JP5712959B2 - Precursor of positive electrode active material for lithium secondary battery, method for producing the same, and method for producing positive electrode active material for lithium secondary battery using the precursor - Google Patents

Description

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

Lithium secondary batteries are lightweight and have high energy density, so they are widely used in small batteries such as mobile phones, notebook computers, and other IT devices. For these applications, LiCoO ₂ and LiCo _1/3 are mainly used. Layered rock salt compound positive electrode active materials such as Ni _1/3 Mn _1/3 O ₂ and LiNiO ₂ are used.
And with the development and popularization of IT equipment, the demand is still growing on a global scale. In addition to these small batteries, industrial large batteries can also be used for hybrid vehicles (HEV), plug-in hybrid vehicles (PHEV), electric vehicles (EV), power leveling, power storage, and more. The demand is expected to expand in the direction, and research and development are also actively conducted.

Under such circumstances, high safety, long life, high output, and low price are required for the positive electrode active material as a problem for full-scale commercialization of large industrial batteries. Among them, olivine-type positive electrode active materials are attracting attention as alternative positive electrode active materials such as LiCoO ₂ and LiCo _1/3 Ni _1/3 Mn _1/3 O ₂ as materials exhibiting high safety and excellent cycle performance. ing.
A typical example of the olivine-type positive electrode active material is lithium iron phosphate (LiFePO ₄ ). LiFePO ₄ is a material that can be synthesized from low-priced raw materials with low resource constraints because all of the constituent elements except for Li are at the top of the number of Clarks, and realizes a capacity close to the theoretical capacity with high efficiency. Yes. In addition, since all oxygen is covalently bonded to phosphorus, has a strong skeleton of phosphoric acid, and has a stable structure, it is highly safe and has a long cycle life. Industrially produced and put to practical use.

However, the above LiFePO ₄ also has some disadvantages. One is a problem that electron conductivity and Li ion conductivity are low as compared with a conventional layered rock salt compound positive electrode active material. With respect to this, improvement has been achieved by making the LiFePO ₄ particles finer to several tens to several hundreds of nanometers, and further coating / compositing with a conductive material such as graphite to impart conductivity. The other is a problem that the weight energy density is low because the potential with respect to Li metal is 3.3 V, which is lower than the layered rock salt compound positive electrode active material. This is an essential property of the material and is difficult to improve.

By the way, the same olivine type lithium manganese phosphate composite salt (LiMnPO ₄ ) and lithium cobalt phosphate composite salt (LiCoPO ₄ ) as LiFePO ₄ have a voltage with respect to Li metal of 4.2 V and 4.8 V, respectively. Since it shows the same potential as the positive active material of rock salt compound and is expected to have high weight energy density, it attracts the attention of developers all over the world.
On the other hand, since LiMnPO ₄ has a lower electronic conductivity than LiFePO ₄ , there is a problem that further ingenuity is required to extract electrochemical characteristics. Further, in the non-aqueous electrolyte used now generally so will decompose at 4.8V is the operating voltage of LiCoPO _4, the LiCoPO ₄ as the positive electrode active material was put to practical use state it can not be used Not in.

As a method for producing the LiMnPO ₄ or LiCoPO ₄ , manganese carbonate (MnCO ₃ ) as a manganese raw material, or cobalt oxide (Co ₃ O ₄ ) as a divalent cobalt raw material, lithium carbonate, ammonium dihydrogen phosphate and the like A production method based on a solid-phase reaction in which mixing and firing are proposed (see, for example, Patent Document 1).
However, in general, since the temperature required for the reaction is high in the solid phase method, the primary particles are likely to be coarsened or agglomerated and the particle diameter is increased. In LiMnPO ₄ or LiCoPO ₄ having a low conductivity as described above, a powerful miniaturization process is required. For extreme micronization treatment, it is common to use alumina or zirconia spheres as a medium in a wet mill, but impurities are likely to be mixed during pulverization, and a drying treatment after treatment is also necessary. As described above, the solid phase reaction method has very good efficiency in the firing step, but there is a problem that it is inevitable that the particles become coarse due to high-temperature treatment, and it takes much time and cost.
Further, imparting conductivity with graphite or the like is necessary for improving conductivity, and it is desirable to uniformly coat the surface of LiMnPO ₄ or LiCoPO ₄ particles. For that purpose, it is necessary to add a carbon source after refining these particles and to perform heat treatment again, resulting in a longer process and an increased cost. In the solid-phase reaction method, if a carbon source is added at the precursor stage, the synthesis reaction is inhibited, so that it is extremely difficult to perform conductive carbon complexation by a single heat treatment.

On the other hand, a production method for obtaining LiMnPO ₄ or LiCoPO ₄ by synthesizing a precursor by a hydrothermal method and firing at a low temperature has been proposed (see, for example, Non-Patent Document 1). Since LiMPO ₄ (M: transition metal) can be synthesized by a low-temperature reaction, it is said that fine particles of 100 nm or less can be obtained.
However, the hydrothermal method has the disadvantages that the Li, M, and P raw material concentrations with respect to the solvent are low and the reaction uses a high-pressure vessel, so that it is not suitable for efficient mass synthesis. Not suitable for use.

Furthermore, a method of obtaining LiMPO ₄ by a low-temperature heat treatment using a precursor in which Li, M, and P raw materials are uniformly blended at a molecular level by a sol-gel method has been actively studied at universities and the like. LiMPO ₄ particles are reported to be obtained. In addition, conductive carbon is combined by thermal decomposition of organic components contained in the raw material, and good conductivity is obtained. However, the use of expensive organic raw materials and depending on the salt used generate cracked gases such as sulfuric acid, nitric acid, hydrochloric acid and organic substances during the synthesis, which requires treatment for these and is not suitable for industrial production.
As described above, the conventional production methods have the above-described problems, and a method for producing an olivine-type positive electrode active material such as fine and high-performance LiMnPO ₄ or LiCoPO ₄ at an industrial and low cost is as follows. The current situation is that it has not been developed.

JP-A-11-259593

J Chen, et al. , Solid State Ionics 178 (2008) 1676-1693

  An object of the present invention is to provide a positive electrode active material for an olivine-type lithium secondary battery that has excellent battery characteristics when used as a positive electrode active material, and has a composition in view of the above-mentioned problems of the prior art. The present invention provides a method for producing a positive electrode active material for a lithium secondary battery using a uniform and fine precursor, and further provides a lithium secondary battery having good characteristics using the positive electrode active material.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies on a lithium transition metal composite phosphate that is uniformly mixed and has a fine particle size. As a result, the ammonium phosphate transition metal salt is mixed as a raw material, It was found that the above lithium transition metal composite phosphate can be obtained by firing with, and based on this finding, the present invention has been completed.

That is, according to the first aspect of the present invention, the general formula: NH ₄ MPO ₄ .nH ₂ O (M is one or more containing at least Co selected from the group consisting of Fe, Mn, Ni and Co, A method for producing a precursor of a positive electrode active material for a lithium secondary battery comprising an ammonium phosphate transition metal represented by 0 ≦ n ≦ 1), wherein a mixed solution of divalent M ions and phosphate ions A mixed solution preparation step to be prepared, ammonia is added, the pH of the mixed solution is adjusted to a range of 7 to 9, and co-precipitated, and ammonium phosphate M salt (NH ₄ MPO ₄ · nH ₂ O) is added. And a method for producing a precursor of a positive electrode active material for a lithium secondary battery.

According to a second invention of the present invention, in the first invention, in the crystallization step, the mixed solution is maintained at 25 to 60 ° C. A manufacturing method is provided.
According to a third aspect of the present invention, in the first or second aspect, the mixed solution preparation step is selected from the group consisting of sulfates and chlorides as a divalent M ion feedstock. There is provided a method for producing a precursor of a positive electrode active material for a lithium secondary battery, wherein one or more water-soluble metal salts are used.
Furthermore, according to the fourth invention of the present invention, in the first or second invention, in the mixed solution preparation step, the feedstock of the phosphor oxide ions is selected from the group consisting of phosphoric acid and ammonium dihydrogen phosphate. The manufacturing method of the precursor of the positive electrode active material for lithium secondary batteries characterized by using the 1 or more types of water-soluble salt by which it is carried out is provided.

According to a fifth aspect of the present invention, there is provided the positive electrode active material for a lithium secondary battery according to any one of the first to fourth aspects, wherein the crystallization step is performed in a non-oxidizing atmosphere. A method for producing a precursor is provided.
Furthermore, according to the sixth invention of the present invention, in any one of the first to fifth inventions, the ammonium phosphate M salt (NH ₄ MPO ₄ .nH ₂ O) obtained in the crystallization step is washed. The manufacturing method of the precursor of the positive electrode active material for lithium secondary batteries characterized by further providing a washing | cleaning process is provided.

According to a seventh aspect of the present invention, there is provided a precursor for a positive electrode active material for a lithium secondary battery, which is obtained by the production method according to any one of the first to sixth aspects and is made of an ammonium phosphate transition metal. And represented by the general formula: NH ₄ MPO ₄ .nH ₂ O (M is at least one selected from the group consisting of Fe, Mn, Ni and Co, 0 ≦ n ≦ 1), sodium The precursor of the positive electrode active material for lithium secondary batteries characterized by content being 0.01 mass% or less is provided.

On the other hand, according to the eighth invention of the present invention, after mixing the precursor of the positive electrode active material for lithium secondary battery and the lithium salt according to the seventh invention, in an inert or reducing atmosphere, 200 to 500 ° C. To obtain a lithium transition metal composite phosphate represented by the general formula: LiMPO ₄ (M is at least one selected from the group consisting of Fe, Mn, Ni and Co, including at least Co). A method for producing a positive electrode active material for a lithium secondary battery is provided.

According to a ninth invention of the present invention, in the eighth invention, when the precursor and the lithium salt are mixed, a carbon source is further mixed and then fired at 600 to 800 ° C. A method for producing a positive electrode active material for a lithium secondary battery is provided.
Furthermore, according to the tenth invention of the present invention, in the eighth invention, the mixture of the lithium transition metal composite phosphate obtained by firing at 200 to 500 ° C. and the carbon source is inert or Provided is a method for producing a positive electrode active material for a lithium secondary battery, characterized by performing a heat treatment at 600 to 800 ° C. in a reducing atmosphere.

According to an eleventh aspect of the present invention, in the eighth or ninth aspect, the precursor is pulverized in advance before the firing, and the positive electrode active material for a lithium secondary battery is manufactured. A method is provided.
Furthermore, according to a twelfth aspect of the present invention, in the tenth aspect, the lithium transition metal composite phosphate is pulverized in advance before the heat treatment. A method of manufacturing a material is provided.

According to the method for producing a precursor of a positive electrode active material for a lithium secondary battery of the present invention, a precursor of a positive electrode active material for an olivine-type lithium secondary battery in which Co and P are uniformly mixed at an atomic level can be obtained. Moreover, the positive electrode active material obtained using the precursor has a fine particle size and is uniform in composition, and a lithium secondary battery using the positive electrode active material exhibits excellent battery characteristics. Is.
In addition, the method for producing a positive electrode active material for a lithium secondary battery of the present invention is suitable for industrial scale production with high yield without using a toxic compound, and its industrial value. Is extremely large.

It is an X-ray diffraction pattern of the precursor obtained in Example 1 according to the present invention. It is an X-ray diffraction pattern of the composite phosphate obtained in Example 1 according to the present invention. It is an X-ray-diffraction pattern of the precursor obtained by the comparative example 1 which concerns on this invention. 3 is an X-ray diffraction pattern of a composite phosphate obtained in Comparative Example 1 according to the present invention.

  Hereinafter, the present invention will be described in detail for each item.

1. Method for Producing Precursor of Positive Electrode Active Material for Lithium Secondary Battery A method for producing a precursor of a positive electrode active material for a lithium secondary battery according to the present invention has a general formula: NH ₄ MPO ₄ .nH ₂ O (M is Fe, Production of a precursor of a positive electrode active material for a lithium secondary battery comprising at least one selected from the group consisting of Mn, Ni and Co, and an ammonium phosphate transition metal represented by 0 ≦ n ≦ 1) Law,
A mixed solution preparation step for preparing a mixed solution of divalent M ions and phosphate ions, and adding ammonia to adjust the pH of the mixed solution to a range of 7 to 9 for coprecipitation, ammonium phosphate And a crystallization step for obtaining M salt (NH ₄ MPO ₄ .nH ₂ O).

In the mixed solution preparation step, a mixed solution of divalent M ions and phosphate ions is prepared. Since the composition of the ammonium phosphate M salt obtained in the crystallization step of the next step matches the composition ratio of the mixed solution, the ratio of M ions and phosphate ions contained in the mixed solution is represented by the following general formula (1 The divalent M salt and phosphorus oxide are dissolved in water so that the composition ratio of
Here, the molar ratio of M to phosphorus oxide is 1: 1 in stoichiometry, but considering the yield during crystallization, the molar ratio of M to phosphorus oxide is 0.9 to 1. The range can be up to 1. When the molar ratio is 0.90 or less, the yield of phosphorus oxide ions deteriorates, while when it is 1.1 or more, impurities such as Co ₃ O ₄ and MnO ₂ are likely to be generated. Preferably it dissolves so that it may become 0.95-1.05. The molar ratio of the transition metal as M may be the molar ratio in the ammonium phosphate M salt to be obtained.
Formula (1): NH ₄ MPO ₄ · nH ₂ O
(M is one or more containing at least Co selected from the group consisting of Fe, Mn, Ni and Co, 0 ≦ n ≦ 1)

A water-soluble salt can be widely used as the divalent M salt, but a divalent inorganic salt is preferable. Specifically, it is preferable to use one or more water-soluble metal salts selected from sulfates or chloride salts as a feedstock for M ions.
In addition, as the phosphorous oxide, a water-soluble one can be used. Specifically, the phosphorous oxide ion feedstock is one or more water-soluble substances selected from phosphoric acid or ammonium dihydrogen phosphate. It is preferable to use a metal salt.

In the next crystallization step, ammonia is added to the acidic mixed solution, the pH of the mixed solution is adjusted to a range of 7 to 9, and M ions and phosphate ions are co-precipitated, and phosphoric acid is added. Ammonium manganese iron is obtained.
In the coexistence state in the solution, the phosphate anion and the metal ion are in a state where they are completely uniformly mixed. By co-precipitation, the M and phosphoric acid are strictly mixed, resulting in a uniform composition. Coprecipitate can be obtained.

Here, it is important to use a pH range to be controlled and ammonia. If the pH is less than 7, ammonia, metal ions and phosphate ions do not completely react and remain in the mixed solution, resulting in a decrease in yield and compositional deviation. Further, when the pH exceeds 9, oxidation of metal ions is unlikely to occur, and impurities such as Co ₃ O ₄ and MnO ₂ are generated and remain as a different phase even after being mixed with a lithium salt and heat-treated, thereby deteriorating characteristics. .
If the purpose is to co-precipitate by controlling the pH to a high pH side, an alkali metal hydroxide or the like can be used. However, if an alkali metal hydroxide is used, the alkali metal remains in the coprecipitate. It becomes an impurity. In particular, when sodium hydroxide is used, sodium is increased as a residual impurity, so that sodium in the finally obtained positive electrode active material for a lithium secondary battery is increased and the characteristics of the positive electrode active material are deteriorated.
By controlling the pH to 7 to 9, it is possible to obtain ammonium manganese iron phosphate suitable as a precursor of a positive electrode active material for a lithium secondary battery having no composition deviation and containing no impurities. At this time, even if only metal ions are dissolved in the raw material solution and a mixed solution of phosphoric acid and ammonia is added dropwise thereto, an ammonium phosphate M salt can be obtained, but many sulfate radicals remain and are removed by washing. It is difficult to do.

In the crystallization step, it is preferable to co-precipitate in a non-oxidizing atmosphere. With a non-oxidizing atmosphere, it is possible to suppress the formation of impurities such as Fe ₃ O ₄ and MnO ₂ by oxidation. The non-oxidizing atmosphere is preferably an inert gas atmosphere such as nitrogen gas.
Moreover, it is preferable to hold | maintain the liquid temperature of a mixed solution at 25-60 degreeC during crystallization. When the liquid temperature is lower than 25 ° C., the solubility of metal ions in the mixed solution is low, and the precipitation rate of M and phosphoric acid is different, which may cause a composition shift. The upper limit of the liquid temperature is preferably 60 ° C. When the liquid temperature exceeds 60 ° C., the solubility of metal ions in the mixed solution increases, the deposition rate decreases, and the crystallinity of the resulting ammonium phosphate M salt becomes too high. The active material may become coarse.

As an apparatus used for the crystallization step, a reaction vessel with a stirrer is preferable in order to cause the reaction to occur uniformly, and in order to control the atmosphere during crystallization, it is preferable to have a sealed structure. preferable.
After completion of the crystallization reaction, in order to remove impurities by filtration and centrifugation, the ammonium phosphate M salt obtained in the crystallization step is sufficiently washed and then dried. Here, since the ammonium phosphate M salt has a fine particle structure, impurities such as sodium can be easily removed by washing with water.

The ammonium phosphate M salt obtained in the crystallization step is easily oxidized during drying, and the metal element may be oxidized to leave a foreign phase as an impurity. For this reason, drying after washing is performed in a non-oxidizing atmosphere. Although it will not specifically limit if it is in a non-oxidizing atmosphere, It is preferable to carry out in an inert atmosphere or a vacuum atmosphere.
Moreover, the drying temperature should just be the range which can suppress oxidation, it is preferable to set it as 250 degrees C or less, and it is more preferable to set it as 150 degrees C or less. On the other hand, the lower limit of the drying temperature is preferably 60 ° C. or higher, and more preferably 90 ° C. or higher. If it is less than 60 degreeC, since it takes time to dry and adhering water and excessive crystallization water remain, it is not preferable. It is more preferable to dry to such an extent that it can be dehydrated.

  In the above production method, when one or more transition metal ions containing at least Co selected from the group consisting of Fe, Mn, Ni and Co are mixed as M, a divalent transition metal ion and a phosphate oxide ion are mixed. In the crystallization process, a mixed solution of each of the divalent transition metal ions and phosphate ions is individually prepared. Alternatively, the pH of each mixed solution may be individually adjusted and coprecipitated, and mixed at a transition metal molar ratio to form a precursor. Since the ammonium phosphate transition metal salt containing the above transition metal has a similar structure, a lithium transition metal composite phosphate having a uniform composition can be obtained even by low-temperature heat treatment by thoroughly mixing each of them. .

2. Precursor of positive electrode active material for lithium secondary battery The precursor of the positive electrode active material for lithium secondary battery of the present invention is obtained by the above production method and is represented by the above general formula (1), and has a sodium content. Is 0.01% by mass or less.

Since the precursor of the positive electrode active material for a lithium secondary battery of the present invention is obtained by the above production method, M and phosphorus oxide are uniformly mixed at an atomic level. For this reason, the composition can be made uniform even by low-temperature firing after mixing with the lithium salt, and a lithium transition metal composite phosphate having a fine particle diameter can be obtained.
Moreover, sodium content is 0.01 mass% or less, and sufficient characteristics are acquired with the positive electrode active material obtained. When the sodium content exceeds 0.01% by mass, the movement of Li ions in the olivine structure is inhibited by Na, so that the positive electrode performance using the obtained positive electrode active material is deteriorated.

3. Method for producing positive electrode active material for lithium secondary battery The method for producing a positive electrode active material for lithium secondary battery according to the present invention is a precursor of a positive electrode active material for lithium secondary battery (hereinafter sometimes referred to simply as a positive electrode active material). The above ammonium phosphate M salt and lithium salt are mixed and then calcined at 200 to 500 ° C. in an inert or reducing atmosphere to obtain a lithium transition metal composite phosphate, that is, a positive electrode active material for a lithium secondary battery It is characterized by obtaining.

  In the above production method, in order to impart conductivity to the lithium transition metal composite phosphate, a compound that becomes a carbon source when the ammonium phosphate M salt and the lithium salt are mixed (hereinafter sometimes simply referred to as a carbon source). May be fired at 600 to 800 ° C. after further mixing.

  Lithium transition metal composite phosphate obtained by firing without mixing a carbon source can also be used as a positive electrode active material, but it reduces the number of steps for imparting conductivity during battery production, and is favorable. In order to obtain conductivity, it is preferable to complex the lithium transition metal complex phosphate with graphite. For this reason, after mixing the lithium transition metal complex phosphate obtained by the said baking and a carbon source, it is preferable to heat-process at 600-800 degreeC in inert or reducing atmosphere, and to make a positive electrode active material.

(3-1) Firing step In the firing step, first, the ammonium phosphate M salt and the lithium salt are mixed. Mixing of ammonium phosphate M salt and lithium salt involves mixing ammonium phosphate M salt and lithium salt so that a lithium transition metal composite phosphate represented by the following general formula (2) is obtained. is there.
General formula (2): LiMPO ₄
(M is one or more containing at least Co selected from the group consisting of Fe, Mn, Ni and Co)

  The lithium salt is not particularly limited, and general lithium salts such as lithium hydroxide, lithium carbonate, and lithium acetate can be used.

  As a mixing method, a mixer capable of sufficiently mixing ammonium phosphate M salt and lithium salt may be used. Specifically, a shaker mixer or a dry or wet mill using alumina or zirconia spheres may be used. it can. In particular, in order to atomize the finally obtained positive electrode active material, it is preferable to pulverize the ammonium phosphate M salt in advance before firing, and the pulverization may be performed simultaneously with the mixing with the lithium salt. preferable. In this case, using a mill such as a ball mill, a planetary mill, a vibration mill, a bead mill or the like is preferable because pulverization can be performed simultaneously with mixing.

After mixing with the lithium salt, the mixture is calcined at 200 to 500 ° C., preferably 300 to 400 ° C., under an inert or reducing atmosphere.
Since the ammonium phosphate M salt of the present invention is in a state in which M and phosphoric acid are uniformly mixed at the atomic level, the lithium transition is homogenized and has good crystallinity even when firing in the above temperature range. A metal composite phosphate (LiMPO ₄ ), that is, a positive electrode active material for a lithium secondary battery can be obtained. When the firing temperature is less than 200 ° C., lithium carbonate, which is a reaction raw material, may remain, and when the firing temperature exceeds 500 ° C., the sintering of the particles proceeds and coarse particles are generated and finally obtained. The conductivity of the positive electrode active material decreases.

When the ammonium phosphate M salt, the lithium salt, and the carbon source are mixed at the same time, grain growth is suppressed by the carbon source, and thus the firing is performed at a temperature at which the carbon source is graphitized. Although depending on the carbon source used, graphitization proceeds at 600 ° C. or higher, and therefore, by calcining at 600 to 800 ° C., preferably 600 to 700 ° C., it is possible to obtain a lithium transition metal composite phosphate having a graphite composite. it can.
When the firing temperature is less than 600 ° C., graphitization of carbon does not proceed, and sufficient conductivity cannot be obtained for the positive electrode active material. On the other hand, when the firing temperature exceeds 800 ° C., the sintering of the particles proceeds and becomes coarse, and the conductivity of the positive electrode active material is lowered.
The reducing atmosphere is preferably a mixed gas of an inert gas and hydrogen gas in order to suppress contamination of impurities, and the hydrogen gas content in the mixed gas is preferably 1 to 20% by volume. The holding time at the firing temperature is preferably 1 to 10 hours in order to obtain good crystallinity.

(3-2) Carbon source mixing step In the carbon source mixing step, in order to impart conductivity to the lithium transition metal composite phosphate, the carbon source is used in the final positive electrode active material, and the carbon content is 1-5. It is the process of mixing so that it may become mass%.
The carbon source is not particularly limited as long as it is graphitized to become a conductive carbonaceous material by firing. Carbon such as natural graphite and artificial graphite, carbon such as acetylene black and ketjen black, etc. Common hydrocarbons such as blacks, carbon fibers and sucrose, ascorbic acid, and other organic compounds that generate carbonaceous matter by decomposition can be widely used.
Further, the amount of carbon atoms contained in the carbon source tends to be smaller than that of the carbon source by firing. For this reason, the compounding amount of the carbon source is preferably increased by 40 to 120%, more preferably by 50 to 120%, by mass ratio with respect to the amount of carbon contained after firing.

The mixing is performed by using a shaker mixer or a dry or wet method using a shaker mixer, alumina, or zirconia sphere so that the ammonium phosphate M salt or the lithium transition metal composite phosphate obtained by firing and the carbon source are uniformly mixed. It is preferable to carry out sufficiently using a mill or the like.
Even in the carbon source mixing step, by pulverizing ammonium phosphate M salt or lithium transition metal composite phosphate obtained by firing, the positive electrode active material finally obtained is atomized and the particles are uniformly formed. Since it can be coated with a conductive carbonaceous material, it is preferably pulverized simultaneously with mixing. For this reason, it is preferable to use a mill such as a ball mill, a planetary mill, a vibration mill, or a bead mill. In addition, when mixing with ammonium phosphate M salt, it is preferable to carry out simultaneously with mixing with lithium salt as mentioned above.

(3-3) Heat treatment step In the carbon source mixing step, the lithium transition metal composite phosphate mixed with the carbon source is the same as in the case where the carbon source is mixed in the firing step, in an inert or reducing atmosphere. By performing heat treatment at 800 ° C., preferably 600 to 700 ° C., a lithium transition metal composite phosphate compounded with a carbonaceous material and having good conductivity, that is, a positive electrode active material for a lithium secondary battery can be obtained. .

As a furnace in the firing step and the heat treatment step, for example, a general heat treatment furnace or firing furnace such as a batch furnace, a roller hearth kiln, a pusher furnace, a rotary kiln, or a fluidized bed furnace can be used. During the treatment, in order to suppress the oxidation of cobalt and manganese, a reducing atmosphere of an inert gas such as nitrogen or argon, or a mixed gas of nitrogen and hydrogen is used. Therefore, it is preferable to use a furnace capable of controlling the atmosphere.
The positive electrode active material is composed of uniform fine primary particles, which can be pulverized and classified as necessary in the battery electrode manufacturing process.

4). Positive electrode active material for lithium secondary battery The positive electrode active material of the present invention is composed of an olivine type lithium transition metal composite phosphate represented by the above general formula (2) composed of uniform fine primary particles, The average particle diameter of the primary particles is 50 to 1000 nm, and the BET specific surface area is 5 to 50 m ² / g. Thereby, sufficient battery capacity is obtained when used as a positive electrode active material.
The primary particle diameter can be measured by observation with a scanning electron microscope, and the secondary particle diameter can be measured by a laser scattering diffraction method.

Here, when M in the general formula (2) is expressed as Me _a Co _1-a (Me is one or more selected from the group consisting of Fe, Mn, and Ni), a is 0.2. It is preferable that ≦ a ≦ 0.6. When a exceeds 0.6, the content of Me is too large, and a sufficient capacity as a battery may not be obtained. When a is less than 0.2, the cobalt content is too high, the battery voltage is increased, and the potential window of the electrolytic solution is exceeded, so that the battery may not operate stably.
When the average particle size of the primary particles is less than 50 nm, the bulk density of the positive electrode active material becomes low, and when used as the positive electrode active material of a battery, the battery capacity per volume becomes too low. On the other hand, when the average particle size of the primary particles exceeds 1000 nm, the lithium ions and the electron conductivity during the battery reaction are low, and the distance that the lithium ions and electrons move inside the high-resistance LiMPO ₄ particles increases. The reaction rate is extremely slow, battery resistance increases, and sufficient battery capacity cannot be obtained. The average particle size of the primary particles is preferably 100 to 800 nm.

The primary particles preferably have a particle size range of 50 to 1000 nm including 80% or more of the number of particles. Thereby, fine battery particles and coarse particles are not included, and good battery characteristics can be obtained. When the number of particles less than 50 nm increases, the battery capacity and cycle characteristics may be deteriorated due to current concentration. On the other hand, if there are many particles exceeding 1000 nm, the distance that lithium ions and electrons move inside the LiMPO ₄ particles becomes large, the reaction rate of the battery becomes extremely slow, the battery resistance increases, and the battery capacity decreases. is there. The particle size range can be determined by measuring 300 or more primary particles. The particle size range of the primary particles is preferably 100 to 1000 nm in order to improve battery characteristics.

The average particle size of the secondary particles is preferably 0.5 μm to 20 μm. When the average particle size of the secondary particles is less than 0.5 μm, the bulk density of the positive electrode active material becomes low, and the capacity per battery volume may become too low. On the other hand, when it exceeds 20 μm, coarse particles are mixed, and the paste at the time of battery production may not be uniform.
On the other hand, when the BET specific surface area is less than 5 m ² / g, when the positive electrode of the battery is constructed, sufficient contact with the electrolytic solution cannot be obtained, resulting in an increase in battery resistance and a decrease in conductivity. Moreover, when it exceeds 50 m < ² > / g, the bulk density of a positive electrode active material will become low too much.

In the said positive electrode active material, in order to acquire sufficient electroconductivity, it is preferable that a carbon content rate is 1-5 mass%. When the carbon content is less than 1% by mass, the conductivity of the positive electrode active material is not sufficient, and the battery capacity and output may decrease. Moreover, when it exceeds 5 mass%, the lithium transition metal composite phosphate (LiMPO ₄ ) in the positive electrode active material decreases, and the battery capacity may decrease.

  The positive electrode active material of the present invention, when used as a positive electrode active material of a C2023 type coin battery, for example, exhibits good battery characteristics in which the initial efficiency, which is the ratio between the initial charge capacity and the discharge capacity, is 65% or more, Suitable for lithium secondary battery.

5. Lithium Secondary Battery The lithium secondary battery according to the present invention is composed of the same components as a general lithium secondary battery, such as a positive electrode, a negative electrode, and a nonaqueous electrolyte.
Hereinafter, the embodiment of the lithium secondary battery of the present invention will be described in detail by dividing into its components, uses, etc., but the following embodiments are merely examples, and the lithium secondary battery of the present invention is The present invention can be implemented in various modifications and improvements based on the knowledge of those skilled in the art, including the embodiments described in this specification.

(A) Positive electrode A positive electrode is formed from the positive electrode compound material containing the positive electrode active material of this invention, the electrically conductive material, and the binder.
Specifically, a powdered positive electrode active material and a conductive material are mixed, a binder is added thereto, and if necessary, a solvent for viscosity adjustment is further added to adjust the positive electrode mixture paste, The positive electrode mixture paste is applied to, for example, the surface of a current collector made of aluminum foil, dried, and pressurized as necessary to produce a sheet-like positive electrode.
The conductive material is for ensuring the electrical conductivity of the positive electrode, and for example, a material obtained by mixing one or more carbon material powders such as carbon black, acetylene black, and graphite can be used. .
The binder plays a role of anchoring the active material particles. For example, a fluorine-containing resin such as polytetrafluoroethylene, polyvinylidene fluoride, and fluorine rubber, a thermoplastic resin such as polypropylene and polyethylene, and other suitable materials. Can be used.

If necessary, the solvent added to the positive electrode mixture, that is, the active material, the conductive material, and the activated carbon is dispersed, and the solvent for dissolving the binder is an organic solvent such as N-methyl-2-pyrrolidone. Can be used.
Activated carbon can also be added to increase the electric double layer capacity.
Such a positive electrode active material, a conductive material, and a binder are mixed, and if necessary, activated carbon and a solvent are added and kneaded to prepare a positive electrode mixture paste.

Each mixing ratio in the positive electrode mixture can also be an important factor that determines the performance of the lithium ion secondary battery. When the total solid content (meaning excluding solvent) of the positive electrode mixture is 100% by mass, the positive electrode active material is 60 to 95% by mass, and the conductive material is the same as the positive electrode of a general lithium secondary battery. 1 to 20% by mass, and the binder is preferably 1 to 20% by mass.
For example, the above positive electrode mixture paste sufficiently kneaded is applied to the surface of a metal foil current collector such as aluminum and dried to disperse the solvent and, if necessary, to increase the electrode density thereafter. By compressing with a roll press or the like, the positive electrode can be formed into a sheet. The sheet-like positive electrode can be cut into an appropriate size according to the intended battery and used for battery production.

(B) Negative electrode For the negative electrode, metallic lithium, lithium alloy, or the like, and a negative electrode mixture made by mixing a binder with a negative electrode active material capable of inserting and extracting lithium ions and adding a suitable solvent to form a paste. The surface of a metal foil current collector such as copper is applied, dried, and compressed as necessary to increase the electrode density. At this time, as the negative electrode active material, for example, a fired organic compound such as natural graphite, artificial graphite, or a phenol resin, or a powdery carbon material such as coke can be used. In this case, the negative electrode binder is a fluorine-containing resin such as polyvinylidene fluoride as in the positive electrode, and the negative electrode active material and the binder are dispersed in a solvent such as N-methyl-2-pyrrolidone. Organic solvents can be used.

(C) Separator A separator is sandwiched and loaded between the positive electrode and the negative electrode. The separator separates the positive electrode and the negative electrode and retains the electrolyte, and a thin microporous film such as polyethylene or polypropylene can be used.

(D) Non-aqueous electrolyte The non-aqueous electrolyte is obtained by dissolving a lithium salt as a supporting salt in an organic solvent.
Examples of the organic solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and trifluoropropylene carbonate, chain carbonates such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, and dipropyl carbonate, and tetrahydrofuran, 2- One kind selected from ether compounds such as methyltetrahydrofuran and dimethoxyethane, sulfur compounds such as ethylmethylsulfone and butanesultone, phosphorous compounds such as triethyl phosphate, triethyl phosphate and trioctyl phosphate alone, or two or more kinds It can be used by mixing.

As the supporting salt, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiASF ₆ , LiN (CF ₃ SO ₂ ) ₂ , and complex salts thereof can be used. Further, the non-aqueous electrolyte may contain a radical scavenger, a surfactant, a flame retardant, and the like.

The lithium secondary battery of the present invention configured as described above can have various shapes such as a cylindrical type and a stacked type. In any case, the positive electrode and the negative electrode are laminated via a separator to form an electrode body, and between the positive electrode current collector and the negative electrode current collector to the positive electrode terminal and the negative electrode terminal. Then, connection is made using a current collecting lead, the electrode body is impregnated with the non-aqueous electrolyte, and the battery case is sealed to complete the battery.
The lithium secondary battery of the present invention includes a positive electrode using the positive electrode active material for a lithium secondary battery of the present invention as a positive electrode material, and can be charged and discharged at a high potential of 4.0 to 4.8V. It is possible to industrially realize a lithium secondary battery that has higher energy density and higher safety than conventional lithium metal composite oxides.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the chemical analysis method of the metal used in the Example, the measurement method of X-ray diffraction and a specific surface area, and the evaluation method of battery capacity are as follows.

(1) Analysis of metal elements:
Analysis was performed by ICP emission analysis using an ICP emission analyzer (Varian, 725ES).
(2) X-ray diffraction:
Using a powder X-ray diffractometer (manufactured by PANALYTICAL, X′Pert PRO), the obtained positive electrode active material was measured by powder X-ray diffraction using Cu—Kα rays.
(3) Specific surface area:
It measured by BET method by nitrogen gas adsorption | suction using the BET method measuring machine (The Yuasa Ionix Co., Ltd. product Kantasorb QS-10).
(4) Battery capacity evaluation:
About the obtained positive electrode active material, the coin type battery was produced in the following procedures, and the charge / discharge capacity of the battery was measured and evaluated.
To the positive electrode active material, 33% by mass of acetylene black as a conductive material, 17% by mass of polyvinylidene fluoride (PVDF) as a binder, and an N-methylpyrrolidone (NMP) solution were added and mixed, and the above positive electrode active material was 50% by mass− A mixture of 33% by mass of the conductive material and 17% by mass of PVDF was obtained.
This mixture was applied onto an aluminum foil, dried at 80 ° C., punched to an electrode size of 11 mmφ, and pressed at a press pressure of 98 MPa (1.0 tonf / cm ² ) to produce an electrode.
This electrode is used as a positive electrode, metal Li as a negative electrode in the glove box, and as an electrolyte, LiMnPO ₄ contains an equal volume mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) containing 1 mol / L of electrolyte LiClO _4. (Volume ratio EC / DMC = 1/1), and LiCoPO ₄ includes ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), etc. containing 1 mol / L of electrolyte LiPF ₆ C2023 type coin batteries were prepared using each of the mixed liquids (volume ratio EC / EMC / DMC = 1/1/1).
The battery was charged and discharged under the conditions of charge 0.2 mA / cm ² , 5.2 V, rest 60 minutes, discharge 0.2 mA / cm ² , 2.0 V, 25 ° C., and the discharge capacity at the second cycle was Used as an evaluation value.

[Comparative Example 1]
Manganese sulfate n hydrate (Chuo Electric Works: 99.9% by mass) 174 g (1 mol as Mn) and phosphoric acid (manufactured by Wako: purity 85.0% by mass or more) 1 mol (115 g) in 1 L of distilled water The mixture was stirred well for 1 h with a stirrer to obtain a raw material solution.
The raw material solution was put into a 2 L separable flask and stirred with a stirrer while the inside was replaced with nitrogen. After 30 minutes, 25% by mass aqueous ammonia (manufactured by Wako) was added dropwise to the raw material solution until the pH reached 8.0-8.2. After completion of the dropwise addition, stirring was continued for 30 minutes while replacing the separable flask with nitrogen to complete the reaction. The reaction solution was filtered by suction filtration and washed with water to recover the generated solid. The recovered solid was dried at 100 ° C. for one day under vacuum to obtain a precursor.
The obtained precursor was identified as ammonium manganese phosphate (NH ₄ MnPO ₄ ) by X-ray diffraction analysis. FIG. 3 shows an X-ray diffraction chart of the precursor (ammonium manganese phosphate) obtained. The sodium content of the obtained precursor was not more than the lower limit of analysis (20 mass ppm).

30 g of the above-mentioned ammonium manganese phosphate, 5.9 g of lithium carbonate (Kanto Chemical Co., Ltd .: 99.0%) and 60 ml of ethanol were placed in a 500 ml zirconia pot with an inner volume of 650 g of φ1 mm zirconia balls. Mixed and ground at 350 rpm for 30 minutes. Zirconia balls were sieved and ethanol was removed by vacuum drying.
The resulting mixture was baked at 500 ° C. for 5 hours after raising the temperature at a heating rate of 10 ° C./min while purging the inside of the furnace with a nitrogen-2 volume% hydrogen mixed gas at 1 L / min in an electric furnace, A lithium transition metal composite phosphate was obtained.
The complex phosphate was identified as lithium manganese complex phosphate (LiMnPO ₄ ) by X-ray diffraction analysis. FIG. 4 shows an X-ray diffraction chart of the obtained composite phosphate (lithium manganese composite phosphate).

30 g of the above complex phosphate and 3.84 g of sucrose were placed in a 250 ml zirconia pot containing 350 g of φ5 mm zirconia balls and mixed for 10 minutes at 250 rpm with a planetary ball mill. After sieving the zirconia balls, this mixture electric furnace was maintained at 190 ° C. at a heating rate of 10 ° C./min for 2 hours while purging the inside of the furnace with a nitrogen-2% by volume hydrogen mixed gas at 1 L / min. Thereafter, the temperature was further raised to 650 ° C. and heat treatment was performed for 5 hours to obtain a positive electrode active material.
The composition of lithium: manganese: phosphorus in this positive electrode active material was 1.03: 1.00: 1.00 in atomic ratio, and the carbon content was 3.0 wt%. When observed with a scanning electron microscope (SEM), the particle size range of the primary particles was 100 to 500 nm, and the average particle size was 300 nm. The specific surface area was 27.2 m ² / g. When the battery was evaluated, the initial charge capacity was 61 mAh / g, the initial discharge capacity was 55 mAh / g, the initial efficiency was 90%, and the charge / discharge capacity was low.

[Example 1]
Instead of manganese sulfate n-hydrate, 1 mol of cobalt sulfate heptahydrate (industrial) was used, the firing temperature was 600 ° C., and heat treatment was not performed by mixing with sucrose. In the same manner as in Example 1, a positive electrode active material was obtained and evaluated.
The obtained precursor was identified as ammonium cobalt phosphate (NH ₄ CoPO ₄ ) by X-ray diffraction analysis. FIG. 1 shows an X-ray diffraction chart of the precursor (ammonium cobalt phosphate) obtained. The sodium content of the obtained precursor was not more than the lower limit of analysis (20 mass ppm).
Moreover, the obtained complex phosphate was identified as lithium cobalt complex phosphate (LiCoPO ₄ ) by X-ray diffraction analysis. FIG. 2 shows an X-ray diffraction chart of the obtained composite phosphate (lithium cobalt composite phosphate).
The composition of lithium: cobalt: phosphorus of this positive electrode active material was 0.97: 1.00: 1.00 in atomic ratio. When observed with a scanning electron microscope (SEM), the particle size range of the primary particles was 500 to 1000 nm, and the average particle size was 750 nm. The specific surface area was 7.18 m ² / g. When the battery was evaluated, the initial charge capacity was 160 mAh / g, the initial discharge capacity was 114 mAh / g, and the initial efficiency was 71%.

[Example 2]
Cobalt sulfate heptahydrate (industrial) 0.500 mol (140.6 g), manganese sulfate n-hydrate (Chuo Electric Works: 99.9% by mass) 0.500 mol (85.27 g)) and phosphoric acid 1 mol (115.3 g) (made by Wako Co., Ltd .: purity 85.0% by mass or more) was made up to 2 L with distilled water and stirred for 1 hour with a stirrer to obtain a raw material solution. Moreover, 25 mass% ammonia aqueous solution was used as pH adjustment solution.
1 L of pure water was put into a 5 L separable flask equipped with a stirrer, and stirred for 30 minutes while the inside was replaced with nitrogen. The raw material solution was added at a rate of 10 mL per minute while the pH adjustment solution was connected to a pH controller and the pH was controlled at 8.0 to 8.2. After completion of dropping, stirring was continued for 30 minutes while replacing the separable flask with nitrogen to complete the coprecipitation reaction. The slurry after the reaction was subjected to solid-liquid separation by suction filtration, and then washed with pure water twice with pure water.
After washing with water and drying under vacuum at 120 ° C. for 24 hours, ammonium manganese cobalt phosphate was obtained.
30 g of the above ammonium manganese cobalt phosphate, 5.94 g of lithium carbonate (Kanto Chemical Co., Ltd. deer special grade: 99.0% by mass) and 60 ml of ethanol are put into a pot made of zirconia having an internal volume of 500 ml containing φ1.0 mm zirconia balls, The mixture was pulverized while being mixed at 350 rpm for 10 minutes with a planetary ball mill (manufactured by Fritsch Japan). After the treatment, the slurry and zirconia balls were sieved and dried at room temperature under vacuum for 24 hours to remove ethanol.
The mixture obtained by using an electric furnace was heated at 10 ° C./min while purging a mixed gas of 98 vol% nitrogen and 2 vol% hydrogen into the furnace at a flow rate of 1 L / min, and then 350 ° C. for 5 hours. Baked.
When the fired product was analyzed by X-ray diffraction, it was identified as an olivine-type lithium manganese cobalt composite phosphate single phase, and it was confirmed that lithium manganese cobalt composite phosphate was obtained. The sodium content of the obtained precursor was not more than the lower limit of analysis (20 mass ppm).

30 g of the lithium manganese cobalt composite phosphate and 3.00 g of sucrose were placed in a 500 ml zirconia pot containing 350 g of φ5 mm zirconia balls and mixed for 10 minutes at 250 rpm with a planetary ball mill (manufactured by Fritsch Japan). After the treatment, the zirconia balls were sieved, and this mixture was heated at a rate of temperature increase of 10 ° C./min while purging the mixed gas of 98 volume% nitrogen + 2 volume% hydrogen into the furnace at a flow rate of 1 L / min using an electric furnace. The temperature was raised to 190 ° C in minutes, held for 2 hours, further heated, and baked at 650 ° C for 5 hours to obtain a positive electrode active material.
The composition of Li: Mn: Co: P of this positive electrode active material was 1.00: 0.50: 0.50: 1.00 in terms of molar ratio, and the carbon content was 2.2 mass%.
From X-ray diffraction analysis, it was confirmed to be an olivine type lithium manganese cobalt composite phosphate single phase. When observed with a scanning electron microscope (SEM), the particle size range of primary particles was 100 to 200 nm, and the average particle size was 150 nm. The specific surface area of the positive electrode active material determined by the BET method was 26.5 m ² / g.
When the battery evaluation of the positive electrode active material was performed, the initial charge capacity was 130 mAh / g, the initial discharge capacity was 90 mAh / g, and the initial efficiency was 69%.

[Example 3]
Cobalt sulfate heptahydrate (industrial) 0.700 mol (190.8 g), iron sulfate heptahydrate (industrial) 0.300 mol (83.4 g), and phosphoric acid (manufactured by Wako: purity 85. 0% by mass or more) 1 mol (115.3 g) was made up to 2 L with distilled water, stirred for 1 hour with a stirrer to obtain a raw material solution, and a positive electrode active material was obtained in the same manner as in Example 2. evaluated.
The composition of Li: Fe: Co: P of this positive electrode active material was 1.00: 0.30: 0.70: 1.00 in terms of molar ratio, and the carbon content was 2.3 mass%.
From the X-ray diffraction analysis, it was confirmed to be an olivine type lithium iron cobalt composite phosphate single phase. When observed with a scanning electron microscope (SEM), the particle size range of the primary particles was 150 to 300 nm, and the average particle size was 250 nm. Further, the specific surface area of the positive electrode active material determined by the BET method was 25.5 m ² / g.
When the battery evaluation of the positive electrode active material was performed, the initial charge capacity was 140 mAh / g, the initial discharge capacity was 97 mAh / g, and the initial efficiency was 69%.

[Comparative Example 2]
In the crystallization step, a precursor was obtained in the same manner as in Example 1 except that the pH was controlled in the range of 6.0 to 6.2 with aqueous ammonia.
Since the obtained precursor was a mixture of NH ₄ CoPO ₄ , CoO (OH) and Co ₃ O ₄ according to X-ray diffraction analysis, the subsequent experiment was stopped.

[Comparative Example 3]
In the crystallization step, a precursor was obtained in the same manner as in Example 1 except that the pH was controlled in the range of 9.5 to 9.7 with aqueous ammonia.
The liquid collected at the time of solid-liquid separation after crystallization exhibited a purple color. As a result of chemical analysis, the raw material yields were as low as 98% cobalt and 97% phosphorus. This is thought to be because cobalt was converted to an ammine complex. Since the recovery rate was low and there was a problem in practical use, the subsequent experiment was stopped.

  According to the method for producing a precursor for a positive electrode active material for a lithium secondary battery of the present invention, an ammonium phosphate M salt that is a suitable uniform fine precursor is obtained as a raw material for producing a positive electrode active material for a lithium secondary battery. In addition, the precursor of the positive electrode active material can be mixed with a lithium salt, and then calcined at 200 to 500 ° C. in an inert or reducing atmosphere to obtain lithium as a positive electrode active material for a lithium secondary battery. A transition metal composite phosphate can be obtained. Furthermore, when the positive electrode active material of the present invention is used, for example, as a positive electrode active material of a C2023 type coin battery, it exhibits good battery characteristics with an initial efficiency of 65% or more, which is the ratio between the initial charge capacity and discharge capacity. Yes, it is suitable for lithium secondary batteries and has high industrial applicability.

Claims (12)

Ammonium phosphate represented by the general formula: NH ₄ MPO ₄ .nH ₂ O (M is one or more containing at least Co selected from the group consisting of Fe, Mn, Ni and Co, 0 ≦ n ≦ 1) A method for producing a precursor of a positive electrode active material for a lithium secondary battery comprising a transition metal,
A mixed solution preparation step of preparing a mixed solution of divalent M ions and phosphate ions;
Ammonia is added to adjust the pH of the mixed solution to a range of 7 to 9, and co-precipitate to obtain an ammonium phosphate M salt (NH ₄ MPO ₄ .nH ₂ O),
A method for producing a precursor of a positive electrode active material for a lithium secondary battery.   2. The method for producing a precursor of a positive electrode active material for a lithium secondary battery according to claim 1, wherein the mixed solution is maintained at 25 to 60 ° C. in the crystallization step.   3. The mixed solution preparing step, wherein at least one water-soluble metal salt selected from the group consisting of sulfate and chloride salt is used as a feedstock for divalent M ions. The manufacturing method of the precursor of the positive electrode active material for lithium secondary batteries as described in any one of.   3. The mixed solution preparation step, wherein at least one water-soluble salt selected from the group consisting of phosphoric acid and ammonium dihydrogen phosphate is used as a feedstock for phosphor oxide ions. The manufacturing method of the precursor of the positive electrode active material for lithium secondary batteries as described in any one of.   The method for producing a precursor of a positive electrode active material for a lithium secondary battery according to any one of claims 1 to 4, wherein the crystallization step is performed in a non-oxidizing atmosphere. The lithium according to claim 1, further comprising a washing step of washing the ammonium phosphate M salt (NH ₄ MPO ₄ .nH ₂ O) obtained in the crystallization step. The manufacturing method of the precursor of the positive electrode active material for secondary batteries. A precursor of a positive electrode active material for a lithium secondary battery obtained by the production method according to claim 1 and comprising an ammonium phosphate transition metal,
Represented by the general formula: NH ₄ MPO ₄ .nH ₂ O (M is at least one selected from the group consisting of Fe, Mn, Ni, and Co, 0 ≦ n ≦ 1), sodium content Is a precursor of a positive electrode active material for a lithium secondary battery, characterized by being 0.01 mass% or less. After mixing the precursor of the positive electrode active material for lithium secondary battery according to claim 7 and a lithium salt, the mixture is calcined at 200 to 500 ° C. in an inert or reducing atmosphere, and the general formula: LiMPO ₄ (M is And a lithium transition metal composite phosphate represented by at least one selected from the group consisting of Fe, Mn, Ni, and Co). Production method.   The method for producing a positive electrode active material for a lithium secondary battery according to claim 8, further comprising calcining at 600 to 800 ° C. after mixing the carbon source when mixing the precursor and the lithium salt.   The mixture of a lithium transition metal composite phosphate obtained by firing at 200 to 500 ° C and a carbon source is heat-treated at 600 to 800 ° C in an inert or reducing atmosphere. A method for producing a positive electrode active material for a lithium secondary battery according to claim 8.   The method for producing a positive electrode active material for a lithium secondary battery according to claim 8 or 9, wherein the precursor is pulverized in advance before the firing.   The method for producing a positive electrode active material for a lithium secondary battery according to claim 10, wherein the lithium transition metal composite phosphate is pulverized in advance before the heat treatment.

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