The name of the invention: ion secondary battery electrode, a method of manufacturing of ion secondary battery electrode, lithium ion secondary battery and a magnesium ion secondary battery
Technical field
[0001]
　The present invention provides ion secondary battery electrode, method of manufacturing the ion secondary battery electrode, a lithium ion secondary battery and a magnesium ion secondary battery.
Background technique
[0002]
　The ion secondary battery, for example, a lithium ion secondary battery or a magnesium ion secondary battery, sodium ion secondary battery, such as calcium ion secondary batteries include a plurality of types depending on the kind of metals responsible for electrical conduction. These ion secondary battery is capable of power storage by performing charging, has high convenience and can be used repeatedly, has been utilized in various fields.
[0003]
　Lithium ion secondary batteries among described above, since the voltage, capacitance, energy density is high, particularly, cellular phones, notebook computers, power generation equipment of the storage battery, such as wind and solar, electric vehicles, uninterruptible power supplies, household storage battery It is widely used in fields such.
[0004]
　Further, among the above, the magnesium ion secondary battery, can be used magnesium present in large amounts and relatively inexpensive in place of lithium as a rare metal, also, it is possible to move the two electrons, charge discharge capacity is expected to double in the lithium ion secondary battery. Therefore, a magnesium ion secondary battery has attracted attention as a next generation ion secondary battery to replace the lithium ion secondary batteries are currently actively research and development is proceeding.
[0005]
　To describe the structure of these ion secondary batteries schematically, graphite and disposed as a negative electrode, a conductor for a strong metal ion ionization tendency can be stored in the form of ions arranged as a positive electrode, these negative electrodes that is between the positive electrode and the structure filled with electrolyte solution or gel electrolyte.
[0006]
　To improve the performance of the ion secondary battery, the electrode such as the cathode and anode, are required even further improvement for other components not described in electrolyte and the various materials in the past and techniques have been proposed.
[0007]
　For example, the electrodes, in particular, the positive electrode, conventionally, after a mixture prepared by kneading an electrode active material and the conductive aid and organic binder, and dried was applied to the surface of the current collector such as aluminum foil, It was produced by press molding. In recent years, maintaining the high charge-discharge capacity at a faster charge and discharge rate, for the purpose of implementing a good positive charge-discharge cycle characteristics, for example, it has been proposed the invention described in Patent Document 1.
[0008]
　The said Patent Document 1, TiO 2 , NiO, MnO 2 and nanocrystalline oxide selected from such as P 2 O 5 of 5 and SiO 2 , Bs 2 O 3 having a glass phase selected from the like, nano size microcrystalline oxide - electrode made ​​of glass composite mesoporous powder or thin film is described.
　Further, as a method for producing the powder or thin film, a block polymer or a surfactant agent as a template, a metal alkoxide or metal chloride, PO (OC 2 H 5 of 5 ) 3 in aqueous solution or them into alcohol such as ethanol the melted solution, adding a hydrochloric acid (HCl), sol - metal oxide glass phase by gel process - a process of producing a powder having an inorganic oxide composite meso structure structure to gel was aged at room temperature ~ 90 ° C. process, which the metal oxide of the glass phase to remove the block polymer or surfactant agent by heat treatment at 350 ~ 400 ℃ in the air - the process of manufacturing the glass phase composite mesoporous powder, further 400 this to 700 It is telling that the step of phase transition of the metal oxide glass phase crystallites is described by a heat treatment at ° C..
CITATION
Patent literature
[0009]
Patent Document 1: Japanese Patent No. 4528975
Summary of the invention
Problems that the Invention is to Solve
[0010]
　However, the conventional methods and the method described in Patent Document 1, the manufacturing process can reduce the cost has been a problem that it is difficult to be complicated.
　Further, in the conventional method, it is necessary to include an organic binder, correspondingly, the charge-discharge capacity is lowered.
[0011]
　The present invention has been made to solve the above problem, a low-cost and high charge-discharge capacity can be realized ion secondary battery electrode, manufacturing method, the lithium ion secondary battery as magnesium ion secondary battery electrode it is an object of the present invention to provide an ion secondary battery.
Means for Solving the Problems
[0012]
　The problems present invention for solving the can, the surface of the conductor, and an ion secondary cell electrode and characterized in that a vanadium oxide coating.
　Further, the present invention is a manufacturing method of the ion secondary cell electrode manufacturing the ion secondary battery electrode described above, the surface of the conductor by thermal spraying a powder thermal spray material including vanadium oxide It was manufacturing method of the ion secondary cell electrode and providing a vanadium oxide coating.
　Further, the lithium ion secondary battery or a magnesium ion secondary battery characterized by using an ion secondary battery electrode described above.
Effect of the invention
[0013]
　According to the present invention, it is possible to provide a low-cost and high charge-discharge capacity can be realized ion secondary battery electrode, method of manufacturing the ion secondary battery electrode, a lithium ion secondary battery and a magnesium ion secondary battery .
Brief description of the drawings
[0014]
FIG. 1 is a cross-sectional view illustrating a configuration of an ion secondary battery electrode according to one embodiment.
It is a schematic block diagram of FIG. 2 apparatus to provide a vanadium oxide film 103 on the surface of the conductor 102 shown in FIG. 1 (film deposition apparatus) 201.
[3] at the same time a portion of the vanadium oxide coating 103 shown in FIG. 1 and to crystallize a cross-sectional view of a film surface portion formed an uneven surface.
[4] Some was crystallized vanadium oxide coating 103 shown in FIG. 1 is a schematic sectional enlarged view showing a state of containing crystalline and amorphous.
[5] partially crystallized vanadium oxide coating 303 shown in FIG. 3 is a cross-sectional schematic enlarged view showing a state of containing crystalline and amorphous.
[6] monoclinic X crystal systems a V 2 O 5 of 5 is a conceptual diagram showing a crystal structure of the crystal (0.26 ≦ a ≦ 0.59). Incidentally, X is at least one element selected Cu, Ag, Fe, from among the alkaline earth metals and alkali metals.
7 is a partial sectional view showing a configuration of an ion secondary battery according to an embodiment.
8 is a schematic configuration diagram showing a schematic configuration of a bipolar model cells used in the characterization of the electrode for a lithium ion secondary battery.
9 is a schematic configuration diagram showing a schematic configuration of a three-electrode model cells used in the characterization of the electrode for a lithium ion secondary battery.
It is a schematic block diagram showing a schematic configuration of a three-electrode model cells used in the characterization of [10] Magnesium ion secondary battery electrode.
DESCRIPTION OF THE INVENTION
[0015]
　Hereinafter, with reference to the drawings, ion secondary battery electrode according to the present invention, a method of manufacturing an ion secondary battery electrode, the embodiments of the lithium ion secondary battery and a magnesium ion secondary battery will be described .
[0016]
　First, a description will be given ion secondary battery electrode according to an embodiment of the present invention.
　As shown in FIG. 1, ion secondary battery electrode 101 according to one embodiment, the surface of the conductor 102, the vanadium oxide coating (hereinafter, sometimes simply referred to as "coating".) 103 is provided there. The vanadium oxide coating 103 includes a vanadium oxide is vanadium oxide, or crystal and amorphous is amorphous.
　Such electrode 101 can be suitably used as a positive electrode of the ion secondary battery.
[0017]
　When using the electrode 101 as the positive electrode, the conductor 102 can be formed of aluminum which has been conventionally used for the positive electrode, an aluminum alloy, copper, at least one of copper alloy and carbon. The electron conductivity, from the viewpoint of battery operating potential, aluminum or an aluminum alloy is preferable. Such conductors 102, foil, but may be a plate, from the viewpoint of high adhesion and weight of the the film 103, preferably in the mesh. The thickness of the case of a foil, for example, preferably set to such 10 ~ 20μm.
[0018]
　The electrode 101 can also be used as the negative electrode. When using the electrode 101 as a negative electrode, wherein the conductor 102 is formed is preferably formed of a metal lithium or a lithium alloy as long as the lithium ion secondary battery, a metal magnesium or a magnesium alloy if the magnesium ion secondary battery It is preferable to. Incidentally, in the case of using the negative electrode of these ion secondary battery, as long as the pre-doping lithium ions and magnesium ions, conductor 102 to be used for the negative electrode, be the same as that of the conductor 102 described as the positive electrode it can. In this case, electron conductivity, from the viewpoint of battery operating potential, copper or its alloy is preferable. For the same reason as above, it takes conductor 102 is preferably a mesh-like. The thickness of the case of a foil, for example, preferably set to such 10 ~ 20μm. Note that the pre-doping of the present invention, such as by electrochemical means, means that you included pre metal ions to the electrodes.
[0019]
　Vanadium oxide film 103 in the present invention, the glass transition temperature is low, since this by techniques such as spraying can be provided directly on the surface of the conductor 102, it is possible to reduce significantly the manufacturing process as compared with the conventional , it is possible to reduce the cost. Further, since it is possible to provide directly by thermal spraying, it is not necessary to add an organic binder such as polyvinylidene fluoride (PVDF), whereby it is possible to also reduce the cost.
　Furthermore, the coating 103 is a highly conductive because it contains vanadium oxide, since it is possible to act as the electrode active material, necessary to add carbon black, graphite, a conductive additive such as carbon fiber there is no. Accordingly, this also not only can reduce the cost, since it is possible to contain only vanadium oxide min without the addition of an organic binder and conductive additive, it is possible to improve the charge-discharge capacity.
　Vanadium oxide is present in the vanadium oxide coating 103, about 0.5 to 0.9 mole fraction, can be included about 0.703 as an example.
[0020]
　Such coating 103 includes a vanadium (V), phosphorus and (P), copper (Cu), silver (Ag), iron (Fe), alkaline earth metal (Group 2 element) and alkali metal (Group 1 element) preferably contains at least one element selected from among.
[0021]
　Vanadium exactly as described above takes the form of an oxide in a vanadium oxide film 103. Details are described later, the vanadium oxide has a specific crystal structure. There is a gap from the atomic level molecular size of for such crystal structure, thereby making it possible to insert and desorption of metal ions such as lithium ion or magnesium ion.
[0022]
　Phosphorus forms an oxide, and has a function of glass phase vanadium oxide coating 103 as a firm stable. As the oxides of phosphorus during vanadium oxide coating 103, for example, PO 4 and the like tetrahedron. Phosphorus, P of the raw material 2 O 5 of 5 in the vanadium oxide coating 103 in terms of, 0.05 to about 0.20 mole fraction, can be included about 0.09 as an example. The glass as used in the present invention, atomic arrangement has a random network structure is meant a solid that indicates the glass transition phenomenon.
[0023]
　Copper, silver, at least one element selected from alkaline earth metals and alkali metals, serves as a nucleating agent when aimed at crystallisation. Thus, it is possible to suitably the orientation crystal structure of the vanadium oxide coating 103, insertion and desorption of ions is facilitated, the deterioration of the crystal structure accompanying the charge / discharge cycle is reduced, the charge and discharge capacity retention rate improvement of is achieved. Here, as the alkaline earth metal, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and the like. Examples of the alkali metal include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and the like. These elements as well as phosphorus, may be contained in the form of oxides vanadium oxide coating 103. The total amount of these elements, in the vanadium oxide coating 103, 0.06 ~ 0.29 mole fraction, as an example, Li 2 may contain about 0.107 if O.
[0024]
　Incidentally, in addition to these, WO 3 , MoO 3 , Fe 2 O 3 , MnO 2 , BaO, Sb 2 O 3 and Bi 2 O 3 may be added as appropriate a glass modifying component, such as. By adding these components, it is possible to adjust properties of the glass amorphous phase, for example water resistance, thermal expansion, and characteristic temperature.
[0025]
　Vanadium oxide film 103 in the present invention, by crushing the glass block manufactured by using the above-mentioned material to prepare a powdery spray material comprising a vanadium oxide, then the surface of the conductor 102 by using the material it can be prepared by spraying the. Powdered spray material, for example, the average particle size may be about 10 .mu.m.
[0026]
　The glass block elements such as vanadium oxide and phosphorus is mixed in the range of respective mole fractions described above, put the mixed powder thus obtained in a container such as a platinum crucible dissolved in a melting furnace such as an electric furnace and it can be produced by casting, such as the graphite mold. Dissolution conditions in the melting furnace, for example, Atsushi Nobori rate of 5 of 5 ° C. / min, the target temperature 1000 ~ 1100 ° C., can be kept for 1 hour with agitation after reaching to the target temperature. Graphite mold, it is preferable to keep pre-heated to 150 ~ 300 ℃ before casting the dissolved glass.
[0027]
　Spraying, and the state close to spray particles melt or so by heating the spray material using a combustion flame or electric energy, is deposited by spraying the spray target surface. In the present invention for forming a coating film 103, powdered glass to be spray material (glass powder) spraying is heated above the glass transition temperature of the glass powder. The thermal spraying, atmospheric plasma spraying, vacuum plasma spraying, flame spraying, high speed flame spraying, arc spraying, it is like cold spraying, the present invention can be applied either approach.
[0028]
　Figure 2 shows a schematic view of an apparatus providing a vanadium oxide film 103 on the surface of the conductor 102 by flame spraying as an example of a spray (coating film deposition apparatus 201).
　As shown in FIG. 2, the coating film forming apparatus 201 includes a gas supply device 202, a gas supply pipe 203, a gas heater 204, the working gas supply pipe 205, a spray nozzle 206, the glass powder feeder 207 When, and a glass powder supply tube 208.
[0029]
　High pressure gas supplied from the gas supply unit 202 through the gas supply pipe 203 is branched into two paths, the gas passing through the one path is supplied to the gas heater 204. Gas heated by the gas heater 204 is fed to the spray nozzle 206 through the working gas supply pipe 205. Further, the gas passed through the other path is fed to the glass powder feeder 207, along with the glass powder as the working gas, is fed to the spray nozzle 206 via a glass powder supply tube 208. Working gas and the glass powder is supplied to the spray nozzle 206, ejected toward the surface of the conductor 102 in a state close melt or in the spray nozzle 206 tip, to form a film 103.
[0030]
　Here, the gas supplied from the gas supply device 202, for example, it is possible to use air. If air is used as the gas, the supply pressure, for example, it is possible to and 0.5 MPa, the temperature may be higher than the softening point of the glass powder of temperatures (e.g., 300 ° C.). The supply rate of the glass powder, for example, may be, eg, 10g / min. Incidentally, when the provision of the vanadium oxide coating 103 on the surface of the conductor 102 is preferably performed while heating the conductor 102, its temperature is, for example, may be, eg 0.99 ° C..
[0031]
　As another embodiment the surface of the conductor 102 providing a vanadium oxide coating 103, for example, a glass powder was prepared as described above was applied to the surface of the conductor 102 to form a paste, below a predetermined temperature in can be obtained also by heating. The glass powder in the paste (a glass powder paste) is, for example, a glass powder, and ethyl cellulose as a binder can be prepared by mixing a solvent of butyl carbitol acetate. Then, in this way the glass powder paste prepared after application to the surface of the conductor 102 by screen printing method or a spray coating method (coating method), to remove the butyl carbitol acetate is heated to about 0.99 ° C.. Then, heated to 330. ° C. or more and higher than the softening point of the glass, to remove the ethyl cellulose and fusing glass powder, a vanadium oxide film 103 in the present invention can be deposited on the surface of the conductor 102 .
[0032]
　Incidentally, in the spraying or coating method, in the case of using a susceptible glass powder relatively crystallisation difficult to crystallize, a low softening point temperature of vanadium oxide glass powder, the glass powder of the former, at a volume fraction of 5 the addition of about to 20%, the more easily forming a coating 103. The glass powder added, for example, V-Te-P-Fe -O -based glass powder having a softening point of 356 ° C. (mole fraction of the glass powder, V 2 O 5 of 5 : Te 2 O: P 2 O 5 of 5 : Fe 2 O 3 = 0.430: 0.313: 0.153:. a is) is preferred 0.104.
[0033]
　As shown in FIG. 1, the surface of the vanadium oxide coating 103 is sprayed on the surface of the conductor 102 has been formed is substantially flat, as shown in FIG. 3, the vanadium oxide coating 303 having irregularities It can also be a. The provision of unevenness on the surface as the coating 303, the specific surface area is increased, thereby improving the reactivity with a liquid electrolyte. Therefore, ion secondary battery electrode 301 having a coating 303, it is possible to improve the improvement and charge and discharge rate of the charge and discharge capacity. Irregularities formed, for example, after forming a flat film on the surface of the conductor 302, by heating at a temperature above the softening point of the film while a stamper formed of irregularities pressed against the surface of the flat film can do. Heating can be carried out in such a microwave heating furnace or electric furnace. Incidentally, unevenness is not necessarily intended regular, it can be irregular unevenness such as cracks obtain the same effect. When heating by the microwave oven, the stamper is preferably made of quartz glass does not absorb microwaves, when heated by an electric furnace heating is suitably made of nickel or stainless steel.
[0034]
　Conductor 102 (conductor 302 as well) of vanadium oxide are sprayed provided on the surface film 103 (film 303 as well), the entire coating 103 is in the amorphous state, is flat shall also be obtained by forming irregularities, it can be a part was crystallized, and those containing crystalline and amorphous. Incidentally, FIG. 4, a portion of the vanadium oxide coating 103 shown in FIG. 1 is crystallized, a cross-sectional schematic enlarged view showing a state of containing a crystal 401 and an amorphous 402, FIG. 5 is a portion of the vanadium oxide coating 303 shown in FIG. 3 was crystallized is a cross-sectional schematic enlarged view showing a state of containing a crystal 501 and an amorphous 502.
[0035]
　When the volume fraction of the amorphous 402 in the vanadium oxide coating 103 (amorphous 502 as well) is high, the atomic spacing in the amorphous 402 wider than the crystal 401 (crystal 501 as well), the charge deintercalation of ions is facilitated at the time of discharge, cycle deterioration is reduced. Therefore, it is possible to improve the charge-discharge capacity retention ratio, on the other hand, the charge and discharge capacity decreases.
[0036]
　In contrast, when the volume fraction of the crystal 401 is higher for the amorphous 402 in the vanadium oxide coating 103, but may improve charge-discharge capacity, on the other hand, the charge and discharge capacity retention rate is lowered.
[0037]
　The entire film 103 or remain amorphous 402, whether it is assumed that includes a crystal 401 and the amorphous 402, or to focus on the charge and discharge capacity retention rate of ion secondary battery, the charge-discharge capacity or emphasis, or to focus on these balance, it can be appropriately determined in accordance with the purpose. For example, as ion secondary battery electric power storage, if the lifetime is required, in order to improve the charge-discharge capacity retention ratio, without going through the step of crystallizing, the complete amorphous phase vanadium oxide film 103 of the remains may be configured the ion secondary battery.
[0038]
　If the vanadium oxide film 103 as including a crystal 401 and an amorphous 402, the volume fraction of the crystal 401 relative to the amorphous 402 in the film 103 is preferably not more than 94%. When such volume fraction exceeds 94%, since the volume fraction of the crystal 401 relative to the amorphous 402 in the coating 103 is too high, there is a possibility that the charge and discharge capacity retention rate is lowered.
[0039]
　Main crystal 401 in the vanadium oxide coating 103 is preferably a monoclinic. In other words, it is preferable that the largest number of accounts crystal in that can be taken by the crystal lattice of vanadium oxide film 103 is monoclinic. 6, X-monoclinic a V 2 O 5 of 5 is a conceptual diagram showing a crystal structure of the crystal (0.26 ≦ a ≦ 0.59). Incidentally, X is at least one element selected Cu, Ag, Fe, from among the alkaline earth metals and alkali metals. Further, in the figure, O atom is an oxygen atom, V atom represents a vanadium atom, X-atom represents at least one element selected from the selection group.
[0040]
　As shown in this FIG. 6, X- a V 2 O 5 of 5 crystals, b chain double that in the axial direction are arranged VO . 6 and an octahedral 601. The duplex is linked to the a-axis direction and the c-axis direction to form a 3-dimensional tunnel structure. a shaft gap tunnel most widely along the direction of the reversible ions are inserted into the tunnel. Insertion of ions into the tunnel, the crystal 401 of the film 103 is carried out when more easily oriented, in particular, when oriented perpendicular to the [100] surface of the crystal orientation conductor 102 further It is easily done. That is, the crystal orientation of the crystal 401 when oriented in this manner to the surface of the conductor 102 is formed as a tunnel along the a-axis direction is parallel to the thickness direction of the conductor 102 since the insertion and desorption of ions is facilitated, the deterioration of the crystal structure accompanying the charge / discharge cycle is reduced, thereby improving the charge-discharge capacity retention ratio. Further, the double chain VO . 6 octahedra 601 cation composed layers to each other by (i.e., X) because the bound regularly, accompanied by expansion and contraction of the tunnel by insertion and desorption of ions peeling between the layers can be suppressed. This reduces the deterioration of the crystal structure accompanying the charge / discharge cycle, thereby improving the charge-discharge capacity retention ratio.
[0041]
　Crystallization of such a vanadium oxide film 103 can be performed by electric furnace heating, in view of the orientation degree and the heating time shortened precipitated crystals, and more preferably carried out in a microwave furnace. Microwave heating can for example be carried out by irradiating by controlling the appropriate time and outputting a microwave of a frequency 2.45 GHz. At the time of heating by microwaves, the temperature of the film 103 is measured by such a radiation thermometer, the crystallization temperature of the film 103 is glass (e.g., about 370 ° C.) may set to be the above. Incidentally, if the heating temperature is less than the crystallization temperature, it can not be crystallized.
　For example, the mole fraction, V 2 O 5 of 5 to 0.703, Li 2 O and 0.107, Fe 2 O 3 to 0.1, P 2 O 5 of 5 vanadium oxide film was formed using 0.09 It performs processing described above for 103, when the X-ray diffraction analysis of such a coating 103, oriented monoclinic Li to [0.89] 0.3 V 2 O 5 of 5 can confirm the deposition of. The volume fraction of the crystal 401 is about 90% for the amorphous 402.
[0042]
　Here, when forming the uneven surface of the film 103 as described above can also be carried out crystallization of the vanadium oxide coating 103 and unevenness of the formation and at the same time. Further, in the present invention, it may be higher than the internal percentage of the amorphous 402 in the surface layer portion of the vanadium oxide coating 103. In this manner, more preferable because the de-insertion of ions is facilitated.
[0043]
　Such vanadium oxide film 103, can be previously pre-doped metal ions such as lithium ion or magnesium ion. These ions can be as long as they are suitable for ion secondary battery to be manufactured. For example, the pre-doped lithium ions as long as the lithium ion secondary battery, it is preferable to pre-doped magnesium ions if the magnesium ion secondary battery.
[0044]
　Pre-doping of the metal ions may be performed by an electrochemical technique. For example, if the ion secondary battery electrode 101 having a vanadium oxide film 103 on the surface of the aluminum alloy foil used as a conductor 102, and the electrode 101 as a cathode, an anode metal to be pre-doping of the lithium or magnesium and then, it was immersed in the electrolyte of the non-aqueous, by applying a voltage between the electrodes, it is possible to pre-doping. As the electrolytic solution in this case, for example, a volume of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) ratio of 1: A mixed solvent 2, lithium hexafluorophosphate (LiPF . 6 a) 1 mol / L It may be used after dissolved. Other solvents which can be used for pre-doping, and the like ionic liquids. Voltage to be applied, for example, be a like 3V, application time, for example, may be, eg 1 hour.
[0045]
　For example, another embodiment of a case of pre-doped lithium ions, a lithium salt such as lithium chloride (LiCl) and lithium acetate (acoli), or butyl lithium (C 4 H . 9 Li) and naphthalene lithium (C 10 H . 8 Li) and an organic lithium compound such as, a mixture of an organic solvent, include a method of dipping the ion secondary battery electrode 101. In this case, in a state of immersing the film 103, or perform ultrasonic irradiation or microwave irradiation, the anode electrode of noble metal is provided, or applying a voltage between the anode electrode and the ion secondary battery electrode 101 it is, thereby improving the efficiency of the pre-doping amount and the pre-doping.
[0046]
　Also, for example, as a further embodiment in which the pre-doping lithium ions, for example, lithium nitrate (LiNO which melts at a temperature lower than the melting point of the aluminum alloy foil used as a conductor 102 3 molten salt containing lithium, etc.), was heated to a temperature between the softening point and glass transition point of the aluminum alloy foil having a melting point or more and the film 103, or by immersing the ion secondary battery electrode 101 therein, the same, yet the anode electrode of a noble metal provided, it can also be pre-doped by or to apply a voltage between the anode electrode and the ion secondary battery electrode 101.
[0047]
　Ion secondary battery electrode 101 according to an embodiment of the present invention is provided with vanadium oxide coating 103 on the surface of the conductor 102. Since such coating 103 does not include an organic binder, correspondingly, it is possible to improve the charge-discharge capacity. Furthermore, when forming such a coating film 103 by spraying, it is possible to reduce significantly the manufacturing process, it is possible to reduce the cost. Furthermore, if such a coating 103 was amorphous 402, it can improve the charge and discharge capacity retention rate, when it is assumed that includes a crystal 401 and an amorphous 402, high charge-discharge capacity and charge and it is possible to achieve both the discharge capacity retention ratio.
　It has been described in detail ion secondary battery electrode 101 according to an embodiment of the present invention.
[0048]
　Next, the ion secondary battery will be described according to an embodiment of the present invention using the ion secondary battery electrode 101 described above.
　Such ion secondary battery, and the like magnesium ion secondary battery using the lithium ion secondary battery or magnesium used lithium. These may be embodied in a similar structure, in the following description, a representative will be described lithium-ion secondary battery.
[0049]
　As shown in FIG. 7, the lithium ion secondary battery 701, when the ion secondary battery electrode 101 (not shown in FIG. 7) was used as a positive electrode 702, and the positive electrode 702, contact with the positive electrode 702 a cathode current collector 703 to current collector electrical on, a negative electrode 704 serving as a counter electrode of the positive electrode 702, a negative electrode current collector 705 to current collector electrical contacts with the negative electrode 704, positive electrode 702, negative electrode 704 and the container 706 There is a separator 708 which can be impregnated with and the electrolyte 707 is provided so as not to contact with each other, are configured in a liquid-tight manner in the container 706. Incidentally, the negative electrode 704 (not shown) of carbon conductive may be attached by such a coating.
[0050]
　Positive electrode current collector 703 may be formed such as an aluminum alloy foil, the negative electrode current collector 705 may be formed such as a copper alloy foil, the separator 708, the lamination of polyethylene and polypropylene having a fine pore structure it can be formed film or the like. Container 706, for example, is formed on the stainless steel or an aluminum alloy bottomed cylindrical shape or a bottomed square cylindrical shape, as long as it can hermetically sealed liquid-tightly by the lid body 709 and the gasket 710.
[0051]
　Electrolyte 707, in the case of a lithium ion secondary battery, for example, a volume of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) ratio of 1: A mixed solvent 2, lithium hexafluorophosphate (LiPF . 6 ) It was dissolved 1 mol / L, and the like can be used and further the addition of 0.8 wt% of vinylene carbonate (VC). On the other hand, in the case of magnesium ion secondary battery, for example, 0.4 mol% / L of Mg (ClO 4 ) 2 and, 0.1mol% / L NaClO of 4 can be used in PC solution and the like.
[0052]
　Naお, positive electrode current collector 703, a negative electrode 704, the negative electrode collector 705, the container 706, the electrolyte 707, se pa RitzーTatari 708, the lid 709おyoびga su keッSuites 710 ha, before the mind shi ta moのni Limited Connecticut made ​​me cry ru moのでwa na ku, ri chiウRousseau-o nn secondary Corning battery ya ma NekoシウRousseau-o nn secondary battery NADOの-o-ni nn secondary battery with a ra me cry ru knownいのでmaterial has now su ru koとgaでki ru.
　Exampleえba, ma Corning NekoシウRousseau-o nn secondary batteryのnegative wa, AZ31 alloy (manufactured Hikaru ミ niウRousseau wo 3%, Ami lead wo 1% add shi ta ma Corning NekoシウRousseau alloy) NADOでformed su ru koとgaでki ru.
[0053]
　Lithium ion secondary batteries having such a configuration, for example, be an initial charge and discharge capacity is 345 mAh / g, the charge-discharge capacity after 51 cycles 331mAh / g, 51 cycles of charge and discharge capacity retention ratio after to achieve 96% it can.
　Further, a magnesium ion secondary battery having the above configuration, for example, the initial charge-discharge capacity of 300 mAh / g, 10 charge-discharge capacity after cycles of 285 mAh / g, after 10 cycles of charge and discharge capacity retention rate to achieve 95% be able to.
Example
[0054]
　Next, a description will be given of an embodiment in which the effect of the present invention was confirmed.
[0055]
(1) preparation of the glass powder
　is first, to produce a glass powder as a spray material. V in a platinum crucible 2 O 5 of 5 , Li 2 O, Fe 2 O 3 , P 2 O 5 of 5 with each mole fraction, were blended so as to be 0.703,0.107,0.100,0.090 were mixed on a mixed powder 200g was prepared.
　Then, it was heated to an electric furnace. Heating in an electric furnace, the Atsushi Nobori rate was 5 ℃ / min, 1 hour from the time it reaches the target temperature (1000 ~ 1100 ℃), was heated and maintained with stirring glass.
　Then removed platinum crucible from the melting furnace to produce a glass block is cast into a graphite mold which has been heated and held in advance 0.99 ~ 300 ° C., and pulverized it. The average particle size of crushed glass powder was 10 .mu.m.
　The differential thermal analysis (DTA), the results of measurement of the characteristic point of the glass powder, the glass transition point (Tg) of 252 ° C., yield point (Mg) is 271 ° C., a first crystallization starting temperature was 315 ° C., the second crystallization starting temperature was 428 ℃.
[0056]
[2] forming the vanadium oxide coating
　was then deposited vanadium oxide coating on the surface of the conductive body using a glass powder prepared in [1]. Deposition of the coating was performed by flame spraying. Flame spraying was carried out using film deposition apparatus (see FIG. 2). It should be noted that the conductor is, using aluminum alloy foil with a thickness of 20μm (Mitsubishi Aluminum Co., Ltd. N5-8X-073). Spraying conditions are as follows, the average thickness of the vanadium oxide coating to be deposited is set to be about 10 .mu.m.
[0057]
"Spraying conditions"
the distance from the spray nozzle tip to the aluminum alloy foil: about 15Mm
-working gas: air
-working gas supply pressure: 0.5MPa
-working gas supply temperature of: 300 ℃
, glass powder feed rate of: 10g / min
heating temperature of the aluminum alloy foil: 150 ℃
[0058]
[3] Crystallization of vanadium oxide coating
　was then subjected to crystallization of the vanadium oxide coating was deposited on the surface of the conductive body (2). Crystallization of vanadium oxide coating was performed using a microwave oven. Microwave heating furnace, Shikokukeisokukogyo microwave reactor μ reactor Co. (microwave frequency: 2.45 GHz) was used. Heating by microwaves, the temperature of the coating was measured by a radiation thermometer, was controlled output and irradiation time of microwaves so that the temperature of the film is about 370 ° C.. Note that in this study was 10min approximately at 1000 W.
　After heating by microwave irradiation in the coating, as a result of the surface of the coating film was subjected to X-ray diffraction analysis, Li monoclinic oriented in [0.89] 0.3 V 2 O 5 of 5 that are precipitated, and amorphous volume fraction of the crystal with respect to quality was found to be 90%.
[0059]
[4] pre-doping of the lithium ions into the vanadium oxide coating
　was then pre-doping the lithium ions into the crystallized vanadium oxide coating in [3]. Pre-doping of the lithium ions was carried out by electrochemical technique. First, a conductor having a coating as a cathode, a lithium metal as the anode, they were immersed in the electrolyte of the non-aqueous, it was applied for 1 hour at a voltage of 3V between the two electrodes was pre-doped lithium ions to the coating. The solvent mixture 2, the lithium hexafluorophosphate (LiPF: Incidentally, the electrolyte, ethylene carbonate (EC) and ethyl methyl carbonate (EMC) volume ratio of 1 6 use those with) dissolved 1 mol / L It had.
[0060]
[5] Evaluation of the lithium ion secondary battery electrode
　punching a conductor that pre-doping the lithium ions into the vanadium oxide coating with (4) into a disk shape having a diameter of 15 mm, was prepared an electrode according to Example 1. Using the electrodes according to Example 1 was prepared as a positive electrode (shown in FIG. 8 as a positive electrode 801) to evaluate the charge-discharge characteristics by the bipolar model cell.
[0061]
　Figure 8 shows a schematic configuration of a bipolar model cells used in the characterization of the electrode for a lithium ion secondary battery. As shown in FIG. 8, the positive electrode 801 and the aluminum collector foil 802, and, PIC the (Pseudo Isotoropic Carbon) negative electrode 803 and the copper collector foil 804 was applied to the copper foil, thickness 30μm of impregnated with electrolyte are layered with a separator 805, then sandwiched them in two SUS-made jig 806, and the battery cells placed in a glass container. Electrolytic solution used was volume of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) ratio of 1: A mixed solvent 2 lithium hexafluorophosphate (LiPF . 6 a) was dissolved 1 mol / L, further 0.8 wt% of vinylene carbonate (VC) was used as the added.
[0062]
　Evaluation of charge and discharge properties was performed at room temperature using a charge-discharge tester (manufactured by Toyo System Co. TOSCAT3100U), it was started from charging. Charging and discharging is carried out in CC (Constant Current) mode, the cell voltage was 1.5 ~ 4.2V. The current density during charge and discharge, first time 0.057MA / cm 2 and, the second and subsequent cycles 0.28MA / cm 2 was.
[0063]
　On the other hand, it was produced electrodes for comparison with the electrode according to Example 1 in a conventional manner. Such electrodes, and the glass powder prepared in (1), as a conductive auxiliary agent, Ketjen black (Lion Co., Ltd. EC600JD, particle size: 34.0nm or less) and, as a binder, N- methyl-2- Pirodorin ( and NMP) to 5 wt% dissolved polyvinylidene fluoride (PVDF) (manufactured by Kureha Corporation # 7305), a mass ratio of 85: 5 were mixed using a mortar in a 10 ratio. At this time, for viscosity adjustment, and slurried with mixing appropriately NMP. Aluminum alloy foil having a thickness of 20μm and the resulting slurry on a (Mitsubishi Aluminum Co. N5-8X-073), was coated with a blade coater gap 200 .mu.m. After drying in the air under the conditions of this the 90 ℃ × 2hr, it was punched out into a disk shape with a diameter of 15mm. Next, after pressing at about 400 MPa, to produce a electrode according to Comparative Example 1 by 1 hour vacuum drying at 120. ° C.. Then, using an electrode according to Comparative Example 1 was prepared as a positive electrode (a positive electrode 901 shown in FIG. 9) to evaluate the charge-discharge characteristics by the three-electrode model cell.
[0064]
　Figure 9 shows a schematic configuration of a three-electrode model cells used in the characterization of the electrode for a lithium ion secondary battery. As shown in FIG. 9, the positive electrode 901 and the aluminum collector foil 902, a negative electrode Li plate 903, and a Li plate 904 of the reference electrode, is laminated with a separator 905 having a thickness of 30μm which is impregnated with an electrolytic solution, after sandwiched these two sheets made ​​of SUS jig 906, and the battery cells placed in a glass container. Electrolytic solution used was ethylene carbonate (EC) and volume ethyl methyl carbonate (EMC) ratio of 1: in a solvent were mixed in 2, lithium hexafluorophosphate (LiPF . 6 was used a) was dissolved 1 mol / L .
[0065]
　Evaluation of charge-discharge property was carried out at room temperature using the same equipment as above. Discharge was performed at CC (Constant Current) mode, the cell voltage is set to 1.5 ~ 4.2 V, it was started from discharging. Current density during charge and discharge, first time 0.057MA / cm 2 and, the second and subsequent cycles 0.28MA / cm 2 was. Incidentally, the charge-discharge capacity of the positive electrode, the resulting discharge capacity was a value obtained by dividing the mixture mass consisting of glass powder and conductive aid and a binder.
[0066]
　The next it was confirmed as an evaluation of the charge / discharge characteristics.
　Electrodes according to Example 1 (positive electrode) charge and discharge capacity retention after 51 cycles of charge and discharge capacity is improved life-and-death had improved compared to the electrode (positive electrode) according to Comparative Example 1.
　Specifically, in the lithium ion secondary battery using the electrode according to Comparative Example 1 as the positive electrode, the initial charge-discharge capacity is 320 mAh / g, the charge-discharge capacity after 51 cycles was 260 mAh / g. That is, the charge and discharge capacity retention rate after 51 cycles was 81%.
　In contrast, in the lithium ion secondary battery using the electrode according to Example 1 as the positive electrode, the initial charge-discharge capacity is 345 mAh / g, the charge-discharge capacity after 51 cycles was 331mAh / g. That is, the charge and discharge capacity retention rate after 51 cycles was 96%.
[0067]
　Further, after performing the [1] to [2] under the same conditions, the conditions of [3], in particular, that carried out the irradiation time of microwaves varied between 0 to 15 minutes, for amorphous the volume fraction of crystals was varied between 0 and 100%, as in the following table 1 No. It was produced electrode according to the 1 to 6. Of the following Table 1, No in. Electrode according to 3 is the same as the electrode according to Example 1 described above. No. Each of the electrodes according to the 1,2,4,5 treated under the same conditions as [4] were evaluated for charge-discharge characteristics by the bipolar model cell described in [5]. Table volume fraction of the crystal with respect to the amorphous to each electrode 1 (%) indicates the initial charge discharge capacity (mAh / g) and the charge-discharge capacity retention ratio after 51 cycles (%).
[0068]
[Table 1]

[0069]
　As shown in Table 1, the volume fraction of the crystal with respect to the amorphous was 0% No. Electrode according to 1, although the initial charge-discharge capacity as compared with other electrodes slightly lower, the charge and discharge capacity retention rate after 51 cycles was maintained 100%, was very good. Therefore, the volume fraction of 0% of the crystal with respect amorphous, i.e., if the vanadium oxide coating is amorphous, it is strongly suggested is suitable for providing a lithium ion secondary battery of long life It was.
　No. volume fraction of the crystal to the amorphous was 94% Electrode according to 4 has a high initial charge capacity, because also was relatively good charge and discharge capacity retention rate after 51 cycles, suggesting that is suitable for providing a high charge-discharge capacity lithium ion secondary battery It was.
　On the other hand, the volume fraction of the crystal with respect amorphous exceeds 94% No. Electrode according to the 5 and 6, was a result both of the initial charge and discharge capacity and the charge-discharge capacity retention rate after 51 cycles not good.
[0070]
Characterization of [6] Magnesium ion secondary battery electrode
　is then deposited vanadium oxide coating on the surface of the aluminum alloy foil under the same conditions as described in [3] to [1], of magnesium ions without pre-doping, as described in [5], punched into a disk shape having a diameter of 15 mm, was prepared an electrode according to example 2. Used as a positive electrode (shown in FIG. 10 as the positive electrode 1001) to evaluate the charge-discharge characteristics by the three-electrode model cell.
[0071]
　Figure 10 shows a schematic configuration of a three-electrode model cells used in the characterization of the magnesium ion secondary battery electrode. As shown in FIG. 10, the positive electrode 1001 and the aluminum collector foil 1002, a magnesium alloy (AZ31 alloy) anode 1003, and a magnesium alloy (AZ31 alloy) plate 1004 of the reference electrode, the thickness 30μm of the impregnated electrolytic solution It is layered with a separator 1005, after sandwiching them with two SUS-made jig 1006, and the battery cells placed in a glass container. Electrolytic solution used was, 0.4mol% / L of Mg (ClO 4 ) 2 and NaClO in% 0.1 mol / L 4 with a PC solution containing.
[0072]
　Charge and discharge evaluation, similar to the above, by using a charge-discharge tester (manufactured by Toyo System Co., Ltd. TOSCAT3100U) was performed at room temperature, it was started from charging. Discharge was performed at CC (Constant Current) mode, the cell voltage was 0.5 ~ 3.0V. The current density during charge and discharge, first time 0.057MA / cm 2 and, the second and subsequent cycles 0.28MA / cm 2 was.
[0073]
　On the other hand, it was produced electrodes for comparison with the electrode according to Example 2 in a conventional manner. Such electrodes, and the glass powder prepared in (1), as a conductive auxiliary agent, Ketjen black (Lion Co., Ltd. EC600JD, particle size: 34.0nm or less) and, as a binder, N- methyl-2- Pirodorin ( and NMP) to 5 wt% dissolved polyvinylidene fluoride (PVDF) (manufactured by Kureha Corporation # 7305), a mass ratio of 85: 5 were mixed using a mortar in a 10 ratio. At this time, for viscosity adjustment, and slurried with mixing appropriately NMP. Aluminum alloy foil having a thickness of 20μm and the resulting slurry on a (Mitsubishi Aluminum Co. N5-8X-073), was coated with a blade coater gap 200 .mu.m. After drying in the air under the conditions of this the 90 ℃ × 2hr, it was punched out into a disk shape with a diameter of 15mm. Next, after pressing at about 400 MPa, to produce a electrode according to Comparative Example 2 by 1 hour vacuum drying at 120. ° C.. Then, using an electrode according to Comparative Example 2 was prepared as a positive electrode were evaluated for charge-discharge characteristics by the same model cell and conditions and three-electrode model cell described with reference to FIG.
[0074]
　The next it was confirmed as an evaluation of the charge / discharge characteristics.
　Electrode according to Example 2 (positive electrode) charge and discharge capacity retention after 10 cycles of charge and discharge capacity is improved life-and-death had improved compared to the electrode (positive electrode) according to Comparative Example 2.
　Specifically, the magnesium ion secondary battery using the electrode according to Comparative Example 2 as the positive electrode, the initial charge-discharge capacity is 250 mAh / g, the charge-discharge capacity after 10 cycles was 175 mAh / g. That is, the charge and discharge capacity retention rate after 10 cycles was 70%.
　In contrast, in the magnesium ion secondary battery using the electrode according to Example 2 as the positive electrode, the initial charge-discharge capacity is 300 mAh / g, the charge-discharge capacity after 10 cycles was 285 mAh / g. That is, the charge and discharge capacity retention rate after 10 cycles was 95%.
Description of the code
[0075]
　101 ion secondary battery electrode
　(electrode) 102 conductor
　103 vanadium oxide film
　(coating) 201 coating film forming apparatus
　202 gas supply device
　203 gas supply pipe
　204 gas heater
　205 working gas supply pipe
　206 spray nozzle
　207 glass powder supply apparatus
　208 glass powder supply tube
　301 ion secondary battery electrode
　302 conductor
　303 vanadium oxide film
　(coating) 401 crystal
　402 amorphous
　501 crystal
　502 amorphous
　601 double chain of VO 6 octahedra
　701 lithium-ion secondary next battery
　702 positive electrode
　703 positive electrode current collector
　704 negative electrode
　705 negative electrode current collector
　706 container
　707 electrolyte
　708 separator
　709 lid
　710 gasket
　801 positive electrode
　802 aluminum collector foil
　803 negative electrode
　804 copper collector foil
　805 separator
　806 SUS-made jig
　901 positive electrode
　902 aluminum collector foil
　903 the negative electrode of the Li plate
　904 reference electrode of Li plate
　905 separator
　906 SUS-made jig
　1001 positive
　1002 aluminum collector foil
　1003 magnesium alloy (AZ31 alloy) negative electrode
　1004 reference magnesium pole alloy (AZ31 alloy) plate
　1005 separator
　1006 SUS-made jig
The scope of the claims
[Claim 1]
　On the surface of the conductor-ion secondary battery electrode, characterized in that provided vanadium oxide coating.
[Claim 2]
　An ion secondary battery electrode according to claim 1,
　wherein the vanadium oxide coating is selected vanadium, phosphorus, copper, silver, iron, from alkaline earth metals and alkali metals at least one element and the ion secondary battery electrode which is characterized by containing that.
[Claim 3]
　An ion secondary battery electrode according to claim 1,
　wherein the vanadium oxide coating, ion secondary battery electrode which is characterized by containing the crystal and amorphous.
[Claim 4]
　An ion secondary battery electrode according to claim 3,
　ion secondary battery volume fraction of crystalline to non-crystalline of the vanadium oxide in the film is equal to or less than 94% use electrode.
[Claim 5]
　An ion secondary battery electrode according to claim 3,
　ion secondary battery electrode, wherein a main crystal in the vanadium oxide coating is monoclinic.
[6.]
　An ion secondary battery electrode according to claim 3,
　ion secondary battery electrode wherein the crystal of the vanadium oxide in the film is characterized in that oriented.
[7.]
　A range Sixth ion secondary battery electrode according to the preceding claims,
　which is perpendicular to the [100] crystal orientation of the oriented with the vanadium oxide coating in the crystal surface of the conductor ion secondary battery electrode, characterized in that.
[8.]
　An ion secondary battery electrode according to claim 1,
　wherein the vanadium oxide coating, ion secondary battery electrode, which is a amorphous.
[9.]
　An ion secondary battery electrode according to claim 1,
　ion secondary battery electrode, characterized in that irregularities in the vanadium oxide coating surface is formed.
[10.]
　An ion secondary battery electrode according to claim 1,
　ion secondary battery electrode of lithium ions in the vanadium oxide coating is characterized in that it is pre-doped.
[11.]
　An ion secondary battery electrode according to claim 1,
　wherein the conductor, and wherein aluminum, aluminum alloy, copper, that are formed of at least one of a copper alloy and carbon ion secondary battery electrode.
[12.]
　A manufacturing method of claims ion secondary battery electrode for producing an ion secondary battery electrode according from the first term to any one of claims 11 wherein,
　the surface of the conductor, vanadium method of manufacturing ion secondary battery electrode, which comprises a step of spraying a powdered spray material including an oxide providing a vanadium oxide coating.
[13.]
　A manufacturing method of an ion secondary battery electrode according to claim 12,
　after the step, the conductor provided with the vanadium oxide coating, heated at the crystallization temperature of the vanadium oxide coating method of manufacturing ion secondary battery electrode, which comprises a step of.
[14.]
　Range lithium ion secondary battery characterized by using an ion secondary battery electrode according from the first term to any one of claim 11 to claim.
[15.]
　Magnesium ion secondary battery characterized by using an ion secondary battery electrode according to any one of claims claim 1 from paragraph 11.
It corrected the scope of the claims (Convention Article 19)
[May 24, 2012 (24.05.2012) The International Bureau acceptance]
[1]
[Corrected] on the surface of the conductor-ion secondary battery electrode, characterized in that provided vanadium oxide film formed by softening.
[2]
[Corrected] An ion secondary battery electrode according to claim 1,
　wherein the vanadium oxide coating, and vanadium, containing phosphorus, copper, silver, iron, alkaline earth metal and ion secondary cell electrode characterized by containing at least one element selected from alkali metals.
[3]
　An ion secondary battery electrode according to claim 1,
　wherein the vanadium oxide coating, ion secondary battery electrode which is characterized by containing the crystal and amorphous.
[4]
　An ion secondary battery electrode according to claim 3,
　ion secondary battery volume fraction of crystalline to non-crystalline of the vanadium oxide in the film is equal to or less than 94% use electrode.
[5]
　An ion secondary battery electrode according to claim 3,
　ion secondary battery electrode, wherein a main crystal in the vanadium oxide coating is monoclinic.
[6]
　An ion secondary battery electrode according to claim 3,
　ion secondary battery electrode wherein the crystal of the vanadium oxide in the film is characterized in that oriented.
[7]
　A range Sixth ion secondary battery electrode according to the preceding claims,
　which is perpendicular to the [100] crystal orientation of the oriented with the vanadium oxide coating in the crystal surface of the conductor ion secondary battery electrode, characterized in that.
[8]
　An ion secondary battery electrode according to claim 1,
　wherein the vanadium oxide coating, ion secondary battery electrode, which is a amorphous.
[9]
　An ion secondary battery electrode according to claim 1,
　ion secondary battery electrode, characterized in that irregularities in the vanadium oxide coating surface is formed.
[10]
　An ion secondary battery electrode according to claim 1,
　ion secondary battery electrode of lithium ions in the vanadium oxide coating is characterized in that it is pre-doped.
[11]
　An ion secondary battery electrode according to claim 1,
　wherein the conductor, and wherein aluminum, aluminum alloy, copper, that are formed of at least one of a copper alloy and carbon ion secondary battery electrode.
[12]
　A manufacturing method of claims ion secondary battery electrode for producing an ion secondary battery electrode according from the first term to any one of claims 11 wherein,
　the surface of the conductor, vanadium method of manufacturing ion secondary battery electrode, which comprises a step of spraying a powdered spray material including an oxide providing a vanadium oxide coating.
[13]
　A manufacturing method of an ion secondary battery electrode according to claim 12,
　after the step, the conductor provided with the vanadium oxide coating, heated at the crystallization temperature of the vanadium oxide coating method of manufacturing ion secondary battery electrode, which comprises a step of.
[14]
　Range lithium ion secondary battery characterized by using an ion secondary battery electrode according from the first term to any one of claim 11 to claim.
[15]
　Magnesium ion secondary battery characterized by using an ion secondary battery electrode according to any one of claims claim 1 from paragraph 11.