JP2012212635A - Active material, electrode containing the same, lithium secondary battery comprising the electrode, and method for manufacturing active material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active material excellent in cycle characteristics, an electrode containing the same, a lithium secondary battery comprising the electrode, and a method for manufacturing the active material.SOLUTION: The active material contains a LiVOPOparticle and a polymer compound film, and the polymer compound film covers the surface of the LiVOPOparticle and exhibits a tensile modulus of elasticity of 0.5 GPa or greater at 25°C.

Description

  The present invention relates to an active material, an electrode including the active material, a lithium secondary battery including the electrode, and an active material manufacturing method.

In the crystal represented by the structural formula LiVOPO ₄ , it is known that lithium ions are reversibly inserted and desorbed. The crystal represented by the structural formula LiVOPO ₄ has different crystal structures such as α-type and β-type, and the α-type is said to be a thermodynamically stable structure compared to the β-type. Patent Document 1 reports that LiVOPO ₄ having an α-type crystal structure (triclinic crystal) has a smaller discharge capacity than LiVOPO ₄ having a β-type crystal structure (orthorhombic crystal).

Non-Patent Document 1 discloses a method for producing LiVOPO ₄ having a β-type crystal structure by heating VOPO ₄ and Li ₂ CO ₃ in the presence of carbon and reducing VOPO ₄ with carbon (a carbothermal reduction method). CTR method)) is disclosed. Non-Patent Document 2 discloses a method for producing LiVOPO ₄ having a β-type crystal structure by using tetravalent vanadium.

JP 2004-303527 A

J. et al. Baker et al. , J .; Electrochem. Soc. 151, A796 (2004) J. et al. Solid State Chem. , 95, 352 (1991)

However, the active material containing LiVOPO ₄ obtained by the methods described in Patent Document 1 and Non-Patent Documents 1 and 2 cannot obtain sufficient cycle characteristics.

  Then, an object of this invention is to provide the active material excellent in cycling characteristics, the electrode containing this, a lithium secondary battery provided with the said electrode, and the manufacturing method of an active material.

That is, the present invention includes LiVOPO ₄ particles and a polymer compound film, the polymer compound film covers the surface of the LiVOPO ₄ particles, and has a tensile elastic modulus at 25 ° C. of 0.5 GPa or more. Provide active material.

Since the surface of the LiVOPO ₄ particles is covered with a polymer compound film having a tensile elastic modulus at 25 ° C. of 0.5 GPa or more, the active material according to the present invention has improved mechanical strength and cycle characteristics. Is thought to improve.

Here, the LiVOPO ₄ particles may have a particle diameter of 0.2 to 2.0 μm.

  The polymer compound film may have a thickness of 0.005 to 0.03 μm. When the film thickness of the polymer compound film is within the above range, it is possible to impart high electronic conductivity to the active material while maintaining the lithium ion diffusing ability at a high level. Can be improved.

  The present invention also provides an electrode comprising a current collector and an active material layer including the active material and provided on the current collector. Thereby, the electrode excellent in cycling characteristics is obtained.

  Moreover, this invention provides a lithium secondary battery provided with the said electrode. Thereby, a lithium secondary battery excellent in cycle characteristics can be obtained.

Furthermore, the present invention includes LiVOPO ₄ and a polymer compound by heating a mixture containing a lithium source, a pentavalent vanadium source, a phosphate source, water, and a polymer compound to 200 ° C. or higher under pressure. A hydrothermal synthesis step for obtaining a product is provided, the polymer compound is insoluble in water, becomes a molten state under pressure and heating, and has a tensile elastic modulus at 25 ° C. of 0.5 GPa An active material manufacturing method as described above is provided.

Although not necessarily clear, the present inventors infer the reason why an active material having excellent cycle characteristics can be produced as follows. That is, in the hydrothermal synthesis step, in a mixture containing a lithium source, a pentavalent vanadium source, a phosphoric acid source, water, and a polymer compound, the polymer compound is insoluble in water and added. Since it will be in a molten state when heated to 200 ° C. or higher under pressure, the aqueous phase and the polymer compound phase are mixed. The aqueous phase contains a large amount of a lithium source, a pentavalent vanadium source, and a phosphoric acid source, and LiVOPO ₄ crystal nuclei are precipitated from these compounds, resulting in crystal growth and a precursor of LiVOPO ₄ particles. Will be formed. On the other hand, the polymer compound phase surrounds the precursor of LiVOPO ₄ particles grown during or after cooling at high temperature and high pressure, and the surface of LiVOPO ₄ particles has a tensile elastic modulus at 25 ° C. of 0.5 GPa or more. It is considered that the active material is formed by being covered with the polymer compound film.

  ADVANTAGE OF THE INVENTION According to this invention, the active material excellent in cycling characteristics, the electrode containing this, a lithium secondary battery provided with the said electrode, and the manufacturing method of an active material can be provided.

It is a schematic cross section which shows an example of the active material which concerns on this embodiment. It is an electron micrograph of the active material which concerns on this embodiment. It is a schematic cross section of the lithium ion secondary battery according to the present embodiment.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. However, the active material of the present invention is not limited to the following embodiments. In addition, the dimensional ratio of drawing is not restricted to the ratio of illustration.

<Active material>
First, the active material according to the present embodiment will be described. FIG. 1 is a schematic cross-sectional view showing an example of an active material according to the present embodiment. An active material 3 according to the present embodiment includes LiVOPO ₄ particles 1 and a polymer compound film 2. The polymer compound film 2 covers the surface of the LiVOPO ₄ particles 1 and has a tensile elastic modulus at 25 ° C. of 0.5 GPa or more. FIG. 2 is a high-resolution scanning electron micrograph of the active material according to the present embodiment. The active material 3 in which the surface of the LiVOPO ₄ particles 1 is covered with the polymer compound film 2 may form an aggregated structure as shown in the electron micrograph.

The LiVOPO ₄ particles 1 contain 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more of LiVOPO _{4 based} on the total amount of particles. Here, LiVOPO ₄ includes different crystal structures ₄ such as LiVOPO of LiVOPO ₄ and β-type crystal structure of the α-type crystal structure. These crystal structures can usually be identified by an X-ray diffraction method. Usually, LiVOPO ₄ of β-type crystal structure peaks appear in 2 [Theta] = 27.0 degrees, LiVOPO ₄ of α-type crystal structure peaks appear in 2 [Theta] = 27.2 degrees. The LiVOPO ₄ particles 1 may contain either an α-type crystal structure LiVOPO _{4 or a} β-type crystal structure LiVOPO ₄ as a main component, but from the viewpoint of discharge capacity, the β-type crystal structure has an α-type crystal structure. It may be contained more than the crystal structure. The LiVOPO ₄ particles 1 may contain a small amount of unreacted raw material components in addition to LiVOPO ₄ having a β-type crystal structure and LiVOPO _{4 having an} α-type crystal structure.

The particle diameter of the LiVOPO ₄ particles 1 is measured as follows. Based on the image observed with the high-resolution scanning electron microscope, the projected area circle equivalent diameter is measured from the projected area of the LiVOPO ₄ particles 1. The projected area equivalent circle diameter is assumed to be a sphere having the same projected area as the projected area of LiVOPO ₄ particles 1, and the diameter (equivalent circle diameter) of the sphere is expressed as a particle diameter (particle diameter of LiVOPO ₄ particles 1). Is. The projected area equivalent circle diameter is measured for each of the 20 LiVOPO ₄ particles 1, and the average value is taken as the particle size of the LiVOPO ₄ particles 1.

The particle diameter of the LiVOPO ₄ particles 1 is preferably 0.2 to 2.0 μm, and more preferably 0.3 to 1.0 μm.

The surface of the LiVOPO ₄ particles 1 is covered with a polymer compound film 2. The film thickness of the polymer compound film 2 is the length from the surface of the LiVOPO ₄ particle 1 to the surface of the polymer compound film 2. The film thickness may be 0.005 to 0.03 μm, preferably 0.007 to 0.02 μm, and more preferably 0.09 to 0.015 μm. When the film thickness of the polymer compound film 2 is within the above range, it is possible to impart high electronic conductivity to the active material 3 while maintaining a high lithium ion diffusivity, and it is possible to provide discharge capacity and cycle. The characteristics are further improved. The film thickness of the polymer compound film 2 is measured by observing a cross section of the active material 3 using a transmission electron microscope (TEM).

The polymer compound film 2 preferably covers the entire LiVOPO ₄ particle 1, but if the coverage is 5% or more, preferably 10% or more, more preferably 20% or more, the effect of the present invention is exhibited. be able to.

  From the viewpoint of improving cycle characteristics, the polymer compound film 2 has a tensile elastic modulus at 25 ° C. of 0.5 GPa or more, preferably 0.6 GPa or more, more preferably 0.7 GPa or more, preferably Is 5 GPa or less, more preferably 3.5 GPa or less.

The polymer compound film 2 may contain LiVOPO ₄ particles having a particle diameter smaller than that of the LiVOPO ₄ particles 1. Also, particulate LiVOPO ₄ particle diameter is smaller than the particulate LiVOPO ₄ 1 may be a plurality of forming aggregates, agglomerates have a diameter smaller than the particle size of the first particulate LiVOPO ₄ 1 It is preferable. Thereby, the diffusibility of lithium ions is improved, and higher rate characteristics can be obtained.

<Method for producing active material>
A method for producing an active material according to this embodiment will be described. The manufacturing method of the active material which concerns on this embodiment is equipped with the following raw material adjustment process, a hydrothermal synthesis process, and a drying process.
[Raw material adjustment process]
A raw material adjustment process is a process of adjusting the mixture containing a lithium source, a pentavalent vanadium source, a phosphoric acid source, water, and a high molecular compound.

(blend)
Examples of the lithium source include lithium compounds such as LiNO ₃ , Li ₂ CO ₃ , LiOH, LiCl, Li ₂ SO _4, and CH ₃ COOLi. Among these, LiOH, LiNO ₃ and Li ₂ CO ₃ are preferable.
Examples of the pentavalent vanadium source include vanadium compounds such as V ₂ O ₅ and NH ₄ VO ₃ .
Examples of the phosphoric acid source include PO ₄ -containing compounds such as H ₃ PO ₄ , NH ₄ H ₂ PO ₄ , (NH ₄ ) ₂ HPO _4, and Li ₃ PO ₄ . Among these, H ₃ PO ₄ and (NH ₄ ) ₂ HPO ₄ are preferable.

  The lithium source is preferably blended so that the ratio of the number of moles of lithium atoms to the number of moles of pentavalent vanadium atoms is 0.95 to 1.2. Moreover, it is preferable to mix | blend a phosphoric acid source so that the ratio of the number of moles of a phosphorus atom with respect to the number of moles of a pentavalent vanadium atom may be 0.95-1.2. If the blending ratio of at least one of lithium atoms and phosphorus atoms is less than 0.95, the discharge capacity of the resulting active material tends to decrease, and the cycle characteristics tend to decrease. When the blending ratio of at least one of lithium atoms and phosphorus atoms is more than 1.2, the discharge capacity of the obtained active material tends to decrease.

  The polymer compound is insoluble in water, is in a molten state under the hydrothermal synthesis temperature and pressure conditions described later, and has a tensile elastic modulus at 25 ° C. of 0.5 GPa or more. Examples of such a polymer compound include polymer compounds containing carbon atoms in the main chain, such as polyethylene, polypropylene, polymethyl methacrylate, and polystyrene. The polymer compound is preferably particulate from the viewpoint of ease of dispersion in water. The polymer compound may be added to the mixture in an amount of 0.1 to 20% by mass, preferably 0.3 to 10% by mass based on the total amount of the mixture.

  When the active material-containing layer of the electrode is produced using the obtained active material 3, a conductive material such as a carbon material may be brought into contact with the surface of the active material in order to further increase the conductivity. As this method, the active material and the conductive material may be mixed after the production of the active material to form the active material-containing layer. For example, the carbon material is used as the conductive material in the mixture as a raw material for hydrothermal synthesis. It can also be added to cause carbon to adhere to the active material.

  Examples of the conductive material in the case where a conductive material that is a carbon material is added to the mixture include activated carbon, graphite, soft carbon, and hard carbon. Among these, it is preferable to use activated carbon that can easily disperse carbon particles in the mixture during hydrothermal synthesis. However, the conductive material is not necessarily mixed in the mixture at the time of hydrothermal synthesis, and it is preferable that at least a part of the conductive material is mixed in the mixture at the time of hydrothermal synthesis. Thereby, the binder at the time of forming an active material content layer can be reduced, and a capacity density can be increased.

  The content of the conductive material such as carbon particles in the mixture in the hydrothermal synthesis step is as follows: the number of moles C of carbon atoms constituting the carbon particles and the number of moles M of vanadium atoms contained in a pentavalent vanadium compound, for example. It is preferable to prepare such that the ratio C / M satisfies 0.04 ≦ C / M ≦ 4. When there is too little content (mole number C) of an electrically conductive material, there exists a tendency for the electronic conductivity and capacity density of the electrode active material comprised with an active material and an electrically conductive material to fall. When there is too much content of a electrically conductive material, the weight of the active material which occupies for an electrode active material will reduce relatively, and there exists a tendency for the capacity density of an electrode active material to reduce. By setting the content of the conductive material within the above range, these tendencies can be suppressed.

  The amount of water in the mixture is not particularly limited as long as hydrothermal synthesis is possible, but the ratio of substances other than water in the mixture is preferably 35% by mass or less.

There are no particular restrictions on the order in which the raw materials are charged when adjusting the mixture. For example, the raw materials contained in the above mixture may be mixed together, or first, water and a PO ₄ -containing compound are mixed, and then a pentavalent vanadium compound, a lithium compound, and a polymer compound are added. May be. The mixture immediately before the hydrothermal synthesis is thoroughly mixed, and the lithium compound, the pentavalent vanadium compound, and the PO ₄ -containing compound are sufficiently dispersed in water, or are completely dissolved in water. However, it is particularly preferable that the lithium compound, the pentavalent vanadium compound, and the PO ₄ -containing compound are completely dissolved in water. Since the polymer compound is insoluble in water, it is separated from the aqueous phase containing a large amount of the lithium compound, the pentavalent vanadium compound, and the PO ₄ -containing compound, but it can be sufficiently dispersed in the aqueous phase by stirring or the like. It is preferable to keep it.

[Hydrothermal synthesis process]
In the hydrothermal synthesis step, first, in a reaction vessel (for example, an autoclave) having a function of heating and pressurizing the inside, the above mixture (lithium compound, pentavalent vanadium compound, PO ₄ -containing compound, water, polymer) Compound). In addition, you may adjust a mixture within reaction container.

Next, the reaction vessel is sealed, and the mixture is heated to 200 ° C. or higher while being pressurized, thereby causing the hydrothermal reaction of the mixture to proceed. As a result, a substance in which the surface of LiVOPO ₄ is covered with a polymer compound having a tensile elastic modulus at 25 ° C. of 0.5 GPa or more is generated (hereinafter referred to as “product containing LiVOPO ₄ and polymer compound”). ).

The product containing LiVOPO ₄ and the polymer compound is usually in the form of a highly viscous paste. For example, water is added to the paste to reduce the viscosity, and then the product is dried.

In the hydrothermal synthesis step, the pressure applied to the mixture is preferably 0.1 to 30 MPa. If the pressure applied to the mixture is too low, the crystallinity of the resulting LiVOPO ₄ tends to decrease, and the volume density of the active material tends to decrease. If the pressure applied to the mixture is too high, the reaction vessel is required to have high pressure resistance, and the active material production cost tends to increase. By setting the pressure applied to the mixture within the above range, these tendencies can be suppressed.

The temperature of the mixture in the hydrothermal synthesis step is preferably 200 to 300 ° C, and more preferably 220 to 280 ° C from the viewpoint of improving the discharge capacity of the obtained active material. If the temperature of the mixture is too low, the crystallinity of the resulting LiVOPO ₄ tends to decrease, and the volume density of the active material tends to decrease. When the temperature of the mixture is too high, the reaction vessel is required to have high heat resistance, and the production cost of the active material tends to increase. By setting the temperature of the mixture within the above range, these tendencies can be suppressed.

[Drying process]
The manufacturing method of the active material which concerns on this embodiment is further equipped with the process of heating the material obtained by hydrothermal synthesis. In this step, moisture adhering to the surface of the product containing LiVOPO ₄ and the polymer compound is removed.

In the drying step, there is no particular limitation as long as moisture can be removed from the product containing LiVOPO ₄ and the polymer compound. For example, in order to dry in a short time, it may be heated to 70 to 110 ° C. If the heating temperature is too high, the grain growth of the active material proceeds and the particle diameter increases, so that the diffusion of lithium in the active material becomes slow and the capacity density of the active material tends to decrease, which is not preferable. On the other hand, if the heating temperature is too low, the firing effect cannot be obtained. By setting the heating temperature within the above range, these tendencies can be suppressed. The heating time is not particularly limited, but is preferably 3 to 8 hours.

  The atmosphere of the drying process is not particularly limited. Any of an inert atmosphere such as argon gas and nitrogen gas, an air atmosphere, and the like may be used.

According to the manufacturing method of the active material according to the present embodiment, the LiVOPO ₄ particles 1 and the polymer compound film 2 are included, and the polymer compound film 2 covers the surface of the LiVOPO ₄ particles 1 at room temperature. Active material 3 having a tensile elastic modulus of 0.5 GPa or more can be obtained. And the electrode using such an active material 3, and the lithium secondary battery using the said electrode are excellent in cycling characteristics.

<Electrode and lithium secondary battery using the electrode>
Next, an electrode using the active material according to the present embodiment and a lithium ion secondary battery using the electrode will be described. The electrode which concerns on this embodiment is an electrode provided with a collector and the active material layer provided on the said collector containing the said active material. FIG. 3 is a schematic cross-sectional view of a lithium ion secondary battery 100 according to this embodiment using the electrode.

  The lithium ion secondary battery 100 mainly includes a laminate 30, a case 50 that accommodates the laminate 30 in a sealed state, and a pair of leads 60 and 62 connected to the laminate 30.

  The laminated body 30 is configured such that a pair of the positive electrode 10 and the negative electrode 20 are opposed to each other with the separator 18 interposed therebetween. The positive electrode 10 is obtained by providing a positive electrode active material layer 14 on a plate-like (film-like) positive electrode current collector 12. The negative electrode 20 is obtained by providing a negative electrode active material layer 24 on a plate-like (film-like) negative electrode current collector 22. The positive electrode active material layer 14 and the negative electrode active material layer 24 are in contact with both sides of the separator 18. Leads 60 and 62 are connected to the end portions of the positive electrode current collector 12 and the negative electrode current collector 22, respectively, and the end portions of the leads 60 and 62 extend to the outside of the case 50.

  Hereinafter, the positive electrode 10 and the negative electrode 20 are collectively referred to as electrodes 10 and 20, and the positive electrode current collector 12 and the negative electrode current collector 22 are collectively referred to as current collectors 12 and 22, and the positive electrode active material layer 14 and the negative electrode The active material layers 24 are collectively referred to as active material layers 14 and 24.

First, the electrodes 10 and 20 will be specifically described.
(Positive electrode 10)
The positive electrode current collector 12 may be a conductive plate material, and for example, a thin metal plate of aluminum, copper, or nickel foil can be used.
The positive electrode active material layer 14 includes an active material according to the present embodiment, a binder, and a conductive material in an amount as necessary.

  The binder binds the active materials to each other and binds the active material to the positive electrode current collector 12.

  The binder may be made of any material as long as the above-described bonding is possible. For example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoro Ethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride A fluororesin such as (PVF) is used.

  In addition to the above, as the binder, for example, vinylidene fluoride-hexafluoropropylene fluorine rubber (VDF-HFP fluorine rubber), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene fluorine rubber (VDF-HFP) -TFE fluorine rubber), vinylidene fluoride-pentafluoropropylene fluorine rubber (VDF-PFP fluorine rubber), vinylidene fluoride-pentafluoropropylene-tetrafluoroethylene fluorine rubber (VDF-PFP-TFE fluorine rubber) , Vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene fluorine rubber (VDF-PFMVE-TFE fluorine rubber), vinylidene fluoride-chlorotrifluoroethylene fluorine It may be used vinylidene fluoride-based fluorine rubbers such as beam (VDF-CTFE-based fluorine rubber).

  In addition to the above, for example, polyethylene, polypropylene, polyethylene terephthalate, aromatic polyamide, cellulose, styrene / butadiene rubber, isoprene rubber, butadiene rubber, ethylene / propylene rubber and the like may be used as the binder. Also, thermoplastic elastomeric polymers such as styrene / butadiene / styrene block copolymers, hydrogenated products thereof, styrene / ethylene / butadiene / styrene copolymers, styrene / isoprene / styrene block copolymers, and hydrogenated products thereof. May be used. Further, syndiotactic 1,2-polybutadiene, ethylene / vinyl acetate copolymer, propylene / α-olefin (carbon number 2 to 12) copolymer may be used.

  Alternatively, an electron conductive conductive polymer or an ion conductive conductive polymer may be used as the binder. Examples of the electron conductive conductive polymer include polyacetylene. In this case, since the binder exhibits the function of the conductive material, it is not necessary to add the conductive material.

As the ion-conductive conductive polymer, for example, those having ion conductivity such as lithium ion can be used. For example, polymer compounds (polyether-based polymer compounds such as polyethylene oxide and polypropylene oxide) A crosslinked polymer of a polyether compound, polyepichlorohydrin, polyphosphazene, polysiloxane, polyvinylpyrrolidone, polyvinylidene carbonate, polyacrylonitrile, etc.) monomers, and LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAsF ₆ , LiCl, LiBr, Examples include Li (CF ₃ SO ₂ ) ₂ N, LiN (C ₂ F ₅ SO ₂ ) ₂ lithium salt, or a composite of alkali metal salt mainly composed of lithium. Examples of the polymerization initiator used for the combination include a photopolymerization initiator or a thermal polymerization initiator that is compatible with the above-described monomer.

  It is preferable that the content rate of the binder contained in the positive electrode active material layer 14 is 0.5-6 mass% on the basis of the mass of an active material layer. When the binder content is less than 0.5% by mass, the amount of the binder is too small and a tendency to fail to form a strong active material layer increases. Moreover, when the content rate of a binder exceeds 6 mass%, the quantity of the binder which does not contribute to an electric capacity will increase, and the tendency for it to become difficult to obtain sufficient volume energy density becomes large. In this case, particularly, when the electronic conductivity of the binder is low, the electric resistance of the active material layer is increased, and a tendency that a sufficient electric capacity cannot be obtained increases.

  Examples of the conductive material include carbon blacks, carbon materials, metal fine powders such as copper, nickel, stainless steel, and iron, a mixture of carbon materials and metal fine powders, and conductive oxides such as ITO.

(Negative electrode 20)
The negative electrode current collector 22 may be a conductive plate material, and for example, a thin metal plate of aluminum, copper, or nickel foil can be used.
The negative electrode active material is not particularly limited, and a known negative electrode active material for a battery can be used. Examples of the negative electrode active material include graphite, non-graphitizable carbon, graphitizable carbon, and low-temperature calcined carbon that can occlude / release (intercalate / deintercalate, or dope / dedope) lithium ions. Carbon materials, metals that can be combined with lithium such as Al, Si, and Sn, amorphous compounds mainly composed of oxides such as SiO ₂ and SnO ₂ , lithium titanate (Li ₄ Ti ₅ O ₁₂ ), etc. The particle | grains containing are mentioned.
As the binder and the conductive material, the same materials as those for the positive electrode can be used.

Next, a method for manufacturing the electrodes 10 and 20 according to this embodiment will be described.
(Method for manufacturing electrodes 10 and 20)
The method for manufacturing the electrodes 10 and 20 according to the present embodiment includes a step of applying a coating material, which is a raw material of the electrode active material layers 14 and 24, onto the aggregate (hereinafter, also referred to as “application step”), And a step of removing the solvent in the paint applied on the electric body (hereinafter, also referred to as “solvent removal step”).

(Coating process)
An application process for applying the paint to the current collectors 12 and 22 will be described. The paint contains the active material, the binder, and the solvent. In addition to these components, the coating material may contain, for example, a conductive material for increasing the conductivity of the active material. As the solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylformamide and the like can be used.

  The mixing method of the components constituting the paint such as the active material, the binder, the solvent, and the conductive material is not particularly limited, and the mixing order is not particularly limited. For example, first, an active material, a conductive material, and a binder are mixed, and N-methyl-2-pyrrolidone is added to the obtained mixture and mixed to prepare a paint.

  The paint is applied to the current collectors 12 and 22. There is no restriction | limiting in particular as an application | coating method, The method employ | adopted when producing an electrode normally can be used. Examples thereof include a slit die coating method and a doctor blade method.

(Solvent removal step)
Subsequently, the solvent in the paint applied on the current collectors 12 and 22 is removed. The removal method is not particularly limited, and the current collectors 12 and 22 to which the paint is applied may be dried, for example, in an atmosphere of 80 ° C. to 150 ° C.

  Then, the electrodes on which the active material layers 14 and 24 are formed in this way may then be pressed by a roll press device or the like as necessary. The linear pressure of the roll press can be, for example, 10 to 50 kgf / cm.

  The electrode according to this embodiment can be manufactured through the above steps.

  According to the electrode according to this embodiment, since the active material according to this embodiment is used as the positive electrode active material, an electrode having a sufficient discharge capacity can be obtained.

  Here, another component of the lithium ion secondary battery 100 using the electrode manufactured as described above will be described.

The electrolyte is contained in the positive electrode active material layer 14, the negative electrode active material layer 24, and the separator 18. The electrolyte is not particularly limited, and, for example, in the present embodiment, an electrolyte solution containing a lithium salt (electrolyte aqueous solution, electrolyte solution using an organic solvent) can be used. However, the electrolyte aqueous solution is preferably an electrolyte solution (non-aqueous electrolyte solution) using an organic solvent because the electrochemical decomposition voltage is low, and the withstand voltage during charging is limited to a low level. As the electrolyte solution, a lithium salt dissolved in a non-aqueous solvent (organic solvent) is preferably used. Examples of the lithium salt include LiPF ₆ , LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CF ₂ SO ₃ , LiC (CF ₃ SO ₂ ) ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN Salts such as (CF ₃ CF ₂ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ), LiN (CF ₃ CF ₂ CO) ₂ , LiBOB can be used. In addition, these salts may be used individually by 1 type, and may use 2 or more types together.

  Moreover, as an organic solvent, propylene carbonate, ethylene carbonate, diethyl carbonate, etc. are mentioned preferably, for example. These may be used alone or in combination of two or more at any ratio.

  In the present embodiment, the electrolyte may be a gel electrolyte obtained by adding a gelling agent in addition to liquid. Further, instead of the electrolyte solution, a solid electrolyte (a solid polymer electrolyte or an electrolyte made of an ion conductive inorganic material) may be contained.

  The separator 18 is an electrically insulating porous body, for example, a single layer of a film made of polyethylene, polypropylene or polyolefin, a stretched film of a laminate or a mixture of the above resins, or a group consisting of cellulose, polyester and polypropylene. Examples thereof include a nonwoven fabric made of at least one selected constituent material.

  The case 50 seals the laminate 30 and the electrolyte solution therein. The case 50 is not particularly limited as long as it can prevent leakage of the electrolytic solution to the outside and entry of moisture and the like into the electrochemical device 100 from the outside. For example, as the case 50, as shown in FIG. 3, a metal laminate film in which a metal foil 52 is coated with a polymer film 54 from both sides can be used. For example, an aluminum foil can be used as the metal foil 52 and a film such as polypropylene can be used as the polymer film 54. For example, the material of the outer polymer film 54 is preferably a polymer having a high melting point such as polyethylene terephthalate (PET) or polyamide, and the material of the inner polymer film 54 is polyethylene (PE) or polypropylene (PP). preferable.

  The leads 60 and 62 are made of a conductive material such as aluminum.

  Then, the leads 60 and 62 are welded to the positive electrode current collector 12 and the negative electrode current collector 22 by a known method, respectively, and a separator is provided between the positive electrode active material layer 14 of the positive electrode 10 and the negative electrode active material layer 24 of the negative electrode 20. 18 may be inserted into the case 50 together with the electrolytic solution with the 18 interposed therebetween, and the entrance of the case 50 may be sealed.

  As described above, the preferred embodiment of the active material of the present invention, the electrode using the same, the lithium ion secondary battery including the electrode, and the manufacturing method thereof has been described in detail. It is not limited.

  For example, the electrode using the active material of the present invention can be used for an electrochemical element other than a lithium ion secondary battery. Electrochemical elements include secondary batteries other than lithium ion secondary batteries such as metal lithium secondary batteries (those using the active material of the present invention as the cathode and metal lithium as the anode), and electric batteries such as lithium capacitors. Examples include chemical capacitors. These electrochemical elements can be used for power sources such as self-propelled micromachines and IC cards, and distributed power sources arranged on or in a printed circuit board.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

Example 1
[Hydrothermal synthesis]
In a 0.5 L autoclave glass cylindrical container, 23.06 g (0.20 mol) of H ₃ PO ₄ (Nacalai Tesque, purity 85%) and 200 g of distilled water (Nacalai Tesque, For HPLC), 18.37 g (0.10 mol) of V ₂ O ₅ (Nacalai Tesque, purity 99%), 8.48 g (0.20 mol) LiOH · H ₂ O (Nacalai Tesque, purity 99) %), 3.00 g polyethylene (PE) porous sheet (thickness 2 mm) coarsely pulverized particles (melting point: about 130 ° C .; AQ-800 (trade name) manufactured by Asahi Kasei Chemicals Corporation) were put in this order. Thereafter, the container was sealed, the heater was turned on, and stirring was continued with a strong magnetic stirrer at 250 ° C. for 16 hours. The container was allowed to cool to room temperature, and about 300 ml of distilled water was added to obtain an orange brown and green patchy paste. The pH of this substance was measured and found to be 3. This material was spread on a vat and evaporated to dryness in an oven at 90 ° C. for 23.5 hours to obtain a greenish yellow solid. The dried product was pulverized to obtain 36.73 g of an ocherous powder.

[Identification of active material by X-ray diffraction measurement]
X-ray diffraction measurement of the obtained active material was performed. Among the plurality of peaks, peaks with relatively high intensity are obtained at 2θ = 27.0 °, 27.5 °, and 28.4 °, and the active material is mainly LiVOPO ₄ having a β-type crystal structure. It was confirmed to contain.

[Observation of active material state]
The shape of the active material was observed with a high-resolution scanning electron microscope (manufactured by JEOL Ltd., apparatus name: JEM-2100F). As shown in FIG. 2, the obtained active material was an aggregate of a plurality of LiVOPO ₄ particles.

[Measurement of particle size]
With respect to the obtained LiVOPO ₄ particles 1, the projected area equivalent circle diameters calculated from the projected areas (20) based on the images observed with the high-resolution scanning electron microscope were calculated. The average value of the projected area equivalent circle diameters for the first LiVOPO ₄ particles 1 thus obtained was calculated, and the particle diameter of the LiVOPO ₄ particles 1 was calculated. The results are shown in Table 1.

[Preparation of electrode and evaluation cell]
A mixture of the active material of Example 1, polyvinylidene fluoride (PVDF) as a binder, and acetylene black as a conductive material is dispersed in N-methyl-2-pyrrolidone (NMP) as a solvent. To prepare a slurry. The slurry was prepared so that the weight ratio of the active material, acetylene black, and PVDF was 84: 8: 8 in the slurry. This slurry was applied onto an aluminum foil as a current collector, dried, and then rolled to obtain an electrode (positive electrode) on which an active material layer containing the active material of Example 1 was formed.

Next, the obtained electrode and the Li foil as the counter electrode were laminated with a separator made of a polyethylene microporous film interposed therebetween to obtain a laminate (element body). This laminate was put in an aluminum laminate pack, and 1M LiPF ₆ solution was injected as an electrolyte into the aluminum laminate pack, followed by vacuum sealing to produce an evaluation cell of Example 1.

[Evaluation of cycle characteristics]
Using the evaluation cell of Example 1, the discharge capacity (unit: mAh / g) when the discharge rate is 1 C (current value at which discharge is completed in 1 hour when constant current discharge is performed at 25 ° C.) Was measured. The ratio of the discharge capacity at the 100th cycle to the discharge capacity at the first time was evaluated as cycle characteristics. The first discharge capacity of the evaluation cell of Example 1 was 1.5 mAh / g, and the cycle characteristics were 81%.

(Example 2)
An active material, an electrode, and an evaluation cell were prepared in the same manner as in Example 1 except that polypropylene (PP) particles (melting point: about 165 ° C .; manufactured by Aldrich) were used in place of the polyethylene particles.
Further, in the same manner as in Example 1, the particle size of LiVOPO ₄ particles was measured, and the cycle characteristics were evaluated. The results are shown in Table 1.

(Example 3)
An active material, an electrode, and an evaluation cell were produced in the same manner as in Example 1 except that polymethyl methacrylate (PMMA) particles (melting point: about 160 ° C .; manufactured by Aldrich) were used instead of polyethylene particles. did.
Further, in the same manner as in Example 1, the particle size of LiVOPO ₄ particles was measured, and the cycle characteristics were evaluated. The results are shown in Table 1.

Example 4
An active material, an electrode, and an evaluation cell were prepared in the same manner as in Example 1 except that polystyrene (PS) particles (melting point: about 230 ° C .; manufactured by Aldrich) were used in place of the polyethylene particles.
Further, in the same manner as in Example 1, the particle size of LiVOPO ₄ particles was measured, and the cycle characteristics were evaluated. The results are shown in Table 1.

(Comparative Example 1)
An active material, an electrode, and an evaluation cell were prepared in the same manner as in Example 1 except that polyethylene particles were not used.
Further, in the same manner as in Example 1, the particle size of LiVOPO ₄ particles was measured, and the cycle characteristics were evaluated. The results are shown in Table 1.

(Comparative Example 2)
An active material, an electrode, and an evaluation cell were prepared in the same manner as in Example 1 except that styrene-butadiene rubber (SBR) particles (melting point: about 80 to 100 ° C .; manufactured by Aldrich) were used instead of polyethylene particles. Produced.
Further, in the same manner as in Example 1, the particle size of LiVOPO ₄ particles was measured, and the cycle characteristics were evaluated. The results are shown in Table 1.

(Comparative Example 3)
An active material, an electrode, and an evaluation cell were produced in the same manner as in Example 1 except that polytetrafluoroethylene (PTFE) particles (melting point: about 330 ° C .; manufactured by Aldrich) were used instead of polyethylene particles. .
Further, in the same manner as in Example 1, the particle size of LiVOPO ₄ particles was measured, and the cycle characteristics were evaluated. The results are shown in Table 1.

The active materials obtained in Examples 1 to 4 are those in which the polymer compound is insoluble in water and is in a molten state when heated to 200 ° C. or higher under pressure, and at 25 ° C. Comparative Example 1 using no polymer compound, Comparative Example 2 using a material whose tensile elastic modulus at 25 ° C. is lower than 0.5 GPa, and Compared to the active material obtained in Comparative Example 3 as a polymer compound, which does not enter a molten state when heated to 200 ° C. or higher under pressure and whose tensile elastic modulus at 25 ° C. is less than 0.5 GPa. It is clear that the cycle characteristics are excellent.
In addition, since the surface of LiVOPO ₄ particles is covered with a polymer compound film having a tensile elastic modulus at 25 ° C. of 0.5 GPa or more, the obtained active material has improved mechanical strength and cycle characteristics. It is thought to have improved.

1 ... LiVOPO ₄ particles, 2 ... polymer membranes, 3 ... active material, 10 ... positive electrode, 20 ... negative electrode, 12 ... cathode current collector, 14 ... positive electrode active material layer, 18 ... separator, 22 ... negative electrode current collector 24 ... negative electrode active material layer, 30 ... laminate, 50 ... case, 52 ... metal foil, 54 ... polymer film, 60, 62 ... lead, 100 ... lithium ion secondary battery.

Claims (6)

LiVOPO ₄ particles,
The polymer compound film,
The polymer compound film is an active material that covers the surface of the LiVOPO ₄ particles and has a tensile elastic modulus at 25 ° C. of 0.5 GPa or more. The active material according to claim 1, wherein the LiVOPO ₄ particles have a particle diameter of 0.2 to 2.0 μm.   The active material according to claim 1, wherein the polymer compound film has a thickness of 0.005 to 0.03 μm. A current collector,
An active material layer comprising the active material according to any one of claims 1 to 3 and provided on the current collector;
Electrode.   A lithium secondary battery comprising the electrode according to claim 4. Water to obtain a product containing LiVOPO ₄ and a polymer compound by heating a mixture containing a lithium source, a pentavalent vanadium source, a phosphate source, water, and a polymer compound to 200 ° C. or higher under pressure. With thermal synthesis process,
Production of an active material, wherein the polymer compound is insoluble in water, becomes a molten state in the pressurized and heated state, and has a tensile elastic modulus at 25 ° C of 0.5 GPa or more. Method.