by thermal decomposition are attached.
  • the carbon source-adhered particles are (i) a state in which particles of the lithium vanadium phosphorus composite oxide represented by the general formula (1) having an average particle diameter of primary particles of 2.0 ⁇ m or less are monodispersed. Even if lithium dihydrogen phosphate (LiH 2 PO 4 ) and an organic compound that produces carbon by thermal decomposition are attached to the particle surface of the monodisperse particles, or (ii) the average particle size of the primary particles is
  • the lithium vanadium phosphorus composite oxide represented by the general formula (1) having a size of 2.0 ⁇ m or less forms secondary particles, and lithium dihydrogen phosphate (LiH 2 PO 4 ) and lithium dihydrogen phosphate (LiH 2 PO 4) are formed on the particle surface of the secondary particles. It may be one to which an organic compound that produces carbon by thermal decomposition is attached, or (iii) one containing both forms of (i) and (ii).
  • step A lithium dihydrogen phosphate (LiH 2 PO) is placed on the particle surface of the lithium vanadium phosphorus composite oxide represented by the general formula (1) in which the average particle size of the primary particles is 2.0 ⁇ m or less. 4 ) And by preparing carbon source-attached particles to which an organic compound that produces carbon by thermal decomposition is attached, single-phase vanadium lithium phosphate can be obtained by X-ray diffraction with a small amount of carbon by firing in step C. It is easy to obtain vanadium lithium phosphate produced with a sharp particle distribution.
  • LiH 2 PO lithium dihydrogen phosphate
  • the lithium vanadium phosphorus composite oxide represented by the general formula (1) according to step A has an average particle size of primary particles of 2.0 ⁇ m or less, preferably 0.1 to 1.5 ⁇ m.
  • the average particle size of the primary particles of the lithium vanadium phosphorus composite oxide represented by the general formula (1) is in the above range, coarse particles are less likely to be generated as the produced vanadium lithium phosphate, and the particle size distribution is sharp. It is easy to obtain a single-phase lithium vanadium phosphate by X-ray diffraction with a small amount of carbon.
  • the average particle size of the primary particles of the lithium vanadium phosphorus composite oxide represented by the general formula (1) exceeds the above range, coarse particles are likely to be mixed as the produced vanadium lithium phosphate, and the particle size distribution. However, it becomes difficult to obtain sharp particles.
  • the average particle size of the primary particles of the lithium vanadium phosphorus composite oxide is obtained as the average value of the particle size (major diameter in the Heywood diameter) of 200 arbitrarily extracted particles from the observation with a scanning electron microscope (SEM). Is.
  • the lithium vanadium phosphorus composite oxide represented by the general formula (1) is a known compound, and for example, vanadium pentoxide, a phosphorus source, and an organic compound having a reducing action are pentoxide in an aqueous solvent at 60 to 100 ° C. After carrying out the reduction reaction of vanadium, a method of adding lithium hydroxide to this reduction solution and carrying out the reaction at 60 to 100 ° C., phosphoric acid, vanadium pentoxide, lithium hydroxide and an organic compound having a reducing action. (For example, see Japanese Patent Application Laid-Open No. 2010-218829) and the like, and further, by pulverizing if necessary, a general formula in which the average particle size of the primary particles is 2.0 ⁇ m or less.
  • the lithium vanadium phosphorus composite oxide represented by (1) can be obtained.
  • lithium dihydrogen phosphate (LiH 2 PO 4 ) is attached to the surface of the lithium vanadium phosphorus composite oxide represented by the general formula (1).
  • the lithium dihydrogen phosphate (LiH 2 PO 4 ) adhering to the particle surface of the lithium vanadium phosphorus composite oxide represented by the general formula (1) is partially or wholly amorphous phosphorus in step B. It becomes a compound (LiH 2 PO 4 , LiPO 3 , etc.) and lithium phosphate (Li 3 PO 4 ), and further, in step C, lithium dihydrogen phosphate (LiH 2 PO 4 ) and amorphous produced in step B.
  • the phosphorus compound and / or lithium phosphate of the above reacts with the lithium vanadium phosphorus composite oxide represented by the general formula (1) to produce vanadium lithium phosphate represented by the general formula (2).
  • the lithium vanadium phosphorus composite oxide represented by the general formula (1) is added to the surface of the particles by addition to lithium dihydrogen phosphate (LiH 2 PO 4 ) and heat decomposition.
  • Organic compounds that generate carbon are attached.
  • As an organic compound that produces carbon by thermal decomposition a part of it is removed from the system or carbon is isolated when the carbon source-adhered particles are heat-treated in step B, or the reaction precursor is fired in step C.
  • carbon is isolated and converted to carbon, it is used.
  • this isolated carbon becomes a component necessary for preventing the oxidation of vanadium during firing in step C.
  • the organic compound that produces carbon by thermal decomposition is not particularly limited as long as it is converted to carbon through steps B and C, but is a lithium vanadium phosphorus composite oxide represented by the general formula (1).
  • Organic compounds that generate carbon by thermal decomposition can be uniformly attached to the surface of the particles, and those that are soluble in an aqueous solvent are preferable, and reduced sugars are particularly preferable.
  • the reducing sugar include glucose, fructose, lactose, maltose, sucrose and the like, and among these, lactose and sucrose are preferable in that a reaction precursor having excellent reactivity can be obtained.
  • the organic compound having the reducing property of vanadium pentoxide for example, the reducing sugar is the reduction of vanadium pentoxide in the preferable form of the step A having the steps A1 to A5 described later. It may also be used as an agent.
  • the carbon source-adhered particles are "organic having the reducing property of vanadium pentoxide and producing carbon by thermal decomposition" after being used for the reduction reaction of vanadium pentoxide.
  • a reaction-converted product produced by using a compound, for example, a reducing sugar as a reducing agent for the reducing reaction of vanadium pentoxide may be attached.
  • the carbon source-adhered particles have "five reduced sugars and the like" that were not used for the reduction of vanadium pentoxide as an organic compound that produces carbon by thermal decomposition.
  • Organic compounds that have the reducing property of vanadium oxide and generate carbon by thermal decomposition and "the reducing property of vanadium pentoxide such as reduced sugar” that was produced by being used as a reducing agent in the reduction reaction of vanadium pentoxide.
  • a reaction-converted product of an "organic compound that produces carbon by thermal decomposition” is attached.
  • the amount of the organic compound that produces carbon by thermal decomposition in the carbon source-adhered particles prepared in step A is uniformly heated and decomposed on the particle surface of the lithium vanadium phosphorus composite oxide represented by the general formula (1).
  • the molar ratio (C / V) of carbon atoms in terms of carbon atoms to the vanadium atoms in the carbon source-attached particles is that the organic compound that produces carbon adheres and the oxidation of vanadium can be suppressed in the firing of step C. , 0.6 is preferred.
  • the amount of carbon attached to the organic compound that produces carbon by thermal decomposition is such that the carbon derived from the organic compound that produces carbon by thermal decomposition is oxygen in step B.
  • heat treatment in the content atmosphere it is efficiently reduced and its content can be easily adjusted. It is preferably greater than 0.6 and 2.0 or less, and particularly preferably 0.7 or more and 1.7 or less.
  • step A a lithium vanadium phosphorus composite oxide represented by the general formula (1) having an average particle diameter of 2.0 ⁇ m or less, lithium dihydrogen phosphate (LiH 2 PO 4 ), and carbon by thermal decomposition are obtained.
  • the step of having a spray-drying treatment for spray-drying the slurry containing the organic compound containing the above is to uniformly apply phosphorus to the particle surface of the lithium vanadium phosphorus composite oxide represented by the general formula (1). It is preferable in that lithium dihydrogen acid (LiH 2 PO 4 ) and an organic compound that produces carbon by thermal decomposition can be attached.
  • the solvent used in the slurry containing the above is inactive, insoluble or sparingly soluble in the lithium vanadium phosphorus composite oxide represented by the general formula (1), and diphosphate. It is not particularly limited as long as it can dissolve lithium hydrogen hydrogen (LiH 2 PO 4 ) and an organic compound that produces carbon by thermal decomposition, but it is industrially advantageous and is water, or water and an organic that is hydrophilic with water.
  • a mixed solvent of the solvent is preferable.
  • the average particle size of the primary particles is expressed by the general formula (1) of 2.0 ⁇ m or less.
  • the lithium vanadium phosphorus composite oxide forms secondary particles, and lithium dihydrogen phosphate (LiH 2 PO 4 ) and an organic compound that produces carbon by thermal decomposition adhere to the particle surface of the secondary particles.
  • the average particle size (secondary particle size) of the particles is 5 to 100 ⁇ m, preferably 10 to 50 ⁇ m, which is the average particle size obtained from SEM observation, which is easy to handle and has excellent reactivity. It is preferable from the viewpoint of The average particle diameter (secondary particle diameter) of the carbon source-attached particles is obtained as an average value of the particle diameters (major diameter in the Heywood diameter) of 200 arbitrarily extracted particles from SEM observation.
  • step A a step having the following steps A1 to A5 is preferable in that a reaction precursor having industrially advantageous and excellent reactivity can be obtained. That is, as step A, vanadium pentoxide, phosphoric acid and reducing sugar are mixed in an aqueous solvent to prepare a mixed slurry (1), and step A1. A2 step of heat-treating the mixed slurry to make a solution to obtain a reduction reaction solution, A solution containing lithium hydroxide is added to the reduction reaction solution under heating to form a lithium vanadium phosphorus composite oxide represented by the general formula (1), lithium dihydrogen phosphate (LiH 2 PO 4 ) and thermal decomposition.
  • step A vanadium pentoxide, phosphoric acid and reducing sugar are mixed in an aqueous solvent to prepare a mixed slurry (1), and step A1.
  • A3 step of preparing a slurry (2) containing an organic compound that produces carbon by A4 step of preparing the wet pulverized slurry (3) by wet pulverizing the slurry (2) with a media mill.
  • the A1 step is a step of preparing a mixed slurry (1) by mixing vanadium pentoxide, phosphoric acid and a reducing sugar in an aqueous solvent.
  • the mixing amount of vanadium pentoxide and phosphoric acid is the molar ratio (V / P) of V atoms in vanadium pentoxide to P atoms in phosphoric acid, which is 0.50 to 0.80, preferably 0. It is preferably .60 to 0.73 in that a single-phase lithium vanadium phosphate can be easily obtained as a final product.
  • the reducing sugar according to the A1 step promotes the reduction reaction of vanadium pentoxide in the A2 step, and is a component necessary for making the reduction reaction solution obtained by performing the A2 step into a reaction solution having a good viscosity that can be stirred. It becomes. Further, the carbon source derived from the reducing sugar that was not used for reduction in the A2 step becomes a component that suppresses the oxidation of vanadium during the firing in the C step.
  • Examples of the reducing sugar according to the A1 step include the above-mentioned reducing sugars, and examples thereof include glucose, fructose, lactose, maltose, and sucrose.
  • lactose and sucrose are reaction precursors having excellent reactivity. Is preferable in that
  • the mixing amount of the reducing sugar is the molar ratio (C / V) of the carbon atom in terms of carbon atom to the V atom in vanadium pentoxide, preferably more than 0.6 and 2.0 or less. Particularly preferably, it is 0.7 or more and 1.7 or less.
  • the mixing amount of the reducing sugar in the A1 step is within the above range, it is excellent in economy, the reduction reaction solution can be made into a solution in the A2 step, and carbon source-attached particles to which the reducing sugar is uniformly adhered can be obtained. ..
  • the mixing amount of the reducing sugar in the A1 step is less than the above range, it is difficult to obtain a solution in which vanadium pentoxide is reduced in the A2 step, and the amount of the reducing sugar is insufficient in the A5 step. It tends to be difficult to obtain carbon source-adhered particles to which reducing sugars are uniformly attached, and if it exceeds the above range, it takes a large amount of time to prepare the amount of reducing sugars in step B, so industrially. Not advantageous.
  • the production history of vanadium pentoxide, phosphoric acid, and reducing sugars in the A1 step is not limited, but in order to produce high-purity vanadium lithium phosphate, the impurity content may be as low as possible. preferable.
  • Examples of the water solvent used in the A1 step include water or a mixed solvent of water and a hydrophilic organic solvent.
  • the order and mixing means for adding vanadium pentoxide, phosphoric acid and reducing sugar to the aqueous solvent are not particularly limited, and the mixed slurry (1) in which each of the above raw materials is uniformly dispersed is obtained. Will be done.
  • the A2 step is an A2 step in which the mixed slurry (1) obtained in the A1 step is heat-treated to form a solution, and at least vanadium pentoxide is subjected to a reduction reaction to form a solution to obtain a reduction reaction solution.
  • the present inventors have reacted with vanadium pentoxide and phosphoric acid in the presence of a reducing sugar to produce VOPO 4 or a water-containing substance thereof (for example, JP-A-2011-96640, JP-A-2011-96641). (Refer to Japanese Patent Application Laid-Open No.
  • the reduction reaction solution obtained in the A2 step includes VOPO 4 or a water-containing substance thereof, excess reduced sugar, dihydrogen phosphate ion ( H2 PO 4- ) , and the like. It is considered that the ions caused by the phosphoric acid of the above are dissolved in an aqueous solvent.
  • the temperature of the heat treatment in the A2 step is 60 to 100 ° C, preferably 80 to 100 ° C.
  • the temperature of the heat treatment in the step A is in the above range, it can be advantageously carried out under atmospheric pressure.
  • the temperature of the heat treatment in the step A is less than the above range, the reaction time becomes long, which is industrially disadvantageous, and if it exceeds the above range, a pressure vessel must be used, which is industrial. Not advantageous.
  • the completion of the reduction reaction can be confirmed by visually observing that the solution becomes a deep blue transparent liquid.
  • the time of the heat treatment in the A2 step is not particularly limited, and is generally 0.2 hours or more, preferably 0.5 to 4 hours. If the heat treatment is performed for a time in the above range, a satisfactory reduction reaction solution can be obtained. Can be done.
  • a solution containing lithium hydroxide is added to the reduction reaction solution, and lithium vanadium phosphorus represented by the general formula (1) is added.
  • This is a step of preparing a slurry (2) containing a composite oxide, lithium dihydrogen phosphate (LiH 2 PO 4 ), and an organic compound that produces carbon by thermal decomposition.
  • the lithium vanadium phosphorus composite oxide represented by the general formula (1) which is precipitated by adding a solution containing lithium hydroxide to the reduction reaction solution, is a collection of plate-shaped primary particles as secondary particles.
  • the body is formed, the average thickness of the plate-shaped primary particles determined by SEM observation is 1 to 20 nm, preferably 3 to 15 nm, and the average particle size of the secondary particles determined by SEM observation is 0. It is 5 to 20 ⁇ m, preferably 1 to 15 ⁇ m.
  • the average thickness of the plate-shaped primary particles of the lithium vanadium phosphorus composite oxide represented by the general formula (1) and the average particle diameter of the secondary particles are 200 particles arbitrarily extracted from SEM observation. It is obtained as the average value of.
  • the lithium vanadium phosphorus composite oxide represented by the general formula (1) produced in the A3 step is easily represented by the fine general formula (1) by being wet-pulverized with a media mill in the A4 step.
  • the lithium vanadium phosphorus composite oxide is pulverized to obtain a slurry (2) containing a fine lithium vanadium phosphorus composite oxide represented by the general formula (1).
  • the solution containing lithium hydroxide according to the A3 step is a solution in which lithium hydroxide is dissolved in water.
  • the concentration of lithium hydroxide in the solution containing lithium hydroxide is 5 to 20% by mass, preferably 10 to 15% by mass.
  • concentration of lithium hydroxide in the solution containing lithium hydroxide is within the above range, the operation of adding the solution to the reduction reaction solution becomes easy, and the production efficiency is controlled while controlling the heat generation associated with the addition of the solution containing lithium hydroxide. It is preferable in that it can enhance.
  • the amount of the lithium hydroxide-containing solution added is 0.70, which is the molar ratio (Li / P) of the Li atom in the lithium hydroxide-containing solution to the P atom in the reduction reaction solution obtained by performing the A2 step.
  • the addition amount is ⁇ 1.30, preferably 0.83 to 1.17.
  • the amount of the solution containing lithium hydroxide added is within the above range, it is preferable in that single-phase vanadium lithium phosphate can be easily obtained as the final product.
  • a lithium vanadium phosphorus composite oxide represented by the general formula (1), lithium dihydrogen phosphate (LiH 2 PO 4 ) and thermal decomposition A solution containing lithium hydroxide is added so that the pH of the "slurry (2)" containing an organic compound that produces carbon is 3 to 7, preferably 4 to 6, particularly preferably 4 to 5.
  • a single-phase lithium vanadium phosphate as a final product can be easily obtained.
  • the production history of lithium hydroxide is not limited, but it is preferable that the content of impurities is as low as possible in order to produce high-purity lithium vanadium phosphate.
  • the solution containing lithium hydroxide is added to the reduction reaction solution while keeping the reduction reaction solution obtained by performing the A2 step at 40 to 100 ° C., preferably 60 to 100 ° C.
  • the temperature at which the solution containing lithium hydroxide is added is less than the above range, the precipitation becomes non-uniform, while if it exceeds the above range, the operability is improved by boiling the solution containing lithium hydroxide. It tends to get worse.
  • the solution containing lithium hydroxide it is preferable to add the solution containing lithium hydroxide at a constant rate in that stable quality can be obtained.
  • the reaction between the reduction reaction solution and lithium hydroxide is completed, so that the aging reaction can be continued if necessary.
  • the temperature at which the aging reaction is carried out is preferably 40 to 100 ° C, preferably 60 to 100 ° C, in that particles having a uniform composition can be obtained.
  • the aging reaction time is not particularly limited, but usually, if the aging reaction is carried out for 0.5 hours or more, a satisfactory slurry (2) can be obtained.
  • the A4 step is a step of wet pulverizing the slurry (2) obtained by performing the A3 step with a media mill to prepare a wet pulverized slurry (3).
  • a wet pulverized slurry (3) containing a fine lithium vanadium phosphorus composite oxide represented by the general formula (1) can be obtained.
  • the reaction precursor obtained from this fine lithium vanadium phosphorus composite oxide represented by the general formula (1) has excellent reactivity, and is X-ray diffractically monophasic vanadium phosphate by firing in step C. Lithium is generated, and it becomes easy to obtain one with a sharp particle distribution.
  • the solid content concentration of the slurry (2) to be wet pulverized by the media mill is 10 to 40% by mass, preferably 15 to 30% by mass, which is good in operability and also has good operability. It is preferable in that the pulverization treatment can be performed efficiently. Therefore, after performing the A3 step, it is desirable to adjust the solid content concentration so that the concentration of the slurry (2) is within the above range, if necessary, and then perform the wet pulverization treatment in the A4 step.
  • the slurry (2) is wet-ground and pulverized by a media mill.
  • the lithium vanadium phosphorus composite oxide represented by the general formula (1) can be pulverized more finely, so that a reaction precursor having further excellent reactivity can be obtained.
  • Examples of the media mill include a bead mill, a ball mill, a paint shaker, an attritor, a sand mill, and the like, and a bead mill is preferable.
  • a bead mill is used, the operating conditions and the type and size of beads may be appropriately selected according to the size and processing amount of the apparatus.
  • a dispersant may be added to the slurry (2) to be wet pulverized.
  • the dispersant include various surfactants, ammonium polycarboxylic acid salts and the like.
  • the concentration of the dispersant in the slurry (2) to be wet-ground is preferably 0.01 to 10% by mass, preferably 0.1 to 5% by mass, from the viewpoint of obtaining a sufficient dispersion effect. ..
  • the average particle size of the solid content is 2.0 ⁇ m or less, preferably 0.1 to 1.5 ⁇ m, particularly preferably 0.2 to 0 by the laser scattering / diffraction method. It is preferable to carry out the process until it reaches 5.5 ⁇ m in that a reaction precursor having excellent reactivity can be obtained.
  • the A5 step is a step of spray-drying the wet pulverized slurry (3) obtained by performing the A4 step to obtain carbon source-adhered particles.
  • the carbon source-attached particles obtained by performing the A5 step are the carbon source-attached particles in the form of (ii) or the above (iii) in that they serve as a reaction precursor having excellent reactivity.
  • the average particle size of the primary particles of the lithium vanadium phosphorus composite oxide represented by the general formula (1) constituting the carbon source-adhered particles is the primary of the solid content in the wet pulverized slurry (3) obtained by performing the A4 step. It is about the same as the average particle size of the particles.
  • a method other than the spray drying method is also known as a method for drying the liquid, but in the present invention, this drying method is adopted based on the finding that it is advantageous to select the spray drying method.
  • the spray drying method in the A5 step the reduced sugar and lithium dihydrogen phosphate (LiH 2 PO) are uniformly formed on the particle surface of the lithium vanadium phosphorus composite oxide represented by the general formula (1). Since 4 ) is attached and a granulated product in a state in which particles of the lithium vanadium phosphorus composite oxide represented by the general formula (1) are densely packed can be obtained, a small amount of carbon is obtained by firing in step C. Therefore, it becomes easy to generate monophasic vanadium lithium phosphate by X-ray diffraction.
  • the liquid is atomized by a predetermined means, and the fine droplets generated by the atomization are dried to obtain a granulated product.
  • atomization of the liquid for example, there are a method using a rotating disk and a method using a pressure nozzle. Any method can be used in the A5 step.
  • the relationship between the size of the droplets of the atomized slurry and the size of the particles of the pulverized product contained therein affects stable drying and the properties of the obtained dried powder. Specifically, if the size of the raw material particles of the pulverized product is too small with respect to the size of the droplets, the droplets become unstable and it becomes difficult to dry them successfully. From this point of view, the size of the atomized droplet is preferably 5 to 100 ⁇ m, particularly preferably 10 to 50 ⁇ m. It is desirable to determine the amount of slurry supplied to the spray dryer in consideration of this viewpoint.
  • the drying temperature in the spray drying device shall be adjusted so that the hot air inlet temperature is adjusted to 180 to 250 ° C, preferably 200 to 240 ° C, and the powder temperature is adjusted to 90 to 150 ° C, preferably 100 to 130 ° C. However, it is preferable because it prevents the powder from absorbing moisture and facilitates the recovery of the powder.
  • the carbon source-adhered particles obtained by performing the A5 step are those having x of 2 in the formula of the lithium vanadium phosphorus composite oxide represented by the general formula (1) in the X-ray diffraction analysis by drying, and the particles in the formula. It may be a mixture with water of crystallization partially removed, and the mixture is also preferably used in the present invention.
  • Step B The step B according to the method for producing lithium vanadium phosphate of the present invention is a step of obtaining a reaction precursor by heat-treating the carbon source-adhered particles prepared in the step A in an oxygen atmosphere.
  • step B by performing step B and adjusting the amount of carbon atoms adhering to the particle surface of the particles adhering to the carbon source, phosphoric acid having a low specific surface area and a sharp particle distribution undergoes step C. Vanadium lithium can be produced.
  • the carbon content of the reaction precursor is 0.3 to 0.6, preferably 0.35 to 0.55, in terms of the molar ratio (C / V) of carbon atoms to V atoms in the reaction precursor. It is preferable to carry out the heat treatment until it becomes.
  • the carbon content of the reaction precursor is in the above range, reduction in the C step occurs sufficiently, and since the carbon content is an appropriate amount, the BET specific surface area of lithium vanadium phosphate becomes low.
  • the carbon content of the reaction precursor is less than the above range, the reduction in the C step is incomplete, and if it exceeds the above range, the carbon content becomes excessive and the BET specific surface area of lithium vanadium phosphate is high. Tend to be.
  • step B the heat treatment is performed in an oxygen-containing atmosphere.
  • the oxygen concentration in the atmosphere during the heat treatment is 5 vol% or more, particularly preferably 10 to 30 vol%, so that the organic compound that produces carbon by thermal decomposition is oxidized with high efficiency and carbon is used. It is preferable in that the content can be easily adjusted within the above range.
  • the temperature of the heat treatment is preferably 270 to 370 ° C, particularly preferably 290 to 360 ° C, because the carbon content can be easily controlled. If the temperature of the heat treatment is lower than the above range, it becomes difficult to reduce the carbon atom content, and if it exceeds the above range, the carbon content decreases at once, so that it tends to be difficult to prepare the carbon content.
  • step B the carbon content can be reduced as the heat treatment time becomes longer. Therefore, it is preferable to perform the heat treatment over a sufficient period of time so that the carbon content is within the above range.
  • the time is 8 hours or more, the vanadium lithium phosphate obtained after the C step becomes a hard sintered body, and it becomes difficult to recover it as a powder.
  • a satisfactory reaction precursor can be obtained, usually in a heat treatment time of 1 hour or more and less than 8 hours, preferably 2 to 5 hours.
  • the reaction precursors obtained by performing step B are the lithium vanadium phosphorus composite oxide represented by the general formula (1) in the X-ray diffraction analysis by the heat treatment in step B, and other than that, phosphoric acid.
  • lithium dihydrogen LiH 2 PO 4
  • amorphous phosphorus compound LiH 2 PO 4 , LiPO 3 , etc.
  • lithium phosphate Li 3 PO 4
  • the step C according to the method for producing lithium vanadium phosphate of the present invention is a step of calcining the reaction precursor obtained by performing the step B at 500 to 1300 ° C. to obtain a single-phase vanadium lithium phosphate by X-ray diffraction. Is.
  • the firing temperature in step C is 500 to 1300 ° C, preferably 600 to 1000 ° C. If the calcination temperature in step C is less than the above range, the calcination time until it becomes a single phase becomes long, and if it exceeds the above range, vanadium lithium phosphate is melted.
  • the firing atmosphere in step C is an inert gas atmosphere or a reducing atmosphere because it prevents oxidation of vanadium and prevents melting.
  • the inert gas used in the step C is not particularly limited, and examples thereof include nitrogen gas, helium gas, and argon gas.
  • the firing time is not particularly limited, and if firing is generally performed for 2 hours or more, particularly 3 to 24 hours, single-phase vanadium lithium phosphate can be obtained by X-ray diffraction.
  • step C the vanadium lithium phosphate obtained by firing may be subjected to a plurality of firings, if necessary.
  • a Me source (Me is an atomic number other than V). 11 or more metal elements or transition metal elements are shown.)
  • the Me source is contained in the carbon source-attached particles, or the carbon source-attached particles are contained.
  • the following vanadium lithium phosphate is doped with a Me element to obtain a substance contained therein.
  • a method of containing the Me source in the particles adhering to the carbon source a method of adding the Me source at any time between the A1 step and the A5 step before spray drying can be mentioned.
  • the Me element exists in the Li-site and / and V-site of vanadium lithium phosphate represented by the general formula (2).
  • Me in the Me source is a metal element or transition metal element having an atomic number of 11 or more other than V, and preferred Me elements are Sr, Ba, Sc, Y, Hf, Ta, W, Ru, Os, Ag, and the like. Zn, Si, Ga, Ge, Sn, Bi, S, Se, Te, Cl, Br, I, Na, K, Mg, Ca, Al, Mn, Co, Ni, Fe, Ti, Zr, Bi, Cr, Examples thereof include Nb, Mo, Cu and the like, and these may be used alone or in combination of two or more.
  • the Me source examples include oxides having Me elements, hydroxides, halides, carbonates, nitrates, carbonates, organic acid salts and the like.
  • the Me source When the Me source is mixed between the A1 step and the A5 step before the spray drying, it may be dissolved in the slurry and exist, or it may be present as a solid substance.
  • Me as a solid substance in a slurry (2) containing a lithium vanadium phosphorus composite oxide represented by the general formula (1), lithium dihydrogen phosphate (LiH 2 PO 4 ) and an organic compound that produces carbon by thermal decomposition.
  • a source it is preferable to use a Me source having an average particle size of 100 ⁇ m or less, preferably 0.1 to 50 ⁇ m, in that a reaction precursor having excellent reactivity can be obtained.
  • the Me source is mixed before the spray drying in the A1 step to the A5 step, the mixing amount of the Me source depends on the type of the Me element to be doped, but in many cases, the slurry (2).
  • the total molar ratio of V atoms to Me atoms ((Me + V) / P) with respect to the P atoms in the mixture is 0.5 to 0.80, preferably 0.60 to 0.73, and the molar ratio of Me atoms to V atoms is high.
  • a mixing amount having a ratio (Me / V) of greater than 0 and 0.45 or less, preferably greater than 0 and 0.1 or less is preferable.
  • the vanadium lithium phosphate obtained by performing the method for producing vanadium lithium phosphate of the present invention is a monophasic vanadium lithium phosphate in X-ray diffraction, and has a BET specific surface area of 10.0 m 2 / g. Hereinafter, it is preferably 3.0 to 8.0 m 2 / g. Further, the vanadium lithium phosphate obtained by the method for producing vanadium lithium phosphate of the present invention has an average particle size of primary particles obtained by SEM observation of 0.3 to 1.5 ⁇ m, preferably 0.4 to 1. It is preferable that the size is 2 ⁇ m and the particle size distribution is sharp.
  • the carbon content of vanadium lithium phosphate obtained by the method for producing vanadium lithium phosphate of the present invention is 0.01 to 1.0% by mass, preferably 0.01 to 0.5% by mass.
  • the obtained vanadium lithium phosphate may be further crushed or crushed as necessary, and further classified.
  • step C it is mixed with conductive carbon or the particle surface is coated with conductive carbon and used as a vanadium lithium phosphate carbon composite. You can also do it.
  • vanadium lithium phosphate obtained by the method for producing lithium vanadium phosphate of the present invention is used in a positive electrode active material such as a lithium secondary battery and an all-solid-state battery.
  • step B the carbon adhering to the surface of the lithium vanadium phosphorus composite oxide represented by the general formula (1) is reduced, and the carbon atom with respect to the vanadium atom is reduced.
  • the molar ratio (C / V) of can be adjusted appropriately. Therefore, in the method for producing vanadium lithium phosphate of the present invention, the vanadium lithium phosphate obtained through the C step has a rounded particle surface. As a result, the specific surface area of vanadium lithium phosphate can be reduced in the method for producing vanadium lithium phosphate of the present invention.
  • step A lithium dihydrogen phosphate (LiH 2 PO 4 ) and a lithium vanadium phosphorus composite oxide to which an organic compound that produces carbon by thermal decomposition is attached are attached.
  • the average particle size of the primary particles is 2.0 ⁇ m or less, preferably 0.1 to 1.5 ⁇ m, the presence of coarse particles is extremely reduced, and therefore, vanadium lithium phosphate obtained through steps B and C.
  • the particle distribution of can be sharpened.
  • Example 1 ⁇ A1 process> Put 2 L of ion-exchanged water in a 5 L beaker, put 605 g of 85% phosphoric acid, 320 g of vanadium pentoxide and 96 g of lactose (milk sugar) into it, and stir at room temperature (25 ° C) to obtain an ocher-colored mixed slurry (1). Obtained.
  • a lithium hydroxide solution was prepared by dissolving 220 g of lithium hydroxide / water salt in 1.5 L of ion-exchanged water. While keeping the reaction solution in the temperature range of 70 to 80 ° C., the lithium hydroxide solution was added to the reaction solution at a constant rate in 40 minutes to obtain a slurry (2) containing a precipitate. Subsequently, the slurry was allowed to cool to room temperature (25 ° C.). After sampling the precipitate, it was filtered, dried, and XRD-measured. As a result, it coincided with the peak of LiVOPO 4.2H 2O .
  • the average thickness of the plate-shaped primary particles determined by SEM observation was 5 nm, and the average particle diameter of the secondary particles determined by SEM observation was 6 ⁇ m.
  • the X-ray diffraction pattern of the obtained LiVOPO 4.2H 2O is shown in FIG. 1, and the SEM photograph is shown in FIGS. 2 (1000 times) and 3 (5000 times).
  • the average thickness of the primary particles of LiVOPO 4.2H 2O and the average particle diameter of the secondary particles were determined as the average value of 200 arbitrarily extracted particles in SEM observation.
  • the slurry (3) after wet pulverization was supplied to a spray drying device having an outlet temperature set to 120 ° C. to obtain carbon source-adhered particles.
  • the average particle size (secondary particle size) obtained from the SEM observation of the carbon source-attached particles was 20 ⁇ m.
  • X-ray diffraction measurement was performed using the obtained carbon source-attached particles as a radiation source, and the carbon source-attached particles contained LiVOPO 4.2H 2 O and LiH 2 PO 4 . See FIG. 4).
  • the residual carbon content of the obtained carbon source-adhered particles was determined as the content of C atoms by measuring with a TOC total organic carbon meter (TOC-5000A manufactured by Shimadzu Corporation). The amount of residual carbon was 4.1% by mass.
  • the average particle size (secondary particle size) of the carbon source-attached particles was determined as the average value of 200 arbitrarily extracted particles in SEM observation.
  • Step B> The obtained carbon source-adhered particles were placed in a mullite saggar and heat-treated at 300 ° C. for 4 hours in an air atmosphere (oxygen concentration 20 Vol%) to obtain a reaction precursor.
  • a reaction precursor As a result of X-ray diffraction analysis of the obtained reaction precursor, it was found to contain LiVOPO 4 and a trace amount of Li 3 PO 4 peak. Although no clear peak of LiH 2 PO 4 was detected by X-ray diffraction analysis, it is probable that LiH 2 PO 4 became an amorphous phosphorus compound (LiH 2 PO 4 , LiPO 3 ).
  • the residual carbon content of the obtained reaction precursor was determined as the C atom content by measuring with a TOC total organic carbon meter (TOC-5000A manufactured by Shimadzu Corporation). The amount of residual carbon was 3.0% by mass.
  • step B the reaction was carried out in the same manner as in Example 1 except that the heat treatment time was 2.5 hours to obtain a vanadium lithium phosphate sample. Moreover, as a result of X-ray diffraction analysis of the obtained vanadium phosphate lithium sample, it was confirmed that all of them were single-phase vanadium lithium phosphate (Li 3 V 2 (PO 4 ) 3 ) (see FIG. 6). This was used as a vanadium lithium phosphate sample.
  • Example 1 A reaction was carried out in the same manner as in Example 1 except that step B was not performed to obtain a vanadium lithium phosphate sample. Moreover, as a result of X-ray diffraction analysis of the obtained vanadium phosphate lithium sample, it was confirmed that all of them were single-phase vanadium lithium phosphate (Li 3 V 2 (PO 4 ) 3 ). This was used as a vanadium lithium phosphate sample.
  • the carbon content indicates the molar ratio of carbon atoms in terms of carbon atoms to V atoms in the particles attached to the carbon source, and the molar ratio of carbon atoms in terms of carbon atoms to V atoms in the reaction precursor. ..
  • Example 1 Average particle size of secondary particles D 50 was determined by laser scattering / diffraction method. In addition, D 90 was also measured. Moreover, the particle size distribution map of the vanadium lithium phosphate sample obtained in Example 1 is shown in FIG. (Amount of residual carbon) It was measured with a TOC total organic carbon meter (TOC-5000A manufactured by Shimadzu Corporation).

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Abstract

Le but de la présente invention est de fournir une méthode de fabrication de phosphate de lithium-vanadium, ladite méthode permettant l'acquisition d'un produit qui est monophasique par diffraction des rayons X, a une surface spécifique faible, c'est-à-dire une surface spécifique BET supérieure ou égale à 10 m2/g et a une distribution de particules nette.　L'invention concerne une méthode de fabrication de phosphate de lithium-vanadium ayant une structure NASICON, ladite méthode étant caractérisée en ce qu'elle comprend : une étape A de préparation de particules fixées à une source de carbone dans lesquelles du dihydrogène phosphate de lithium (LiH2PO4) et un composé organique capable de générer du carbone lors de la décomposition thermique sont fixés à la surface de particules d'oxyde composite de phosphore de lithium-vanadium représenté par la formule générale (1) : LiVOPO4xH2O (x étant un nombre entier de 0 à 2), dont les particules primaires ont une taille moyenne de particule inférieure ou égale à 2,0 µm ; une étape B de chauffage des particules fixées à une source de carbone dans une atmosphère contenant de l'oxygène pour donner un précurseur de réaction ; et une étape C de cuisson du précurseur de réaction dans une atmosphère de gaz inerte ou une atmosphère réductrice à 500 à 1300°C pour donner du phosphate de lithium-vanadium.
PCT/JP2021/047758 2020-12-28 2021-12-23 Méthode de fabrication de phosphate de lithium-vanadium WO2022145323A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011096641A (ja) * 2009-09-29 2011-05-12 Tdk Corp 活物質の製造方法及びリチウムイオン二次電池の製造方法
WO2014006948A1 (fr) * 2012-07-04 2014-01-09 富士重工業株式会社 Dispositif de stockage électrique du type comprenant un solvant non aqueux
JP2017160107A (ja) * 2016-03-08 2017-09-14 日本化学工業株式会社 リン酸バナジウムリチウムの製造方法
JP2019034877A (ja) * 2017-08-17 2019-03-07 日本化学工業株式会社 リン酸バナジウムリチウムの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011096641A (ja) * 2009-09-29 2011-05-12 Tdk Corp 活物質の製造方法及びリチウムイオン二次電池の製造方法
WO2014006948A1 (fr) * 2012-07-04 2014-01-09 富士重工業株式会社 Dispositif de stockage électrique du type comprenant un solvant non aqueux
JP2017160107A (ja) * 2016-03-08 2017-09-14 日本化学工業株式会社 リン酸バナジウムリチウムの製造方法
JP2019034877A (ja) * 2017-08-17 2019-03-07 日本化学工業株式会社 リン酸バナジウムリチウムの製造方法

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