KR101205456B1 - Method of preparing positive active material for rechargeable lithium battery using iron3 oxide, positive active material for rechargeable lithium battery prepared by using the method, and rechargeable lithium battery including the same - Google Patents

Abstract

Dissolving iron (III) oxide (Fe ₂ O ₃ ) with a solvent to form trivalent iron ions; Reducing the trivalent iron ions with a reducing agent to form divalent iron ions; Mixing the divalent iron ions, a lithium source, a phosphoric acid source and a solvent to form a precipitate; And it provides a lithium secondary battery comprising a method of manufacturing a positive electrode active material for a lithium secondary battery comprising the step of heat-treating the precipitate, a positive electrode active material for a lithium secondary battery prepared according to the manufacturing method, and the positive electrode active material for a lithium secondary battery.

Description

A method of manufacturing a cathode active material for a lithium secondary battery using iron oxide (III), a cathode active material for a lithium secondary battery prepared according to the above method, and a lithium secondary battery comprising the same OXIDE, POSITIVE ACTIVE MATERIAL FOR RECHARGEABLE LITHIUM BATTERY PREPARED BY USING THE METHOD, AND RECHARGEABLE LITHIUM BATTERY INCLUDING THE SAME}

The present invention relates to a method for producing a cathode active material for a lithium secondary battery using iron (III) oxide, a cathode active material for a lithium secondary battery prepared according to the manufacturing method, and a lithium secondary battery comprising the same.

Cells generate electricity by using materials that can electrochemically react to the positive and negative electrodes. A typical example of such a battery is a lithium secondary battery that generates electrical energy by a change in chemical potential when lithium ions are inserted / desorbed at a positive electrode and a negative electrode.

The lithium secondary battery is manufactured by using a material capable of reversible insertion / desorption of lithium ions as a positive electrode active material and a negative electrode active material, and filling an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode.

As a negative electrode active material of a lithium secondary battery, various types of carbon-based materials including artificial graphite, natural graphite, and hard carbon capable of inserting / desorbing lithium are used.

A lithium composite metal compound is used as a cathode active material of a lithium secondary battery, and examples thereof include LiCoO ₂ , LiMn ₂ O ₄ , LiNiO ₂ , LiNi _{1- x} Co _x O ₂ (0 <x <1), LiMnO ₂ , and LiFePO ₄ Composite metal oxides such as are being studied. Among these, in recent years, research on LiFePO ₄ having high energy density, low cost, high stability and environmentally friendly characteristics has been made.

One aspect of the present invention is to provide a method for producing a positive electrode active material for lithium secondary batteries which is excellent in economic efficiency and environmentally friendly using iron (III) oxide.

Another aspect of the present invention is to provide a cathode active material for a lithium secondary battery manufactured according to the method for producing a cathode active material for a lithium secondary battery.

Another aspect of the present invention is to provide a lithium secondary battery including the cathode active material for a lithium secondary battery.

Method for producing a cathode active material for a lithium secondary battery according to an aspect of the present invention comprises the steps of dissolving iron (III) oxide (Fe ₂ O ₃ ) with a solvent to form trivalent iron ions; Reducing the trivalent iron ions with a reducing agent to form divalent iron ions; Mixing the divalent iron ions, a lithium source, a phosphoric acid source and a solvent to form a precipitate; And heat treating the precipitate.

The iron oxide (III) may be derived from waste iron.

The prepared cathode active material for a lithium secondary battery may be LiFePO ₄ .

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The solubilizer may comprise an acid, a chelating agent or a combination thereof.

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The acid may comprise oxalic acid, sulfuric acid, hydrochloric acid, nitric acid or a combination thereof.

The chelating agent is ethylene diamine tetraacetic acid (EDTA), (phosphonate, R ¹ -PO (OR ² ) ₂ , wherein R ¹ and R ² are the same or different from each other and each independently Hydrogen, a C1 to C20 aliphatic organic group, a C3 to C30 alicyclic organic group, or a C2 to C30 aromatic organic group) or a combination thereof.

The reducing agent is 2,3-dihydroxy benzoic acid (2,3-DHBA), 2,5-dimethoxyhydroquinone (2,5-dimethoxyhydroquinone), sodium borohydride (sodium borohydride, NaBH ₄ ), formaldehyde (HCHO) or a combination thereof.

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The lithium source may include lithium hydroxide (LiOH), lithium carbonate (Li ₂ CO ₃ ), lithium carbonate (LiCO ₃ ), lithium acetate (CH ₃ COOLi) or a combination thereof.

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The phosphoric acid source may include phosphoric acid (H ₃ PO ₄ ), ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ), ammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) or a combination thereof.

The solvent may comprise H ₂ O.

The precipitate may include lithium phosphate (Li ₃ PO ₄ ) and iron phosphate (II) (Fe ₃ (PO ₄ ) ₂ ).

The heat treatment may be performed in an inert atmosphere or a reducing atmosphere.

The heat treatment may be performed at a temperature of about 600 ℃ to about 700 ℃.

According to another aspect of the present invention provides a cathode active material for a lithium secondary battery manufactured according to the method for producing a cathode active material for a lithium secondary battery.

According to another aspect of the invention provides a lithium secondary battery comprising a positive electrode including the positive electrode active material, a negative electrode including the negative electrode active material and an electrolyte.

Other aspects of the present invention are included in the following detailed description.

The method for manufacturing a cathode active material for a lithium secondary battery according to an aspect of the present invention uses iron oxide (III), and the iron oxide (III) may be derived from waste iron, so it is economical and can solve waste resource processing problems. It is environmentally friendly.

FIG. 1 is a photograph showing that trivalent iron ions were dissolved by reacting iron (III) with oxalic acid in Example 1. FIG.
FIG. 2 is a scanning electron microscope (SEM) photograph of lithium iron phosphate (LiFePO ₄ ) prepared in Example 1. FIG.
3 is a view schematically illustrating a structure of a lithium secondary battery according to one embodiment.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. Like parts are designated by like reference numerals throughout the specification.

When a portion of a layer, film, region, plate, etc. is said to be "on top" of another part, this includes not only when the other part is "right over" but also when there is another part in the middle. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.

Unless otherwise specified herein, "aliphatic" means C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, specifically C1 to C15 alkyl, C2 to C15 alkenyl, C2 to C15 Alkynyl, more specifically C1 to C10 alkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, and "alicyclic" means C3 to C30 cycloalkyl, C3 to C30 cycloalkenyl, C3 to Means C30 cycloalkynyl, specifically C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, and “aromatic” means C6 to C30 aryl, C2 to C30 heteroaryl Specifically, C6 to C20 aryl, C2 to C20 heteroaryl.

In addition, "heteroaryl group" refers to an aryl group containing 1 to 3 heteroatoms of N, O, S, Si, or P in one ring, and the rest are carbons unless otherwise specified.

According to an embodiment of the present invention, a method of manufacturing a cathode active material for a lithium secondary battery may include forming trivalent iron ions by dissolving iron (III) oxide (Fe ₂ O ₃ ) as a solvent; Reducing the trivalent iron ions with a reducing agent to form divalent iron ions; Mixing the divalent iron ions, a lithium source, a phosphoric acid source and a solvent to form a precipitate; And heat treating the precipitate.

The iron oxide (III) may be derived from waste iron, but is not limited thereto. As a result of analyzing the waste iron obtained from POSCO, it can be seen that the waste iron contains iron (III) oxide (Fe ₂ O ₃ ) as a main component, a small amount of iron (II) oxide (FeO) and a small amount of impurities. .

According to one embodiment of the present invention, a method of manufacturing a cathode active material for a lithium secondary battery is manufactured by manufacturing a cathode active material for a lithium secondary battery using iron oxide (III), for example, iron oxide (III) derived from waste iron. It can save money, simplify the manufacturing process, and solve the waste disposal problem.

The cathode active material for a lithium secondary battery manufactured according to the method of manufacturing a cathode active material for a lithium secondary battery may be LiFePO ₄ , but is not limited thereto.

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The solubilizer may include, but is not limited to, an acid, a chelate, or a combination thereof.

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Specifically, the acid may include oxalic acid, sulfuric acid, hydrochloric acid, nitric acid, or a combination thereof, but is not limited thereto.

Specifically, the chelating agent is ethylene diamine tetraacetic acid (EDTA), phosphonate (phosphonate, R ¹ -PO (OR ² ) ₂ , wherein R ¹ and R ² are the same or different from each other. Independently hydrogen, a C1 to C20 aliphatic organic group, a C3 to C30 alicyclic organic group, or a C2 to C30 aromatic organic group) or a combination thereof, but is not limited thereto.

Specifically, the reducing agent is 2,3-dihydroxy benzoic acid (2,3-DHBA), 2,5-dimethoxyhydroquinone (2,5-dimethoxyhydroquinone), sodium borohydride Lead (sodium borohydride, NaBH ₄ ), formaldehyde (formaldehyde, HCHO) or a combination thereof may be included, but is not limited thereto.

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The lithium source may include lithium hydroxide (LiOH), lithium carbonate (Li ₂ CO ₃ ), lithium carbonate (LiCO ₃ ), lithium acetate (CH ₃ COOLi), or a combination thereof, but is not limited thereto.

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The phosphoric acid source may include phosphoric acid (H ₃ PO ₄ ), ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ), ammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) or a combination thereof, but is not limited thereto. It is not.

The solvent may include H ₂ O, but is not limited thereto.

The precipitate formed may include lithium phosphate (Li ₃ PO ₄ ) and iron phosphate (II) (Fe ₃ (PO ₄ ) ₂ ), but is not limited thereto. The lithium phosphate may be formed by reacting lithium ions of the lithium source with phosphate ions of the phosphate source. In addition, the iron phosphate (II) may be formed by reacting the divalent iron ions with the phosphate ions of the phosphate source.

In the heat treatment of the precipitate, the heat treatment may be performed in an inert atmosphere or a reducing atmosphere. Specifically, the inert atmosphere may be an argon (Ar) atmosphere or a nitrogen (N ₂ ) atmosphere, and the reducing atmosphere may be a hydrogen (H ₂ ) atmosphere, but is not limited thereto.

The heat treatment may be performed at a temperature of about 600 ℃ to about 700 ℃. When the heat treatment is performed in the above temperature range, the compounds included in the precipitate may be reacted to effectively form a positive electrode active material for a lithium secondary battery having one composition, and effectively control the particle size of the positive electrode active material for a lithium secondary battery to be formed. have. In this case, the average particle diameter of the cathode active material for a lithium secondary battery formed may be about 200 nm to about 500 nm. Specifically, the heat treatment may be performed at a temperature of about 650 ℃ to about 700 ℃.

According to the above process it can be prepared a cathode active material for a lithium secondary battery according to an embodiment of the present invention.

The positive electrode active material for a lithium secondary battery may be usefully used for the positive electrode of an electrochemical cell such as a lithium secondary battery. The lithium secondary battery includes a negative electrode and an electrolyte including a negative electrode active material together with the positive electrode.

The positive electrode includes a current collector and a cathode active material layer formed on the current collector.

The cathode active material layer also includes a binder and a conductive material.

The binder adheres positively to the positive electrode active material particles, and also serves to adhere the positive electrode active material to the current collector well, and examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and polyvinyl. Chloride, carboxylated polyvinylchloride, polyvinylfluoride, polymer comprising ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene- Butadiene rubber, acrylic styrene-butadiene rubber, epoxy resin, nylon and the like can be used, but is not limited thereto.

The conductive material is used for imparting conductivity to the electrode. Any conductive material can be used without causing any chemical change in the battery. Examples of the conductive material include natural graphite, artificial graphite, carbon black, acetylene black, Metal powders such as black, carbon fiber, copper, nickel, aluminum, and silver, metal fibers, and the like, and conductive materials such as polyphenylene derivatives may be used alone or in combination.

As the current collector, Al may be used, but the present invention is not limited thereto.

The negative electrode includes a current collector and a negative active material layer formed on the current collector, and the negative active material layer includes a negative active material.

The negative electrode active material includes a material capable of reversibly inserting / desorbing lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and undoping lithium, or a transition metal oxide.

As a material capable of reversibly inserting / desorbing lithium ions, a carbon material may be used, and any carbon-based negative active material generally used in a lithium ion secondary battery may be used, and representative examples thereof include crystalline carbon, amorphous carbon, or the like. Can be used in combination. Examples of the crystalline carbon include graphite such as natural graphite or artificial graphite in the form of amorphous, plate-like, flake, spherical or fibrous type. Examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, fired coke, and the like.

Examples of the alloy of the lithium metal include lithium and metals of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, or Sn. Alloys can be used.

Examples of the material capable of doping and undoping lithium include Si, SiO _x (0 <x <2), Si-M alloys (wherein M is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, Rare earth elements or combinations thereof, not Si), Sn, SnO ₂ , Sn-M (wherein M is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof, Sn is not used), and at least one of these and SiO ₂ may be mixed and used. Examples of the element M include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe , Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S , Se, Te, Po or a combination thereof.

Examples of the transition metal oxide include vanadium oxide, lithium vanadium oxide, and the like.

The negative electrode active material layer also includes a binder, and optionally may further include a conductive material.

The binder adheres the anode active material particles to each other well, and also serves to adhere the anode active material to the current collector well, and representative examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, and carboxylation. Polyvinylchloride, polyvinylfluoride, polymers including ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic ray Tied styrene-butadiene rubber, epoxy resin, nylon, and the like may be used, but is not limited thereto.

The conductive material is used to impart conductivity to the electrode, and may be used as long as it is an electronic conductive material without causing chemical change in the battery to be constructed. Examples thereof include natural graphite, artificial graphite, carbon black, acetylene black, and ketjen black. Carbon-based materials such as carbon fibers; Metal powders such as copper, nickel, aluminum, and silver, or metal-based materials such as metal fibers; Conductive polymers such as polyphenylene derivatives; Or a mixture thereof may be used.

The current collector may be copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam (foam), copper foam, a polymer substrate coated with a conductive metal, or a combination thereof.

The positive electrode and the negative electrode are each prepared by mixing an active material, a conductive material and a binder in a solvent to prepare an active material composition, and applying the composition to a current collector. The method of manufacturing the electrode is well known in the art, and therefore, a detailed description thereof will be omitted herein. N-methylpyrrolidone may be used as the solvent, but is not limited thereto.

As the electrolyte to be charged into the lithium secondary battery, a non-aqueous electrolyte or a known solid electrolyte may be used, and a lithium salt dissolved therein may be used.

Examples of the solvent for the non-aqueous electrolyte include cyclic carbonates such as ethylene carbonate, diethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate, methyl acetate, and ethyl acetate. , Esters such as propyl acetate, methyl propionate, ethyl propionate and γ-butyrolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane , Ethers such as 2-methyltetrahydrofuran, nitriles such as acetonitrile, amides such as dimethylformamide, and the like can be used, but are not limited thereto. These can be used singly or in combination. In particular, a mixed solvent of cyclic carbonate and chain carbonate can be used.

As the electrolyte, a gelated polymer electrolyte in which an electrolyte solution is impregnated with a polymer electrolyte such as polyethylene oxide or polyacrylonitrile, or an inorganic solid electrolyte such as LiI or Li ₃ N can be used, but is not limited thereto.

As the lithium salt, LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlO ₂ , LiAlCl ₄ , LiCl, and LiI may be used, but the present invention is not limited thereto.

Depending on the type of the lithium secondary battery, a separator may exist between the positive electrode and the negative electrode. The separator may be polyethylene, polypropylene, polyvinylidene fluoride or a multilayer film of two or more thereof. The separator may be a polyethylene / polypropylene double layer separator, a polyethylene / polypropylene / polyethylene triple layer separator, a polypropylene / It is needless to say that a mixed multilayer film such as a propylene three-layer separator and the like can be used.

The lithium secondary battery may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the type of separator and electrolyte used, and may be classified into a cylindrical shape, a square shape, a coin type, a pouch type, and the like, Depending on the size, it can be divided into bulk type and thin film type. The structure and the manufacturing method of these cells are well known in the art, and detailed description thereof will be omitted.

3 schematically shows a structure of a lithium secondary battery according to one embodiment of the present invention. As illustrated in FIG. 8, the lithium secondary battery 100 includes a negative electrode 112, a positive electrode 114, a separator 113 positioned between the negative electrode 112, and the positive electrode 114. Lithium secondary composed mainly of the sealing member 140 encapsulating the electrolyte 114 (not shown), the battery container 120, and the electric container 120 impregnated in the positive electrode 114 and the separator 113. The battery 100 is shown. The form of the lithium secondary battery of the present invention is not particularly limited, and any shape such as cylindrical, coin type, pouch type, etc. is possible as long as it includes an electrolyte for a lithium secondary battery according to an embodiment of the present invention and can operate as a battery. Do.

Example

Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are only specific examples of the present invention, and the present invention is not limited to the following examples.

Example  1: Preparation of cathode active material for lithium secondary battery

0.24 g of 0.1 M iron (III) (Fe ₂ O ₃ ) aqueous solution was added to 1.89 g of 1.0 M oxalic acid aqueous solution to dissolve trivalent iron ions.

The photograph after melt | dissolving trivalent iron ion from the said iron oxide (III) is shown in FIG.

As shown in FIG. 1, it can be seen that when iron (III) oxide is dissolved in oxalic acid, trivalent iron ions are effectively dissolved from the iron (III) oxide.

Next, 0.48 g of 2,3-dihydroxy benzoic acid (2,3-DHBA) is added thereto to reduce the trivalent iron ions to divalent iron ions. Subsequently, 0.09 g of lithium hydroxide (LiOH) and 0.13 g of phosphoric acid (H ₃ PO ₄ ) are added thereto and precipitated to form a precipitate. The precipitate comprises lithium phosphate (Li ₃ PO ₄ ) and iron phosphate (II) (Fe ₃ (PO ₄ ) ₂ ).

The precipitate is heat-treated at 700 ° C. for 6 hours in an argon (Ar) atmosphere to form a cathode active material LiFePO ₄ for a lithium secondary battery.

Test Example  1: Scanning electron microscope scanning electron microscope , SEM ) Picture

A sample was prepared by depositing the cathode active material for a lithium secondary battery prepared in Example 1 on a carbon coated grid, and a SEM photograph of the cross section was taken. At this time, an ultra-high performance electron microscope (field emission gun scanning electron microscope, FEG-SEM) JSM-6390 (manufactured by JEOL) was used.

The scanning electron micrograph of the produced positive electrode active material for lithium secondary batteries is shown in FIG.

As shown in FIG. 2, the cathode active material for a lithium secondary battery may be formed of particles having a particle diameter of about 300 nm.

Although specific embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

100: lithium secondary battery, 112: negative electrode,
114: anode, 113: separator,
120: battery container, 140: sealing member

Claims (19)

Dissolving iron (III) oxide (Fe ₂ O ₃ ) with a solvent to form trivalent iron ions;
Reducing the trivalent iron ions with a reducing agent to form divalent iron ions;
Mixing the divalent iron ions, a lithium source, a phosphoric acid source and a solvent to form a precipitate; And
Heat-treating the precipitate
Method for producing a positive electrode active material for a lithium secondary battery comprising a.
The method of claim 1,
The said iron oxide (III) is a manufacturing method of the positive electrode active material for lithium secondary batteries which originates in waste iron.
delete The method of claim 1,
The positive electrode active material for lithium secondary batteries is LiFePO ₄ Method of producing a positive electrode active material for lithium secondary batteries.
delete The method of claim 1,
The solubilizer comprises an acid, a chelating agent, or a combination thereof.
The method according to claim 6,
The acid is oxalic acid, sulfuric acid, hydrochloric acid, nitric acid or a combination thereof, a method for producing a positive electrode active material for lithium secondary batteries.
The method according to claim 6,
The chelating agent is ethylene diamine tetraacetic acid (EDTA), phosphonate (phosphonate, R ¹ -PO (OR ² ) ₂ , wherein R ¹ and R ² are the same or different from each other and independently hydrogen , C1 to C20 aliphatic organic group, C3 to C30 alicyclic organic group, or C2 to C30 aromatic organic group) or a combination thereof.
delete The method of claim 1,
The reducing agent is 2,3-dihydroxy benzoic acid (2,3-DHBA), 2,5-dimethoxyhydroquinone (2,5-dimethoxyhydroquinone), sodium borohydride (sodium borohydride, NaBH ₄ ), formaldehyde (formaldehyde, HCHO) or a combination thereof, a method for producing a positive electrode active material for a lithium secondary battery.
delete The method of claim 1,
The lithium source is a lithium hydroxide (LiOH), lithium carbonate (Li ₂ CO ₃ ), lithium carbonate (LiCO ₃ ), lithium acetate (CH ₃ COOLi) or a combination thereof manufacturing method of a positive electrode active material for a lithium secondary battery. .
The method of claim 1,
The phosphoric acid source may include phosphoric acid (H ₃ PO ₄ ), ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ), ammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ), or a combination thereof. Method for producing an active material.
The method of claim 1,
The solvent is a method for producing a positive electrode active material for a lithium secondary battery containing H ₂ O.
The method of claim 1,
The precipitate comprises a lithium phosphate (Li ₃ PO ₄ ) and iron phosphate (II) (Fe ₃ (PO ₄ ) ₂ ) It is a manufacturing method of a positive electrode active material for a lithium secondary battery.
The method of claim 1,
The heat treatment is a method for producing a cathode active material for a lithium secondary battery that is carried out in an inert atmosphere or a reducing atmosphere.
The method of claim 1,
The heat treatment is a method of manufacturing a positive electrode active material for a lithium secondary battery that is carried out at a temperature of 600 ℃ to 700 ℃.
The cathode active material for a lithium secondary battery manufactured according to any one of claims 1, 2, 4, 6 to 8, 10, and 12 to 17.
A positive electrode including a positive electrode active material;
A negative electrode comprising a negative electrode active material; And
Comprising an electrolyte,
The positive electrode active material is a lithium secondary battery of claim 18 is the positive electrode active material for lithium secondary batteries.

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