JPH10321224A - Lithium battery positive electrode material and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve preservability and safety of a lithium battery so as to have excellent cycle characteristics such as large discharge quantity and small decrease of battery characteristic and suppress gas generation which is caused by decomposition of a positive electrode material after charging. SOLUTION: This positive electrode material consists of a complex oxide represented by the general formula Liw Nix Coy Alz O2 , wherein w=0.90-1.10, x=0.80-0.95, y=0.04-0.19, z=0.01-0.16, and x+y+z=1.0. This complex oxide is obtained by filtering, washing, drying, and burning a deposit, which is formed by mixing Ni nitrate or an aqueous solution of sulfate, Co nitrate or an aqueous solution of sulfate, and an aqueous solution of an Al compound and an alkaline aquesous solution where an atomic ratio of Ni/Co/Al is the above mentioned x/y/z, to form an oxide containing Ni, Co, and Al, then adding a Li compound to the oxide, and burning the obtained mixture at 650-850 deg.C in an oxygen atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION For equipment utilizing a battery as a power source, such as a tape recorder, a mobile phone, and a radio, a battery that is small / lightweight, has a large capacity, and can be repeatedly charged and used many times is desired. At present, a lithium battery meets the demand, and lithium nickel oxide is used as a positive electrode material of the lithium battery.

[0002]

2. Description of the Related Art As a positive electrode material of a lithium battery, lithium cobalt oxide has been put to practical use, but it is expensive and the effective charge amount is only about 50% of the theoretical amount. Materials are required. Lithium nickelate, which is said to be inexpensive and has a large effective storage capacity, is said to be 1.4 times as good as lithium cobalt oxide in effective performance, but lithium nickelate is charged / discharged. There is a problem that the amount of discharge is greatly reduced due to repetition of the above, and the cycle characteristics are inferior. For this reason, it has been studied to improve the cycle characteristics by adding a third substance such as Co or Al. However, it is desired that the safety / storage characteristics be equal to or higher than those of conventional products even when the amount of stored electricity is increased and the energy density is increased. / There is a problem that the cathode material is decomposed to generate gas. It is considered that the main cause of gas generation is that Li ⁺ escapes from the positive electrode material due to the charge reaction to become unstable MO ₂ , and is decomposed to generate O ₂ . Li MO ₂ → Li ⁺ + e + MO ₂ (charge) MO ₂ → MO + 1/2 O ₂

[0003] obtained by adding Co to Li Ni O _2, the cycle characteristics are improved compared to the Li Ni O _2, Li Co O
_The same level as ₂ , but the storage characteristics / safety is Li
It could not be equal to CoO ₂ . Li Ni O ₂
In the case where Al is added to Ni: Ni: Al = 0.85:
If it is not about 0.15, there is no effect of improving the storage characteristics / safety, so that the discharge amount is reduced.

[0004]

SUMMARY OF THE INVENTION The present invention provides a large amount of discharge, a small decrease in battery characteristics due to repeated charging / discharging, excellent cycle characteristics, and suppresses gas generation due to decomposition of a positive electrode material after charging. An object of the present invention is to provide a lithium battery positive electrode material having improved storage stability and safety, and a method for producing the same.

[0005]

Means for Solving the Problems] lithium battery positive electrode material according to the present invention consists of a composite oxide represented by the general formula _{Li w Ni x Co y Al z} 0 2. However, w = 0.90 to 1.10 x = 0.80 to 0.95 y = 0.04 to 0.19 z = 0.01 to 0.16 x + y + z = 1.0

The atomic ratio z of Al is 0.01 to 0.16. If it is less than this, the effect of suppressing gas generation due to decomposition of the positive electrode material after charging, particularly at high temperatures, is reduced. If the amount is too large, the discharge amount will be small. Preferably 0.02-
The range is 0.05.

The atomic ratio y of Co is 0.04 to 0.19. If it is less than this, the effect of suppressing gas generation due to decomposition of the positive electrode material after charging, particularly at high temperatures, is reduced. Also, if it is large, the cost increases. Preferably 0.10 to 0.15
Range.

The atomic ratio of Li / (Ni + Co + Al) is
Basically, it is 1.0, but a range of 0.90 to 1.10.

This general formula Li _w Ni _x Co _y Al _z O ₂
Is an aqueous solution of a nitrate or sulfate of Ni, an aqueous solution of a nitrate or sulfate of Co, or an aqueous solution of an Al compound in such a ratio that the atomic ratio of Ni: Co: Al becomes the following x: y: z: And an alkaline aqueous solution are mixed to form a precipitate, which is filtered, washed, dried, and calcined to obtain an oxide containing Ni, Co, and Al. The oxide contains Li / (Ni + Co +
Al) at an atomic ratio of 0.90 to 1.10.
The compounds are added and mixed, and 650 to 850 ° C. in an oxygen atmosphere.
It is manufactured by firing. However, w = 0.90 to 1.10 x = 0.80 to 0.95 y = 0.04 to 0.19 z = 0.01 to 0.16 x + y + z = 1.0

[0010] Nickel oxide powder, cobalt oxide powder, alumina powder and lithium hydroxide powder are well pulverized and mixed, and the mixture is fired in an oxygen atmosphere at a temperature in the range of 600 to 850 ° C (Comparative Example 4 described later). It is merely a mixture of LiNiO ₂ (lithium nickelate) and LiCoO ₂ (lithium cobaltate) and is not a uniform compound (see FIG. 5 described below).
), The discharge amount is inferior (see Table 1 below). In the present invention, the atomic ratio of Ni: Co: Al is x: y:
An aqueous solution of nitrate or sulfate of Ni at a ratio of
A precipitate formed by mixing an aqueous solution of a nitrate or a sulfate, an aqueous solution of an Al compound and an aqueous alkali solution is filtered, washed, dried and calcined to obtain an oxide containing Ni, Co and Al. The Li compound is added and mixed at a ratio where the atomic ratio of / Ni / Co + Al is 0.90 to 1.10, and the mixture is baked at 650 to 850 ° C. in an oxygen atmosphere, whereby Ni, Co and Al have a crystal structure. Lithium nickelate is obtained.

The fact that Ni, Co and Al are included in the crystal structure of lithium nickelate can be confirmed by X-ray (Test Example 1 and FIGS. 1 and 2 described later). It can be determined from the discharge capacity retention ratio (discharge capacity at the first cycle / discharge capacity at the 30th cycle) that the discharge amount is large and the battery characteristics due to repetition of charge / discharge are small and the cycle characteristics are excellent. (Test Example 2 and Table 1 described below). After charging, even in a high-temperature atmosphere, it can be determined from the starting temperature of desorption of oxygen (Test Example 3 and Table 2 described later) that generation of gas due to decomposition of the positive electrode material is suppressed and storage stability / safety is improved.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As a procedure for forming a precipitate, an aqueous solution of a nitrate or sulfate of Ni, an aqueous solution of a nitrate or sulfate of Co, an aqueous solution of an alkali and an aqueous solution of an Al compound are simultaneously poured and mixed to form a precipitate. Let it. Alternatively, Al
When sodium aluminate or potassium aluminate is used as the compound, a mixed aqueous solution (solution A) of Ni nitrate or sulfate and Co nitrate or sulfate, and a mixture of sodium aluminate or potassium aluminate and alkali Aqueous solution (B
Liquid) in advance, and when both are mixed, or when aluminum nitrate or aluminum sulfate is used as the Al compound, a mixed aqueous solution of a nitrate or sulfate of Ni and a nitrate or sulfate of Co and aluminum nitrate or aluminum sulfate ( Solution C) is prepared in advance, and this is mixed with an alkaline aqueous solution. The concentration of solution A, solution B or solution C is
Each is preferably in the range of 0.15 to 1.5 mol / L (liter).

Suitable alkali compounds are hydroxides or carbonates of sodium, potassium or ammonia. When sodium or potassium is used, it is necessary to filter and wash the coprecipitate to remove the sodium salt or potassium salt. When ammonia is used, nickel forms complex ions when it forms a precipitate with an aqueous solution, and escapes into the wastewater when partially dissolving and filtering the coprecipitate. It is necessary to devise such measures as drying all at once. However, there is an advantage that washing for removing sodium salts and potassium salts is unnecessary. As the Al compound, it is preferable to use at least one or two or more selected from the group consisting of sodium aluminate, potassium aluminate, aluminum nitrate and aluminum sulfate.

As the lithium compound, lithium hydroxide (LiOH) is preferable. Firing after the addition of LiOH is preferably performed in a rotary kiln.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.

[0016]

Example 1 465.2 g (1.6 mol) of nickel nitrate
And 89.1 g (0.3 mol) of 98% cobalt nitrate were dissolved in water to obtain a mixed solution (solution A) of 2 L of nickel nitrate and cobalt nitrate. 318.0 g of sodium carbonate
(3.0 mol) and 9.5 g of sodium aluminate
(0.1 mol) was dissolved in water to prepare 1.8 L of a mixed solution (solution B) of sodium carbonate and sodium aluminate.
The solution A and the solution B were simultaneously poured into 1 L of hot water at 80 ° C. over 80 minutes at a constant rate to cause a reaction. At this time, the temperature was maintained at 80 ° C., and a good stirring state was maintained. After completion of the pouring, this state was maintained for an additional 60 minutes for aging. The precipitate thus obtained was filtered, washed with water and dried at 120 ° C. for 16 hours to obtain a coprecipitate of a basic carbonate of nickel, cobalt and aluminum. The precipitate was pulverized with a wet pulverizer using water as a medium to obtain a powder slurry having an average particle diameter of about 1 μm. The slurry was dried and granulated with a spray dryer to obtain granules having an average particle size of about 13 μm. The temperature of the granules having an average particle diameter of about 13 μm was increased to 400 ° C. under air flow,
The temperature was maintained at this temperature for about 2 hours until the generation of carbon dioxide gas was no longer observed, to obtain an oxide. The composition of the oxide is Ni: 6
0.3 wt%, Co: 11.3 wt%, Al: 1.7 w
t%. 100.0 g of this oxide powder (Ni + C
o = 1.28 mol) and 98% pure lithium hydroxide 5
2.2 g (1.28 mol) [Ni + Co + Al: Li atomic ratio = 0.80 + 0.15 + 0.05: 1 = 1: 1] was pulverized and mixed well in a mortar. This was calcined at 750 ° C. for 10 hours under flowing oxygen to synthesize LiAl _0.05 Co _0.15 Ni _0.80 O ₂ .

[0017]

Example 2 Solution A was prepared by adding 494.2 g (1.7) of nickel nitrate.
Mol) and 59.4 g (0.2 mol) of 98% cobalt nitrate.
A 1.8 L solution of 18.0 g (3.0 mol) and 9.5 g (0.1 mol) of sodium aluminate;
And the mixing ratio of oxide powder and lithium hydroxide is Ni + Co
+ Al: Li atomic ratio = 0.85 + 0.10 + 0.05:
LiAl in the same manner as in Example 1 except that 1 = 1: 1.
_0.05 Co _0.10 Ni _0.85 O ₂ was synthesized.

[0018]

Example 3 471.0 g of nickel nitrate (1.6 g)
2 mol) and 89.1 g (0.3 mol) of 98% cobalt nitrate.
A 1.8 L solution of 18.0 g (3.0 mol) and 7.6 g (0.08 mol) of sodium aluminate was used, and the mixing ratio between the oxide powder and lithium hydroxide was Ni +
Co + Al: Li atomic ratio = 0.81 + 0.15 + 0.0
In the same manner as in Example 1 except that 4: 1 = 1: 1
LiAl _0.04 Co _0.15 Ni _0.81 O ₂ was synthesized.

[0019]

Embodiment 4 Solution A was prepared by adding 494.2 g (1.7) of nickel nitrate.
0 mol) and 65.3 g (0.22%) of 98% cobalt nitrate.
Mol), and the B solution is a 1.8 L dissolution of 318.0 g (3.0 mol) of sodium carbonate and 7.6 g (0.08 mol) of sodium aluminate; and The mixing ratio of powder and lithium hydroxide is Ni +
Co + Al: Li atomic ratio = 0.85 + 0.11 + 0.0
In the same manner as in Example 1 except that 4: 1 = 1: 1
LiAl _0.04 Co _0.11 Ni _0.85 O ₂ was synthesized.

[0020]

Example 5 A solution was prepared by adding 476.8 g (1.6) of nickel nitrate.
4 mol) and 89.1 g of 98% cobalt nitrate (0.30
Solution B), and the B solution is a 1.8 L solution of 318.0 g (3.0 mol) of sodium carbonate and 5.7 g (0.06 mol) of sodium aluminate; and The mixing ratio of powder and lithium hydroxide is Ni +
Co + Al: Li atomic ratio = 0.82 + 0.15 + 0.0
In the same manner as in Example 1 except that 3: 1 = 1: 1
LiAl _0.03 Co _0.15 Ni _0.82 O ₂ was synthesized.

[0021]

Embodiment 6 Solution A was prepared by adding 494.2 g (1.7) of nickel nitrate.
0 mol) and 68.4 g (0.24%) of 98% cobalt nitrate.
Solution B), and the B solution is a 1.8 L solution of 318.0 g (3.0 mol) of sodium carbonate and 5.7 g (0.06 mol) of sodium aluminate; and The mixing ratio of powder and lithium hydroxide is Ni +
Co + Al: Li atomic ratio = 0.85 + 0.12 + 0.0
In the same manner as in Example 1 except that 3: 1 = 1: 1
LiAl _0.03 Co _0.12 Ni _0.85 O ₂ was synthesized.

[0022]

Example 7 Liquid A was treated with nickel nitrate (482.6 g, 1.6).
6 mol) and 89.1 g of 98% cobalt nitrate (0.30
Mol), and the B solution is a 1.8 L solution of 318.0 g (3.0 mol) of sodium carbonate and 3.8 g (0.04 mol) of sodium aluminate; and The mixing ratio of powder and lithium hydroxide is Ni +
Co + Al: Li atomic ratio = 0.83 + 0.15 + 0.0
In the same manner as in Example 1 except that 2: 1 = 1: 1
LiAl _0.02 Co _0.15 Ni _0.83 O ₂ was synthesized.

[0023]

Embodiment 8 Solution A was prepared by adding 494.2 g (1.7) of nickel nitrate.
0 mol) and 74.1 g (0.26%) of 98% cobalt nitrate.
Mol), and the B solution is a 1.8 L solution of 318.0 g (3.0 mol) of sodium carbonate and 3.8 g (0.04 mol) of sodium aluminate; and The mixing ratio of powder and lithium hydroxide is Ni +
Co + Al: Li atomic ratio = 0.85 + 0.13 + 0.0
In the same manner as in Example 1 except that 2: 1 = 1: 1
LiAl _0.02 Co _0.13 Ni _0.85 O ₂ was synthesized.

[0024]

[Comparative Example 1] A solution was prepared by adding 581.4 g (2.0%) of nickel nitrate.
0 mol) of a 2 L solution, solution B of 318.0 g (3.0 mol) of a 1.8 L solution, and a mixture ratio of oxide powder and lithium hydroxide of N
LiNiO ₂ was synthesized in the same manner as in Example 1 except that the i: Li atomic ratio was 1: 1.

[0025]

COMPARATIVE EXAMPLE 2 Solution A was coated with 570.3 g of cobalt nitrate (2.0
0 mol) of a 2 L solution, solution B of 318.0 g (3.0 mol) of a 1.8 L solution, and a mixture ratio of oxide powder and lithium hydroxide of C
LiCoO ₂ was synthesized in the same manner as in Example 1 except that the o: Li atomic ratio was 1: 1.

[0026]

Comparative Example 3 Solution A was prepared by adding 494.2 g (1.7) of nickel nitrate.
0 mol) and 89.1 g of 98% cobalt nitrate (0.30
Mol), a solution B of 318.0 g (3.0 mol) of 1.8 L and a mixing ratio of oxide powder and lithium hydroxide of Ni +
LiCo _0.15 Ni _0.85 O _{2 in the} same manner as in Example 1 except that the Co: Li atomic ratio = 0.85 + 0.15: 1 = 1: 1.
Was synthesized.

[0027]

Comparative Example 4 Commercially available nickel oxide powder (Ni content 70.5 w
83.0 g (1.00 mol as Ni), 14.2 g of commercially available cobalt oxide powder (Co content: 75.5 wt%)
(0.18 mol as Co) and commercially available alumina powder (A
2.83 g (0.03 as Al)
37 mol) and 52.1 g (1.217) of lithium hydroxide
Mol) [Ni + Co + Al: Li atomic ratio = 0.82 +
0.15 + 0.03: 1 = 1: 1] in a mortar. This is calcined at 750 ° C. for 10 hours under flowing oxygen to produce Li
Al _0.03 Co _0.15 Ni _0.82 O ₂ was synthesized.

[0028]

Comparative Example 5 Solution A was prepared by adding 494.2 g (1.7) of nickel nitrate.
0 mol) of a 2 L solution, Solution B is a 1.8 L solution of 318.0 g (3.0 mol) of sodium carbonate and 28.5 g (0.3 mol) of sodium aluminate, and oxidation The mixing ratio of the product powder and lithium hydroxide is Ni +
Al: Li atomic ratio = 0.85 + 1.1.5: 1 = 1: 1
LiAl _0.15 Ni _{0.85 in the} same manner as in Example 1 except that
O ₂ was synthesized.

[0029]

Test Example 1 (X-ray Diffraction Measurement) The X-ray diffraction patterns of the samples synthesized in Examples 1 to 4 are shown by A (Example 1), B (Example 2), C (Example 3), D (Example 4), and the X-ray diffraction patterns of the samples synthesized in Examples 5 to 8 are shown in FIG.
The results are shown in F (Example 6), G (Example 7), and H (Example 8). The X-ray diffraction pattern of the sample synthesized in Comparative Example 3 is shown in FIG. As is clear from the figure, LiNiO ₂
No peak other than the peak attributed to the crystal structure of was observed, and it was confirmed that the added third component (Co, Al) was uniformly dissolved without breaking the basic crystal structure of LiNiO ₂ . The X-ray diffraction pattern of the sample synthesized in Comparative Example 1 is shown in FIG. All peaks are LiNiO
_This was confirmed to belong to the crystal structure of ₂ . FIG. 4 shows an X-ray diffraction pattern of the sample synthesized in Comparative Example 2. It was confirmed that all peaks belonged to the crystal structure of LiCoO ₂ . FIG. 5 shows an X-ray diffraction pattern of the sample synthesized in Comparative Example 4. LiNiO ₂
And LiCoO ₂ were observed, indicating that they were merely a mixture of each and were not uniform compounds. ◇ symbol indicates a peak attributed to LiCoO ₂ .
Therefore, even if a commercially available oxide raw material is simply mixed and fired, LiN
A high-quality crystal in which the third component was uniformly dissolved in the crystal structure of iO ₂ was not obtained.

[0030]

Test Example 2 (Evaluation of Battery Performance) For each of the samples synthesized in Examples 1 to 8 and Comparative Examples 1 to 5, acetylene black and Teflon powder were mixed at a weight ratio of 75: 20: 5, and mixed in a mortar. The scale-like positive electrode material obtained by kneading for minutes was formed into a sheet having a thickness of 0.1 mm by a spreading roller, punched out to a diameter of 16 mm, and then dried in vacuum at 110 ° C. to obtain a positive electrode material for testing. The positive electrode material thus obtained, a nonwoven fabric (made of polypropylene), a separator (made of polypropylene, trade name: Celgard), and a lithium metal foil having a thickness of 0.2 μm were laminated in a cell for a coin-type battery. 1 mol / L LiClO as electrolyte
A mixed solvent of propylene carbonate and dimethoxyethane having a volume ratio of 1: 1 in which ₄ was dissolved was used. A battery was prepared with such a configuration, and a charge / discharge test was performed. The charge and discharge conditions were a constant current and a current density of 0.5 mA / cm ² , and the charging potential was regulated to 4.3 V and the discharge voltage was regulated to a potential of 3.0 V. Table 1 shows the measurement results. By adding / synthesizing cobalt and aluminum as the third component by the coprecipitation method, lithium cobaltate (Comparative Example 2:15)
0 mAh / g), a lithium nickel oxide cathode material having a high capacity of 175 mAh / g or more and a high stability of oxygen desorption onset temperature and high stability as shown in Test Example 3 (Table 2). Was.

[0031]

[Table 1]

[0032]

Test Example 3 (TPD Measurement) A coin battery was prepared in the same manner as in Test Example 2, and after charging to 4.3 V, the battery was disassembled, and the positive electrode material was taken out and washed well with a dimethoxyethane solution. This was set in a TPD device (thermal desorption device), and after deaeration and drying, oxygen was detected while the temperature was raised, and the desorption start temperature of oxygen was measured. The apparatus used was MULTI TASK TPD manufactured by Nippon Bell. Measurement conditions were as follows: carrier gas: helium, heating rate: 2 ° C /
Min, upper limit temperature: 250 ° C., detector: Q-mass. Table 2 shows the measurement results. LiNiO ₂ was substituted with 15% of cobalt, and LiCo _0.15 Ni _0.85 O ₂ (Comparative Example 3)
, The oxygen desorption initiation temperature can be increased to 200 ° C., but by further substituting 2 to 5% of aluminum, the oxygen desorption initiation temperature can be increased to about 230 ° C. (Comparative Example 2: 23
(0 ° C.), which has the same level of safety.

[0033]

[Table 2]

The material obtained by adding Co only Li Ni O ₂ (Comparative Example 3), the cycle characteristics were improved as compared with LiNi O ₂ (Comparative Example 1), equivalent to Li Co O ₂ (Comparative Example 2) despite, storage characteristics / safety could not be equal to the Li Co O _2. A material obtained by adding Al only Li Ni O ₂ (Comparative Example 5), Ni: Al = 0.85:
Unless it is not about 0.15, there is no effect of improving storage characteristics / safety, so that the discharge amount is inferior.

Table 3 shows the molecular formula, molecular weight and purity of the raw materials (reagents) used in the examples and comparative examples.

[0036]

[Table 3]

[0037]

EFFECTS OF THE INVENTION A large amount of discharge, little deterioration in battery characteristics due to repeated charge / discharge, and excellent cycle characteristics, gas generation due to decomposition of the positive electrode material after charging is suppressed, and storage stability / safety is improved. Thus, a lithium battery positive electrode material is obtained.

[Brief description of the drawings]

FIG. 1 is a view showing an X-ray diffraction pattern of a sample synthesized in Examples 1 to 4.

FIG. 2 is a view showing an X-ray diffraction pattern of a sample synthesized in Examples 5 to 8.

FIG. 3 is a view showing an X-ray diffraction pattern of a sample synthesized in Comparative Examples 1 and 3.

FIG. 4 is a view showing an X-ray diffraction pattern of a sample synthesized in Comparative Example 2.

FIG. 5 is a view showing an X-ray diffraction pattern of a sample synthesized in Comparative Example 4.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Mizusawa, Inventor Koji Mizusawa 1-26 Takiya Honmachi, Niitsu City, Niigata Prefecture Inside JGC Chemicals Research Laboratory (72) Inventor Makoto Maeda 1-26, Takiya Honmachi, Niitsu City, Niigata Prefecture JGC Chemicals Co., Ltd. (72) Inventor Tsutomu Toida, 1-26 Takiya Honmachi, Niitsu City, Niigata Prefecture JGC Chemicals Co., Ltd. Inside (72) Inventor Masami Sakaguchi 1-26, Takiya Honmachi, Niitsu City, Niigata Prefecture JGC Chemicals Co., Ltd. Inside the company development laboratory

Claims (6)

[Claims] 1. A lithium battery cathode material comprising a composite oxide represented by the general formula Li _w Ni _x Co _y Al _z O ₂ . However, w = 0.90 to 1.10 x = 0.80 to 0.95 y = 0.04 to 0.19 z = 0.01 to 0.16 x + y + z = 1.0 2. The method according to claim 1, wherein the atomic ratio of Ni: Co: Al is x:
an aqueous solution of Ni nitrate or sulfate in a ratio of y: z,
A precipitate formed by mixing an aqueous solution of a nitrate or sulfate of Co, an aqueous solution of an Al compound and an aqueous alkaline solution is filtered,
The oxide containing Ni, Co and Al is washed, dried and fired to form an oxide containing Li, (Ni + Co + Al), and a Li compound is added to the oxide at a ratio of 0.90 to 1.10. General formula Li _w Ni _x Co comprising firing at 650 to 850 ° C. in an oxygen atmosphere to form a composite oxide
Preparation of lithium battery cathode materials represented by _y Al _z 0 _2. However, w = 0.90 to 1.10 x = 0.80 to 0.95 y = 0.04 to 0.19 z = 0.01 to 0.16 x + y + z = 1.0 3. The method according to claim 2, wherein the Al compound is at least one or more selected from the group consisting of sodium aluminate, potassium aluminate, aluminum nitrate and aluminum sulfate. 4. An aqueous solution of Ni nitrate or sulfate of Ni, Co
Aqueous solution of nitrate or sulfate, alkaline aqueous solution and Al
3. The method of claim 2 wherein an aqueous solution of the compound is simultaneously poured and mixed to form a precipitate. 5. The method according to claim 2, wherein the Li compound is LiOH. 6. The method according to claim 2, wherein the calcination after the addition of LiOH is performed in a rotary kiln.