JP2015176684A - Method for manufacturing olivine type silicate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an olivine type silicate compound, by which a positive electrode material exhibiting high battery physical properties even under rapid charge/discharge conditions can be obtained.SOLUTION: In a method for manufacturing an olivine type silicate compound, the following components (A), (B), (C) and (D) are mixed and then subjected to a hydrothermal reaction. (A) transition metal sulfate represented by MSO(where, M represents Fe, Ni, Co, Al, Zn, V, Zr or Mn) or an organic acid transition metal salt represented by (R)M (where, R represents an organic acid residue, and M represents Fe, Ni, Co, Al, Zn, V, Zr or Mn), (B) a lithium compound, (C) a silicic acid compound, and (D) spherical carbon particles obtained through a hydrothermal reaction.

Description

  The present invention relates to a method for producing an olivine silicate compound capable of obtaining a positive electrode material having a large charge / discharge capacity.

  Lithium ion batteries are a type of non-aqueous electrolyte battery and are used in a wide range of fields such as mobile phones, digital cameras, notebook PCs, hybrid cars, and electric cars. Lithium ion batteries mainly use lithium metal oxide as a positive electrode material and a carbon material such as graphite as a negative electrode material.

As this positive electrode material, lithium cobaltate (LiCoO ₂ ), lithium manganate (LiMnO ₂ ), lithium iron phosphate (LiFePO ₄ ), lithium iron silicate (Li ₂ FeSiO ₄ ) and the like are known. Among these, LiFePO ₄ and Li ₂ FeSiO ₄ have an olivine structure and are useful as positive electrode materials for high-capacity lithium ion batteries. In particular, so-called olivine-type silicate compounds such as Li ₂ FeSiO ₄ are excellent positive electrodes. It is attracting attention as a material.

  Such an olivine-type silicate compound is known to be obtained by subjecting a lithium source, a silicic acid source and a transition metal source to a hydrothermal reaction, and can be treated at a low temperature. Useful. Various researches have been conducted on production methods utilizing such hydrothermal synthesis in order to obtain a finer and higher purity olivine-type silicate compound. For example, Patent Document 1 discloses a method in which a lithium source, a silicic acid source and an antioxidant are used as a basic aqueous dispersion, a transition metal source is added thereto, and then subjected to a hydrothermal reaction. Yes. Patent Document 2 discloses a method in which a transition metal source, a lithium source, and a silicic acid source are placed as a basic aqueous dispersion and then subjected to a hydrothermal reaction.

JP 2012-193087 A JP 2012-193088 A

  However, the physical properties of the battery tend to decrease as the charge / discharge is accelerated, and even a positive electrode material using the olivine-type silicate compound obtained by the method described in the above patent document is sufficient for rapid charge / discharge. There is still room for improvement in order to develop high battery properties that can be handled.

  Therefore, the subject of this invention is providing the manufacturing method of the olivine type | mold silicate compound which can obtain the positive electrode material which expresses a high battery physical property also under rapid charging / discharging.

  Accordingly, the present inventors have found that, in producing an olivine-type silicate compound, a positive electrode material capable of sufficiently increasing charge / discharge capacity can be obtained by subjecting it to hydrothermal synthesis using a specific carbon material. The present invention has been completed.

That is, the present invention includes the following components (A), (B), (C) and (D):
(A) Transition metal sulfate represented by MSO ₄ (wherein M represents Fe, Ni, Co, Al, Zn, V, Zr or Mn) or (R) ₂ M (wherein R is An organic acid residue, wherein M represents Fe, Ni, Co, Al, Zn, V, Zr or Mn), (B) a lithium compound,
(C) A silicic acid compound and (D) spherical carbon particles obtained by hydrothermal reaction are mixed and then hydrothermally reacted, and a method for producing an olivine-type silicate compound is provided.
Moreover, this invention provides the manufacturing method of the positive electrode active material for lithium ion batteries characterized by carrying | supporting carbon on the olivine type silicate compound obtained by the said manufacturing method, and baking it.
Furthermore, this invention provides the lithium ion battery which has a positive electrode containing the positive electrode active material for lithium ion batteries obtained by the said manufacturing method.

  If it is the olivine type | mold silicate compound obtained by the manufacturing method of this invention, the lithium ion battery which has a high charging / discharging capacity | capacitance which can fully respond even under rapid charging / discharging is realizable.

The TEM image of the olivine type | mold silicate compound obtained in Example 1 is shown.

Hereinafter, the present invention will be described in detail.
In the production method of the present invention, first, the following components (A), (B), (C) and (D):
(A) Transition metal sulfate represented by MSO ₄ (wherein M represents Fe, Ni, Co, Al, Zn, V, Zr or Mn) or (R) ₂ M (wherein R is An organic acid residue, wherein M represents Fe, Ni, Co, Al, Zn, V, Zr or Mn), (B) a lithium compound,
(C) Silicic acid compound and (D) Spherical carbon particles obtained by hydrothermal reaction are mixed.

As the transition metal sulfate MSO ₄ of the component (A), FeSO ₄ , NiSO ₄ , CoSO ₄ , Al ₂ (SO ₄ ) ₃ , ZnSO ₄ , V ₂ (SO ₄ ) ₃ , Zr (SO ₄ ) ₂ or MnSO ₄ , and these may be used alone or in combination of two or more. Of these, FeSO ₄ and MnSO ₄ are more preferable, and FeSO ₄ is more preferable. The amount of transition metal sulfate (MSO ₄ ) added is a reaction mixture containing components (A) to (D) from the viewpoint of increasing the synthesis yield of the olivine-type silicate compound and the physical properties of the resulting battery. The total amount is preferably 0.15 to 1.50 mol / l, more preferably 0.50 to 1.40 mol / l, and even more preferably 0.80 to 1.40 mol / l. .
In this case, the Li content in the reaction mixture is preferably 2 mol or more with respect to M.

The organic acid represented by R of the organic acid transition metal salt (R) ₂ M of the component (A) is preferably an organic acid having 1 to 20 carbon atoms, and more preferably an organic acid having 2 to 12 carbon atoms. More specific organic acids include dicarboxylic acids such as oxalic acid and fumaric acid, hydroxycarboxylic acids such as lactic acid, and fatty acids such as acetic acid. The concentration of the organic acid transition metal salt (R) ₂ M in the total amount of the reaction mixture containing component (A) to component (D) is based on the viewpoint of increasing the synthesis yield of the olivine-type silicate compound and the physical properties of the resulting battery. From the viewpoint of increasing, 0.15 to 1.50 mol / l is preferable, 0.5 to 1.40 mol / l is more preferable, and 0.80 to 1.40 mol / l is more preferable.
In this case, Li in the reaction mixture is preferably used in a molar ratio of 2 times or more with respect to the transition metal, and Li: M is more preferably about 2.5: 1 to 3: 1.

Examples of the lithium compound of component (B) include lithium hydroxide (eg, LiOH.H ₂ O), lithium carbonate (Li ₂ CO ₃ ), lithium sulfate, and lithium acetate, with lithium hydroxide and lithium carbonate being particularly preferred. . The concentration of the lithium compound in the total amount of the reaction mixture containing the component (A) to the component (D) is 0.30 from the viewpoint of increasing the synthesis yield of the olivine-type silicate compound and the physical properties of the resulting battery. 3.00 mol / l is preferable, 1.00-2.80 mol / l is more preferable, and 1.50-2.80 mol / l is more preferable.

The silicic acid compound of component (C) is not particularly limited as long as it is a reactive silica compound, and amorphous silica and Na ₄ SiO ₄ (for example, Na ₄ SiO ₄ .H ₂ O) are preferable. Among these, from the viewpoint of suppressing side reactions, it is preferable to use Na ₄ SiO ₄ and to make the reaction mixture containing components (A) to (D) basic. The concentration of the silicic acid compound in the total amount of the reaction mixture containing the components (A) to (D) is 0.15 from the viewpoint of increasing the synthesis yield of the olivine-type silicate compound and the physical properties of the resulting battery. ˜1.50 mol / l is preferable, 0.50 to 1.40 mol / l is more preferable, and 0.80 to 1.40 mol / l is more preferable.

  The component (D) is a spherical carbon particle obtained by a hydrothermal reaction, and is an extremely fine spherical particle that exhibits high conductivity when carbonized by a heat treatment such as firing. Since this component (D) is mixed together with the components (A) to (C), it adheres to or penetrates into the surfaces of the primary particles or secondary particles of the olivine type silicate compound or between the particles. By doing so, the electron conduction area (electron conduction path) of the olivine-type silicate compound can be effectively increased. Therefore, sufficient electronic conductivity can be ensured, and in a lithium ion battery using such an olivine type silicate compound, a high charge / discharge capacity that can cope with rapid charge / discharge can be realized.

Component (D) can be obtained by adding a solvent to the carbon material for spherical carbon particles and subjecting it to a hydrothermal reaction, and is also referred to as a carbon sphere. Such a component (D) can be obtained, for example, by using the production method described in Procedia Environmental Sciences, 11 (2011, p1322-1327).
Specifically, for example, usable carbon materials for spherical carbon particles include glucose, starch, xylose, sucrose, cellulose, dextrin, fructose, N-acetylglucosamine, lactose, rhamnose, and phloroglucinol. These may be used alone or in combination of two or more. Among these, glucose is preferable from the viewpoint of further improving battery physical properties and improving efficiency in production.

As the solvent, not only water but also water and polyol can be used as the solvent. When a polyol is used together with water, the polyol acts as a chelating agent or a surfactant, effectively increasing the synthesis yield of the olivine-type silicate compound obtained through a hydrothermal reaction while enhancing the dispersibility of each component. It is estimated that
Examples of water include distilled water and ion exchange water.
From the viewpoint of effectively suppressing the generation of impurities and increasing the synthesis yield of the olivine-type silicate compound, the polyol is preferably a divalent or trivalent alcohol. When using water and a polyol as a solvent, content of the polyol in a solvent becomes like this. Preferably it is 20-80 mass%, More preferably, it is 20-70 mass%, More preferably, it is 22-60 mass%, More preferably, it is 25-55 mass%.

  Specific examples of the divalent alcohol include ethylene glycol, propylene glycol, diethylene glycol, tetraethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl -1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl , 3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol. It is done. These may be used alone or in combination of two or more.

  Among these dihydric alcohols, ethylene glycol, propylene glycol, diethylene glycol, tetraethylene glycol, and 1,4-butane are used from the viewpoint of increasing the synthesis yield of the olivine-type silicate compound and the physical properties of the obtained battery. At least one selected from the group consisting of diols is preferred, ethylene glycol and polyethylene glycol are more preferred, and ethylene glycol is even more preferred. The average added mole number of ethyleneoxy groups in polyethylene glycol is preferably 10 to 600, more preferably 50 to 500, and still more preferably 100 to 400.

  Specific examples of the trivalent alcohol include glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methylpropanetriol, 2-methyl-1,2,4- Examples include butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-adamantanetriol, 1,3,5-cyclohexanetriol, and 1,2,3-cyclohexanetriol. These may be used alone or in combination of two or more.

Among these trivalent alcohols, at least one selected from the group consisting of glycerin, trimethylolethane, trimethylolpropane, and 2-methylpropanetriol is preferable, and glycerin is more preferable.
Among the above-mentioned divalent and trivalent alcohols, at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, tetraethylene glycol, 1,4-butanediol, and glycerin is preferable, and ethylene glycol and glycerin are preferable. Is more preferable.

  After adding the solvent, the content of the carbon material for spherical carbon particles in the obtained solution is preferably 1 to 70% by mass from the viewpoint of further improving the battery physical properties and the efficiency in production. More preferably, it is 5-50 mass%.

  A solution obtained by adding a solvent to the carbon material for spherical carbon particles is subjected to a hydrothermal reaction. The temperature of the hydrothermal reaction is preferably 130 to 200 ° C, more preferably 140 to 170 ° C, from the viewpoint of increasing the synthesis yield of the spherical carbon particles. Moreover, hydrothermal reaction time becomes like this. Preferably it is 1 to 12 hours, More preferably, it is 3 to 9 hours. The pressure during the reaction is preferably 0.2 to 1.5 MPa, more preferably 0.3 to 0.7 MPa.

  Next, the obtained reaction product is washed with water, ethanol, or the like and then dried, whereby spherical carbon particles of the component (D) can be obtained. At this time, the solution obtained by washing the reaction product after the hydrothermal reaction with water is used as it is as a solution containing the component (D), that is, a component (D) ′ described later, without drying. Also good.

The component (D) thus obtained is a fine particle having a spherical shape that exhibits high conductivity by being carbonized by heat treatment, and is a very useful component for enhancing battery physical properties. The carbonization degree of a component (D) becomes like this. Preferably it is 1-100, More preferably, it is 1.1-100, More preferably, it is 1.2-100. The peak intensity of the component and the carbide of the (D), the peak intensity of D-band attributed to the carbon measured by Raman spectroscopy (1350cm ^-1) (I _D) and G band (1600 cm ^-1) ( I _G ) means the value calculated by the ratio I _G / I _D.

  The average particle diameter of the component (D) is preferably 1 to 1000 nm, more preferably 1 to 500 nm, and still more preferably 1 to 100 nm. In addition, the average particle diameter of a component (D) can be measured by observation in a scanning electron microscope or a transmission electron microscope.

  The mixing order of component (A) to component (D) is not particularly limited, and they may all be mixed at the same time. After preparing component (D) in advance, this is mixed with components (A) to (C). May be. In preparing component (D) in advance, from the viewpoint of improving the synthesis yield of the olivine-type silicate compound, component (D) is dispersed in water, and solution (D) ′ containing component (D) is prepared. After being obtained, it is preferable to mix such component (D) ′ with components (A), (B) and (C). By using component (D) ′, when these mixtures are later subjected to a hydrothermal reaction to obtain an olivine-type silicate compound, these components are mixed and then directly subjected to a hydrothermal reaction without adding a solvent. Can be migrated.

  Furthermore, when mixing these components, you may mix a polyol. Thereby, it can be expected that the polyol acts as a chelating agent or a surfactant and effectively increases the synthesis yield of the olivine-type silicate compound obtained through the hydrothermal reaction while enhancing the dispersibility of each component. As a polyol, the thing similar to the polyol used when obtaining a component (D) can be used. In addition, when using a polyol when obtaining a component (D), it is not necessary to mix a polyol here. The mass ratio ({(A) + (B) + (C)} / polyol) of the total amount of the component (A), the component (B) and the component (C) and the amount of polyol effectively improves the battery physical properties. From the viewpoint of increasing the thickness, it is preferably 1 to 10, more preferably 1.5 to 8, and further preferably 2 to 6.

  When using the component (D) ′, which is a solution containing the component (D), as described above, when the component (D) is produced, the solution obtained after washing with water may be used as it is without drying. Alternatively, component (D) ′ may be prepared by dispersing component (D) obtained after washing and drying in water. At this time, the content of the component (D) in the component (D) ′ is preferably 1 to 70% by mass, more preferably 3 to 60% by mass, from the viewpoint of effectively improving battery physical properties. More preferably, it is 5-50 mass%.

  Further, the mass ratio of the total amount of component (A), component (B) and component (C) to the amount of component (D) ′ ({(A) + (B) + (C)} / (D) ') Is preferably from 0.2 to 3, more preferably from 0.4 to 2, and even more preferably from 0.5 to 1.5 from the viewpoint of effectively enhancing battery physical properties.

In addition to the components (A) to (D), an antioxidant may be further added before hydrothermal synthesis. As the antioxidant, hydrosulfite sodium (Na ₂ S ₂ O ₄ ), aqueous ammonia, sodium sulfite and the like can be used. Since the content of the antioxidant in the total amount of the liquid mixture containing the reaction mixture of the components (A) to (D) and the antioxidant, when added in a large amount, the formation of the olivine-type silicate compound is suppressed. An equimolar amount or less is preferable with respect to the transition metal (M), and a molar ratio with respect to the transition metal (M) is more preferably 0.5 or less.

The obtained reaction mixture is preferably basic from the viewpoint of preventing side reactions and dissolving the silicate compound. Specifically, the pH of the reaction mixture is 12.0 to 13.5. Is preferred. The pH of the reaction mixture may be adjusted by adding a base such as sodium hydroxide, but it is more preferable to use Na ₄ SiO ₄ as the silicate compound.

  In the production method of the present invention, the components (A) to (D) are mixed and then hydrothermally reacted. The temperature of the hydrothermal reaction should just be 100 degreeC or more, and 130-200 degreeC is preferable from a viewpoint which raises the synthetic | combination yield of an olivine type silicate compound, and also 140-180 degreeC is preferable. The hydrothermal reaction is preferably performed in a pressure vessel, and the pressure when the reaction is performed at 130 to 200 ° C is preferably 0.3 to 1.5 MPa, and the pressure when the reaction is performed at 140 to 180 ° C is It is preferably 0.4 to 1.0 MPa. The hydrothermal reaction time is preferably 1 to 24 hours, more preferably 3 to 12 hours.

By the hydrothermal reaction, primary particles of the olivine-type silicate compound containing the transition metal M in which the spherical carbon particles of the component (D) are scattered everywhere are obtained in high yield. Such an olivine type silicate compound is specifically represented by any of the following formulas (1) to (5).
Li ₂ M'SiO ₄ (1)
(In the formula, M ′ represents one or more selected from Fe, Ni, Co and Mn.)
_{Li a 'Fe x Mn y Al} z SiO 4 ··· (2)
(Where, a ′, x, y and z are 1 <a ′ ≦ 2, 0 ≦ x <1, 0 ≦ y <1, 0 <z <2/3, a ′ + 2x + 2y + 3z = 4, and x + y ≠ Indicates a number satisfying 0.)
_{Li a "Fe x Mn y V} z 'SiO 4 ··· (3)
(Where a ^" , x, y and z 'are 1 <a ^" ≤2, 0≤x <1, 0≤y <1, 0 <z'<1, a ^" + 2x + 2y + (2-5) z '= 4 and a number satisfying x + y ≠ 0.)
_{Li a "Fe x Mn y Zr} z" SiO 4 ··· (4)
(Where a ^" , x, y and z ^" are 1 <a ^" ≤2, 0≤x <1, 0≤y <1, 0 <z ^" <0.5, a ^" + 2x + 2y + 4z ^" = 4, And a number satisfying x + y ≠ 0.)
_{Li 2 Fe x Mn y Zn q} SiO 4 ··· (5)
(In the formula, x, y, and q represent numbers satisfying 0 ≦ x <1, 0 ≦ y <1, 0 <q <1, x + y + q = 1, and x + y ≠ 0.)

  The primary particles of the obtained olivine type silicate compound can be isolated as secondary particles by filtering after washing and then drying. Examples of the drying means include spray drying, box drying, fluidized bed drying, external heat drying, freeze drying, and vacuum drying. Of these, spray drying using a spray dryer is preferred. Moreover, when drying, it is good to use the slurry previously prepared using the primary particle of the olivine type silicate compound. By dispersing the spherical carbon particles of the component (D) together with the primary particles in the slurry, the spherical carbon particles can be efficiently arranged on the surface of the obtained secondary particles and the gaps between the particles. The content (solid content concentration) of primary particles of the olivine-type silicate compound in such a slurry is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, from the viewpoint of enhancing the physical properties of the obtained battery. More preferably, it is 35-45 mass%.

At this time, a small amount of a dispersant or a thickener may be added to the slurry. As the dispersant, for example, polycarboxylic acid-based, polyether-based, polyacrylic acid-based, and the like can be used.
As the thickener, for example, a base such as sodium hydroxide, lithium hydroxide or ammonia, or an organic acid such as acetic acid or citric acid can be used.

  The dried product thus obtained may be classified with a separator, cyclone, sieve or the like during or after drying, or may be pulverized with a mortar pin mill, roll mill, crusher or the like.

  Further, a conductive carbon material other than the component (D) and the component (D) ′ may be used, and the primary particles or secondary particles of the olivine silicate compound obtained in advance may be subjected to a carbon support treatment. By doing so, a carbon thin film can be further formed on the particle surface to which the spherical carbon particles of component (D) adhere, and the electron conduction area of the olivine-type silicate compound is further increased, thereby providing more sufficient electron conduction. It becomes possible to ensure the sex.

  Examples of the conductive carbon material used for the carbon-supporting treatment include carbon such as cellulose, lignin, chitosan, chitin, carbon nanotube, graphene, graphene oxide, carbon black, acetylene black, ketjen black, graphite, graphite, and synthetic fiber. Containing compounds. The amount of the conductive carbon material added in this case is 0.5 to 20% by mass in terms of carbon atoms contained in the conductive carbon material in the primary particle theoretical generation amount of the olivine-type silicate compound obtained after the hydrothermal reaction. Is preferably added in an amount of 2.5 to 17.5% by mass. In adding the conductive carbon material, it is preferable to use a solvent to form a solution from the viewpoint of improving dispersibility. The content of the conductive carbon material in the solution is preferably 40% by mass or less, and more preferably 20% by mass or less. Examples of the solvent include distilled water and ion exchange water.

  The amount of the conductive carbon material added is from 0.5 to 20 parts by mass in terms of carbon atoms with respect to 100 parts by mass of the primary particles of the olivine silicate compound in the slurry, from the viewpoint of good charge / discharge capacity and economy. Is preferable, and an amount of 2.5 to 17.5 parts by mass is more preferable.

  Thus, after adding a conductive carbon material using a solvent as needed, it can be set as the positive electrode active material for lithium ion batteries by baking. Firing conditions in the carbon-supporting treatment are 400 ° C. or higher, preferably 400 to 800 ° C. for 10 minutes to 3 hours, preferably 0.5 to 1.5 hours under an inert gas atmosphere or reducing conditions. .

  The method for producing a lithium ion battery using the positive electrode active material for a lithium ion battery of the present invention thus obtained is not particularly limited, and any known method can be used. For example, such a positive electrode active material is mixed with additives such as a binder and a solvent to obtain a coating liquid. At this time, if necessary, a conductive additive may be further added and mixed. The binder is not particularly limited, and any known agent can be used. Specific examples include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, and ethylene propylene diene polymer. Moreover, it does not specifically limit as this conductive support agent, Any well-known agent can be used. Specific examples include acetylene black, ketjen black, natural graphite, artificial graphite, and fibrous carbon. Next, such a coating solution is applied onto a positive electrode current collector such as an aluminum foil and dried to obtain a positive electrode.

  The positive electrode active material for a lithium ion battery of the present invention is useful in that it exhibits a very excellent discharge capacity as a positive electrode of a lithium ion battery. A lithium ion battery to which such a positive electrode can be applied is not particularly limited as long as it has a positive electrode, a negative electrode, an electrolytic solution, and a separator as essential components.

  Here, as long as lithium ions can be occluded at the time of charging and released at the time of discharging, the material structure is not particularly limited, and a known material structure can be used. For example, a carbon material such as lithium metal, graphite, or amorphous carbon. It is preferable to use an electrode formed of an intercalating material capable of electrochemically inserting and extracting lithium, particularly a carbon material.

  The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that is usually used for an electrolyte solution of a lithium ion battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones, nitriles, lactones, oxolanes, and the like. A compound or the like can be used.

The type of the supporting salt is not particularly limited, but an inorganic salt selected from LiPF ₆ , LiBF ₄ , LiClO ₄ and LiAsF ₆ , a derivative of the inorganic salt, LiSO ₃ CF ₃ , LiC (SO ₃ CF ₃ ) ₂ and LiN (SO ₃ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ and LiN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), and organic salt derivatives It is preferable that it is at least 1 sort of.

  The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

[Production Example 1: Production of spherical carbon particles]
27.5 cm ³ of ultrapure water was added to 2.82 g of glucose and mixed. The obtained mixed solution was put into an autoclave and subjected to a hydrothermal reaction at 150 ° C. for 6 hours. As a reaction solution, a solution (D) ′ containing spherical carbon particles (containing 9% by mass of spherical carbon particles) was obtained.

[Example 1]
_{LiOH · H 2 O 4.20g (100mol} ), the _{Na 4 SiO 4 · nH 2 O} 13.98 (50mmol), were added and mixed glycerol 10.0 cm ³ (pH at this time was about 13). FeSO ₄ .7H ₂ O 3.92 g (14.1 mmol), MnSO ₄ .5H ₂ O 7.93 g (32.9 mmol), ZrSO ₄ .4H ₂ O 0.53 g (1.5 mmol) and Production Example The solution (D) ′ containing spherical carbon particles obtained in 1 was added and mixed ((A) + (B) + (C)) / (D) ′ = 1). The obtained mixed solution was put into an autoclave and subjected to a hydrothermal reaction at 150 ° C. for 12 hours. The reaction solution was filtered and then lyophilized. Glucose (carbon concentration: 10%) and ultrapure water (10 cm ³⁾ were added to 8.4 g of the powder obtained by freeze-drying (about 12 hours), and calcined at 650 ° C. for 1 hr in a reducing atmosphere to obtain an olivine-type silicate compound. Obtained.
A TEM image of the obtained olivine-type silicate compound is shown in FIG. 1 that the olivine-type silicate compound obtained in Example 1 has spherical carbon particles efficiently attached or invaded into the surface of the secondary particles and the gaps between the particles.

  Subsequently, the positive electrode of the lithium ion battery was produced using the obtained olivine type silicate compound. The obtained compound, ketjen black (conductive agent), polyvinylidene fluoride (binding agent) are mixed at a mass ratio of 75: 20: 5, and N-methyl-2-pyrrolidone is added thereto and kneaded sufficiently. Thus, a positive electrode slurry was prepared. The positive electrode slurry was applied to a current collector made of an aluminum foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press to obtain a positive electrode.

Next, a coin-type lithium ion battery was constructed using the positive electrode. A lithium foil punched to φ15 mm was used for the negative electrode. As the electrolytic solution, a solution obtained by dissolving LIPF ₆ at a concentration of 1 mol / l in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 1: 1 was used. As the separator, a known one such as a polymer porous film such as polypropylene was used. These battery components were assembled and housed in a conventional manner in an atmosphere having a dew point of −50 ° C. or lower to produce a coin type lithium ion battery (CR-2032).

  One cycle of charge and discharge at a constant current density was performed using the manufactured lithium ion battery. The charging conditions at this time were constant current and constant voltage charging with a current of 0.1 CA (33.3 mA / g) and a voltage of 4.5 V, and the discharging conditions were constant current discharging with a current of 0.6 CA and a final voltage of 1.5 V. All temperatures were 30 ° C. Table 1 shows the charge / discharge capacity of the battery constructed with the positive electrode material obtained in Example 1.

[Comparative Example 1]
An olivine silicate compound was obtained in the same manner as in Example 1 except that 27.5 cm ³ of ultrapure water was used instead of the solution (D) ′ containing the spherical carbon particles obtained in Production Example 1. Next, a lithium ion battery was produced in the same manner as in Example 1, and charging and discharging were performed for one cycle. Table 1 shows the charge / discharge capacity of the battery constructed from the positive electrode material obtained in Comparative Example 1.

  From the results in Table 1, it can be seen that the battery obtained in Example 1 has excellent battery physical properties even under rapid charging and discharging, as compared with Comparative Example 1.

Claims (7)

The following components (A), (B), (C) and (D):
(A) Transition metal sulfate represented by MSO ₄ (wherein M represents Fe, Ni, Co, Al, Zn, V, Zr or Mn) or (R) ₂ M (wherein R is An organic acid residue, wherein M represents Fe, Ni, Co, Al, Zn, V, Zr or Mn), (B) a lithium compound,
(C) A silicic acid compound, and (D) a spherical carbon particle obtained by a hydrothermal reaction, and then a hydrothermal reaction, followed by a method for producing an olivine-type silicate compound.   After component (D) is dispersed in advance to obtain a solution (D) ′ containing component (D), component (D) ′ is mixed with components (A), (B) and (C). The manufacturing method of the olivine type | mold silicate compound of Claim 1 to do.   Content of component (D) in component (D) 'is 1-70 mass%, The manufacturing method of the olivine type silicate compound of Claim 2.   The carbonization degree of a component (D) is 1-100, The manufacturing method of the olivine type | mold silicate compound of any one of Claims 1-3.   Mass ratio of the total amount of component (A), component (B) and component (C) to the amount of component (D) ′ ({(A) + (B) + (C)} / (D) ′) Is 0.2-3, The manufacturing method of the olivine type | mold silicate compound of any one of Claims 2-4.   A method for producing a positive electrode active material for a lithium ion battery, wherein carbon is supported on the olivine-type silicate compound according to any one of claims 1 to 5, and then fired.   The lithium ion battery which has a positive electrode containing the positive electrode active material for lithium ion batteries obtained by the manufacturing method of Claim 6.