TW201332203A - Carbon-deposited alkali metal oxyanion electrode material and process for preparing same - Google Patents

Abstract

The present invention relates to a process for the synthesis of a carbon-deposited alkali metal oxyanion cathode material comprising particles, wherein said particles carry, on at least a portion of the particle surface, carbon deposited by pyrolysis, said process comprising a dry high-energy milling step performed on precursors of said carbon-deposited alkali metal oxyanion prior to a solid-state thermal reaction.

Description

Alkali metal oxyanion electrode material for carbon deposition and preparation method thereof

The present invention relates to the field of electrode materials, and more particularly to alkali metal oxyanion electrode materials for carbon deposition and methods for their preparation.

The positive electrode of a lithium ion battery typically includes an electrochemically active cathode material, a binder and carbon particles as an electrically conductive additive. In the circulation of the battery, an increase in the electrode resistance of this positive electrode is generally observed, and this increase in resistance is detrimental. It has been suggested that as the cycle increases, the cathode material will show a change in the volume/expansion/contraction of the unit cell due to the insertion/de-insertion of the basic cation at the cathode material. It is believed that these changes induce loss of the conductive network in contact with the cathode material and/or breakage of the cathode material particles. As a result, the capacity of the battery is reduced and the battery life is shortened.

In order to solve this problem, it has been proposed to fine tune the group of cathode materials to reduce the change in the volume of the battery unit accompanying the insertion/de-insertion of the alkaline cation.

Publication WO 2009/096255 (transfer to Sharp Corp.), this publication incorporated herein by reference, describes a _{Li y K a Fe 1-x} X x PO ₄ cathode material of which this change has reduced the cell volume Where X represents at least one element selected from the 2nd to the 13th, a and x are 0 < a ≦ 0.25, 0 ≦ x ≦ 0.25, and y is (1-a).

Publication WO 2010/134579 (transfer to Sharp Corp.), this publication incorporated herein by reference, describes the _{LiFe 1-x M x P 1} -y Si y O 4 phosphate of an alkali metal silicate materials of the general formula Wherein the average valence of Fe is +2 or above, M is an element having a valence of +2 or more, and at least a group consisting of Zr, Sn, Y and Al; the valence of M and the average of Fe The valence is different; 0 < x ≦ 0.5, and y = x * (the valence of M - 2) + (1 - x) * (the average valence of Fe - 2).

JP 2011/77030 (transferred to Sharp Co., Ltd.), which is hereby incorporated by reference, describes the general formula Li _(1-a) A _a Fe _(1-xb) M _(xc) P _{(1-y )} Si _y O ₄ phosphate of an alkali metal silicate material, wherein A is at least one optional consisting Na, K, Fe and the group consisting of M in the element. The average valence of Fe is +2 or more, M is an element of valence +2 or more, and at least one is selected from the group consisting of Zr, Sn, Y and Al; the average valence of M and the average valence of Fe Different, 0<a≦0.125, the total number of moles of Na and K in A is d, the number of moles of Fe in A is b, and the number of moles of M in A is c, a=b+c+d, 0<x≦0.5 and 0<y≦0.5.

A feature of the present invention is an alkali metal oxyanion cathode material for carbon deposition, and a method of obtaining the cathode material.

Another feature of the invention is a method of synthesizing a carbon-deposited alkali metal oxyanion electrode material comprising at least one thermal step wherein a pair of carbon-deposited alkali metal oxyanions are carried out prior to at least one thermal step The electrode material precursor is subjected to a dry high energy milling step.

Another feature of the invention is the method of the invention for synthesizing a carbon-deposited alkali metal oxyanion cathode material, wherein the cathode material comprises particles which are at least in part of the surface of the particle Thermal decomposition of deposited carbon, this method includes carbon sinking prior to the first solid state thermal reaction The precursor of the alkali metal oxyanion cathode is subjected to a first dry high energy milling step to produce a first solid thermal reaction product; and a second dry high energy milling step is performed on the product prior to the second solid thermal reaction .

These and other features of the present invention will become more apparent from the description of the embodiments of the invention.

The inventors of the present invention were surprised and unpredictably found in the synthesis of a specific carbon-deposited alkali metal phosphonium silicate, C-LiFe _0.9 Zr _0.01 (PO ₄ ) _0.9 (SiO ₄ ) _0.1 R&D. A method of obtaining an alkali metal oxyanion by carbon deposition, such as a method of C-LiFePO ₄ . That is, the wet method, the solid state thermal process, and the polyol process all produce low quality materials.

The present invention relates to a carbon-deposited alkali metal oxyanion cathode material and a method of obtaining the cathode material. In a non-limiting embodiment, the carbon-deposited alkali metal oxyanion cathode material of the present invention can provide a cathode having energy A property that prevents and/or minimizes the expansion/contraction of the cathode. Therefore, the internal resistance of the battery can be prevented from increasing or minimizing as the number of cycles of charging/discharging increases. Thus, a cathode active material can be produced which allows the production of the battery to outperform the conventional ones in terms of safety and cost, and has a long life.

In one non-limiting embodiment, the present invention is directed to a method of synthesizing carbon-deposited alkali metal oxyanion electrode materials comprising a dry high energy milling step of the reactants performed prior to at least one thermal step.

In another non-limiting embodiment, the invention relates to the synthesis of a carbon a method of depositing an alkali metal oxyanion electrode material, the method comprising performing a first dry high energy milling step on a carbon deposition alkali metal oxyanion electrode material prior to a first thermal step, and a first in the first A second dry high energy milling step of the product after the thermal step, wherein the second high energy milling step is performed prior to the second thermal step.

In another non-limiting embodiment, the method includes thermally decomposing a carbon source to provide a carbon deposition over the basic oxyanion material and/or its precursor. In a non-limiting embodiment, this thermal decomposition can be carried out during the first thermal step and/or the second thermal step described herein. In another non-limiting embodiment, an optional rapid thermal decomposition is performed after the synthesis reaction to improve carbon deposition graphitization.

The deposition of carbon can exhibit a somewhat uniform, adherent and non-powder deposit. In a non-limiting embodiment, this carbon deposit constitutes up to 15% of the total weight of the material. In another embodiment, this carbon deposit comprises from 0.5 to 5 wt% of the total weight of the material. The carbon deposition by thermal decomposition of the carbon source can be deposited on top of the final product or deposited in its precursors, as described, for example, in WO 02/027824, WO 02/027823, CA 2,307,119, WO 2011/072397, US 2002/ 195,591 and US Patent Application Publication No. 2004/157126, the entireties are hereby incorporated by reference.

In a non-limiting embodiment, which is carried out on an industrial scale, the method of the present invention can be controlled continuously or batchwise in a rotary kiln, push kiln, fluidized bed, belt driven kiln. Composition and circulation of the gas atmosphere. The use of large batch kiln, such as coal kilns, is not excluded. The skilled person, from the above description, knows that any suitable replacement of the reactor, and not It is within the scope of the invention.

In the field of mechanochemistry, the term "high energy grinding" is often used to emphasize that the characteristics of the grinding equipment (grinder) used are for the preparation of micron and nanometer-sized solids. See (P. Balaz, Mechanochemistry in Nanoscience and Minerals Engineering, Chapter 2, Springer-Verlag Berlin Heidelberg 2008; De Castro and Mitchell, Synthesis, Functionalization and surface treatment of nanoparticles, Chapter 1, American Scientific Publishers 2002; Zoz, Ren, Reichardt and Benz, High Energy Milling/Mechanical Alloying/Reactive Milling,Zoz GmbH, available on Zoz website at "http://www.zoz-group.de/zoz.engl/zoz.main/pdf_content/publications/v14.pdf ") These materials are hereby incorporated by reference.

High-quality grinding of precursors can be carried out in a wide variety of devices, such as, but not limited to, high energy ball mills, pulverizing mixing mills, ball mills, drum/ball mills, rocking mills, mixing ball mills, mixing balls. Grinding machines, vertical and horizontal abraders and equivalent grinding devices. A person skilled in the art can confirm appropriate equipment without undue experimentation and without departing from the scope of the invention, high energy grinding equipment is commercially available, for example, but not limited to SPEX CertiPrep Group LLC (8000M Mixer/Mill) ^® , etc.), Zoz GmbH (Simoloyer ^® ), Retsch GmbH (surrounding ball mill PM 200/400/400 MA) and Union Process Inc. (Attritor ^® ).

In a non-limiting embodiment, the high energy milling apparatus is selected to be free of reactant contamination, particularly metal contamination. In order to perform metal-free grinding, the abrasive parts of the apparatus are preferably made of ceramic or coated with ceramics, such as, but not limited to, alumina, zirconium silicate, zirconia, yttria stabilized by yttrium or yttria, Tantalum nitride, tungsten carbide or tantalum carbide. From this description, the skilled artisan will be able to identify any optional, suitable abrasive elements of the apparatus without departing from the scope of the invention.

In a non-limiting embodiment, the high energy mill is a high energy ball mill.

In a non-limiting embodiment, the method of the present invention comprises a first solid state thermal step operating at a temperature range selected from the group consisting of between about 200 ° C and 600 ° C, at about 250 ° C and about 600 Between °C, between about 275 ° C and about 600 ° C, between about 300 ° C and about 600 ° C, between about 325 ° C and about 600 ° C, between about 350 ° C and about 600 ° C, at about Between 375 ° C and about 600 ° C, between about 400 ° C and about 600 ° C, between about 200 ° C and about 500 ° C, between about 250 ° C and about 450 ° C, at about 300 ° C and about 400 ° C between. Those skilled in the art can select any suitable temperature within the scope of the present invention without departing from the spirit of the invention.

In a non-limiting embodiment, the method of the present invention comprises a second solid state thermal step operating at a temperature range selected from the group consisting of between about 400 ° C and about 800 ° C at about 450 ° C. Between about 800 ° C, between about 500 ° C and about 800 ° C, between about 525 ° C and about 800 ° C, between about 550 ° C and about 800 ° C, between about 575 ° C and about 800 ° C, Between about 600 ° C and about 800 ° C, between about 400 ° C and about 700 ° C, at about 450 Between °C and about 650 ° C, between about 500 ° C and about 600 ° C. Those skilled in the art can select any suitable temperature within the scope of the present invention without departing from the spirit of the invention.

In a non-limiting embodiment, the method of the present invention comprises a first high energy milling step that is carried out in a time range selected from the group consisting of from about 5 minutes to about 4 hours, from about 10 minutes to about 4 hours. , in about 30 minutes to about 4 hours, in about 60 minutes to about 4 hours, in about 90 minutes to 4 hours, in about 120 minutes to about 4 hours, in about 150 minutes to 4 hours, in about 180 minutes to about 4 hours, from about 210 minutes to about 4 hours, from about 230 minutes to about 4 hours. The skilled person can arbitrarily select a time range within the scope of the present invention without departing from the spirit of the invention.

In a non-limiting embodiment, the method of the present invention includes a second high energy milling step that is carried out for a time range selected from about 5 minutes to about 4 hours, from about 10 minutes to about 4 hours, From about 30 minutes to about 4 hours, from about 45 minutes to about 4 hours, from about 60 minutes to about 4 hours, from about 90 minutes to about 4 hours, from about 120 minutes to about 4 hours, from about 150 minutes to About 4 hours, from about 180 minutes to about 4 hours, from about 210 minutes to about 4 hours, or from 230 minutes to about 4 hours. The skilled person can arbitrarily select a time range within the scope of the present invention without departing from the spirit of the invention.

In a non-limiting embodiment, the process of the present invention involves the subsequent rapid thermal processing of a pair of oxyanion end products to improve graphitization of carbon deposition while avoiding partial decomposition of the oxyanion. The rapid thermal processing can be operated at a temperature ranging from about 650 ° C to about 900 ° C. Between about 700 ° C and about 900 ° C, between about 750 ° C and about 900 ° C, between about 800 ° C and about 900 ° C, between about 825 ° C and about 900 ° C, or about 850 ° C Between approximately 900 ° C and about 900 ° C. Any suitable temperature range falling within the scope of the invention can be arbitrarily selected by those skilled in the art without departing from the scope of the invention.

The rapid thermal processing can be operated within a time range selected from about 10 seconds to about 10 minutes, from about 30 seconds to about 10 minutes, from about 1 minute to about 10 minutes, from about 2 minutes to about 10 minutes. From about 3 minutes to about 10 minutes, from about 4 minutes to about 10 minutes, or from about 5 minutes to about 10 minutes. Those skilled in the art can select any suitable time frame or fall within the above time range without departing from the spirit of the invention.

In a non-limiting embodiment, the high energy milling step described herein produces a substantially amorphous product. This substantially amorphous product then becomes a substantially crystalline product after the thermal reaction is carried out at a sufficiently high temperature as described herein. Those skilled in the art can select an appropriate temperature without departing from the scope of the invention.

In a non-limiting embodiment, the first thermal reaction and/or the second high energy milling step described herein produces a substantially amorphous product which is then described herein at a relatively high temperature. 2 After the thermal reaction, it becomes a substantially crystalline product. One skilled in the art can select an appropriate temperature without departing from the scope of the invention.

In a non-limiting embodiment, the oxyanion described herein is a phosphonium silicate.

In a non-limiting embodiment, the method of the present invention includes a carbon sink a precursor reaction of an alkali metal or phosphonium citrate cathode material, wherein the precursor comprises: a) at least one source compound of an alkali metal; b) at least one metal-derived compound selected from Fe and/or Mn; c) a source compound of at least one metal M', wherein M' is a final product of a metal of 2+ or more; d) a source compound of at least one P, if P is not present in any of the source compounds; and e) at least one Si Source compound, if Si is not present in any source compound, f) at least one carbon source compound.

In a non-limiting embodiment, the source compound of carbon is present prior to the first thermal step described herein and/or prior to the second thermal step described herein.

In one non-limiting embodiment, the source compounds described herein are entirely present in the first thermal step described herein, or any portion thereof, for the first and second thermal steps described herein. In other words, those skilled in the art will appreciate that the method can include the addition of one or more of the source compounds described herein during or prior to the second high energy milling and/or second thermal step.

In a non-limiting embodiment, the source compound b) is partially or up to 15% selected from one or other metals of Ni and Co, and/or one or more of the non-Ni or Co valence or equivalent. The atom of the metal; and/or the atom of Fe(III) is substituted.

In another non-limiting embodiment, the source compound b) is partially Up to 15% of the choice from Ni and Co; and / or more than one different price or the same price from Mg, Mo, Mn, V, Pb, Sn, Nb, Ti, Al, Ta, Ge, La, Y, Yb Substituting atoms of Cu, Ag, Sm, Ce, Hf, Cr, Zr, Bi, Zn, Ca, B and W, and/or Fe(III).

In the present invention, "one or more" as used herein is used by those skilled in the art to refer to a metal that is suitable for one or more of the battery art. For example, but not limited to, "one or more metals" as used herein refers to a metal of the second, third, fourth, fifth or sixth period of the periodic table, which is suitable for use in a battery without departing from the invention. The scope. In another embodiment, "one or more metals" as described herein may be selected from at least one element from the second to thirteenth periodic elements without departing from the scope of the invention. In another embodiment, the "one or more metals" described herein may be selected from Mg, Mo, Mn, V, Co, Ni, Pb, Sn, Nb, Ti, Al without limitation. , Ta, Ge, La, Y, Yb, Cu, Ag, Sm, Ce, Hf, Cr, Zr, Bi, Zn, Ca, B and W. The skilled person can select an appropriate "one or more metals" from the above without departing from the scope of the invention.

In a non-limiting embodiment, the carbon-deposited alkali metal phosphonium nitrate of the present invention is characterized in that the cathode material comprising the material exhibits a unit cell (lattice) volume accompanying alkali cation insertion/deinsertion. Reduce the change. One feature is that the reduction in volume change per unit cell (lattice) can be represented by the volume change of a cationized (e.g., lithiated) product by a decationized (e.g., delithiated) product. In a non-limiting embodiment, the unit cell (lattice) volume of a particular product can be evaluated by XRD measurement of the product. In a non-limiting practice of the concept, the inventors measured the unit cell (lattice) volume of a specific product with respect to the unit cell (lattice) volume of C-LiFePO ₄ as a parameter to evaluate the performance of the synthesis method. For example, a final product having an undue increase in unit cell volume represents a low purity and/or insufficient replacement and/or a cathode material in the presence of M' in the phosphonate matrix.

In a non-limiting embodiment, the source compound a) is a basic compound selected from, for example, the group consisting of lithium oxide, sodium oxide, lithium hydroxide, sodium hydroxide, hydrogen. Potassium oxide, lithium carbonate, sodium carbonate, Li ₃ PO ₄ , Na ₃ PO _{4 ,} K ₃ PO _{4 ,} hydrogen phosphate LiH ₂ PO ₄ , LiNaHPO ₄ , LiKHPO ₄ , NaH ₂ PO ₄ , KH ₂ PO ₄ , Li ₂ HPO ₄ , lithium, sodium, potassium, phosphorus - bit position or polysilicate, lithium sulfate, sodium sulfate, potassium sulfate, lithium oxalate, sodium oxalate, potassium oxalate, lithium acetate, sodium acetate, potassium acetate, and mixtures thereof . Compounds a) may be selected from any suitable source from the above without departing from the scope of the invention.

In a non-limiting embodiment, the source compound b) comprises a compound selected from, for example, iron, iron (III) oxide or magnetite, trivalent iron phosphate, lithium oxyphosphate or iron, or trivalent nitric acid. Iron, ferrous phosphate, hydrated or non-hydrated laponite Fe ₃ (PO ₄ ) ₂ , iron acetate (CH ₃ COO) ₂ Fe, iron sulfate (FeSO ₄ ), iron oxalate, iron (III) nitrate, ferrous nitrate (II), FeCl ₃ , FeCl ₂ , FeO, ammonium iron phosphate (NH ₄ FePO ₄ ), Fe ₂ P ₂ O ₇ , ferrocene or a mixture thereof; and or manganese MnO, MnO ₂ , manganese acetate, Manganese oxalate, manganese (III) acetylacetonate, manganese (II) acetylacetonate, manganese (II) chloride, MnCO ₃ , manganese sulfate, manganese nitrate, manganese phosphate, manganocene or One of its mixtures. Those skilled in the art can arbitrarily select an appropriate source compound b) without departing from the scope of the invention.

In a non-limiting embodiment, the source compound c) is a metal-derived compound which is a metal having a valence electron of 2+ or more in the final product. For example, it is a source compound of a metal selected from the group consisting of Zr ⁴⁺ , Ti ⁴⁺ , Nb ⁴⁺ , Mo ⁴⁺ , Ge ⁴⁺ , Ce ⁴² and Sn ⁴⁺ , and/or a a source compound of a metal selected from the group consisting of Al ³⁺ , Y ³⁺ , Nb ³⁺ , Ti ³⁺ , Ga ³⁺ , Cr ³⁺ and V ³⁺ , and/or a metal-derived compound. The metal is selected from the group consisting of Ta ⁵⁺ and Nb ⁵⁺ , and or a source compound of a metal selected from the group consisting of Zn ²⁺ and Ca ²⁺ . For example, in a specific example of a 2+ valence source compound, the source compound c) may be selected from zinc acetate, zinc chloride, zinc acetylacetonate, zinc nitrate, zinc sulfate, zinc stearate, calcium carbonate, calcium hydroxide. , calcium acetate or a mixture thereof. For example, in a specific example of a source compound of 3+ valence, the source compound c) may be selected from cerium (III) 2-ethylhexanoate, cerium (III) acetate, cerium (III) acetyl sulfonate, cerium nitrate (III). ), aluminum acetate, aluminum isopropoxide, aluminum acetylacetonate, aluminum ethoxide, aluminum metaphosphate, aluminum monostearate or a mixture thereof. For example, in a specific example of a source compound of 4+ valence, the source compound c) is selected from the group consisting of zirconium hydroxide hydroxide, zirconium alkoxide, zirconium acetyl acetonate (V), zirconium (IV) ethoxide, zirconium hydroxyphosphate (IV). ), zirconium (IV) silicate, titanium (IV) 2-ethylhexoxide, titanium (IV) butoxide (IV), tin (IV) acetate or a mixture thereof. For example, in a special case of a source compound of 5+ valence, the source compound c) may be selected from butoxy oxime (V), ethoxylated oxime (V), phenoxy oxime (V) or a mixture thereof. Those skilled in the art will be free to select the appropriate source compound c) without departing from the scope of the invention.

In a non-limiting embodiment, the source compound d) is a phosphorus compound selected from, for example, phosphoric acid and its esters, hydrogen phosphate, M ₃ PO ₄ wherein M is selected from at least one of Li, Na and K. . Monoammonium phosphate or diammonium phosphate, ferric triphosphate or ammonium manganese phosphate (NH ₄ MnPO ₄ ), MnHPO ₄ , Fe ₂ P ₂ O ₇ . The skilled artisan will be free to select the appropriate source compound d) without departing from the scope of the invention.

In a non-limiting embodiment, the source compound e) is a compound of ruthenium selected from, for example, an organic ruthenium, a decyl alkoxide, a tetraethyl orthosilicate, a nano-sized SiO ₂ , Li ₂ SiO ₃ , Li ₄ SiO ₄ or a mixture thereof. Those skilled in the art can arbitrarily select an appropriate source compound e) without departing from the scope of the invention.

In a non-limiting embodiment, all sub-combinations of the source compounds of a) to e) may additionally be sources of oxygen and/or sources of at least two elements.

The skilled artisan can determine the ratio of the compounds of each source in accordance with the desired carbon-deposited alkali metal oxyanion product without departing from the spirit of the invention. For example, in the case of carbon-deposited alkali metal phosphonate products, the source compound is selected to produce a cathode metal having an alkali metal: M:M':P:Si ratio of about 1:0.7 to 1:>0 to 0.3:>0.7 to 1:>0 to 0.3, where "0" is not including 0, but means "greater than 0".

The deposition of carbon on the surface of the alkali metal oxyanion or its precursor is obtained by thermally decomposing the source compound of carbon f). The deposition of carbon on the surface of the oxyanion or its precursor can be obtained by thermally partitioning or converting a source compound of a very different carbon. In a non-limiting embodiment, the source compound of carbon is a liquid or gaseous compound, a compound which can be used in the form of a solution or a liquid solvent, or a compound which changes to a liquid or gaseous state upon thermal decomposition, how much to be The compound is coated in the mixture. The carbon source compound may be selected from, for example, liquid, solid or gaseous hydrocarbons and derivatives thereof (especially polycyclic aromatics such as coal tar or bitumen), perylene and its derivatives, polyhydroxy compounds. (such as sugars and carbohydrates and their derivatives), polymers, cellulose, starch and their esters and carbons, fatty acid salts (such as stearic acid, oleic acid or lithium stearate, fatty acid esters, fatty alcohols Esters, alkoxylated alcohols, alkoxylated amines, fatty alcohols, sulfates, phosphates, imidazolines and quaternary ammonium salts, ethylene oxide/propylene oxide copolymers, ethylene oxide/butene oxide copolymers And mixtures thereof. Examples of polyolefin polymers which may be mentioned are polyethylene, polypropylene, polybutadiene, polyvinyl alcohol, phenol condensation products (including those obtained by reaction with aldehydes), derived from mercapto alcohols. , styrene, divinyl benzene, naphthalene, perylene, acrylonitrile, ethyl acetate the polymer. of a non-limiting embodiment examples are ^{Unithox TM 550 ethoxylate (Baker Hughes)} .Unithox TM ethoxylates of high molecular weight and high melting point of Nonionic emulsifiers and wetting agents. These Baker Petrolit e is the product of ethoxylation of alcohols produced from Unilin ^TM, which is fully saturated long-chain, linear, C ₂₀ to C ₅₀ synthetic alcohols of This art person can freely choose the suitable carbon without departing from the spirit of the invention Source compound.

In a non-limiting embodiment, any of the process steps described herein are carried out in an inert hydrogen atmosphere such as, but not limited to, nitrogen, hydrogen, and/or nitrogen. In a non-limiting embodiment, any of the thermal steps described herein are carried out in a humidified atmosphere; for example, as described in WO 2011/072397, the disclosure of which is incorporated herein by reference.

In a non-limiting embodiment, any of the method steps described herein are carried out in a reducing atmosphere which participates in the reduction and/or prevents oxidation of the oxidation state of at least one metal in the precursor and does not completely reduce to the element. state. example For example, the reducing atmosphere is present during the first high energy polishing step, the second high energy polishing step, the first thermal step, the second thermal step, or a combination thereof.

In a non-limiting embodiment, the reducing atmosphere is not limited to an externally applied reducing atmosphere, a reducing atmosphere derived from degradation of a source compound or a reducing atmosphere derived from a synthesis reaction.

In a non-limiting embodiment, the externally applied reducing atmosphere comprises a gas such as, but not limited to, CO, H ₂ , NH ₃ , HC, and any combination thereof, which participates in the reduction reaction or prevents in the precursor The oxidation of at least one metal is oxidized without being completely reduced to the elemental state. Wherein HC refers to any hydrocarbon or carbonaceous product in gaseous or vapor form. The reducing atmosphere applied at the other portion may also include an inert gas such as, but not limited to, CO ₂ , N ₂ , argon, helium, nitrogen or other inert gas.

In a non-limiting embodiment, the above-described reducing atmosphere derived from degradation of the source compound is, but not limited to, a reducing atmosphere which is produced when the source compound is degraded or converted into a thermal step. .

In a non-limiting embodiment, the compound is a source of reducing agent that is degraded or converted in a thermal step and produces a reducing atmosphere that participates in the reduction reaction or prevents it from occurring in the precursor. Oxidation of at least one metal oxidation state, but not complete reduction to elemental state. In a non-limiting embodiment, the reducing atmosphere comprises CO, CO/CO ₂ , H ₂ or any combination thereof.

In a non-limiting embodiment, the above-mentioned reducing atmosphere derived from the synthesis reaction is, but not limited to, a reducing atmosphere produced by the thermal step, and it participates in the reduction reaction or prevents at least one metal in the precursor. Oxidation of the oxidized state is not completely reduced to the elemental state. In a non-limiting embodiment, the reducing atmosphere comprises CO, CO/CO ₂ , H _{2 ,} and any combination thereof.

According to a specific non-limiting embodiment, the carbon-deposited alkali metal oxyanion material of the present invention may include an additive on its surface or in its entirety, such as, but not limited to, carbon particles, carbon fibers and nanofibers, carbon. Tube, graphene, vapor grown conductive fiber (VGCF), metal oxide and any mixture thereof. These additives may be in any form including spherical, (granular), sheet, fibrous, and the like. These additives can be added at any step, for example in a two-step thermal process, these additives can be added before the first and/or second thermal step.

By "general formula" is meant that the stoichiometry of the material may differ from the stoichiometric amount of the material, such as, but not limited to, substitutions or other defects in the structure of the material, including reaction defects, structural defects, for example, but It is not limited to cation disorder of iron and lithium in the cathode material crystal. See, for example, Maier et al. [Defect Chemistry of LiFePO ₄ , Journal of the Electrochemical Society, 155, 4, A339-A344, 2008] and Nazar et al. [Proof of Supervalent Doping in Olivine LiFePO ₄ , Chemistry of Materials, 2008 , 20(20), 6313-6315].

The inventors of the present invention have found that the carbon-deposited alkali metal phosphonate cathode material of the present invention can be most suitably obtained by optimizing the ratio of precursors. Although the inventors of the present invention have noted that the possible final theoretical formula may differ from at least electrical neutrality, it is believed that the carbon-deposited alkali metal phosphonate cathode material of the present invention may comprise different phases without being bound by any theory. balance The total potential of the material is ultimately electrically neutral. Therefore, the invention is not limited to any defined theoretical formula. As the skilled artisan will understand how to optimize the ratio of precursors to obtain the desired carbon-deposited alkali metal phosphonium silicate cathode material of the present invention without departing from the scope of the invention.

In a non-limiting embodiment, the invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising particles having carbon deposited by thermal decomposition on at least the surface of the particles.

In a non-limiting embodiment, the particles have an olivine structure. However, the scope of the invention is not limited to the manner of having an olivine structure. Thus, a manner of not having an olivine structure is also within the scope of the present invention.

In a non-limiting embodiment, the carbon-deposited alkali metal phosphonium silicate cathode material comprises a metal having a 2+ valence. For example, the carbon-deposited alkali metal phosphonate cathode material includes Fe(II) and/or Mn(III).

In a non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonate cathode material comprising particles having at least a portion of its surface having carbon deposited by thermal decomposition, wherein The particles have the general formula A _z M _1-x M' _x P _1-y Si _y O ₄ wherein the valence of M is +2 or more; M is Fe and/or Mn; and A is at least one selected from Li, Na And alkali metal of K. Alternatively, up to 15% of this Fe and/or Mn is replaced by at least one of or above the oxidation order of +1 and +5. M' is a metal having a valence of 2+ or more. x, y and z are defined as follows: 0.8<z 1.2; 0<x 0.25; and y=x* (the valence of M'-2) + (1-x)* (the average price of M-2).

In a non-limiting embodiment, z is 0.9 z 1.1.

In another non-limiting embodiment, z is 0.95 z 1.05.

In yet another non-limiting embodiment, z is 0.97 z 1.03.

In yet another non-limiting embodiment, z is 0.98 z 1.02.

In a non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising particles having at least a portion of a surface with carbon deposited by thermal decomposition, The particles have the general formula: AM _1-x M' _x P _1-y Si _y O ₄ , wherein the average valence of M is +2 or above; M is Fe and/or Mn; A is selected from Li, Na and K At least one alkali metal is optional. Up to 15% of Fe and/or Mn is replaced by a metal having one or more of +1 and/or +5. M' is a metal having a valence of 2+ or more. x, y and z are defined as follows: 0<x 0.25; y = x * (the valence of M' - 2) + (1-x) * (the valence of M - 2).

In yet another non-limiting embodiment, the invention relates to a carbon-deposited alkali metal phosphonate cathode material. A particle is included which has an olivine structure. And at least a part of its surface is provided with carbon deposited by thermal decomposition, the particle having the general formula: LiM _1-x M' _x P _1-y Si _y O ₄ , wherein the average valence of M is +2 or Above, M is Fe and/or Mn. Alternatively, Fe and/or Mn may be substituted with up to 15% of the metal having one or more of +1 to +5. M' is a metal with a valence of 2+ or more, and x, y, and z are defined as follows: 0<x 0.25; y = x * (the valence of M' - 2) + (1-x) * (the average price of M - 2).

In the present invention, the phosphate polyanion (PO ₄ ) and/or SiO ₄ may also be partially substituted by another XO ₄ oxyanion, wherein X is one of P, S, V, Si, Nb, Mo Or a combination thereof.

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonate cathode material comprising particles having at least a portion of the surface with carbon deposited by thermal decomposition, wherein the particles have Element ratio: Li: (Fe + Zr): PO ₄ : SiO ₄ is about 1:1: 0.7-1: > 0-0.3.

In a non-limiting embodiment, the present invention is directed to an optimized carbon-deposited alkali metal phosphonate cathode material comprising particles having at least a portion of its surface with carbon deposited by thermal decomposition Where the particles have a general elemental ratio: Li:Fe:Zr:PO ₄ :SiO ₄ , which is about 1 +/- x:0.95 +/- x:0.05 +/- x:0.95 +/- x:0.05 + /- x, where x is independently a value of approximately 20%.

In another non-limiting embodiment, the present invention is directed to an optimized carbon-deposited alkali metal phosphonate cathode material comprising particles having carbon deposited by thermal decomposition on at least a portion of the surface This particle has a general element ratio: Li:Fe:Zr:PO ₄ :SiO ₄ , which is about 1 +/- x:0.95 +/- x:0.05 +/- x:0.95 +/- x:0.05 + /- x, where x is independently a value of about 10%.

In a non-limiting embodiment, the value of x is about 5%.

In another non-limiting embodiment, the value of x is about 4%.

In yet another non-limiting embodiment, the value of x is about 3%.

In yet another non-limiting embodiment, the value of x is about 2%.

In yet another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonate cathode material comprising particles having at least a portion of its surface with carbon deposited by thermal decomposition, The particles have the general formula: LiM _1-x M' _x (PO ₄ ) _1-2x (SiO ₄ ) _2x wherein M is Fe and/or Mn and M' is 4+ metal. Alternatively, the phosphate polyanion (PO ₄ ) may be partially replaced by a sulfate polyanion (SO ₄ ), and/or the lithium metal may be partially replaced by Na and/or.

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising particles having at least a portion of its surface with carbon deposited by thermal decomposition, Wherein the particles have the general formula: LiFe _1-x M' _x (PO ₄ ) _1-2x (SiO ₄ ) _2x , wherein M' is a 4+ metal. Alternatively, the phosphate polyanion (PO ₄ ) may be partially replaced by a sulfate polyanion (SO ₄ ), and/or the lithium metal may be partially replaced by Na and/or K.

In another non-limiting example, the present invention is directed to a carbon-deposited alkali metal phosphonate cathode material comprising particles having carbon deposited by thermal decomposition on at least a portion of the surface, Wherein the particles have the formula: AM _1-x M' _x (XO ₄ ) _1-2x (SiO ₄ ) _2x , wherein -A is Li, alone or partially up to 30%, by atomic Na and/or Replaced by K.

- M is a metal comprising at least 90% of Fe(II) or Mn(II) or a mixture thereof; and at least one or more of at least 10% of the atoms are in an oxidation state between +1 and +5; M' is a 4+ valence metal including at least Zr ⁴⁺ , Ti ⁴⁺ , Nb ⁴⁺ , Mo ⁴⁺ , Ge ⁴⁺ , Ce ⁴⁺ or Sn ⁴⁺ ; - XO ₄ is PO ₄ , alone or in part 30 mol% of SO ₄ replaced; and - 0.03 x 0.15.

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising particles having thermally decomposed carbon deposited on at least a portion of a surface thereof, wherein the particles have General formula: AM _1-x M' _x (XO ₄ ) _1-2x (SiO ₄ ) _2x , wherein - A is Li, alone or in part up to 10%, substituted by atomic Na or K; - M Is a metal comprising at least 90% of Fe(II) or Mn(II) or a mixture thereof, and at most: I. 10% by atom; Ni and/or Co; II. 10% by atom One or more non-Ni or Co equivalent or equivalent metals; III. 10% atomic Fe(III); or IV. I to III any combination; - M' is a 4+ price a metal comprising at least one of Zr ⁴⁺ , Ti ⁴⁺ , Nb ⁴⁺ , Mo ⁴⁺ , Ge ⁴⁺ , Ce ⁴⁺ or Sn ⁴⁺ ; - XO ₄ is PO ₄ , alone or partially at least 10 mol Replaced by SO _{4 of 4} ; and - 0.03 x 0.15.

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising particles having particles deposited by thermal decomposition on at least a portion of the surface, Wherein the particles have the formula: AM _1-x M' _x (XO ₄ ) _1-2x (SiO ₄ ) _2x , wherein: - A is Li; - M is Fe(II); - M' is a 4+ valence metal Including Zr ⁴⁺ , Ti ⁴⁺ , Nb ⁴⁺ , Mo ⁴⁺ , Ge ⁴⁺ , Ce ⁴⁺ or Sn ⁴⁺ at least one; - XO ₄ is PO ₄ ; and - 0.03 x 0.15.

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonate cathode material comprising a particle on at least a portion of its surface with carbon deposited by thermal decomposition, wherein The particles have the general formula of AM _1-x M' _x (XO ₄ ) _1-2x (SiO ₄ ) _2x wherein: -A is Li; -M is Fe(II); -M' is Zr ⁴⁺ ;- XO ₄ is PO ₄ ; and - 0.03 x 0.15.

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonate cathode material comprising a particle having at least a portion of a surface with carbon deposited by thermal decomposition, wherein The particles have the general formula: LiFe _1-x Zr _x (PO ₄ ) _1-2x (SiO ₄ ) _2x where 0.03 x 0.1 or 0.03 x 0.08, or 0.04 x 0.06.

In still another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising a particle having at least a portion of a surface with carbon deposited by thermal decomposition, wherein the particle It has the general formula: LiFe _0.9 Zr _0.1 (PO ₄ ) _0.8 (SiO ₄ ) _0.2 .

In still another non-limiting embodiment, the present invention is directed to an alkali metal ruthenate cathode material for carbon deposition comprising a particle having at least a portion of a surface having carbon deposited by thermal decomposition, wherein the particle There is a general formula: LiM _1-x M' _x (PO ₄ ) _1-x (SiO ₄ ) _x , wherein M is Fe and/or Mn, and M' is a 3+ metal. Alternatively, the phosphate polyanion (PO ₄ ) may be partially substituted with a sulfate polyanion (SO ₄ ), and/or the lithium metal may be substituted with Na and/or K.

In another non-limiting embodiment, the invention relates to a carbon-deposited alkali metal phosphonium citrate cathode material comprising a particle having particles deposited by thermal decomposition on at least a portion of a surface thereof, wherein This particle has the general formula: LiFe _1-x M' _x (PO ₄ ) _1-x (SiO ₄ ) _x , where M' is a 3+ metal. Alternatively, the phosphate polyanion (PO ₄ ) may be partially replaced by a sulfate polyanion (SO ₄ ), and/or the lithium metal may be partially replaced by Na and/or K.

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising a particle having at least a portion of its surface with carbon deposited by thermal decomposition, Wherein the particles have the formula: AM _1-x M' _x (XO ₄ ) _1-x (SiO ₄ ) _x , wherein: - A is Li, alone or in part up to 30%, by atomic Na and/or Or K is substituted; - M is a metal comprising at least 90% of Fe(II) or Mn(II) or a mixture thereof, and the oxidation state of one or more metals of up to 10% of atoms is at +1 and + Between 5; - M' is a 3+ valence metal including at least Al ³⁺ , Y ³⁺ , Nb ³⁺ , Ti ³⁺ , Ga ³⁺ , Cr ³⁺ or V ³⁺ ; - XO ₄ is PO ₄ , alone Or partially replaced by at least 30 mol% of SO ₄ ; and - 0.03 x 0.15.

In still another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonate cathode material comprising a particle having at least a portion of a surface with a carbon deposited by thermal decomposition, wherein The particles have the general formula: AM _1-x M' _x (XO ₄ ) _1-x (SiO ₄ ) _x , wherein: - A is Li, alone or partially up to 10%, replaced by Na or K by atom ;- M is a metal comprising at least 90% of Fe(II) or Mn(II) or a mixture thereof, and at most: I. 10% by atom of Ni and/or Co; II. 10% by atom One or more equivalent or heterogeneous metals other than Ni or Co; III. 10% Fe(III) by atom; or any combination of IV. I to III; - M' is a 3+ valence metal, including At least Al ³⁺ , Y ³⁺ , Nb ³⁺ , Ti ³⁺ , Ga ³⁺ , Cr ³⁺ or V ³⁺ ; - XO ₄ is PO ₄ , alone or partially replaced by up to 10 mol% of SO ₄ ;and- 0.03 x 0.15.

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising a particle having at least a portion of its surface with carbon deposited by thermal decomposition, wherein This particle has the general formula: AM _1-x M' _x (XO ₄ ) _1-x (SiO ₄ ) _x , wherein: - A is Li; - M is Fe(II); - M' is a 3+ valence metal, Including at least one of Al ³⁺ , Y ³⁺ , Nb ³⁺ , Ti ³⁺ , Ga ³⁺ , Cr ³⁺ or V ³⁺ ; - XO ₄ is PO ₄ , and - 0.03 x 0.15.

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonate cathode material comprising a particle having at least a portion of its surface with carbon deposited by thermal decomposition, wherein the particle Has the general formula: AM _1-x M' _x (XO ₄ ) _1-x (SiO ₄ ) _x , wherein: - A is Li; - M is Fe(II); - M' is Y ³⁺ or Al ³⁺ ;- XO ₄ is PO ₄ ; and - 0.03 x 0.15.

In still another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising a particle having at least a portion of its surface with carbon deposited by thermal decomposition, wherein柆 has the general formula: LiFe _1-x M" _x (PO ₄ ) _1-x (SiO ₄ ) _x , where M" is Y ³⁺ and / or Al ³⁺ , and 0.03 x 0.1 or 0.03 x 0.08 or 0.04 x 0.06.

In still another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonium citrate cathode material comprising a particle having at least a portion of its surface with carbon deposited by thermal decomposition, the particle having General formula: LiFe _0.9 M" _0.1 (PO ₄ ) _0.9 (SiO ₄ ) _0.1 , wherein M" is Y ³⁺ and/or Al ³⁺ .

In another non-limiting embodiment, the present invention is directed to a carbon-deposited alkali metal phosphonate cathode material comprising a particle having at least a portion of a surface with carbon deposited by thermal decomposition, wherein The particles have the formula: LiFe _0.95 M" _0.05 (PO ₄ ) _0.95 (SiO ₄ ) _0.05 , where M" is Y ³⁺ and/or Al ³⁺ .

Example 1:1 - Step solid state reaction

Will be used as phosphorus (P) and iron source FePO ₄ . 2H ₂ O (0.4 mol); iron oxalate dihydrate (0.05 m) as iron source, Li ₂ CO ₃ (0.25 m) as lithium source, as the fourth source of bismuth (Si) Base orthosilicate Si(OC ₂ H ₅ ) ₄ (0.1 mol), atomic ratio of Zr(IV) acetate hydroxide (0.05 mol) derived from Zr ⁴⁺ Li:Fe:Zr:P : Si = 1: 0.9: 0.1 : 0.8: polymer ratio and as a source of carbon Unithox ^TM 550 of 0.2 (. 5 wt% of the precursor, Baker Hughes manufactured by a) mixing together in a bowl mill. The resulting mixture was heated at 550 ° C for about 6 hours under a hydrogen atmosphere. The product obtained from the X-spectrum shown in Fig. 1 shows the formation of Li ₃ PO ₄ , ZrO ₂ and the impure phase of LiZr ₂ (PO ₄ ) ₃ . The unit cell volume of the obtained olivine is 291 Å ³ .

Example 2: 1-step high energy milling and 1-step solid state reaction

FePO ₄ will be used as a source of phosphorus (P) and iron. 2H ₂ O (0.4 mol), iron-oxalate dihydrate (0.05 mol) as iron source, Li ₂ CO ₃ (0.25 mol) as lithium source, tetraethyl orthoquinone as a source of cerium (Si) Acid salt Si(OC ₂ H ₅ ) ₄ (0.1 mol) as Zr ⁴⁺ source Zr(IV) acetate hydroxide (0.05 m) as Li:Fe:Zr:P:Si=1:0.9 : 0.1: 0.8: 0.2 ratio of atoms of a polymer and a carbon source of Unithox ^TM 550 (. 5 wt% precursor, Baker Hughes manufactured by) high energy milling for about 2 hours in a SPEX mill. The resulting high energy ground mixture was then heated at about 550 ° C for about 6 hours under nitrogen. The obtained product showed the X spectrum of Fig. 2 showing the formation of the Li ₃ PO ₄ , ZrO ₂ and LiZr ₂ (PO ₄ ) ₃ impurity phases. The resulting olivine unit cell volume was 291.1 Å ^{3 and} the glass bead/precursor ratio of 20:1 was replaced by a SPEX mill. This experiment gave similar results.

Example 3: 2-step high energy milling and 2-step solid state reaction, high temperature

FePO ₄ will be used as a source of phosphorus (P) and iron. 2H ₂ O (0.4 mol), iron oxalate dihydrate (0.05 mol) as iron source, Li ₂ CO ₃ (0.25 mol) as lithium source, tetraethyl orthoquinone as bismuth (Si) source Acid salt Si(OC ₂ H ₅ ) ₄ (0.1 mol) as Zr ⁴⁺ source Zr(IV) acetate hydroxide (0.05 m) as Li:Fe:Zr:P:Si=1:0.9 : 0.1: 0.8: 0.2 ratio of atoms of a polymer and a carbon source of Unithox ^TM 550 (. 5 wt% precursor, Baker Hughes manufactured by) high energy milling for about 2 hours in a SPEX mill. The resulting high energy ground mixture was then heated at about 550 ° C under nitrogen for about 6 hours. This process is then repeated a second time using the same high energy grinding and heating conditions. In other words, after the first heating step, the second high energy polishing step and the first second heating step are performed. The product obtained shows that the X-ray spectrum in Fig. 3 shows the formation of the Li ₃ PO ₄ and ZrO ₂ impurity phases. The unit lattice volume of the obtained olivine is 291.8 Å ³ . Similar results were obtained by repeating this experiment with Attritor ^® replacing the SPEX mill with a glass bead/precursor ratio of 20:1.

Experimental Example 4: 2-step high energy milling and 2-step solid state reaction, low temperature

Will be used as phosphorus (P) and iron source FePO ₄ . 2H ₂ O (0.4 mol), iron-oxalate dihydrate (0.05 mol) as iron source, Li ₂ CO ₃ (0.25 mol) as lithium source, tetraethyl ortho-nicotinic acid derived from cerium (Si) Salt Si(OC ₂ H ₅ ) ₄ (0.1 mol) as Zr ⁴⁺ source of Zr(IV) acetate hydroxide (0.05 m) as Li:Fe:Zr:P:Si=1:0.9: 0.1: 0.8: 0.2 ratio of atoms of a polymer and a carbon source of Unithox ^TM 550 (. 5 wt% precursor, Baker Hughes manufactured by) high energy milling for about 1 hour in a SPEX mill. The resulting high energy ground mixture was then heated at about 550 ° C for about 1 hour under nitrogen. A gas product was produced during this heating step and the resulting product was then ground at high energy with a SPEX mill for about one hour to give an amorphous precursor. The resulting high energy ground amorphous precursor was then heated at about 550 ° C for about 5 hours under nitrogen. The resulting carbon-deposited lithium iron zirconium phosphite product is shown in the X-ray spectrum of Figure 4, which shows a unit cell volume of 292.6 Å ³ . Repeated experiments with Attritor ^® to replace the SPEX mill with a glass bead/precursor ratio of 20:1 gave similar results.

Substituting Zr(IV) acetate hydroxide with tetra-n-butyl zirconate solution (Tyzor ^® NBZ, about 87% active ingredient in butanol, manufactured by Dorf Ketal) in butanol, using SPEX grinding The machine and the same atomic ratio were used: Li:Fe:Zr:P:Si=1:0.9:0.1:0.8:0.2 Repeating this experiment gave similar results.

Substituting Zr(IV) acetate hydroxide with bis[tri-n-butyltin(IV)] oxide (0.025 mol) as Sn ⁴⁺ source, using SPEX mill and using atomic ratio Li:Fe:Sn: A similar result was obtained by repeating this experiment with P:Si=1:0.9:0.1:0.8:0.2. This experiment produced a carbon deposition of lithium iron tin phosphate. Titanium (IV) 2-ethylhexyl oxide (0.025 mol) was used as the Ti ⁴⁺ source to replace the Zr(IV) acetate hydroxide. A similar result was obtained using a SPEX mill and repeating this experiment with a precursor having an atomic ratio of Li:Fe:Ti:P:Si = 1:0.9:0.1:0.8:0.2. This result yields a carbon deposition of lithium iron titanium phosphonium citrate.

The results obtained from the above-mentioned Zr ⁴⁺ display experimental examples are summarized in the following Table 1.

The results in Table 1 indicate that the reaction comprising a precursor single high energy milling step prior to the thermal step provides a change of about 8.8% relative to the unit lattice volume of the unit cell volume of commercial C-LiFePO ₄ . This result also indicates that the reaction comprising the two solid thermal steps and the two high energy milling steps prior to each thermal step provides about a 44.7% change in the unit cell volume relative to the unit cell volume of commercial C-LiFePO ₄ .

The results also indicate that the two thermal steps are included, wherein the first thermal step is at a relatively low temperature of about 300 ° C, and the reaction at about 550 ° C relative to a relatively high temperature provides a unit lattice volume relative to commercial C-LiFePO ₄ . The higher % of the unit cell volume changes, which is 91.2% vs. 44.7%, respectively. Further, the inventors have observed that a relatively high temperature during the second thermal step may cause decomposition of the final compound, resulting in an impurity phase, that is, the impurity phase of the final compound in these experimental examples includes ZrO ₂ and LiZr ₂ (PO _{4 ).} ) ₃ .

Experimental Example 5: 2-step high energy milling and 2-step solid state reaction, low temperature

It will be used as iron source of iron oxalate dihydrate (590.11 g), as iron source Li ₂ CO ₃ (6.38 g), as phosphorus (P) and lithium source LiH ₂ PO ₄ (340.92 g). Tetraethyl orthosilicate Si(OC ₂ H ₅ ) ₄ (35.96 g) as a source of Zr ⁴⁺ source of Zr(IV) acetate hydroxide (36.63 g) in atomic ratio Li:Fe :Zr:P:Si=1:0.95:0.05:0.95:0.05, stearic acid (13.7 g) and grade M 5005 micronized polyethylene wax powder (13.7 g, manufactured by Marcus Oil & Chemical), both as carbon sources The material was fed into a high-energy ball-milling vertical agitating mill (Union Process 1-S), which included 10 kg of yttrium-stabilized ZrO ₂ balls (10 mm in diameter) as grinding media. The mill was operated at 350 rpm for 2 hours. The resulting high energy ground mixture was then heated under nitrogen at about 300 ° C for about 1 hour. A gaseous product is produced during this thermal step. The resulting product is then subjected to high energy milling in a mill for about 2 hours to produce an amorphous precursor. The resulting high energy amorphous precursor is then heated at about 570 ° C for about 6 hours in a wet nitrogen gas (a gas bag is produced in water at about 80 ° C) during the heating step (about 90 minutes) and a cooling step. Dry nitrogen was used during the period (about 180 minutes). The X-ray spectrum of the carbon-deposited lithium iron zirconium phosphite obtained in Fig. 5 shows a unit lattice volume of 291.3 Å ³ and no impurity phase is formed.

The following precursors were used as the iron source of iron oxalate dihydrate (576.19 g), as lithium source Li ₂ CO ₃ (12.46 g), as phosphorus (P) lithium source LiH ₂ PO ₄ ( 315.36 g), tetraethyl orthosilicate Si(OC ₂ H ₅ ) ₄ (70.23 g) as cerium (Si) source, Zr(IV) acetate hydroxide as Zr ⁴⁺ source (35.76 g), atomic ratio Li:Fe:Zr:P:Si=1:0.95:0.05:0.9:0.1, as a carbon source stearic acid (13.7 g) and grade M 5005 micronized polyethylene wax powder (13.7 g, manufactured by Marcus Oil & Chemical, repeated this experiment to obtain similar results. The X-ray pattern of the resulting carbon-deposited lithium iron zirconium phosphite is shown in Figure 6, which shows a unit lattice volume of 291.6 Å ³ .

Example 6: 2-step high energy milling and 2-step solid state reaction, low temperature

LiOH, which is a lithium source, is used as an iron source and a phosphorus (P) source of FePO ₄ as a source of Y ³⁺ (III). 2-ethylhexyl alkoxide as phosphorus (P) source (NH ₄ ) ₂ HPO ₄ , tetraethyl orthosilicate Si(OC ₂ H ₅ ) ₄ as a source of cerium (Si) in atomic ratio: Li :Fe:Y:P:Si=1:0.95:0.05:0.95:0.05, as a carbon source stearic acid (2.5 wt.% of the precursor) and grade 500 500 micronized polyethylene wax powder (precursor 2.5 wt.%) High energy milling in a SPEX mill and heating as in Example 4. A carbon-deposited lithium iron lanthanum phosphate is obtained.

This experiment was used as an Al ³⁺ source of aluminum 2-4 pentanediol salt instead of ruthenium (III) 2-ethylhexanolate, atomic ratio: Li:Fe:Al:P:Si=1:0.95:0.05:0.95 : 0.05, thus obtaining carbon-deposited lithium iron aluminum phosphate.

Example 7: 2-step high energy milling and 2-step solid state reaction, low temperature

LiOH as lithium source, iron oxalate dihydrate as iron source, MnO as manganese source, Zr(IV) acetate hydroxide as Zr ⁴⁺ source, (NH ₄ ) ₂ HPO ₄ as phosphorus source , as a source of cerium (Si), tetraethyl orthosilicate Si(OC ₂ H ₅ ) ₄ , atomic ratio: Li:Fe:Mn:Zr:P:Si=1:0.8:0.15:0.05:0.9:0.1 , as a carbon source stearic acid (2.5 wt.% of the precursor) and grade 500 500 micronized polyethylene wax powder (2.5 wt.% of the precursor), as described in Example 4, in a SPEX grinding High energy grinding in the machine. Thus, carbon deposition of lithium iron manganese zirconium phosphate is obtained.

The same precursor was used but the atomic ratios were Li:Fe:Mn:Zr:P:Si=1:0.5:0.45:0.05:0.9:0.1 and Li:Fe:Mn:Zr:P:Si=1:0.2: 0.75: 0.05: 0.9: 0.1, this experiment was repeated to obtain similar results. Carbon deposition of lithium iron manganese zirconium phosphite was obtained in both cases.

Example 8: 2-step high energy milling and 2-step solid state reaction, low temperature

Li ₂ CO ₃ as lithium source, Na ₂ CO ₃ as sodium source, iron oxalate dihydrate as iron source, Zr(IV) acetate hydroxide as Zr ⁴⁺ source, as phosphorus (P) Source and lithium source LiH ₂ PO ₄ , as a source of cerium (Si) tetraethyl orthosilicate Si(OC ₂ H ₅ ) ₄ , such as atomic ratio: Li:Na:Fe:Zr:P:Si=0.95 : 0.05:0.95:0.05:0.9:0.1, and as a carbon source stearic acid (2.5 wt.% of the precursor) and grade 500 500 micronized polyethylene wax powder (2.5 wt.% of the precursor) High energy milling in SPEX and heat treatment as in Example 4. Thus, carbon deposition of lithium sodium iron zirconium phosphate is obtained.

The same precursor was used but the atomic ratios were: Li:Na:Fe:Zr:P:Si=0.85:0.15:0.95:0.05:0.9:0.1 and Li:Na:Fe:Zr:P:Si=0.75:0.25 :0.95:0.05:0.9:0.1 Repeat this experiment to obtain similar results. In both cases, carbon deposition of lithium sodium zirconium phosphonate was obtained.

Example 9: 2-step high energy milling and 2-step solid state reaction, low temperature

As a source of lithium Li ₂ CO _3, an iron source of iron oxalate dihydrate, (IV) acetate monohydrate as the source of Zr ⁴⁺ Zr, as phosphorus (P) and the source of lithium LiH ₂ PO _4, as silicon (Si) source of tetraethyl orthosilicate Si(OC ₂ H ₅ ) ₄ , in atomic ratio: Li:Fe:Zr:P:Si=1.03:0.95:0.05:0.9:0.1 ratio, and as phosphorus Source stearic acid (1.5 wt.% of the precursor) and grade 500 500 micronized polyethylene wax powder (1.5 wt.% of the precursor) were ground in a SPEX mill and heat treated as in Example 4. Thus, carbon deposition of lithium iron zirconium phosphate is obtained.

The same experiment was used, but the atomic ratio: Li:Fe:Zr:P:Si=0.97:0.95:0.05:0.9:0.1 The same experiment was repeated to obtain similar results. Thus, carbon deposition of lithium iron zirconium phosphate is obtained.

Example 10: 2-step high energy milling and 2-step solid state reaction, low temperature

Li ₂ CO ₃ as a lithium source, iron oxalate dihydrate as iron source, ^bismuth (V) ethoxide as Nb ⁵⁺ source, LiH ₂ PO ₄ as (P) and lithium source, as bismuth (Si) Source of tetraethyl orthosilicate Si(OC ₂ H ₅ ) ₄ to atomic ratio: Li:Fe:Nb:P:Si=1:0.97:0.03:0.91:0.09, and stearic acid as a carbon source The acid (2 wt.% of the precursor) and the grade M 5005 micronized polyethylene wax powder (2 wt.% of the precursor) were ground in a SPEX mill and heat treated as in Example 4, thereby obtaining carbon-deposited lithium iron. Bismuth phosphonate.

Replacing ruthenium (V) ethoxide with ruthenium (V) butoxide as a source of Ta ^{5+ is} repeated in this atomic ratio: Li:Fe:Ta:P:Si=1:0.98:0.02:0.94:0.06. result. Thus, carbon-deposited lithium iron lanthanum phosphate is obtained.

Example 11: 2-step high energy milling and 2-step solid state reaction, low temperature

As a source of lithium Li ₂ CO _3, an iron source of iron oxalate dihydrate, as a source of Cobalt (II) oxalate dihydrate, Zr ⁴⁺ as the source of Zr (IV) acetate hydrate, as Phosphorus (P) and lithium-derived LiH ₂ PO ₄ , as a source of cerium (Si) tetraethyl orthosilicate Si(OC ₂ H ₅ ) ₄ in atomic ratio: Li:Fe:Co:Zr:P:Si =1: 0.9:0.05:0.05:0.9:0.1 ratio, and as a carbon source stearic acid (2.5 wt.% of the precursor) and grade M 5005 micronized polyethylene wax powder (2.5 wt. %) ground in a SPEX mill and heat treated as in Example 4. Thus, carbon deposition of lithium iron cobalt zirconium phosphate is obtained.

Substituting cobalt (II) oxalate dihydrate atomic ratio with nickel oxalate dihydrate as nickel source: Li:Fe:Ni:Zr:P:Si=1:0.9:0.05:0.05:0.9:0.1 repeat This experiment yielded similar results. Thus, carbon deposition of lithium iron nickel zirconium phosphate is obtained.

Example 12: 2-step high energy milling and 2-step solid state reaction, low temperature

Li ₂ CO ₃ as lithium source, iron oxalate dihydrate as iron source, MnO as manganese source, magnesium acetonide acetone dihydrate as magnesium source, Zr(IV) acetate as Zr ⁴⁺ source Salt hydrate, as phosphorus (P) and lithium source LiH ₂ PO ₄ , as cerium (Si) source of tetraethyl orthosilicate Si(OC ₂ H ₅ ) ₄ in atomic ratio: Li:Fe:Mn: Mg: Zr: P: Si = 1: 0.8: 0.1: 0.05: 0.05: 0.9: 0.1 ratio, and as a carbon source stearic acid (2.5 wt.% of the precursor) and grade M 5005 micronized polyethylene The wax powder (2.5 wt.% of the precursor) was ground in a SPEX mill and heat treated as in Example 4. Thus, carbon deposition of lithium iron manganese magnesium zirconium phosphate is obtained.

The same precursor is used but the atomic ratio: Li:Fe:Mn:Mg:Zr:P:Si=1:0.45:0.45:0.05:0.05:0.9:0, Li:Fe:Mn:Mg:Zr:P:Si =1: 0.2:0.7:0.05:0.05:0.9:0.1 This experiment was repeated to obtain similar results. In both cases, carbon deposition of lithium iron manganese magnesium zirconium phosphate was obtained.

Example 13: 2-step high energy milling and 2-step solid state reaction, low temperature

It will be used as iron source of iron oxalate dihydrate (590.11 g), as lithium source of Li ₂ CO ₃ (6.38 g), as phosphorus (P) and lithium source of LiH ₂ PO ₄ (340.92 g). As a cerium (Si) source of tetraethyl phthalate Si(OC ₂ H ₅ ) ₄ (35.96 g), as Zr ⁴⁺ source Zr(IV) acetate hydroxide (36.63 g) in atomic ratio: Li:Fe:Zr:P:Si=1:0.95:0.05:0.95:0.05, stearic acid (9.13 g) and grade M 5005 micronized polyethylene wax powder (9.13 g, manufactured by Marcus Oil & Chemical), both The carbon source was fed to a high energy ball mill vertical agitating mill (Union Process 1-S) which included 10 kg of yttrium stabilized ZrO ₂ balls (10 mm diameter) as grinding media. The mill was operated at 350 rpm for 2 hours. The resulting high energy mixture was then heated under nitrogen at about 300 ° C for about 1 hour. A gaseous product is produced during this thermal step. The obtained product, and a stearic acid (4.57 g) as a carbon source and a grade 500 mg micronized polyethylene wax powder (4.57 g) were subjected to high energy grinding in a grinder for about 1 hour. The resulting high energy ground amorphous precursor. It was then heated at about 570 ° C for about 6 hours in wet nitrogen (in a water nitrogen bubble at about 80 ° C). Dry nitrogen was used during the heating step (about 90 minutes) and the cooling step (about 180 minutes). Thus, carbon deposition of lithium iron zirconium phosphate is obtained.

Example 14: Electrochemical properties

A liquid battery was prepared in accordance with the following procedure.

The cathode material of the present invention, PVdF-HFP copolymer (supplied by Atochem) and EBN-1010 graphite powder (supplied by Superior Graphite) in a pot mill equipped with zirconia balls of N-methylpyrrolidone (NMP) A ball mill was used to obtain a dispersion consisting of a mixture of cathode/PVdF-HFP/graphite 80/10/10 by weight. Thereafter, the resulting mixture using a Gardner ^® deposition apparatus having a process of coating with carbon (supplied by Exopack Advanced Coating) on the aluminum sheet, and in this film deposition in vacuo and dried through 80 ℃ 24 hours. It is then stored in a glove box. A carbon-treated aluminum sheet with a coating layer containing the carbon-deposited alkali metal phosphonium salt was used as a cathode, and a lithium film was used as an anode, and a thickness of 25 μm was immersed in the 1M LiPF _{6 of the} EC/DEC 3/7 mixture. The separators of the solution (provided by Celgard) are combined into a button type battery.

The cell was subjected to a scanning voltammetry test at ambient temperature using a VMP2 multichannel potentiometer (Biologic Science Instruments) at a rate of 20 mV/80, first in the oxidation state from the stop potential to 4V, then in the reduced state at 4 to Between 2.2 V. This voltammetry test was repeated once and the capacity of the cathode material (C, mAh/g) was determined from the second reduction cycle.

The same cell received C/12 galvanostatic cycling at 2.2 °C and 4 volts at 60 °C.

Some batteries are rated for capacity (mAh/g) at different discharge rates (C-rate, relative to the 1C rate of discharge for all capacities in 1 hour) and power capacity tests (Ragone chart) at ambient temperature.

The following claims provide further elaboration of an example of a method in accordance with the present invention: claim

A method of synthesizing a carbon-containing alkali metal oxyanion cathode material comprising particles, wherein the particles have at least a portion of the surface of the particle with carbon deposited by thermal decomposition, the method comprising: a first dry high An energy milling step applied to the precursor of the carbon-deposited alkali metal oxyanion prior to the first solid thermal reaction, wherein the first solid thermal reaction produces a first solid thermal reaction product; and a second drying A high energy milling step that is applied to the product prior to a second solid state thermal reaction.

2. The method of claim 1 wherein the method comprises adding a source compound of carbon to the precursor prior to or during the first high energy milling step, and/or adding a period before or during the second high energy milling step The source compound of carbon is to the product.

3. The method of claim 2 wherein the source of carbon is a liquid, solid or gaseous hydrocarbon.

4. The method of claim 3, wherein the carbon source is selected from the group consisting of polycyclic aromatic, perylene and its derivatives, polyhydroxy compounds, cellulose, starch and esters and ethers thereof, polyolefins, polybutylene Condensation products of olefins, polyvinyl alcohols, phenols, derived from mercapto alcohol, styrene, divinylbenzene, naphthalene, perylene A group of polymers of benzene, vinyl nitrile and vinyl acetate.

5. The method of claim 4 wherein the polycyclic aromatic is selected from the group consisting of free tar and bitumen.

6. The method of claim 4 wherein the polyhydroxy compound is selected from the group consisting of free sugars, carbohydrates and derivatives thereof.

The method according to any one of claims 1 to 6, wherein the precursor comprises at least one source compound of an alkali metal, at least one source compound of iron and/or manganese, and at least one source compound of metal M'. Wherein M' is a metal of 2+ or more of the carbon-deposited alkali metal oxyanion, and a source compound of at least one oxyanion if the oxyanion is not present in the other source compound.

8. The method of claim 7, wherein the source of the oxyanion comprises a source compound of phosphorus (P) if the element P is not present in the other source compound; and at least one source of the cerium (Si).

9. The method of claim 7 or 8, wherein the source compound of the M is selected from the group consisting of iron (III) oxide, magnetite (Fe ₃ O ₄ ), ferric trivalent iron phosphate, lithium iron hydroxy phosphate, and trivalent nitric acid. Iron, ferrous phosphate, blue iron ore Fe ₃ (PO ₄ ) ₂ , iron acetate (CH ₃ COO) ₂ Fe, iron sulfate (FeSO ₄ ), iron oxalate, ammonium iron phosphate (NH ₄ FePO ₄ ) and combinations thereof Among the constituent families.

10. The method of any one of claims 7 to 9, wherein the source compound of M is MnO, MnO ₂ , acetate, manganese oxalate, manganese sulfate, manganese nitrate, and combinations thereof.

The method according to any one of claims 7 to 10, wherein the source compound of the alkali metal is selected from lithium oxide, lithium hydroxide, lithium carbonate, Li ₃ PO ₄ , LiH ₂ PO ₄ , lithium positive-bias or A group consisting of polyphosphate, lithium sulfate, lithium oxalate, lithium acetate, and combinations thereof.

The method according to any one of claims 7 to 11, wherein the compound of P is selected from the group consisting of phosphoric acid and its ester, Li ₃ PO ₄ , LiH ₂ PO ₄ , monoammonium phosphate or diammonium phosphate, trivalent phosphoric acid A group of iron, manganese iron phosphate, and combinations thereof.

The method according to any one of claims 7 to 12, wherein the source compound of Si is selected from the group consisting of tetra-n-decanoate, nano-sized SiO ₂ , Li ₂ SiO ₃ , Li ₄ SiO ₄ and combinations thereof. Among the constituent families.

The method according to any one of claims 7 to 12, wherein the source compound of the metal of 2+ or higher is Zr ⁴⁺ , Ti ⁴⁺ , Nb ⁴⁺ , Mo ⁴⁺ , Ge ⁴⁺ , A source compound of a 4+ valence metal composed of Ce ⁴⁺ and Sn ⁴⁺ .

15. The method of claim 14 wherein the 4+ valence metal is Zr4 ⁺ and the source compound is selected from the group consisting of zirconium acetate hydroxide, zirconium alkoxide, and combinations thereof.

The method according to any one of claims 7 to 15, wherein the source compound is selected after the second heat treatment to provide an alkali metal: M:M':P:Si ratio of about 1:1:0.7. To 1: cathode of >0 to 0.3.

The method of any one of claims 1 to 16, wherein the high energy grinding step is performed by a high energy ball mill, a pulverizing mixing mill, a planetary ball mill, a drum-ball mill, a shaking mill, A grinding device consisting of a stirring ball mill, a mixer ball mill, a vertical mill, and a horizontal grinder is used.

The method of any one of claims 1 to 17, wherein the first solid The thermal step has an operator operating at a temperature ranging from about 200 ° C to about 600 ° C.

The method of any one of claims 1 to 18, wherein the second solid state thermal step is an operator operating at a temperature ranging from 400 ° C to about 600 ° C.

The method of any one of claims 1 to 18, wherein the first and/or second solid state thermal step is carried out in an inert gas or a reducing atmosphere.

The method of any one of claims 1 to 20, wherein the 1 and/or 2nd high energy milling step is carried out in an inert gas or a reducing atmosphere.

22. The method of claim 20 or 21, wherein the reducing atmosphere participates in the reduction of at least one metal in the precursor to prevent oxidation of its oxidized state without complete reduction to the elemental state.

23. The method of claims 20 to 22, wherein the reducing atmosphere comprises an additional reducing atmosphere, a reducing atmosphere derived from degradation of the compound, a reducing atmosphere derived from the synthesis reaction, and combinations thereof.

24. The method of claim of claim 23, wherein the plus a reducing atmosphere, comprising _{CO, H 2, NH 3,} HC and combinations thereof, wherein the hydrocarbons HC or carbon-containing compound.

25. The method of claim 23 or 24, wherein the reducing atmosphere derived from degradation of a compound comprises a reducing atmosphere which is degraded or converted by a compound under heating.

26. The method of claim of claim 23, wherein the compound is derived from a reducing atmosphere including degradation of _{CO, CO / CO 2, H} 2 , or a combination thereof.

27. The method of the claim 1 to 24, wherein the precursor comprises FePO _4, iron oxalate, Li ₂ CO _3, tetraethyl silicate, and zirconium acetate Zr (IV) hydroxide.

28. A method of synthesizing a carbon-deposited phosphonium citrate cathode material, wherein the cathode material comprises particles corresponding to a compound of the formula: AM _1-x M' _x (XO ₄ ) _1-2x (SiO ₄ ) _2x , It has at least a portion of the surface of the particle with thermally decomposed carbon, wherein -A is Li, alone or in part up to 30%, substituted by atomic Na and/or K; -M is a metal Including at least 90% atomic Fe(II) or Mn(II) or a mixture; -M' is a metal having at least one 2+ or more; - XO ₄ is PO ₄ , alone or partially up to 30 mol% SO ₄ substitution; and - 0.05 x 0.15

The method comprises reacting a precursor of the compound in at least one solid thermal step, and wherein the at least one high energy milling step is performed on the reaction precursor prior to the at least one thermal step.

29. The method of claim 28, wherein the precursor comprises: a) at least one source compound of A; b) at least one source compound of M; c) at least one source compound of M'; d) source of at least one P a compound if P is not present in another source compound; e) at least one source compound of Si, if Si is not present in another source Among the compounds.

30. A method of synthesizing an alkali metal oxyanion cathode material comprising particles, wherein the particles have carbon deposited by thermal decomposition on at least a portion of the surface of the crucible; the method comprising prior to the first solid state thermal reaction A first high energy milling step is performed on the alkali metal oxyanion.

31. The method of claim 30, wherein the first solid state thermal reaction produces a first solid thermal reaction product, and wherein the product is subjected to a second high energy milling step prior to a second solid state thermal reaction.

The method of any one of claims 30 and 31, wherein the precursor comprises: a) at least one source compound of an alkali metal; b) at least one source compound of Fe and/or Mn; c) at least one having 2 a source compound of a metal having a valence or higher; d) a source compound of at least one oxyanion if the oxyanion is not in the compound of another source; and e) a source of a carbon.

33. The method of claim 31, wherein the precursor comprises: a) at least one source compound of an alkali metal; b) at least one source compound of Fe and /Mn; c) at least one source having a metal of 2+ or higher a compound; d) at least one source compound of an oxyanion if the oxyanion is not in another source compound; and e) a source of carbon, wherein the source compound is not completely present in the first thermal step Medium, or any part thereof, is present in each of the first and second thermal steps.

Those skilled in the art will appreciate that while this example exemplifies that the oxyanion is a phosphonium salt, other variations, modifications, and improvements within the spirit and scope of the present invention are possible. For example, U.S. Patent No. 6,085,015, the disclosure of which is incorporated herein by reference in its entirety the entire entire entire entire entire entire disclosure Instead of ruthenium, such as boron and aluminum, a wide selection of materials is provided and the charge density is fully controlled at the anion position. A further example is U.S. Patent No. 6,514,640, which is incorporated herein by reference. It discloses an equivalent charge substitution for replacing an element with a similarly charged element at a particular crystal position. For example, Mg ²⁺ is considered to be a similar charge to Fe ²⁺ , while V ⁵⁺ and P ⁵⁺ are similarly equivalent charges. Similarly, the (PO ₄ ) ₃ tetrahedron can be substituted with a (VO ₄ ) ₃ tetrahedron. Heterovalent substitution refers to the replacement of an element with a different valence or charge element at a particular crystal position. An example of an isovalent substitution is substitution of Cr ³⁺ or Ti ⁴⁺ at the Fe ²⁺ position.

The above description of the embodiments should not be construed as limiting, as other variations, modifications and improvements are possible within the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims and their equivalents.

All of the components and/or methods disclosed and claimed herein can be made and executed without undue experimentation. Although the composition and method of the present invention are described in the preferred embodiments, it is obvious to those skilled in the art that the changes may be applied to the compositions and/or methods and steps or steps described herein. The concept, spirit and scope of the present invention. All such similar substitutes and modifications as those skilled in the art are considered to be within the spirit, scope and concept of the invention as defined by the scope of the application.

All references cited in this document are hereby incorporated by reference.

Figure 1 represents the XRD spectrum (CoK α) of carbon-deposited lithium iron zirconium phosphonate, obtained from FePO ₄ , iron oxalate, Li ₂ CO ₃ , Si(OC ₂ H ₅ ) ₄ , Zr(IV) acetate Hydroxide, atomic ratio Li:Fe:Zr:P:Si=1:0.9:0.1:0.8:0.2, prepared by Example 1. The unit cell volume was calculated from the XRD data for the 291 Å ^3, compared with C-LiFePO ₄ of 291 Å ^3.

Figure 2 represents the XRD spectrum (CoK α) of carbon-deposited lithium iron zirconium phosphonate, obtained from FePO ₄ , oxalate, Li ₂ CO ₃ , Si(OC ₂ H ₅ ) ₄ , Zr(IV) acetic acid. Salt hydroxide, atomic ratio Li:Fe:Zr:P:Si=1:0.9:0.1:0.8:0.2, prepared from Example 2. The unit lattice volume calculated from the XRD data is 291.1 Å ³ , which is compared with 291 Å ^{3 of} C-LiFePO ₄ .

Figure 3 represents the XRD spectrum (CoK α) of the carbon-deposited lithium iron strontium phosphonate, which is obtained from FePO ₄ , iron oxalate, Li ₂ CO ₃ , Si(OC ₂ H ₅ ) ₄ , Zr ( IV) Acetate hydroxide, atomic ratio Li:Fe:Zr:P:Si=1:0.9:0.1:0.8:0.2, prepared from Example 3. The unit lattice volume calculated from the XRD data is 291.8 Å ³ compared to 291 Å ^{3 of} C-LiFePO ₄ .

Figure 4 represents the XRD spectrum (CoK α) of the carbon-deposited lithium iron zirconium phosphonate, which is obtained from FePO ₄ , iron oxalate, Li ₂ CO ₃ , Si(OC ₂ H ₅ ) ₄ , Zr (IV). Acetate hydroxide, atomic ratio Li:Fe:Zr:P:Si=1:0.9:0.1:0.8:0.2, prepared from Example 4. The unit lattice volume calculated from the XRD data is 292.6 Å ³ compared to 291 Å ^{3 of} C-LiFePO ₄ .

Figure 5 represents the XRD spectrum (CoK α) of the carbon-deposited lithium iron zirconium phosphonate, which is obtained from iron oxalate, LiH ₂ PO ₄ , Li ₂ CO ₃ , Si(OC ₂ H ₅ ) ₄ , Zr(IV) acetate hydroxide, atomic ratio Li:Fe:Zr:P:Si=1:0.95:0.05:0.95:0.05, prepared from Example 5. The unit lattice volume calculated from the XRD data is 291.3 Å ³ compared to 291 Å ^{3 of} C-LiFePO ₄ .

Figure 6 represents the XRD spectrum (CoK α) of the carbon-deposited lithium iron zirconium phosphonate, which is obtained from iron oxalate, LiH ₂ PO ₄ , Li ₂ CO ₃ , Si(OC ₂ H ₅ ) ₄ , Zr(IV) acetate hydroxide, atomic ratio Li:Fe:Zr:P:Si=1:0.95:0.05:0.9:0.1, prepared from Example 6. The unit lattice integral calculated from the XRD data is 291.6 Å ³ , which is compared with 291 Å ^{3 of} C-LiFePO ₄ .

Figure 7 represents the cathode capacitance measured at room temperature at a C/12, C and 10 C discharge rate for a Li/1M LiPF ₆ EC:DEC 3:7/carbon deposited lithium iron zirconium phosphate cell. The battery voltage (volts vs Li ⁺ /Li) is shown on the Y-axis, and the capacitance (mAh/g) is shown on the X-axis. The prepared battery has the cathode material of Example 2 of the present invention prepared in Example 2 as positive electrode.

Figure 8 represents the cathode capacitance measured at room temperature at a C/12, C and 10 C discharge rate for a Li/1M LiPF ₆ EC:DEC 3:7/carbon deposited lithium iron zirconium phosphate cell. The battery voltage (volts vs Li ⁺ /Li) is shown on the Y-axis and the capacitance (mAh/g) is shown on the X-axis. The prepared battery had the carbon deposition, lithium ion, zirconium, and phosphonium salt of Example 5 of the present invention prepared in Example 5 as a positive electrode, and the atomic ratio Li:Fe:Zr:P:Si=1:0.95 : 0.05:0.9:0.1.

Figure 9 represents the anion capacitance measured at room temperature at a C/12, C and 10 C discharge rate for a Li/1M LiPF ₆ EC:DEC 3:7/carbon deposited lithium iron zirconium phosphate cell. The battery voltage (volts vs Li ⁺ /Li) is shown on the Y-axis and the capacitance (mAh/g) is shown on the X-axis. The prepared battery has an example comprising the carbon deposition, lithium, iron, zirconium, and phosphonium salt of Example 5, and the atomic ratio Li:Fe:Zr:P:Si=1:0.95:0.05:0.95:0.05, as positive electrode.

Figure 10 represents the energy capability of the battery (ragone plot), measured at room temperature with a Li/1M LiPF ₆ EC:DEC 3:7/carbon deposited lithium iron zirconium phosphate cell. The capacitance (mAh/g) is shown on the Y-axis, and the discharge rate (C-rate, corresponding to a full-capacity discharge in 1 hour) is shown on the X-axis, and the initial capacity is measured by a slow-scan voltmeter. The fabricated battery had a carbon-deposited lithium iron zirconium phosphonate sample containing Example 5 as a positive electrode, and an atomic ratio of Li:Fe:Zr:P:Si = 1:0.95:0.05:0.95:0.05.

Figure 11 shows the cycle capacity measured at 60 ° C at a C/4 discharge rate for a Li/1M LiPF ₆ EC:DEC 3:7/C-LiFePO ₄ carbon deposited lithium iron zirconium phosphate cell. The capacitance (mAh/g) is shown on the Y-axis, and the number of cycles is shown on the X-axis. The initial capacity is measured by a slow-scan voltmeter. The prepared battery has an example of carbon deposition, lithium, iron, zirconium, phosphonium silicate containing the fifth embodiment of the present invention, and an atomic ratio of Li:Fe:Zr:P:Si=1:0.95:0.05:0.95:0.05. . □ indicates the battery capacity, and ○ indicates the charge/discharge ratio.

Claims (40)

A method of synthesizing carbon-deposited alkali metal oxyanion cathode material comprising particles, wherein the particles have at least a portion of the surface of the particle with carbon deposited by thermal decomposition, the method comprising: a first dry high energy milling step And applying to the precursor of the carbon-deposited alkali metal oxyanion prior to the first solid state thermal reaction, wherein the first solid thermal reaction produces a first solid thermal reaction product; and a second dry high energy grinding The step is applied to the product prior to a second solid state thermal reaction. The method of claim 1, wherein the method comprises adding a source compound of carbon to the precursor before or during the first high energy milling step, and/or before or during the second high energy milling step A source compound of one carbon is added to the product. The method of claim 2, wherein the carbon source is a liquid, solid or gaseous hydrocarbon. The method of claim 2, wherein the carbon source is a free polycyclic aromatic, perylene and its derivatives, a polyhydroxy compound, cellulose, starch and esters and ethers thereof, a fatty acid, a fatty acid salt, Aliphatic esters, aliphatic alcohol esters, alkoxylated alcohols, alkoxylated amines, aliphatic alcohol sulfates, phosphates, imidazolines and quaternary ammonium salts, ethylene oxide/propylene oxide copolymers, ethylene oxide/buteneization Oxygen copolymer, polyolefin, polybutene, polyvinyl alcohol, phenol condensation product, polymer derived from mercapto alcohol, styrene, divinylbenzene, naphthalene, perylene, vinyl nitrile and vinyl acetate Among the constituent families. The method of claim 4, wherein the polycyclic aromatic It is a group of people who choose free tar and asphalt. The method of claim 4, wherein the polyhydroxy compound is selected from the group consisting of sugars, carbohydrates, and derivatives thereof. The method of any one of claims 1 to 6, wherein the precursor comprises at least one source compound of an alkali metal, at least one source compound of metal M, wherein M is Fe and/or Mn; at least one metal M a source compound, wherein M' is a metal of 2+ or more in the carbon-deposited alkali metal phosphonic acid; at least one phosphorus (P) source compound if P is not present in any of the source compounds; at least one 矽 (S1 a source compound if Si is not present in any of the other source compounds, and in a family of at least one carbon source compound. The method of claim 7, wherein the source compound of the M is selected from iron, iron (III) oxide, magnetite (Fe ₃ O ₄ ), trivalent iron phosphate, lithium iron hydroxy phosphate, trivalent Ferric nitrate, ferrous phosphate, blue iron ore Fe ₃ (PO ₄ ) ₂ , iron acetate (CH ₃ COO) ₂ Fe, iron sulfate (FeSO ₄ ), iron oxalate, iron (III) nitrate, iron (II) nitrate , FeCl ₃ , FeCl ₂ , FeO, ammonium iron phosphate (NH ₄ FePO ₄ ) and Fe ₂ P ₂ O ₇ , ferrocene (iron), a combination of the members. The method of claim 7 or 8, wherein the source compound of the M is selected from the group consisting of manganese, MnO, MnO ₂ , manganese acetate, manganese oxalate, manganese (III) acetylacetonate, and manganese acetylacetonate. (II), manganese chloride, MnCO ₃ , manganese sulfate, manganese nitrate, manganese phosphate, manganese (manganese) manganese, and combinations thereof. The method of any one of claims 7 to 9, wherein the source compound of the alkali metal is selected from the group consisting of lithium oxide, sodium oxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, Li ₃ PO ₄ , Na ₃ PO ₄ , K ₃ PO ₄ , hydrogen phosphate, LiH ₂ PO ₄ , LiNaHPO ₄ , LiKHPO ₄ , NaH ₂ PO ₄ , KH ₂ PO ₄ , Li ₂ HPO ₄ , n-, m- or lithium polysilicate, sodium or Potassium, lithium sulfate, sodium sulfate, potassium phosphate, lithium oxalate, sodium oxalate, potassium oxalate, lithium acetate, sodium acetate, potassium acetate, and combinations thereof. The method of any one of claims 7 to 10, wherein the source compound of the P is a free phosphoric acid and an ester, M ₃ PO ₄ , wherein M is at least selected from Li, Na and K, and hydrogen phosphate MH ₂ PO ₄ wherein M is at least selected from Li, Na and K, monoammonium or diammonium phosphate, ferric triphosphate or ammonium manganese phosphate (NH ₄ MnPO ₄ ), MnHPO ₄ , Fe ₂ P ₂ O ₇ and combinations thereof . The method of any one of claims 7 to 11, wherein the source compound of the Si is selected from the group consisting of organic hydrazine, decyl alkoxide, tetramethyl orthosilicate, tetraethyl orthosilicate, and nanometer. Of the group consisting of SiO ₂ , Li ₂ SiO ₃ , Li ₄ SiO ₄ , and combinations thereof. The method of any one of claims 7 to 12, wherein the source compound of the M' is free Zr ⁴⁺ , Ti ⁴⁺ , Nb ⁴⁺ , Mo ⁴⁺ , Ge ⁴⁺ , Ce ⁴⁺ and a source compound of a group consisting of Sn ⁴⁺ , and/or a group of freely composed of Al ³⁺ , Y ³⁺ , Nb ³⁺ , Ti ³⁺ , Ga ³⁺ , Cr ³⁺ and V ³⁺ a source compound of a metal, and/or a metal-derived compound selected from the group consisting of Ta ⁵⁺ and Nb ⁵⁺ , and/or a source compound of a metal composed of Zn ²⁺ and Ca ²⁺ . The method of claim 13, wherein the metal is Zr ⁴⁺ and the source compound is selected from the group consisting of zirconium acetate hydroxide, zirconium alkoxide, n-butyl zirconate, zirconium acetylate pyruvate ( IV), zirconium (IV) glycolate, zirconium (IV) hydroxyphosphate, zirconium ruthenate (IV), and any combination thereof. The method of any one of claims 7 to 14, wherein the source compound is selected to provide an alkali metal: M:M':P:Si ratio of from about 1:0.7 to 1:>0 to 0.3. :>0.7 to 1: cathode of 0 to 0.3. The method of any one of claims 1 to 15, wherein the high energy grinding step is by a high energy ball mill, a pulverizing mixing mill, a planetary ball mill, a drum-ball mill, a shaking mill A grinding device consisting of a stirring ball mill, a mixer ball mill, a vertical mill, and a horizontal grinder is used. The method of any one of claims 1 to 16, wherein the first solid state thermal step is an operator operating at a temperature ranging from about 200 ° C to about 600 ° C. The method of any one of claims 1 to 17, wherein the second solid state thermal step is an operator operating at a temperature ranging from about 400 ° C to about 800 ° C. The method of any one of claims 1 to 18, wherein the first and/or second solid thermal step is performed in an inert gas or a reducing atmosphere, wherein the atmosphere is optionally humidified. The method of any one of claims 1 to 19, wherein the first and/or second high energy grinding step is carried out in an inert gas or a reducing atmosphere. The method of claim 19, wherein the reducing atmosphere participates in the reduction or prevention of oxidation of at least one metal in the precursor Oxidation without complete reduction to elemental state. The method of claim 19, wherein the reducing atmosphere comprises an additional reducing atmosphere, a reducing atmosphere derived from degradation of the compound, a reducing atmosphere derived from the synthesis reaction, and combinations thereof. The method of claim 22, wherein the additional reducing atmosphere comprises CO, H ₂ , NH ₃ , HC, and combinations thereof, wherein HC is a hydrocarbon or a carbon-containing compound. The method of claim 22, wherein the reducing atmosphere derived from degradation of a compound comprises a reducing atmosphere which is degraded or converted by a compound under heating. The method of claim 22, wherein the reducing atmosphere derived from degradation of a compound comprises CO, CO/CO ₂ , H ₂ or a combination thereof. The scope of the patent application method of any one of 1 to 23, wherein the precursor comprises a source comprising FePO ₄ iron or iron oxalate, Li ₂ CO ₃ comprising a source of lithium or of LiH ₂ PO _4; a SiO ₄ Source and source of a Zr(IV). The method of any one of claims 1 to 26, wherein the first thermal reaction produces a substantially amorphous product, and/or wherein the second high energy milling produces a substantially amorphous product . A carbon-deposited alkali metal phosphonium citrate cathode material comprising particles having an olivine structure with at least a portion of a surface having carbon deposited by thermal decomposition, wherein the particles have a general formula wherein the element Li:Fe: M':PO ₄ : SiO _{4 is} present at a ratio of about 1 +/- x:0.95 +/- x:0.05 +/- x:0.95 +/- x:0.05 +/- x, where x is independently about 20 The value of %, and M' is a 4+ valence metal. The carbon-deposited alkali metal phosphonium citrate cathode material of claim 28, wherein x is independently a value of about 10%. For example, the carbon-deposited alkali metal phosphonium citrate cathode material of claim 28, wherein x is independently a value of about 5% For example, the carbon-deposited alkali metal phosphonium citrate cathode material of claim 28, wherein x is independently a value of about 4% For example, the carbon-deposited alkali metal phosphonium citrate cathode material of claim 28, wherein x is independently a value of about 3%. For example, the carbon-deposited alkali metal phosphonium citrate cathode material of claim 28, wherein x is independently a value of about 2% The carbon-deposited alkali metal phosphonate cathode material according to any one of claims 28 to 33, wherein M' is Zr ⁴⁺ . A carbon-deposited alkali metal phosphonium citrate cathode material according to claim 28, wherein M' is Zr ⁴⁺ and wherein the particles have a general formula wherein the ratio of the element Li:Fe:Zr:PO ₄ :SiO ₄ is 1 : 0.95: 0.05: 0.95: 0.05. The method of any one of claims 1 to 27, wherein the high energy milling is high energy ball milling. The method of any one of claims 1 to 27, wherein the first solid thermal step is in the range of about 400 ° C and about 600 ° C, or about 200 ° C and about 500 ° C. Or at a temperature in the range of about 250 ° C and about 450 ° C, or in the range of about 300 ° C and about 400 ° C, or in the range of about 500 ° C and about 600 ° C. For example, any of the patent scopes 1 to 27 and 36 to 38 The method of claim 2, wherein the second solid thermal step is performed at a temperature ranging from about 400 ° C to 700 ° C, or from about 450 ° C to about 650 ° C, or from about 500 ° C to about 600 ° C. . The method of any one of claims 1 to 27, wherein the first and/or second high energy grinding step is in the range of about 5 minutes to about 4 hours, about 10 Divided into a range of about 4 hours, about 30 minutes to 4 hours, about 60 minutes to 4 hours, about 90 minutes to 4 hours, about 120 minutes to 4 hours, about 150 minutes to about 4 The range of hours, from about 180 minutes to 4 hours, from about 210 minutes to 4 hours, or from about 230 minutes to 4 hours. The method of any one of claims 1 to 27 and 36 to 39, further comprising a subsequent rapid thermal treatment, which is about 650 ° C and about 900 ° C, about 700 ° C and about 900 ° C, respectively. The operator is at a temperature of about 750 ° C and about 900 ° C, about 800 ° C and about 900 ° C, about 825 ° C and about 900 ° C, or about 850 ° C and about 900 ° C.