JPH0950811A - Production of lithium battery active material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an active material with narrow particle size distribution and excellent crystallinity by using an aqueous solution in which a lithium compound, a transition metal compound, and an organic acid are mixed. SOLUTION: Production of a lithium battery's active material involves a dissolving process to produce a solution by mixing and dissolving A lithium compound and a transition metal compound with an organic acid represented by citric acid simultaneously having carboxyl group (-COOH) and hydroxyl group (-OH) in one molecule or an organic acid having at least two carboxyl groups or hydroxyl groups and a firing process to give an electrode active material for a battery by heating dew drops produced by spraying the solution. A cathode active material produced in this production method has excellent crystallinity, excellent battery properties, and thus a lithium battery having high power can be produced. It is preferable that the mole ion concentration ratio of Li and Mn as starting raw materials to synthesize the cathode active material is controlled to be 0.5<Li/Mn<=0.62.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a positive electrode active material composed of lithium and a transition metal compound used for producing a lithium battery.

[0002]

2. Description of the Related Art A lithium battery using a transition metal oxide as a positive electrode active material has been studied as a battery having a high energy density. The synthesis technology has a problem that the capacity performance and cycle characteristics of the battery are poor. As a solution to this problem, a solvent containing a lithium compound, a transition metal compound,
A liquid phase method is known in which, after citric acid is dissolved, the solvent is evaporated, the organic citric acid is burned, and the remaining lithium compound and transition metal compound are pyrolyzed to synthesize the active material. (Kaihei 2-74505).

However, when a large amount of active material is synthesized by such a liquid phase method, lithium and a transition metal cause segregation due to a difference in solubility between a solution stage and a solvent evaporation stage,
It is difficult to synthesize a uniform active material. Further, when citric acid burns, it consumes oxygen, so that a large amount is synthesized, oxygen becomes insufficient, and the desired valence of the transition metal of the active material cannot be obtained.

[0004]

The present invention has been made in view of the above circumstances, and an active material having a narrow particle size distribution and good crystallinity is obtained by using an aqueous solution obtained by mixing a lithium compound, a transition metal compound and an organic acid. Is intended to be manufactured.

[0005]

The method for producing a lithium battery active material according to the present invention comprises a lithium compound, a transition metal compound,
Carboxyl group (-CO
OH) and a hydroxyl group (-OH) at the same time, or a dissolving step of mixing an organic acid having two or more of any one of a carboxyl group and a hydroxyl group into a dissolving solution, and a liquid formed by spraying the solution. And a firing step of heating the droplets into an electrode active material for a battery.

In the production method of the present invention, in order to uniformly mix the lithium salt and the transition metal salt in the dissolution step, an organic acid having a carboxyl group (-COOH) and a hydroxyl group (-OH) in the molecule at the same time, or a carboxyl group A lithium salt and a transition metal salt are dissolved by adding an organic acid having two or more groups or hydroxyl groups, the solution is sprayed in the firing step, and the droplets are heated to obtain a continuous composition. It is a method for producing a uniform active material.

In this method, fine droplets formed in the firing step are instantly pyrolyzed from the solution to synthesize the electrode active material, so that segregation of the lithium salt and the transition metal salt is hindered and the organic acid Since the composition of the lithium salt and the transition metal salt in the droplets is always stable due to the presence of, the active material having uniform properties can be obtained. Further, when atomized gas is used to form droplets by using a gas containing oxygen, it is possible to synthesize an active material having good characteristics without causing oxygen shortage during thermal decomposition.

In the dissolving step, for example, pure water contains 0.8 mol / liter of lithium hydroxide and 1.6 manganese acetate.
Mol / liter and citric acid are dissolved and mixed at a concentration of 1.3 mol / liter to prepare. At this time, ammonia water is added to the dissolution solution to keep the pH of the solution within the range of 4 to 7, which is preferable because the solution becomes stable. In the firing step, for example, the above solution is sprayed using a spray nozzle capable of atomizing using the pressure of air so as to form droplets of 100 μm or less. Then, the droplets are introduced into the furnace by the air used for spraying or another carrier gas to cause a thermal decomposition reaction. The heating temperature of the liquid droplets can be synthesized in the range of 250 to 1100 ° C, and the optimum temperature is in the range of 400 ° C to 900 ° C. The active material obtained here can be further baked in the range of 400 to 1100 ° C. to obtain LiMn ₂ O ₄ having higher crystallinity.

As the lithium compound, for example, at least one of lithium hydroxide, lithium acetate, lithium carbonate and lithium nitrate is used. The transition metal compound is manganese,
At least one of hydroxides, carbonates, acetates and nitrates of cobalt, nickel, vanadium, iron, copper, titanium and chromium is used.

Manganese compound is used as the transition metal compound
If the lithium ion and the manganese ion
So that the ratio of the gas concentrations is 0.5 <Li / Mn ≦ 0.62
It is preferred that That is, lithium in the dissolution solution
And the molar ion concentration of manganese are Li / Mn = 0.5
Stykometric LiMn solution of₂O _Four
Li containing more lithium than_{1 + x}Mn_2-xO
_FourBy combining (where x> 0), the capacitance characteristics and
An active material having excellent cycle characteristics can be manufactured. What
The molar ion concentrations of lithium and manganese in the solution
The ratio of 0.54 <Li / Mn ≦ 0.62
Manufacturing active materials with even better capacity and cycle characteristics
Can be built.

When a manganese compound and a compound of a transition metal (Me) other than manganese are adopted as the transition metal compound, the ratio of the molar ion concentration of lithium to the transition metal (Me) other than manganese and manganese in the solution is 0.5.
<Li / Mn ≦ 0.62 and 0.5 <(Li +
By setting Me) /Mn≦0.67, an active material having excellent capacity characteristics and cycle characteristics can be manufactured. In this case, the ratio of the molar ion concentrations of manganese and other transition metal (Me) other than manganese in the dissolution solution is Me / Mn ≦ 0.
It is preferably 06.

As the organic acid, those having a carboxyl group (-COOH) and a hydroxyl group (-OH) in the molecule at the same time,
Alternatively, one having two or more of either a carboxyl group or a hydroxyl group is used. As such an organic acid, for example, citric acid, tartaric acid, glycolic acid, lactic acid or the like can be used. These organic acids include lithium and transition metal 1
More than one molecule can be coordinated and held in the molecule, the composition of the lithium salt and the transition metal salt is always stable, and the efficiency of the thermal decomposition reaction can be increased.

The dissolution solution is preferable, for example, by using aqueous ammonia so that the pH is in the range of 4 to 7 because the stability of the dissolution solution and the droplets during heat treatment is increased. The diameter of the sprayed droplets of the dissolved solution is preferably 100 μm or less, since a fine powdery product is obtained. The active material obtained by spraying and heating the solution is 400 to 1
400 ~ 11 by heat treatment at 100 ℃ or by granulating and compacting
By heat treatment at 00 ° C., the crystallinity can be further increased to produce an active material having a high density.

[0014]

In the production method of the present invention, the lithium salt and the transition metal salt are uniformly dissolved in the dissolution step due to the presence of the organic acid, and the lithium compound and the transition metal compound are mixed and dispersed at the atomic level. Further, the organic acid can form a complex by coordinating more than one lithium ion and transition metal ion in one molecule so that the lithium salt and the transition metal salt in the solution do not become biased during thermal decomposition. .

By spraying this mixed solution in the form of mist and heating the droplets, the compound of lithium and the transition metal can be synthesized by a thermal decomposition reaction in a short time. Therefore, the compound obtained by this method has good crystallinity, a small amount of impurities, and a spherical particle size. Therefore, when the produced substance is used as a positive electrode active material for a lithium battery, the battery has good capacity characteristics, cycle characteristics, and storage characteristics,
Since the filling rate into the battery is also increased, it is possible to manufacture a battery having a higher energy density.

In the melting step, the ratio of the molar ion concentrations of lithium and manganese in the melting solution is 0.5 <Li / Mn ≦.
An excellent positive electrode active material for a lithium battery can be obtained by forming a solution having a thickness of 0.62 and pyrolyzing and firing this dissolved solution to synthesize lithium manganese oxide. This is the ratio of the molar ion concentration of lithium and manganese, Li / Mn is 0.5.
By increasing the amount, Mn of LiMn ₂ O ₄ with spinel structure
It is considered that the structure has 16d replaced by Li. This substitution increases the average valence of Mn and suppresses the expansion and contraction of the lattice due to the inflow and outflow of Li during charge and discharge.
It is considered that the battery characteristics are improved.

Furthermore, the molar ion concentration of lithium and manganese is high.
The degree ratio is 0.5 <Li / Mn ≦ 0.62 and lithium
Moles of manganese and transition metals (Me) other than manganese
The ion concentration ratio is 0.5 <(Li + Me) / Mn ≦ 0.
67, a dissolution solution is formed, and then pyrolysis baking is performed.
Lithium, which is superior to that obtained by synthesizing active materials
A positive electrode active material for batteries is obtained. This allows you to
LiMn with pinel structure ₂O_FourPlace 16d of Mn of with Li
And replace 16d of Mn with a transition metal other than Mn
Structure, the average valence of Mn increases,
Since the expansion and contraction of the lattice due to the entry and exit of Li is suppressed,
It is considered that the battery characteristics will be further improved.

Further, this synthetic reaction is not a solid phase method in which a lithium raw material powder and a manganese raw material powder, which have been widely used in the past, are mixed in a solid phase and then a firing reaction is performed. It is possible to more uniformly replace Li with Mn and other elements by spraying mist and heating the droplets.

[0019]

EXAMPLES The present invention will be specifically described below with reference to examples. In this embodiment, the LiOH · H ₂ O, Mn compound as a Li compound using _{Mn (CH 3 COO) 2 ·} 4H 2 O, citric acid as organic acid _{H 2 C 6 H 5 O 7} · H 2 O . These were weighed in a 3: 6: 5 molar ratio, and each was dissolved in deionized water to prepare a 0.8 mol / liter lithium hydroxide aqueous solution, a 1.6 mol / liter manganese acetate aqueous solution. A 33 mol / liter citric acid aqueous solution was prepared.

Next, an aqueous lithium hydroxide solution and an aqueous citric acid solution were mixed. Further, an aqueous solution of manganese acetate was mixed with this mixed solution to obtain a mixed solution as a raw material. Ammonia water may be added to the mixed solution to adjust the pH for increasing the stability. If ammonia water is not added, the pH of the solution =
4, the stability of the dissolution solution increases as the pH is increased by adding ammonia.

In the firing step, as shown in the block diagram of the apparatus in FIG. 1, a mixed solution material tank 1 is pressurized by a pump 2 to be sprayed as droplets from a spray nozzle, and then introduced into a thermal decomposition furnace 3. The droplets exposed to high temperature in the thermal decomposition furnace 3 are instantly dried and pyrolyzed into powder of the positive electrode active material, and the powder is separated by the dust collector 4 and the gas is discharged from the blower 5 to the outside of the system.

Further, in the state of the dissolved solution containing the organic acid, the binding force between the organic acid and the transition metal or Li is strong,
These compounds are likely to precipitate, the composition of the solution is displaced, and the piping is easily clogged. Therefore, it is better to add the organic acid immediately before spraying the solution. Specifically, as shown in FIG. 8, the raw material tank 1- (1) contains 0.8 mol / liter of an aqueous lithium hydroxide solution, and the raw material tank 1-
1.6 mol / liter of manganese acetate aqueous solution in (2),
A 1.33 mol / liter citric acid aqueous solution is prepared in the raw material tank 1- (3), and each is stored alone. Then, pumps 2- (1) are pumped from each raw material tank at a constant flow rate.
2- (2) and 2- (3) are used to draw up the three types of solutions and once mix them in the mixing tank 6 in the middle of the piping. This dissolved mixed solution is pressure-fed to the spray nozzle by a pump, and thereafter sprayed and pyrolyzed in the same manner to produce an active material.

By using this mixing method, it was possible to continuously supply the solution containing the organic acid for 24 hours or more, whereas it was necessary to change the solution every about 2 hours from the beginning.
In addition, the solution of the lithium compound and the solution of the transition metal compound were put in the individual raw material tanks 1-1 and 1-2 in FIG.
The solutions of these compounds may be mixed. The nebulization method pumps the solution to a nebulizing nozzle where air is blown to atomize the solution. The size of the liquid droplets can be controlled by the spray amount of the pump, the air pressure, and the concentration of the solution. The temperature of pyrolysis is controlled by the temperature of the furnace.

In this embodiment, the mixed solution is pumped by a pump 3
It was pressurized at 0 cc / min and introduced into the fluid nozzle. Therefore, it was atomized with 0.4 MPa air. The droplets obtained here were about 10 μm. The sprayed droplets are
It was introduced into a furnace whose temperature was maintained at 880 ° C. Here, after the solvent was instantly evaporated, the pyrolysis synthesis of the burning lithium manganese oxide of citric acid was performed. Further, the crystallinity was enhanced by staying in the furnace.

The active material LiMn ₂ O ₄ obtained here had no impurities and had a spherical particle size. Further, since the spray droplets are formed by heating, they have a porous shape and a high specific surface area of 20 m ² / g. A battery was manufactured as follows using the obtained active material. The positive electrode active material was kneaded with Ketjen Black as a conductive agent and PTFE as a binder at 90: 6: 4, and then pressure-molded on a stainless mesh to prepare a positive electrode. Metal lithium was used for the negative electrode, and polypropylene nonwoven fabric was used for the separator. 1 mol LiPF ₆ / PC (50) + DME (5
0) was used.

The charge and discharge of the battery was evaluated by charging at 2 mA / cm.
^{It is} carried out at a constant current of ² until it reaches 4.1 V, and then 4.
It was carried out at a constant voltage of 1 V for a total of 5 hours. Discharge is 2mA / cm
² until 2.0V is reached. The initial discharge capacity of the positive electrode active material obtained in this example was as high as 210 mAh / g. Further, the electric capacity of the positive electrode active material for each cycle is shown in the diagram of reference numeral 1 in FIG.

For reference, in order to investigate the influence of the thermal decomposition temperature, the thermal decomposition temperature at which the liquid droplets are heated and thermally decomposed is 450 ° C., 580 ° C.
It carried out at each temperature of 730 degreeC, and each synthesize | combined the positive electrode active material. FIG. 3 shows a diagram showing the relationship between the half-value widths of the peaks of the respective positive electrode active materials and the thermal decomposition temperatures obtained for each thermal decomposition temperature.

As shown in FIG. 3, when the product was pyrolyzed at a high temperature of 880 ° C., the peak half width (111) of the crystal of the product was obtained.
And the crystallinity was small. This indicates that the high temperature treatment increased the crystallinity. This 88
The battery using the active material obtained by thermal decomposition at 0 ° C. exhibited excellent initial capacity and cycle characteristics. However, when thermally decomposed at 1100 ° C. or higher, Li sublimes and the characteristics deteriorate. Therefore, the thermal decomposition temperature is 580 ℃
The range of ˜1100 ° C. is preferable. Particularly, the range of 730 to 950 ° C. is an active material having good characteristics.

The positive electrode active material obtained by the above-mentioned spray pyrolysis was further heat-treated at 900 ° C. for 8 hours in order to improve the crystallinity. Then, the battery characteristics were evaluated in the same manner as in the example. The discharge capacity of the positive electrode active material subjected to this heat treatment is 215.
mAh / g. Further, the battery capacity for each cycle is shown by the diagram of reference numeral 2 in FIG. As is clear from FIG. 2, the heat treatment increases the discharge capacity of the positive electrode active material and the discharge capacity of each cycle.

When the heat treatment is carried out for reference, the thermal decomposition temperature is set at 450 ° C.
After carrying out at each temperature of 0 ° C., 730 ° C. and 880 ° C., heat treatment was further performed to synthesize a positive electrode active material. The relationship of the particle size distribution of each positive electrode active material obtained for each thermal decomposition temperature is shown in FIG. As shown in FIG. 4, a positive electrode active material having a narrow particle size distribution was obtained by performing decomposition synthesis at a low thermal decomposition temperature of 450 ° C. to 730 ° C. and then performing heat treatment at 900 ° C. It is considered that this is because the crystal skeleton is formed at a low temperature to grow the crystal uniformly. Therefore, the thermal decomposition temperature is 250 ° C. to 110 ° C. at which LiMn ₂ O ₄ can be formed.
The range of 0 ° C is good, and especially 450 ° C to 7 ° C for the above reason.
The 50 ° C. starch becomes a positive electrode active material with good characteristics.

For reference, the active acid was prepared by the same procedure as in Example 1 except that an organic acid was not used in the preparation of the mixed solution, and the same thermal treatment as in Example 1 was performed. Instead, the mixed solution was evaporated to dryness at 80 to 150 ° C., then baked at 400 to 900 ° C. to synthesize an active material, and the heat-treated active material was similarly examined for battery characteristics. The results are shown in FIG. The diagram indicated by the reference numeral 3 is the discharge capacity of the positive electrode active material which is evaporated and dried without being spray-pyrolyzed, and then calcined and heat-treated. The discharge capacity of the heat-treated positive electrode active material is shown.

80% of the mixed solution was prepared without using the spray pyrolysis method.
When heated at ~ 150 ° C to slowly evaporate the solvent,
The discharge capacity of the positive electrode active material was 200 mAh / g, which was lower than that of this example. It is considered that this is because, compared with the spray pyrolysis method, the time required for the solution to evaporate is longer, and the composition shifts during the evaporation, so that impurities are mixed in the product. Incidentally, the discharge capacity of the positive electrode active material was further deteriorated to 120 mAh / g when it was evaporated and baked from a larger amount of solution.

The characteristics of the positive electrode active material obtained by spray pyrolysis of a mixed solution containing no organic acid are also 180 mAh / g.
The discharge battery capacity was inferior to that of this example. Next, Li ₂ CO ₃ as the Li compound, MnCO _{3 as} the Mn compound, and citric acid H ₂ C ₆ H as the organic acid.
_A similar test was conducted using ₅ O ₇ .H ₂ O. The dissolution of the solution is such that the Li concentration is 0.07 mol / liter, the Mn concentration is 0.14 mol / liter, and the citric acid concentration is 0.3.
Dilute these with 3 parts of distilled pure water so that the concentration becomes 5 mol / liter.
Mix and dissolve types. At this time, as the order of dissolution, citric acid, MnCO ₃ , and Li ₂ CO ₃ are dissolved in this order.

The dissolved solution thus obtained was atomized in the same manner with 0.4 MPa air, and its droplets were introduced into a furnace in which the temperature inside the furnace was maintained at 880 ° C. Manganese oxide was synthesized. The lithium manganese oxide thus obtained was heat-treated at 900 ° C. for 8 hours to obtain a positive electrode active material.

The discharge capacity of this positive electrode active material is 215 mAh.
/ G and the characteristics when LiOH.H ₂ O is used as the Li compound and Mn (CH ₃ COO) ₂ .4H ₂ O is used as the Mn compound, and MnCO ₃ is inexpensive as a raw material cost.
I found that you can use. Next, in order to evaluate the battery characteristics depending on the material composition of the lithium manganese oxide, the same Li raw material and Mn raw material used in the above-described examples were used, and Li and Mn in the dissolution solution formed in the dissolution step were used. Molar ion concentration ratio of Li / Mn = 0.43, 0.5
The mixing ratios of the Li raw material and the Mn raw material were adjusted so as to be 0, 0.54, 0.58, 0.62 and 0.67, respectively. After that, each of the obtained dissolved solutions was sprayed into a furnace at 730 ° C. for pyrolysis synthesis, and then main firing was performed at 900 ° C. to synthesize each lithium manganese oxide. The respective lithium manganese oxides obtained at this time were Li _{1 + x} Mn _2-x O
₄ (Li / Mn corresponds to each of the above ratios, x = -0.
It is considered that the composition is 1, 0, 005, 0.1, 0.15 and 0.2).

Charging / discharging characteristics of each of the obtained lithium manganese oxides as a positive electrode active material were examined under the following conditions. Charging is performed at a constant current of ² mA / cm ² until it reaches 4.3 V,
After that, the operation was performed at a constant voltage of 4.3 V for 3 hours in total. The discharge was performed at ² mA / cm ² until 2.0 V was reached. A 10-minute standing time was provided between each charge. FIG. 5 and FIG. 6 show the effects of the capacity characteristics and the initial efficiency of the lithium manganese oxide synthesized at the ratio of the Li raw material and the Mn raw material. From these results, LiMn ₂ O _{4 with} Li / Mn = 0.5
Than Li / Mn = 0.54, 0.58, 0.62,
Li _{1 + x} Mn _2-x O ₄ (Li / Mn synthesized at 0.67)
For each of the above ratios, x = 005, 0.1, 0.
It is understood that the battery using the lithium manganese oxide (15, 0.2) as the active material can improve both the initial capacity and the cycle characteristics. In particular, a battery using a lithium manganese oxide having a composition of Li / Mn = 0.58 as a positive electrode active material has high positive electrode capacity and initial efficiency, and exhibits a maximum value.

FIG. 7 shows the cycle characteristics of a battery using each lithium manganese oxide as an active material. The numbers 0.43, 0.5, 0.54, 0.58, 0.62, and 0.67 shown in FIG. 7 indicate the Li / Mn molar ratios and indicate that each synthesized lithium manganese oxide is active. The cycle characteristic of the positive electrode capacity of the battery used as a substance is shown. Also from this result, Li / Mn = 0.54 than LiMn ₂ O ₄ ,
It was found that the lithium manganese oxides synthesized with 0.58, 0.62, and 0.67 can improve the cycle characteristics.

From the above results, the L of the Li raw material and the Mn raw material are
The ratio Li / Mn of the molar ion concentration of i and Mn is increased from 0.5 to 0.5 to obtain Li / Mn ratios of 0.54, 0.58,
It was found that the battery characteristics can be improved by synthesizing at 0.62 and 0.67. Next, studies were conducted to replace Mn with not only Li but transition metals other than Mn. Cu was used as the transition metal.

As the Cu raw material, copper acetate, Li raw material, Mn
As the raw material, the same raw material as above was used. The molar ion ratio of Li, Cu, and Mn is Li / Cu / Mn = 1 / 0.05 /
1.95, 1.05 / 0.05 / 1.9, 1.1 / 0.
05 / 1.85, 1 / 0.1 / 1.9, 1.05 / 0.
Using the solutions adjusted to be 1 / 1.85 and 1.1 / 0.1 / 1.8, active materials were synthesized in the same manner as described below. The composition of this active material is Li _{1 + x} Cu _y Mn
_2-xy (x = 0, 0.005, 0.1, y = 0.05,
0.1).

Table 1 shows the capacity characteristics of the active material obtained by synthesizing at the above raw material ratio, and the capacity characteristics after 50 cycles. From this result, Li / Cu / Mn substituted with Cu = 1.05
/0.05, 1.9, 1.1 / 0.05 / 1.85 C
It was found that the cycle characteristics can be improved as compared with the case where u is not substituted. In addition, Li / Cu / in which the substitution amount of Cu is increased
Mn = 1 / 0.1 / 1.9, 1.1 / 0.1 / 1.85
Since the initial capacity decreases as shown in Table 1, Cu and M
It was found that the characteristics are improved when the ratio Cu / Mn of the molar ion concentration of n is 0.06 or less.

[0041]

[Table 1]

[0042]

EFFECT OF THE INVENTION The positive electrode active material obtained by the production method of the present invention has a small peak half-value width (111) of crystals and good crystallinity. Therefore, a lithium battery having high discharge characteristics and higher performance can be obtained.

[Brief description of drawings]

FIG. 1 shows a schematic configuration of a firing process of an example of the present invention.

FIG. 2 is a diagram showing battery characteristics of positive electrode active materials of this example and a comparative example.

FIG. 3 is a diagram showing the thermal decomposition temperature of the present invention and the crystallinity of the active substance after spraying.

FIG. 4 is a diagram showing the relationship between the thermal decomposition temperature of the present invention and the particle size distribution of the obtained active material.

FIG. 5 is a diagram showing a relationship between a Li / Mn molar ion concentration ratio of a starting material for synthesizing a lithium manganese oxide used as an active material in Examples and a positive electrode capacity.

FIG. 6 is a diagram showing a relationship between a Li / Mn molar ion concentration ratio of a starting material for synthesizing a lithium manganese oxide used as an active material in Examples and an initial efficiency.

FIG. 7 is a diagram showing cycle characteristics of a Li / Mn molar ion concentration ratio of a starting material for synthesizing a lithium manganese oxide used as an active material in Examples and a positive electrode capacity of a battery.

FIG. 8 shows a schematic configuration of a manufacturing process including a solution mixing process of the present invention.

Claims (16)

[Claims] 1. A carboxyl group (—COO) in a molecule represented by a lithium compound, a transition metal compound, and citric acid.
H) and an organic acid having a hydroxyl group (-OH) at the same time, or a dissolving step of mixing an organic acid having two or more of any one of a carboxyl group and a hydroxyl group to obtain a dissolving solution, and a liquid formed by spraying the solution. A method for producing a lithium battery active material, comprising: a step of heating the droplet to obtain an electrode active material for a battery. 2. The method for producing a lithium battery active material according to claim 1, wherein the lithium compound is one kind or two or more kinds of lithium hydroxide, lithium acetate, lithium carbonate and lithium nitrate. 3. The transition metal compound is at least one of manganese, cobalt, nickel, vanadium, iron, copper, titanium and chromium hydroxides, carbonates, acetates and nitrates.
The method for producing a lithium battery active material according to claim 1, which is a seed. 4. The lithium battery activity according to claim 1, wherein the transition metal compound is a manganese compound, and a ratio of molar ion concentrations of lithium and manganese in the solution is 0.5 <Li / Mn ≦ 0.62. Method of manufacturing substance. 5. The method for producing a lithium battery active material according to claim 4, wherein a ratio of molar ion concentrations of lithium and manganese in the solution is 0.54 ≦ Li / Mn ≦ 0.62. 6. One of the transition metal compounds is a manganese compound, the ratio of the molar ion concentration of lithium to manganese in the solution is 0.5 <Li / Mn ≦ 0.62, and the manganese in the solution is Other transition metals (Me) other than lithium and manganese having a molar ion concentration ratio of 0.5
The method for producing a lithium battery active material according to claim 1, wherein <(Li + Me) /Mn≦0.67. 7. The ratio of the molar ion concentrations of manganese and a transition metal (Me) other than manganese in the dissolution solution is Me / M.
The method for producing a lithium battery active material according to claim 6, wherein n ≦ 0.06. 8. The organic acid is one or more of citric acid, tartaric acid, glycolic acid and lactic acid.
The method for producing the lithium battery active material according to. 9. The method for producing a lithium battery active material according to claim 1, wherein the lithium compound is lithium hydroxide, the transition metal compound is manganese acetate, and the organic acid is citric acid. 10. The heating temperature of the droplet is 250 to 1100.
The method for producing a lithium battery active material according to claim 1, wherein the temperature is in the range of ° C. 11. The method for producing a lithium battery active material according to claim 1, wherein the diameter of the sprayed droplets is 100 μm or less. 12. The method for producing a lithium battery active material according to claim 1, wherein the pH of the dissolution solution is in the range of 4 to 7. 13. The method for producing a lithium battery active material according to claim 12, wherein ammonia is used to adjust the pH of the solution. 14. The method for producing a lithium battery active material according to claim 1, wherein the active material obtained by spraying and heating is further heat-treated at 400 to 1100 ° C. to synthesize the active material. 15. The production of a lithium battery active material according to claim 1, wherein the active material obtained by the firing step is granulated, pressed and further fired at 400 to 950 ° C. to synthesize a high density active material. Method. 16. A solution of a lithium compound and a solution of a transition metal compound, or a solution prepared by mixing and dissolving them independently and a solution prepared by dissolving an organic acid are prepared independently of each other, and then prescribed before spraying each solution. The method for producing a lithium battery active material according to claim 1, further comprising a dissolution step of mixing the above components to obtain the dissolution solution.