KR100805875B1 - Olivine type positive active material precursor for lithium battery, and method for preparing the same - Google Patents

Abstract

An olivine type cathode active material precursor for a lithium battery is provided to realize excellent crystallinity and a high tab density and to obtain a cathode active material having a high bulk energy density. An olivine type cathode active material precursor for a lithium battery comprises MxO4-zBz particles (wherein M is an element selected from Fe, Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, Mg, B and combinations thereof; X is an element selected from P, As, Bi, Sb and combinations thereof; B is an element selected from F, S and combinations thereof; and z ranges from 0 to 0.5), and has a particle diameter of 0.1-10 micrometers and a tab density of 0.8-2.0 g/cm^3.

Description

OLIVINE TYPE POSITIVE ACTIVE MATERIAL PRECURSOR FOR LITHIUM BATTERY, AND METHOD FOR PREPARING THE SAME}

1 is a scanning electron microscope (SEM) photograph of the iron-phosphate hydrate prepared in Example 2. FIG.

2 is a scanning electron micrograph of the iron-phosphate prepared in Example 2. FIG.

3 is a scanning electron micrograph of the iron-phosphate prepared in Example 9. FIG.

4 is a graph showing the results of X-ray diffraction analysis (XRD) of the iron-phosphate prepared in Example 2.

5 is a graph showing the results of X-ray diffraction analysis of the iron-phosphate prepared in Example 9.

[Industrial use]

The present invention relates to an olivine-type positive electrode active material precursor for a lithium battery, and a method for manufacturing the same. More specifically, the present invention relates to an olivine-type positive electrode active material precursor, and more particularly, a pure crystal having few impurities, which has better crystallinity and a higher tap density than a conventional olivine-type positive electrode active material precursor. The present invention relates to a blank cathode active material precursor, and a method of manufacturing the same.

[Prior art]

Recently, charging and discharging are repeated using portable electronic devices for information and communication such as mobile phones, PDAs, notebook PCs, portable electronic devices such as digital cameras, camcorders, MP3s, electric bicycles, and electric vehicles. The demand for secondary batteries used is growing exponentially. Commercially available lithium secondary batteries mainly use LiCoO ₂ for the positive electrode and carbon for the negative electrode.

However, cobalt, which is a starting material of the positive electrode active material, has a low reserve and is expensive, and there is a demand for development of an alternative positive electrode material due to toxicity and environmental pollution problems. LiNiO ₂ , LiCo _x Ni _{1 - x} O ₂ , LiMn ₂ O ₄ , and the like are currently being actively researched and developed as positive electrode active materials. LiNiO ₂ , which has the same layer structure as LiCoO ₂ , is not commercialized due to difficulty in synthesizing materials at a stoichiometric ratio and thermal stability problems, and LiMn ₂ O ₄ is commercialized in low cost products. However, LiMn ₂ O ₄ , a 4V spinel cathode active material, has the advantage of using manganese as a starting material, but its life characteristics are poor due to a structural variation called Jahn-Teller distortion caused by manganese ³⁺ .

Accordingly, there is a demand for a positive electrode active material that is more economical, stable, high capacity, and has good cycle characteristics. As a compound having an olivine structure as a cathode active material of a lithium secondary battery, a compound of formula Li _x M _y PO ₄ (where x is 0 <x ≦ 2, y is 0.8 ≦ y ≦ 1.2, and M is a periodic table 3d transition) Metal).

The use of LiFePO ₄ as a positive electrode of a lithium ion battery among the compounds represented by Li _x M _y PO ₄ is disclosed in Japanese Patent Laid-Open No. 9-171827. LiFePO ₄ is environmentally friendly, rich in reserves and very low in raw material prices. In addition, it is possible to implement low power and low voltage more easily than the conventional cathode active material, the theoretical capacity is 170 mAh / g, the battery capacity is also excellent.

However, the solid phase reaction method and the wet reaction method, which are the synthesis methods of the olivine-type FePO ₄ precursor of LiFePO ₄ , cannot control the particle size and the shape of the particles, and it is difficult to synthesize the powder composed of single particles. That is, there is a need for a new synthesis method of an olivine-type positive electrode active material that suppresses a small specific surface area and has a high volumetric energy density.

In order to solve the above problems, the present invention provides a olivine-type positive electrode active material precursor for a lithium battery, which has excellent crystallinity and higher tap density than a conventional olivine-type positive electrode active material precursor.

Another object of the present invention to provide a method for producing the olivine-type positive electrode active material precursor.

In order to achieve the above object, the present invention is MXO _{4 - z} B _z (wherein M is Fe, Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, Mg, Element selected from the group consisting of B, and combinations thereof, X is an element selected from the group consisting of P, As, Bi, Sb, and combinations thereof, and B is composed of F, S, and combinations thereof An element selected from the group and 0 ≦ z ≦ 0.5.) An olivine-type positive electrode active material precursor for a lithium battery including particles, having a particle diameter of 0.1 to 10 μm, and a tap density of 0.8 to 2.0 g / cm ³ is provided.

The olivine-type positive electrode-active material precursor is preferably spherical.

Preferably MXO _{4 - z} B _z is iron-phosphate.

The olivine positive electrode active material precursor preferably has a particle size of 0.2 to 8 µm, more preferably 0.3 to 5 µm. In addition, the olivine-type positive electrode active material precursor preferably has a tap density of 1.0 to 1.8 g / cm ³ , and more preferably 1.2 to 1.6 g / cm ³ .

The present invention also relates to M-containing compounds, wherein M is Fe, Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, Mg, B, and combinations thereof ), An X-containing compound (where X is an element selected from the group consisting of P, As, Bi, Sb, and combinations thereof), and a pH adjusting agent is added to the solvent and mixed Preparing an MX containing hydrate; It provides a method for producing an olivine-type positive electrode active material precursor for a lithium battery comprising the step of vacuum drying the M-X-containing hydrate, followed by firing.

The M-containing compound is acetate containing acetate, nitrate, sulfate, carbonate, citrate, phthalate, perchlorate, acetylacetonate (acetylacetonate), acrylate, formate, oxalate, halide, oxyhalide, boride, oxide, sulfide, fur It is preferable to use those selected from the group consisting of oxides, alkoxides, hydroxides, ammonium, acetylacetone, hydrates thereof, and combinations thereof.

The X-containing compound is acetate containing acetate, nitrate, sulfate, citrate, perchlorate, halide, oxyhalide, oxide ), Sulfide, alkoxide, hydrates thereof, and combinations thereof may be preferably used.

In addition, as the X-containing compound, a compound selected from the group consisting of phosphoric acid, bismuth neodecanoate, hydrates thereof, and combinations thereof may also be preferably used.

The pH adjusting agent is preferably selected from the group consisting of aqueous ammonia solution, carbon dioxide gas, OH group, and combinations thereof, and the compound containing OH is preferably NaOH. In addition, the solvent is preferably water.

The step of preparing the M-X-containing hydrate is preferably made at pH 1.5 to 9.0, the mixing is preferably made for 12 to 24 hours.

The step of preparing the MX-containing hydrate may further comprise adding a B-containing material (where B is an element selected from the group consisting of F, S, and combinations thereof). The B-containing material is nickel fluoride, iron fluoride, cobalt fluoride, manganese fluoride, chromium fluoride, chromium fluoride, zirconium fluoride fluoride, niobium fluoride, copper fluoride, vanadium fluoride, titanium fluoride, zinc fluoride, aluminum fluoride , Gallium fluoride, manganese fluoride, boron fluoride, Boron fluoride, NH ₄ F, LiF, AlF ₃ , S, Li ₂ S, hydrates thereof, and combinations thereof It is preferably selected from the group.

The vacuum drying is preferably made at 50 to 90 ℃, preferably for 12 to 24 hours.

Baking the M-X-containing hydrate is preferably made for 450 to 600 ℃, preferably for 5 to 20 hours. In addition, the step of firing the M-X-containing hydrate is preferably made in a reducing atmosphere.

Hereinafter, the present invention will be described in more detail.

The present invention relates to MXO _{4 - z} B _z (wherein M is Fe, Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, Mg, B, and combinations thereof An element selected from the group consisting of: X is an element selected from the group consisting of P, As, Bi, Sb, and combinations thereof, B is an element selected from the group consisting of F, S, and combinations thereof, 0 ≦ z ≦ 0.5.) An olivine-type positive electrode active material precursor for a lithium battery including particles, having a particle diameter of 0.1 to 10 μm, and a tap density of 0.8 to 2.0 g / cm ³ is provided.

The olivine-type positive electrode active material precursor is a precursor capable of producing an olivine-type positive electrode active material for a lithium battery by mixing with a lithium-containing compound and firing. The olivine positive electrode active material precursor is preferably spherical. Here, the spherical form includes all round, elliptical and the like. When manufacturing the positive electrode active material for lithium secondary batteries using the said spherical olivine-type positive electrode active material precursor, since a spherical olivine-type positive electrode active material can be manufactured, it is preferable.

The olivine-type positive electrode active material precursor MXO ₄ nanosized it is _preferred that the primary particles of _z B _z is united composed of secondary particles.

The MXO _{4 - z} B _z is preferably iron-phosphate.

Preferably, the olivine-type positive electrode active material precursor has a particle diameter of 0.1 to 10 µm, more preferably 0.2 to 8 µm, and still more preferably 0.3 to 5 µm. When the particle size of the olivine-type positive electrode active material precursor is 0.1 to 10 μm, the positive electrode active material may be manufactured without being broken or deformed because it is harder and heavier than nano-sized particles.

Preferably, the olivine-type positive electrode active material precursor has a tap density of 0.8 to 2.0 g / cm ³ , more preferably 1.0 to 1.8 g / cm ³ , and still more preferably 1.2 to 1.6 g / cm ³ . When the tap density of the olivine-type positive electrode active material precursor is 0.8 to 2.0 g / cm ³ , the side reaction with the electrolyte may be reduced, but the capacity per volume may be increased.

The present invention also relates to M-containing compounds, wherein M is Fe, Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, Mg, B, and combinations thereof ), An X-containing compound (where X is an element selected from the group consisting of P, As, Bi, Sb, and combinations thereof), and a pH adjusting agent is added to the solvent and mixed Preparing an MX containing hydrate; It provides a method for producing an olivine-type positive electrode active material precursor for a lithium battery comprising the step of vacuum-drying the M-X-containing hydrate and firing.

First, an M-containing compound, an X-containing compound, and a pH adjuster are added to a solvent and mixed to prepare an M-X-containing hydrate.

The M-containing compound is acetate containing acetate, nitrate, sulfate, carbonate, citrate, phthalate, perchlorate, acetylaceto Acetylacetonate, acrylate, formate, oxalate, halide, oxyhalide, boride, oxide, sulfide, Peroxide, alkoxide, hydroxide, ammonium, acetylacetone, hydrates thereof, and combinations thereof may be preferably used.

In addition, specific examples of the M-containing compound include iron ethylenediammonium sulfate (Iron ethylenediammonium sulfate), titanium bis (ammonium lactato) dihydroxide (manganese monoperoxyphthalate), manganese monoperoxyphthalate (Magnesium monoperoxyphthalate ), Aluminum phnoxide, boric acid, boron trifluoride diethyl etherate, boron trifluoride-propanol, hydrates thereof, and The compound chosen from the group which consists of these combinations is mentioned.

The X-containing compound is acetate containing acetate, nitrate, sulfate, citrate, perchlorate, halide, oxyhalide, oxide ), Sulfides, alkoxides, hydrates thereof, and combinations thereof may be preferably used. In addition, the X-containing compound may be preferably selected from the group consisting of phosphoric acid, bismuth neodecanoate, hydrates thereof, and combinations thereof.

The pH adjusting agent is preferably selected from the group consisting of ammonia aqueous solution, carbon dioxide gas, a compound containing an OH group, and a combination thereof, and more preferably, the compound containing OH is NaOH. In addition, the solvent is preferably water.

The step of preparing the M-X-containing hydrate is preferably made at pH 1.5 to 9.0. When the step of preparing the M-X-containing hydrate is performed at pH 1.5 to 9.0, it is preferable because the atomic ratio of M and X in the olivine-type positive electrode active material precursor approaches 1: 1. Moreover, it is preferable that it is 1-10 M, and, as for the density | concentration of the said pH adjuster, it is more preferable that it is 2-5M.

Mixing for preparing the M-X-containing hydrate is preferably performed for 12 to 24 hours. When the mixing is less than 12 hours, it is difficult to obtain spherical positive electrode active material precursor particles, there is a problem that the tap density is lowered, and when the mixing is more than 24 hours, the size of the prepared positive electrode active material precursor particles is too large electrochemical There is a problem that adversely affects the characteristics.

The step of preparing the M-X-containing hydrate may further include adding a B-containing material (where B is an element selected from the group consisting of F, S, and combinations thereof).

The step of preparing the MX-containing hydrate may further comprise adding a B-containing material (where B is an element selected from the group consisting of F, S, and combinations thereof). The B-containing material is nickel fluoride, iron fluoride, cobalt fluoride, manganese fluoride, chromium fluoride, chromium fluoride, zirconium fluoride fluoride, niobium fluoride, copper fluoride, vanadium fluoride, titanium fluoride, zinc fluoride, aluminum fluoride , Gallium fluoride, manganese fluoride, boron fluoride, Boron fluoride, NH ₄ F, LiF, AlF ₃ , S, Li ₂ S, hydrates thereof, and combinations thereof It is preferably selected from the group.

It is preferable to blow a gas selected from the group consisting of N ₂ gas, Ar gas, and combinations thereof while mixing the M-containing compound and the X-containing compound in the step of preparing the MX-containing hydrate. Injecting N ₂ gas or Ar gas into the reactor can reduce the size of the prepared MX-containing compound particles and increase the tap density.

The prepared M-X-containing hydrate was washed with distilled water, and dried at 50-90 ° C. for 12-24 hours at a vacuum pressure of −65 cmHg or less to completely remove impurities. The vacuum pressure is more preferably -70 to -76 cmHg.

If the vacuum drying temperature is less than 50 ℃ it takes a long time to completely remove the water that is chemically adsorbed in the MX-containing hydrate particles, if it exceeds 90 ℃ the MX-containing hydrate is oxidized if the vacuum is not stable there is a problem. In addition, when the vacuum drying time is less than 12 hours, there is a problem in that the water that is chemically adsorbed in the MX-containing hydrate particles cannot be completely removed, and when it exceeds 24 hours, the process time is because the MX-containing hydrate is already completely dried. This is undesirable because it wastes money. In addition, when the vacuum drying pressure is -65 cmHg or more, it is difficult to completely remove impurities in the M-X-containing hydrate particles.

The vacuum dried M-X-containing hydrate was fired to prepare an olivine positive electrode active material precursor.

Baking the M-X-containing hydrate is preferably made of a temperature of 450 to 600 ℃. When the firing temperature is less than 450 ℃, there is a problem that an amorphous positive electrode active material precursor is formed, when it exceeds 600 ℃, a positive crystal active material precursor with high crystallinity is formed, if the crystallinity of the positive electrode active material precursor is high, the positive electrode active material The MX-containing precursors are not well reduced during production and are not preferred.

In addition, the step of calcining the M-X-containing hydrate is preferably made for 5 to 20 hours. If the firing time is less than 5 hours, there is a problem that a positive crystal active material precursor having high crystallinity cannot be formed. If the firing time is more than 20 hours, the firing is already completed and economically undesirable.

Firing the M-X-containing hydrate is preferably performed in a reducing atmosphere. When the calcining of the M-X-containing hydrate is performed in a reducing atmosphere, the prepared cathode active material precursor contains less impurities, which is preferable. The reducing atmosphere is preferably an atmosphere selected from the group consisting of nitrogen gas, argon gas, argon / hydrogen mixed gas, and combinations thereof.

The olivine-type positive electrode active material precursor prepared by the above manufacturing method is a pure crystal with few impurities, and has better crystallinity than the conventional olivine-type positive electrode active material precursor. In addition, the positive electrode active material for a lithium secondary battery may be prepared by mixing the olivine-type positive electrode active material precursor and the lithium-containing compound according to the present invention.

Hereinafter, although an Example of this invention is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

(Production of the positive electrode active material precursor)

(Example 1)

2L of distilled water was put into a co-precipitation reactor (capacity 2L, the output of a rotating motor of 90 W or more), and iron nitrate aqueous solution (2.4M), H ₃ PO ₄ aqueous solution (2.4M), and ammonia water were supplied. An aqueous iron nitrate solution and a phosphate aqueous solution were supplied at a rate of 0.1 to 1 L / hr so that the total molar concentration of iron nitrate and phosphate in the reactor was 2.4 M, and a pH of 2 to 5 M was maintained at a pH of 1.5 in the reactor. Ammonia water at a concentration was supplied at an appropriate flow rate.

The temperature in the reactor was maintained at 30 ° C. to 70 ° C. while stirring at a speed of 800 to 1000 rpm to coprecipitate. The average residence time of the reactants in the reactor was adjusted to a flow rate of about 12 hours to 24 hours. After the reaction reached steady state, spherical iron-phosphate hydrate was continuously obtained through an overflow pipe.

The iron-phosphate hydrate obtained above was dried at 90 ° C. for 24 hours under vacuum atmosphere.

The iron-phosphate hydrate was calcined at 550 ° C. for 10 hours under a reducing atmosphere to obtain iron-phosphate.

(Example 2)

The iron-phosphate was obtained in the same manner as in Example 1 except that the pH in the reactor was maintained at 2.1.

(Example 3)

The iron-phosphate was obtained in the same manner as in Example 1 except that the pH in the reactor was maintained at 3.0.

(Example 4)

The iron-phosphate was obtained in the same manner as in Example 1 except that the pH in the reactor was maintained at 4.1.

(Example 5)

The iron-phosphate was obtained in the same manner as in Example 1 except that the pH in the reactor was maintained at 5.0.

(Example 6)

The iron-phosphate was obtained in the same manner as in Example 1 except that the pH in the reactor was maintained at 6.0.

(Example 7)

The iron-phosphate was obtained in the same manner as in Example 1 except that the pH in the reactor was maintained at 7.0.

(Example 8)

The iron-phosphate was obtained in the same manner as in Example 1 except that the pH in the reactor was maintained at 8.0.

(Example 9)

After injecting N ₂ gas and Ar gas into the reactor, the iron-phosphate was obtained in the same manner as in Example 1 except for stirring for 1 hour and continuously injecting N ₂ gas at the time of coprecipitation.

(Particle diameter of the prepared cathode active material precursor and Tap density  Measure)

The particle size and tap density of the iron-phosphate prepared in Examples 1 to 9 were measured, and the results are summarized in Table 1.

Particle size (㎛) Tap Density (g / cm ³ ) Example 1 3 to 10 0.9 to 1.1 Example 2 8 to 10 1.3 to 1.5 Example 3 1 to 8 1.0 to 1.3 Example 4 0.1 to 2 0.8 to 0.93 Example 5 0.1 to 3 0.8 to 0.9 Example 6 0.2 to 5 0.85 to 1.0 Example 7 0.2 to 3 0.8 to 1.0 Example 8 0.5 to 3 0.8 to 0.9 Example 9 0.5 to 5 1.2 to 1.5

Referring to Table 1, it can be seen that the iron-phosphate prepared in Examples 1 to 9 has a particle diameter of 0.1 to 10 μm and a tap density of 0.8 to 2.0 g / cm ³ .

(Scanning Electron Microscopy of the Prepared Cathode Active Material Precursor)

The iron-phosphate hydrate prepared in Example 2 was observed with a scanning electron microscope (SEM, model number JSM 6400 JEOL), and a scanning electron micrograph of the iron-phosphate hydrate prepared in Example 2 is shown in FIG. 1. .

The iron-phosphate prepared in Examples 1 to 9 was observed with a scanning electron microscope, and scanning electron micrographs of the iron-phosphate prepared in Example 2 and Example 9 are shown in FIGS. 2 to 3, respectively.

Referring to Figure 1, it can be seen that the particle diameter of the iron-phosphate hydrate particles prepared in Example 2 is 8 to 10㎛.

2 to 3, it can be seen that the particle diameter of the iron-phosphate prepared in Example 2 is 8 to 10㎛, the particle diameter of the iron-phosphate prepared in Example 9 is 0.5 to 5㎛.

(X-ray of the prepared cathode active material precursor diffraction  analysis)

X-ray diffraction analysis (XRD, model number Rint-2000, Rigaku Co., Ltd.) was performed on the iron-phosphate prepared in Examples 2 and 9, and the results are shown in FIGS. 4 and 5, respectively.

Referring to FIGS. 4 and 5, the same peaks as those of Card No. 29-0715 of Joint Committee on Powder Diffraction Standards (JCPDS) can be seen that the materials prepared in Examples 1 and 9 are iron-phosphate.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

The olivine-type positive electrode active material precursor according to the present invention is a pure crystal with few impurities, and has better crystallinity and higher tap density than the conventional olivine-type positive electrode active material precursor.

Claims (22)

MXO _{4 - z} B _z (wherein M is Fe, Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, Mg, B, and combinations thereof Is an element selected, X is an element selected from the group consisting of P, As, Bi, Sb, and combinations thereof, B is an element selected from the group consisting of F, S, and combinations thereof, 0 ≦ z ≤ 0.5) particles; Particle diameter of 0.1 to 10 탆, tap density of 0.8 to 2.0 g / cm ³ Olivine Type Cathode Active Material Precursor for Lithium Battery . The method of claim 1, The olivine-type positive electrode active material precursor is a spherical olivine-type positive electrode active material precursor . The method of claim 1, Wherein MXO _{4 - z} B _z is iron-phosphate olivine-type positive electrode active material precursor for a lithium battery. The method of claim 1, The olivine-type positive electrode active material precursor has a particle diameter of 0.2 to 8㎛, tap density of 1.0 to 1.8g / cm ³ olivine-type positive electrode active material precursor. The method of claim 4, wherein The olivine-type positive electrode active material precursor has a particle size of 0.3 to 5㎛, tap density of 1.2 to 1.6g / cm ³ olivine-type positive electrode active material precursor for a lithium battery. The method of claim 1, The olivine-type positive electrode active material precursor is a olivine-type positive electrode active material precursor for a lithium battery that is the secondary particles formed by agglomeration of the primary particles of the MXO _{4 - z} B _z . M-containing compound, where M is Fe, Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, Mg, B, and combinations thereof .), An X-containing compound (wherein X is an element selected from the group consisting of P, As, Bi, Sb, and combinations thereof), and a pH adjusting agent is added to the solvent and mixed to prepare an MX-containing hydrate. Doing; Calcining the M-X-containing hydrate after vacuum drying Method for producing an olivine-type positive electrode active material precursor for a lithium battery comprising a. The method of claim 7, wherein The M-containing compound is acetate containing acetate, nitrate, sulfate, carbonate, citrate, phthalate, perchlorate, acetylacetonate (acetylacetonate), acrylate, formate, oxalate, halide, oxyhalide, boride, oxide, sulfide, fur Olivine-type positive electrode active material for lithium batteries, which is selected from the group consisting of oxides, alkoxides, hydroxides, ammonium, acetylacetone, hydrates thereof, and combinations thereof Method for preparing the precursor. The method of claim 7, wherein The M-containing compound is iron ethylenediammonium sulfate (Iron ethylenediammonium sulfate), titanium bis (ammonium lactato) dihydroxide, manganese monoperoxyphthalate (Magnesium monoperoxyphthalate), aluminum phenoxide (Aluminum phnoxide), boric acid, boron trifluoride diethyl etherate, boron trifluoride-propanol, hydrates thereof, and combinations thereof The manufacturing method of the olivine-type positive electrode active material precursor for lithium batteries which is chosen from the group. The method of claim 7, wherein The X-containing compound is acetate containing acetate, nitrate, sulfate, citrate, perchlorate, halide, oxyhalide, oxide ), Sulfide, alkoxide, hydrates thereof, and combinations thereof, the method for producing an olivine-type positive electrode active material precursor for a lithium battery. The method of claim 7, wherein The X-containing compound is selected from the group consisting of phosphoric acid (Phosporic acid), bismuth neodecanoate, hydrates thereof, and a combination thereof, a method for producing an olivine-type positive electrode active material precursor for a lithium battery. The method of claim 7, wherein The pH adjusting agent is a method for producing an olivine-type positive electrode active material precursor for a lithium battery that is selected from the group consisting of aqueous ammonia solution, carbon dioxide gas, OH group, and combinations thereof. The method of claim 7, wherein The solvent is a method for producing an olivine-type positive electrode active material precursor for a lithium battery. The method of claim 7, wherein The step of preparing the M-X-containing hydrate is a method for producing an olivine-type positive electrode active material precursor for a lithium battery that is made at pH 1.5 to 9.0. The method of claim 7, wherein The mixing is a method for producing an olivine-type positive electrode active material precursor for a lithium battery that is made for 12 to 24 hours. The method of claim 7, wherein The step of preparing the MX-containing hydrate further comprises the step of adding a B-containing material (wherein B is an element selected from the group consisting of F, S, and combinations thereof). Method for producing a positive electrode active material precursor. The method of claim 16, The B-containing material is nickel fluoride, iron fluoride, cobalt fluoride, manganese fluoride, chromium fluoride, chromium fluoride, zirconium fluoride Zirconium fluoride, Niobium fluoride, Copper fluoride, Vanadium fluoride, Titanium fluoride, Zinc fluoride, Aluminum fluoride ), Gallium fluoride, manganese fluoride, boron trifluoride, NH ₄ F, LiF, AlF ₃ , S, Li ₂ S, hydrates thereof, and combinations thereof Method for producing an olivine-type positive electrode active material precursor for a lithium battery that is selected from the group consisting of. The method of claim 7, wherein The vacuum drying is a method for producing an olivine-type positive electrode active material precursor for a lithium battery that is made for 12 to 24 hours. The method of claim 7, wherein The vacuum drying is a method for producing an olivine-type positive electrode active material precursor for a lithium battery that is made at 50 to 90 ℃. The method of claim 7, wherein The firing of the M-X-containing hydrate is a manufacturing method of an olivine-type positive electrode active material precursor for a lithium battery that is made at 450 to 600 ℃. The method of claim 7, wherein The firing of the M-X-containing hydrate is a method for producing an olivine-type positive electrode active material precursor for a lithium battery that is made for 5 to 20 hours. The method of claim 7, wherein The step of firing the M-X-containing hydrate is a method for producing an olivine-type positive electrode active material precursor for a lithium battery that is made in a reducing atmosphere.

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