JP2013229227A - Method for producing cathode material for secondary battery, cathode material for secondary battery, cathode for secondary battery using the same, and secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cathode material for a secondary battery, capable of obtaining a cathode material for a secondary battery which is excellent in charge/discharge efficiency and contains lithium sulfide and carbon fine particles.SOLUTION: The method of the present invention for producing a cathode material for a secondary battery is a method for producing a cathode material for a secondary battery which contains lithium sulfide and carbon fine particles. The method of the present invention for producing a cathode material for a secondary battery includes a step of mixing and heating fine particles containing lithium sulfate and the carbon fine particles to reduce the lithium sulfate, thereby obtaining the lithium sulfide carrying the carbon fine particles.

Description

  The present invention relates to a method for producing a positive electrode material for a secondary battery, a positive electrode material for a secondary battery, and a positive electrode for a secondary battery and a secondary battery using the same.

  Lithium sulfide is attracting attention as a positive electrode material for secondary batteries with a high capacity (for example, Patent Document 1). However, it is known that lithium sulfide has a low electronic conductivity. Therefore, in order to improve the performance of lithium sulfide as a positive electrode material for secondary batteries, it is necessary to improve electronic conductivity.

In Patent Document 1 (International Publication No. 2010/035602 pamphlet), a mixture of lithium sulfide and a carbon material having a specific surface area of 60 m ² / g or more is filled in a non-oxidizing atmosphere in a non-oxidizing atmosphere. A method for producing a lithium sulfide-carbon composite is described in which a DC pulse current is applied in a state where the mixture is pressurized under an atmosphere to cause lithium sulfide and a carbon material to undergo a heat reaction.
According to this manufacturing method, it is said that the performance as a positive electrode active material for lithium ion secondary batteries is improved by improving the electronic conductivity of lithium sulfide.

International Publication No. 2010/035602 Pamphlet

  However, lithium sulfide obtained by a method of mixing lithium sulfide and a carbon material as in the production method described in Patent Document 1 has poor charge / discharge efficiency and is not satisfactory as a positive electrode material for a secondary battery. It was.

  Then, this invention makes it a subject to provide the manufacturing method of the positive electrode material for secondary batteries which can obtain the positive electrode material for secondary batteries containing the lithium sulfide and carbon fine particle which is excellent in charging / discharging efficiency.

According to the present invention,
A method for producing a positive electrode material for a secondary battery containing lithium sulfide and carbon fine particles,
A positive electrode material for a secondary battery comprising a step of reducing the lithium sulfate by mixing and heating the fine particles containing lithium sulfate and the carbon fine particles to obtain the lithium sulfide carrying the carbon fine particles. A manufacturing method is provided.

  Furthermore, according to this invention, the positive electrode material for secondary batteries obtained by the manufacturing method of the positive electrode material for secondary batteries of the said invention is provided.

    Furthermore, according to this invention, the positive electrode for secondary batteries obtained by forming the active material layer containing the positive electrode material for secondary batteries of the said invention on the surface of a collector is provided.

  Furthermore, according to this invention, the secondary battery provided with the positive electrode and secondary electrode for secondary batteries of the said invention is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the positive electrode material for secondary batteries which can obtain the positive electrode material for secondary batteries which is excellent in charging / discharging efficiency and contains lithium sulfide and carbon microparticles can be provided.

It is a figure which shows the SEM image of the positive electrode material obtained in the Example. It is a figure which shows the SEM image of the positive electrode material obtained by the comparative example.

  Hereinafter, embodiments of the present invention will be described.

  The method for producing a positive electrode material for a secondary battery according to the present embodiment includes a method in which lithium sulfate-containing fine particles and carbon fine particles are mixed and heated to reduce the lithium sulfate, and the sulfide in which the carbon fine particles are supported. A step of obtaining lithium.

(Fine particles containing lithium sulfate)
First, the fine particles containing lithium sulfate will be described.
Microparticles containing lithium sulfate according to the present embodiment is preferably not more than an average particle diameter _{d 50} 15.0 .mu.m, more preferably not more than 10.0 [mu] m, particularly preferably not more than 7.0 .mu.m. By making the average particle diameter d ₅₀ equal to or less than the above upper limit value, the contact area between the lithium sulfate and the carbon fine particles can be increased, so that the reduction reaction of lithium sulfate can be promoted. Then, since the amount of unreacted lithium sulfate in the obtained lithium sulfide can be reduced, a positive electrode material with high purity can be obtained.
Further, the lower limit value of the average particle diameter d ₅₀ of the fine particles containing lithium sulfate is not particularly limited, but is, for example, 3.0 μm or more from the viewpoint of handleability.

Although microparticles containing lithium sulfate according to the present embodiment is not particularly limited, the weight-based particle size distribution by a laser diffraction scattering particle size distribution measuring method, preferably a particle size d ₁₀ is at 0.1μm or more, more preferably It is 1.0 μm or more, and particularly preferably 2.0 μm or more.
Further, the fine particles containing lithium sulfate according to the present embodiment are not particularly limited, but the particle size d ₉₀ in the weight-based particle size distribution by the laser diffraction / scattering particle size distribution measurement method is preferably 50.0 μm or less, more preferably It is 30.0 μm or less, more preferably 15.0 μm or less, and particularly preferably 13.0 μm or less.
By setting the particle size distribution of the fine particles containing lithium sulfate within the above range, the reduction reaction between the fine particles containing lithium sulfate and the carbon fine particles can be performed more uniformly. As a result, the amount of unreacted lithium sulfate in the obtained lithium sulfide can be further reduced, and as a result, a cathode material with higher purity can be obtained.

The specific surface area by the BET method of microparticles containing lithium sulfate according to the present embodiment is preferably not more than 0.3 m ² / g or more ^{30 m} 2 / g.
When the specific surface area by the BET method is within the above range, the contact area between lithium sulfate and the carbon fine particles can be increased, so that the reduction reaction of lithium sulfate can be promoted. As a result, the amount of unreacted lithium sulfate in the obtained lithium sulfide can be further reduced, and as a result, a cathode material with higher purity can be obtained.

  The method for preparing the fine particles containing lithium sulfate is not particularly limited. For example, a reprecipitation method in which a powder containing lithium sulfate is dissolved in a first solvent and then reprecipitated into fine particles in a second solvent, or lithium sulfate is used. Examples thereof include a method in which the contained powder is made into fine particles by a mechanical pulverization method, and then the particle diameter is adjusted by classification operation or granulation operation.

Here, the powder containing the lithium sulfate is not particularly limited, and a commercially available powder may be used. For example, a powder obtained by a reaction between lithium carbonate and sulfuric acid may be used.
From the viewpoint of obtaining a high purity positive electrode material, it is preferable to use lithium sulfate with few impurities.

Hereinafter, the reprecipitation method will be described.
First, a powder containing lithium sulfate is dissolved in a first solvent such as water to prepare a lithium sulfate solution. Next, the obtained lithium sulfate solution is added to a second solvent such as alcohol, and reprecipitated into fine particles while dispersing the lithium sulfate, whereby the powder containing lithium sulfate is finely divided.

  Although it does not specifically limit about the 1st solvent which dissolves the powder containing lithium sulfate, Distilled water, ion-exchange water, city water, industrial water, etc. can be used. From the viewpoint of obtaining high-purity lithium sulfide, it is preferable to use distilled water or ion-exchanged water.

The second solvent for reprecipitation of lithium sulfate in fine particles is not particularly limited as long as lithium sulfate can be dispersed in fine particles. For example, methanol, ethanol, propyl alcohol, isopropyl alcohol, acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylimidazolidinone, ethylene glycol, tetraethylene glycol, dimethylacetamide, N-methyl-2-pyrrolidone, tetrahydrofuran, dioxane, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), ethyl acetate and the like. These second solvents may be used alone or in combination of two or more.
Among these, alcohols such as methanol, ethanol, propyl alcohol, and isopropyl alcohol are preferable. Ethanol is particularly preferred from the viewpoint of safety and price.

In the operation of reprecipitation of lithium sulfate into fine particles, it is preferable to add the lithium sulfate solution while stirring the second solvent. In this case, the particle diameter of the resulting fine particles containing lithium sulfate can be adjusted to a desired value by adjusting the stirring speed and the addition speed of the lithium sulfate solution.
The stirring speed and the addition speed of the lithium sulfate solution can be appropriately determined depending on the processing amount of the lithium sulfate solution and the desired particle size.

  The reaction apparatus used in the reprecipitation method is not particularly limited, but an apparatus having a reaction vessel and a stirring blade and equipped with a lithium sulfate solution supply means, a solvent removal means, a heating and cooling means, and the like is preferable.

The method for separating the precipitate containing lithium sulfate obtained by the reprecipitation operation from the solvent is not particularly limited. For example, the suction filtration method using filter paper or the solvent is evaporated by raising the temperature to remove the solvent. The method etc. are mentioned.
The obtained precipitate is preferably washed with the second solvent described above. By so doing, even more pure lithium sulfate can be obtained.

  The fine particles containing lithium sulfate obtained by such an operation are preferably dehydrated by heating. By dehydrating, the obtained fine particles containing lithium sulfate can be further refined.

  Although it does not specifically limit as heating temperature at the time of making it dehydrate, For example, it is the range of 130 to 250 degreeC. The heating time is appropriately determined depending on the amount of fine particles containing lithium sulfate.

  Next, a method for finely pulverizing the powder containing lithium sulfate by a mechanical pulverization method and then adjusting the particle diameter by classification operation or granulation operation will be described.

The mechanical pulverization method is not particularly limited, and examples thereof include a method using a stone mortar, a ball mill, a jet mill, an airflow pulverizer, and the like.
The classification operation is not particularly limited, and examples thereof include a classification method using a sieving machine, a gravity classification method, a classification method using a centrifuge, an inertia classification method, and the like.
Fine particles containing lithium sulfate having a desired particle size can be obtained by making the particles fine by a mechanical pulverization method and then adjusting the particle size by classification operation or granulation operation.

(Step of reducing lithium sulfate to obtain lithium sulfide)
Next, a process of obtaining lithium sulfide carrying carbon fine particles by reducing lithium sulfate by mixing and heating fine particles containing lithium sulfate and carbon fine particles will be described.

In the method for producing a positive electrode material for a secondary battery according to this embodiment, fine particles containing lithium sulfate and carbon fine particles are stirred and mixed, and heated to reduce lithium sulfate to carry lithium sulfide carrying carbon fine particles. Generate. At this time, it is considered that the reaction represented by the following formula (1) occurs.
Li ₂ SO ₄ + 2C → Li ₂ S + 2CO ₂ (1)
When the reduction reaction progresses and the raw material lithium sulfate disappears from the reaction system, the generation of carbon dioxide due to the reaction stops, so the progress of the reaction can be known by monitoring the amount of carbon dioxide generated.
Moreover, the carbon fine particles of this embodiment have a role as a reducing agent and a role as a conductive auxiliary agent that imparts electronic conductivity to lithium sulfide.
In the method for producing a positive electrode material for a secondary battery according to the present embodiment, the mixing ratio of carbon fine particles is increased with respect to lithium sulfate. By doing so, the carbon fine particles are not completely consumed in the above-described reduction reaction of lithium sulfate, and a part thereof remains in the obtained lithium sulfide. As a result, a positive electrode material in which lithium sulfide and carbon fine particles are uniformly dispersed can be obtained.

  The carbon fine particles are not particularly limited, and examples thereof include carbon black and graphite powder. Among these, carbon black having a small particle size and a low price is preferable.

The average particle diameter d ₅₀ in the weight-based particle size distribution measured by the laser diffraction / scattering particle size distribution measurement method of the carbon fine particles is preferably 0.1 μm or less, more preferably 0.05 μm or less. When the average particle size d ₅₀ carbon fine particles is more than the above upper limit, more and lithium sulfate, the contact area becomes larger reduction reaction is accelerated with the carbon particulates agent, the unreacted starting materials in lithium sulfide obtained It can be further reduced. As a result, an even higher purity positive electrode material can be obtained.
The lower limit of the average particle size _{d 50} of carbon fine particles, for example, not less than 0.02 [mu] m. When it is at least the lower limit, the handleability of the carbon fine particles can be improved.

The method of mixing and heating lithium sulfate and carbon fine particles is not particularly limited. For example, bead mill, jet mill, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, ang mill And a method of heating while stirring and mixing using a pulverizer / disperser.
By using such a pulverizer / disperser, the reduction reaction can be performed while mixing and pulverizing lithium sulfate and carbon fine particles. If it does so, since the contact efficiency of lithium sulfate and carbon microparticles improves and a reduction reaction is accelerated | stimulated, the unreacted raw material in the lithium sulfide obtained can be reduced further. As a result, an even higher purity positive electrode material can be obtained.
Moreover, it is preferable to stir and mix in the state which added 2nd solvents, such as ethanol, and each raw material was disperse | distributed to the solvent at the time of stirring and mixing. By carrying out like this, a reduction reaction can be advanced more efficiently.

  Reaction conditions such as stirring speed, treatment time, heating temperature, reaction pressure, and the like when mixing and heating lithium sulfate and carbon fine particles can be appropriately determined depending on the amount of fine particles containing lithium sulfate.

In the reduction step according to this embodiment, the mixing molar ratio of the carbon fine particles to the fine particles containing lithium sulfate is preferably 3.6 or more and 6.4 or less, and more preferably 3.0 or more and 5.5 or less.
By setting the mixing molar ratio of the carbon fine particles to the fine particles containing lithium sulfate within the above range, the unreacted lithium sulfate in the obtained lithium sulfide can be further reduced. As a result, an even higher purity positive electrode material can be obtained.
Moreover, the positive electrode material excellent in balance of electroconductivity and capacity | capacitance can be obtained by making the mixing molar ratio of the carbon microparticles with respect to the microparticles | fine-particles containing lithium sulfate into the said range.

In the reduction process according to the present embodiment, the mixing weight ratio of the carbon fine particles to the fine particles containing lithium sulfate is preferably 0.4 or more and 0.7 or less.
By setting the mixing weight ratio of the carbon fine particles to the fine particles containing lithium sulfate within the above range, the unreacted lithium sulfate in the obtained lithium sulfide can be further reduced. As a result, an even higher purity positive electrode material can be obtained.
Moreover, the positive electrode material excellent in balance of electroconductivity and capacity | capacitance can be obtained by making the mixing weight ratio of the carbon microparticles with respect to the microparticles | fine-particles containing lithium sulfate into the said range.

Finally, the obtained powder is dried by vacuum heating or the like as necessary, whereby a positive electrode material containing lithium sulfide and carbon fine particles can be obtained.
Drying conditions such as the heating temperature, heating time, and pressure in the container at this time can be appropriately determined depending on the amount of the positive electrode material obtained.

(Positive electrode material for secondary battery)
The lithium sulfide carrying the carbon fine particles obtained by the production method of the present embodiment can be suitably used as, for example, a positive electrode material for a lithium ion secondary battery.
The positive electrode material obtained by the production method of the present embodiment is superior in charge / discharge efficiency compared to the positive electrode material obtained by a method of mixing lithium sulfide and a carbon material. The reason for this is not necessarily clear, but is considered as follows.
First, since the positive electrode material obtained by the manufacturing method of the present embodiment has high purity, irreversible side reactions due to impurities hardly occur. Therefore, it is thought that charging / discharging efficiency is excellent.
Moreover, the positive electrode material obtained by the manufacturing method of this embodiment forms a good network by uniformly dispersing lithium sulfide and carbon fine particles (FIG. 1). Therefore, the positive electrode material of this embodiment has improved conductivity, and as a result, it is considered that the charge / discharge efficiency is excellent.

(Lithium ion secondary battery)
Next, a lithium ion secondary battery using the positive electrode material obtained according to the present embodiment will be described.
The lithium ion secondary battery of the present embodiment includes a positive electrode and a negative electrode, and can be manufactured by a generally known method. For example, it is manufactured by forming a positive electrode and a negative electrode overlaid on the center of the separator into a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape and enclosing a non-aqueous electrolyte.

The positive electrode for secondary battery of this embodiment is obtained by forming an active material layer containing the positive electrode material of this embodiment on the surface of a current collector such as aluminum. The positive electrode active material layer includes, for example, a binder and a positive electrode material.
Moreover, the negative electrode for secondary batteries of this embodiment is obtained by, for example, forming an active material layer containing a negative electrode material on the surface of a current collector such as copper. The negative electrode active material layer is composed of a binder and a negative electrode material.
Carbon materials such as carbon black, graphite powder, and vapor grown carbon fiber (VGCF) may be added to each electrode as a conductive additive.

  As the negative electrode material, any of metallic lithium, lithium alloy, carbon material, tin oxide, niobium oxide, vanadium oxide, titanium oxide, silicon, and transition metal nitride can be used. Among these, a carbon material that can dope / dedope lithium ions is preferable. Such a carbon material may be graphite or amorphous carbon, and artificial graphite, natural graphite, hard carbon and the like are used.

  The separator used to electrically insulate the positive electrode from the negative electrode is a membrane that allows lithium ions to pass through. For example, a porous membrane or a polymer electrolyte is used. A microporous polymer film is preferably used as the porous film, and examples of the material include polyolefin, polyimide, polyvinylidene fluoride, and polyester. In particular, a porous polyolefin film is preferable, and specific examples include a porous polyethylene film and a porous polypropylene film.

  In this embodiment, a solid electrolyte layer or a gel electrolyte layer may be used instead of the separator used for electrically insulating the positive electrode and the negative electrode.

As the non-aqueous electrolyte, for example, an electrolyte such as LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ N / Li is used alone or in combination of two or more. What was melt | dissolved in the solvent can be used. Examples of the organic solvent in the non-aqueous electrolyte include propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethyl sulfoxide, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, Tetrahydrofuran etc. are mentioned, and any one is used alone or in admixture of two or more.

Moreover, the positive electrode for secondary batteries of this embodiment can be made into an all-solid-state lithium ion secondary battery by using a lithium ion conductive solid electrolyte layer as an electrolyte layer.
Although it does not specifically limit as a lithium ion conductive solid electrolyte layer, Generally a well-known thing can be used.
When the positive electrode material of this embodiment is used as a positive electrode material of an all-solid-state lithium ion secondary battery, a lithium ion secondary battery having good battery characteristics such as charge / discharge efficiency and cycle characteristics and high safety is obtained. be able to.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these.

(Example)
(Micronization process)
2100 g of lithium sulfate monohydrate (chemical formula Li ₂ SO ₄ .H ₂ O, manufactured by Foot Mineral Co., Ltd.) was dissolved in 100 mL of distilled water to prepare an aqueous lithium sulfate solution.
Next, the prepared lithium sulfate aqueous solution was added to 500 mL ethanol to precipitate lithium sulfate monohydrate fine particles. The resulting precipitate was washed with ethanol and then suction filtered to obtain a lithium sulfate monohydrate precipitate. The obtained precipitate was 24.83 g, and the yield was 99.3%.
Finally, the obtained precipitate was heated at 200 ° C. for 2 hours under atmospheric pressure to dehydrate lithium sulfate monohydrate.
Here, the particle diameters d ₁₀ , d ₅₀ , and d ₉₀ after dehydration of lithium sulfate were measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by Malvern, Mastersizer 3000). The particle diameters were d ₁₀ : 2.9 μm, d ₅₀ : 6.2 μm, and d ₉₀ : 12.8 μm.

(Reduction process)
Subsequently, 10 g of dehydrated lithium sulfate together with ZrO ₂ balls was put into an Al ₂ O ₃ pot, and 20 mL of dehydrated ethanol and carbon black (average particle diameter d ₅₀ : 28 nm, manufactured by Tokai Carbon Co., Ltd., Seast 300) ) 6.36 g was added respectively.
Next, lithium sulfate and carbon black were mixed and ground at 160 rpm for about 16 hours.
After the mixing and pulverization, the reduction reaction was performed under vacuum (933 Pa) under the conditions of 830 ° C. and 1.5 h.

The X-ray diffraction pattern of the powder obtained by drying was measured with an X-ray diffractometer (XRD). From the intensity ratio of lithium sulfide (Li ₂ S) and lithium sulfate (Li ₂ SO ₄ ), The remaining amount was quantified. Reagents lithium sulfide and lithium sulfate were used for the calibration curve.
Moreover, the residual amount of carbon in the powder obtained by drying was quantified by fluorescent X-ray analysis (EDX). Reagents lithium sulfide and carbon black were used for the calibration curve.
The residual amount of lithium sulfate was 0.01% by weight, and the residual amount of carbon was 4.18% by weight. Moreover, the SEM image of the powder obtained by drying is shown in FIG.

Further, 4.5 g of the obtained positive electrode material and 0.5 g of polytetrafluoroethylene powder were mixed to form a sheet and punched out to φ15. Next, the punched sheet was pressure-bonded to a SUS plate that is a current collector to produce a positive electrode.
Further, the positive electrode obtained by the above method as a positive electrode of a lithium ion secondary battery, lithium metal as a negative electrode, LiPF ₆ dissolved in an ethylene carbonate / diethyl carbonate mixed solution as an electrolyte, and Celgard # 2500 as a separator, respectively. The lithium ion secondary battery was produced using it. Next, the charge / discharge test was performed three times under the conditions of a charge / discharge range of 3.6 to 1.0 V and a charge / discharge current of 0.22 mA. The obtained results are shown in Table 1.

(Comparative example)
7.0 g of lithium sulfide (chemical formula Li ₂ S, manufactured by afaChem) and 7.0 g of carbon black (average particle diameter d ₅₀ : 28 nm, manufactured by Tokai Carbon Co., Ltd., Seast 300) were weighed in a glove box in an argon gas atmosphere. And ZrO ₂ balls were put into an Al ₂ O ₃ pot and stirred and mixed at 160 rpm for about 16 hours. An SEM image of the obtained powder is shown in FIG.

  Moreover, the charge / discharge test was performed 3 times like the Example except using this powder as a positive electrode material. The obtained results are shown in Table 1.

(Evaluation results)
Aggregates of lithium sulfide and carbon fine particles were not observed in the positive electrode material obtained in the example (FIG. 1). On the other hand, aggregates of lithium sulfide and carbon fine particles were observed in the positive electrode material obtained in the comparative example (FIG. 2).
Moreover, the positive electrode material obtained by the Example was excellent in charging / discharging efficiency compared with the positive electrode material obtained by the comparative example.

Claims (8)

A method for producing a positive electrode material for a secondary battery containing lithium sulfide and carbon fine particles,
A positive electrode material for a secondary battery comprising a step of reducing the lithium sulfate by mixing and heating the fine particles containing lithium sulfate and the carbon fine particles to obtain the lithium sulfide carrying the carbon fine particles. Manufacturing method. In the manufacturing method of the positive electrode material for secondary batteries of Claim 1,
The average particle size d ₅₀ is below 15.0 .mu.m, method for producing a cathode material for a secondary battery in weight particle size distribution by a laser diffraction scattering particle size distribution measuring method of the microparticles containing the lithium sulfate. In the manufacturing method of the positive electrode material for secondary batteries of Claim 1 or 2,
The average particle size d ₅₀ is 0.1μm or less, method for producing a cathode material for a secondary battery in weight particle size distribution by a laser diffraction scattering particle size distribution measurement method of the carbon fine particle. In the manufacturing method of the positive electrode material for secondary batteries as described in any one of Claims 1 thru | or 3,
The manufacturing method of the positive electrode material for secondary batteries whose mixing weight ratio of the said carbon microparticles with respect to the said microparticles | fine-particles containing the said lithium sulfate is 0.4-0.7. In the manufacturing method of the positive electrode material for secondary batteries as described in any one of Claims 1 thru | or 4,
The method for producing a positive electrode material for a secondary battery, wherein the carbon fine particles include carbon black.   The positive electrode material for secondary batteries obtained by the manufacturing method of the positive electrode material for secondary batteries as described in any one of Claims 1 thru | or 5.   The positive electrode for secondary batteries obtained by forming the active material layer containing the positive electrode material for secondary batteries of Claim 6 on the surface of an electrical power collector.   A secondary battery comprising the secondary battery positive electrode and negative electrode according to claim 7.