JP2011249254A - Positive electrode body for nonaqueous electrolyte battery and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive electrode body and manufacturing method thereof for producing a nonaqueous electrolyte battery whose discharge capacity is large and in which cycle characteristics and high rate discharge characteristics are excellent.SOLUTION: A positive electrode body for a nonaqueous electrolyte battery includes: a porous collector made of metal; and a positive electrode active material phase which is supported in a gap of the porous collector. The positive electrode active material phase has a group of particles of a positive electrode active material and solid electrolyte coagulating the group of the particles. In addition, parts of contour lines of the neighboring particles run along one another, which interpose the solid electrolyte. An oxygen amount of a surface of the porous collector contacting the positive electrode active material phase is 3.1 wt.% or less.

Description

  The present invention relates to a positive electrode body used for a positive electrode layer of a nonaqueous electrolyte battery and a method for producing the same.

  As a power source for electric devices such as portable information terminals, electric vehicles, and household power storage devices, a positive electrode layer having a positive electrode current collector and a positive electrode active material layer, and a negative electrode layer having a negative electrode current collector and a negative electrode active material layer In addition, a nonaqueous electrolyte battery including an electrolyte layer disposed between these electrode layers is used. Among nonaqueous electrolyte batteries, a lithium ion battery that charges and discharges by movement of lithium ions between positive and negative electrodes is particularly excellent in charge and discharge characteristics. Therefore, research and development of lithium ion batteries are being actively conducted.

  For example, Patent Literature 1 discloses a technique of using a sintered body of a lithium composite oxide for a positive electrode active material layer of a nonaqueous electrolyte battery. Thereby, it is disclosed that the conductivity, the active material filling density and the reaction area at the positive electrode are increased, the charge / discharge efficiency of the battery is improved, and the energy density is improved.

  By the way, the case where an aluminum foil is used for the positive electrode current collector constituting the positive electrode layer is known, and the case where a porous metal body having three-dimensional porosity is used. As the porous metal body, an aluminum nonwoven fabric entangled with fibrous aluminum and an aluminum foam made by foaming molten aluminum metal are known. As an example of the aluminum foam, Patent Document 2 discloses a method for producing an aluminum foam in which a foaming agent and a thickener are added and stirred in a state where aluminum metal is melted. This aluminum foam contains a large number of closed cells (closed pores) due to the characteristics of the manufacturing method.

  As a porous metal body, a nickel porous body having continuous air holes and a porosity of 90% or more is widely known. A nickel porous body is manufactured by forming a nickel layer on the surface of a foamed resin skeleton having communicating holes such as urethane foam, then pyrolyzing the foamed resin, and then reducing the oxidized nickel by thermal decomposition. Has been. In this manufacturing method, the nickel layer is formed on the surface of the foamed resin skeleton by applying carbon powder or the like to the surface of the foamed resin skeleton and conducting a conductive treatment, and then depositing nickel by electroplating. Yes. However, when this nickel porous body is used as a positive electrode current collector of an organic electrolyte-based lithium ion battery, when the potential of the nickel porous body becomes noble, the resistance to electrolytic solution of the nickel porous body is poor. Has been pointed out. On the other hand, when the material of the positive electrode current collector is aluminum, such a problem does not occur.

  In view of this, a method for producing a porous aluminum body using a method for producing a nickel porous body has also been developed. For example, Patent Document 3 states that “a eutectic alloy is formed on a foamed resin skeleton having a three-dimensional network structure at a temperature lower than the melting point of Al by a vapor phase method such as a plating method, a vapor deposition method, a sputtering method, or a CVD method. After forming a film made of a metal to be applied, a paste mainly composed of Al powder, a binder, and an organic solvent is impregnated and applied to the foamed resin formed with the film, and then 550 ° C. or higher and 750 ° C. or lower in a non-oxidizing atmosphere. Discloses a method for producing a porous metal body that is heat-treated at a temperature of 5 ° C.

JP-A-8-180904 JP 2002-371327 A JP-A-8-170126

  However, in a nonaqueous electrolyte battery in which the positive electrode active material layer is formed of a sintered body, there is a possibility that sufficient discharge capacity cannot be obtained. This is because the electron conductivity and lithium ion conductivity at the grain boundary interface of the positive electrode active material are low. In addition, as the battery is charged and discharged, the positive electrode active material layer made of a sintered body repeatedly expands and contracts, and the positive electrode active material layer is damaged such as cracking, or the positive electrode active material layer is bonded to the positive electrode current collector. May peel off. In particular, when the battery is discharged at a high rate, the above problem tends to be remarkable. When such a malfunction occurs, the battery is likely to have a reduced discharge capacity (so-called battery with poor cycle characteristics) according to the charge / discharge cycle.

  As a measure for preventing such a battery having poor cycle characteristics, an attempt has been made to prevent cracking and breakage by three-dimensionally surrounding the positive electrode active material layer with a positive electrode current collector. However, it was found that if a nickel porous body is used, the above-described problem of poor resistance to electrolyte solution occurs, and even if a porous current collector made of aluminum is used, another problem arises. .

  That is, among the porous current collectors, the aluminum foam has closed pores and is not suitable for use as a current collector. This is because the entire surface cannot be used effectively. With regard to aluminum porous bodies in which the nickel porous body manufacturing method is applied to aluminum, it is necessary to heat the aluminum to a temperature equal to or higher than the melting point in the manufacturing method. It is easy to form an oxide film on the surface. Therefore, such a conventional aluminum porous body has a large amount of oxygen on its surface. That is, an oxide is formed on the surface of the aluminum porous body. Thus, the positive electrode using an aluminum porous body rich in oxides as a positive electrode current collector has a problem that discharge characteristics are inferior when used in a non-aqueous electrolyte battery. In addition, a metal that forms a eutectic alloy below the melting point of aluminum must be included in the porous aluminum body.

The present invention has been made in view of the above problems, and its object is to produce a nonaqueous electrolyte battery having a large discharge capacity and excellent cycle characteristics, and further a nonaqueous electrolyte battery excellent in high rate discharge characteristics. An object of the present invention is to provide a positive electrode body and a manufacturing method thereof.

(1) The present invention is a positive electrode body for a non-aqueous electrolyte battery comprising a porous current collector made of a metal and a positive electrode active material phase carried in a pore portion of the porous current collector, The positive electrode active material phase has a group of particles of the positive electrode active material and a solid electrolyte that hardens these particle groups, and a part of the contour line between adjacent particles is along each other via the solid electrolyte, The amount of oxygen on the surface of the porous current collector in contact with the positive electrode active material phase is 3.1% by mass or less.

  In the positive electrode body of the present invention, the conduction of lithium ions between adjacent active material particles can be ensured by the solid electrolyte disposed in the gap between the plastically deformed positive electrode active material particles in the positive electrode active material phase. Originally, the lithium ion conductivity at the interface between the positive electrode active material particles in contact with each other is greatly inferior to the lithium ion conductivity in the particles, so that simply contacting the particles results in a positive electrode body with low lithium ion conductivity. .

  On the other hand, if the solid electrolyte is arranged in the gap between the particles as in the positive electrode body of the present invention, the exchange of lithium ions between the adjacent particles becomes smooth, so that the discharge capacity of the battery is improved. be able to. When the active material particles are sintered, the lithium ion conductivity at the grain boundary interface is higher than simply bringing the particles into contact with each other, but lower than interposing the solid electrolyte between the particles as in the present invention.

  Further, in the configuration of the present invention, stress due to expansion / contraction of the positive electrode active material can be absorbed by the solid electrolyte disposed in the gap between the positive electrode active material particles, and therefore the positive electrode body of the present invention is used for a non-aqueous electrolyte battery. In this case, the cycle characteristics of the battery can be improved.

  Further, in the configuration of the present invention, in the positive electrode active material phase of the positive electrode body of the present invention, the active material particles are plastically deformed so that part of the contour lines of the particles are aligned with each other. Will improve. As a result of the alignment through the solid electrolyte, the distance between the particles is also uniform. As a result, when the positive electrode body of the present invention is used for a nonaqueous electrolyte battery, an increase in the internal resistance of the battery can be suppressed, and the discharge capacity of the battery can be improved. In addition, the positive electrode active material particles are cracked by plastic deformation, and the expansion and contraction of the particles accompanying charging / discharging of the battery can be absorbed by the cracks.

  Further, according to the configuration of the present invention, since the positive electrode active material phase is formed in the void portion of the porous current collector, the current collector can be brought into contact with the positive electrode active material phase in three dimensions. . That is, in the configuration of the present invention, the current collection area can be increased as compared with the use of a non-porous layered or plate-like current collector, so that the current density of the battery can be improved. And since a porous electrical power collector plays the role of frame | skeleton and suppresses the crack of the positive electrode body resulting from expansion | swelling and shrinkage | contraction of a positive electrode active material phase, the cycling characteristics of a battery can be improved.

  Furthermore, in the configuration of the present invention, since the amount of oxygen on the surface of the porous current collector is 3.1% by mass or less, no metal oxide is generated on the surface of the porous current collector. Electronic transfer is performed quickly. Therefore, the positive electrode for nonaqueous electrolyte batteries of the present invention is excellent in discharge characteristics. The amount of oxygen here is specified by EDX analysis of the surface of the porous body current collector with an acceleration voltage of 15 kV. A specific measuring method will be described later.

  In order to set the oxygen content on the surface of the porous current collector to 3.1 mass% or less, as described later in (7), in the step of manufacturing the porous current collector, “immerse the resin in the molten salt”. In this state, it is necessary to perform thermal decomposition while keeping the metal layer at a lower potential than the standard electrode potential of the metal. By passing through such a manufacturing method, the amount of oxygen on the surface of the porous current collector can be suppressed to be equal to or less than the detection of EDX decomposition. The term “below detection of decomposition of EDX” means that the amount of oxygen on the surface of the porous body current collector is 3.1 mass% or less.

(2) The positive electrode body for a nonaqueous electrolyte battery according to the present invention is characterized in that the porous current collector is made of aluminum.

  In the case of a porous current collector made of aluminum, even if the positive electrode body for a nonaqueous electrolyte battery of the present invention is used for an organic electrolyte-based nonaqueous electrolyte battery and the potential of the positive electrode is made noble, There is no problem in the resistance to electrolyte of the porous current collector.

(3) The nonaqueous electrolyte battery of the present invention is characterized in that the porous current collector has a hollow fiber skeleton.

  The porous current collector used in the present invention is manufactured by a manufacturing method as described in (7) below, and the portion that was originally a resin finally becomes a hollow state, so the porous current collector The body skeleton has a hollow fiber shape. In this respect, the porous current collector used in the positive electrode for a non-aqueous electrolyte battery of the present invention has a structure different from that of a conventional foam (for example, an aluminum foam).

(4) The present invention is a positive electrode body for a non-aqueous electrolyte battery comprising a porous current collector made of a metal and a positive electrode active material phase carried in the pores of the porous current collector, The positive electrode active material phase has a group of particles of the positive electrode active material and a solid electrolyte that hardens these particle groups, and a part of the contour line between adjacent particles is along each other via the solid electrolyte, The porous current collector has communication holes, does not have closed pores, and the porous current collector is made of only aluminum.

  In the positive electrode body of the present invention, as described above, in the positive electrode active material phase, lithium ion conduction between adjacent active material particles is ensured by the solid electrolyte disposed in the gap between the plastically deformed positive electrode active material particles. Can do. Further, since the porous current collector has communication holes but does not have closed pores, the entire surface is used for contact with the active material, and the efficiency is high. Furthermore, since the porous current collector is made of only aluminum, even if the positive electrode body of the present invention is used in an organic electrolyte-based nonaqueous electrolyte battery and the positive electrode potential is made noble, the electrolyte solution of the porous current collector No problem with sex.

  In the present invention, in order to make “the porous current collector has communication holes, no closed pores, and the porous current collector is made of only aluminum”, as described in (7) below In the process of manufacturing a porous current collector, it is necessary to “decompose the aluminum layer corresponding to the metal layer by heating and decomposing while maintaining the potential lower than the standard electrode potential of aluminum in a state where the resin is immersed in the molten salt”. is there.

  In addition, the description “consisting only of aluminum” in the present invention is not intended to exclude from the scope of the present invention the case where elements other than aluminum are inevitably contained.

(5) In the positive electrode body of the present invention, the area ratio of the solid electrolyte in an arbitrary cross section of the positive electrode active material phase is preferably 20% or less.

  When the proportion of the solid electrolyte in the positive electrode active material phase is within the above range, a sufficient amount of active material particles can be secured in the positive electrode active material phase. As the proportion of the active material particles increases, the capacity as a battery improves, but a solid electrolyte that mediates the conduction of lithium ions between the particles must also be secured, so the area proportion of the solid electrolyte is 5% or more. It is preferable to do.

(6) The positive electrode body of the present invention preferably has a porosity of 90 to 98% by volume, which is the proportion of the pores in the porous current collector.

  The setting of the porosity is determined in consideration of the volume ratio of both in a general battery including a plate-like positive electrode current collector and a positive electrode active material layer. For example, in the case of a battery for high output use, the volume of the plate-like positive electrode current collector: the volume of the positive electrode active material layer = 1: 7 to 1:12, so the positive electrode body of the present invention is referred to with reference to this volume ratio. When the porosity of the porous current collector is set to 90 to 98% by volume in producing the positive electrode body of the present invention, the positive electrode body of the present invention can be used for a battery for high output use. When the porosity is in the above range, the active material component and the current collecting component in the positive electrode body are well balanced. Therefore, if this positive electrode body is used, a high output battery can be produced. A more preferable porosity is 95 to 98% by volume.

(7) The manufacturing method of the positive electrode body of the present invention is a manufacturing method of a positive electrode body for a non-aqueous electrolyte battery, and includes the following steps.

A step of preparing an alkoxide solution in which a metal alkoxide or a hydrolyzate of metal alkoxide that becomes a lithium ion conductive solid electrolyte by condensation polymerization is dissolved in a solvent.
A step of preparing a raw material sol by mixing active material particles in the alkoxide solution.
-Forming a metal layer on the surface of the resin having communication holes, and thermally decomposing the resin while maintaining the metal layer at a base potential lower than the standard electrode potential of the metal while the resin is immersed in a molten salt A step of obtaining a porous current collector made of metal by
A step of filling the raw material sol in the pores of the porous current collector.
-By forming a solid electrolyte by polycondensation of the metal alkoxide or metal alkoxide hydrolyzate contained in the raw material sol by heat treatment, a positive electrode active material phase formed by solidifying the active material particles with the solid electrolyte is formed in the pores. Process.
A process of pressurizing the positive electrode active material phase and plastically deforming each particle so that a part of the contour line between adjacent particles in the positive electrode active material phase passes along the solid electrolyte.

  According to the manufacturing method including the above steps, the positive electrode body of the present invention having a large discharge capacity and excellent cycle characteristics can be manufactured.

  Here, in the manufacturing method of the positive electrode body of the present invention, since the positive electrode active material phase is formed from the raw material sol, in the process of changing the metal alkoxide or its hydrolyzate contained in the raw material sol into a solid electrolyte, The solvent contained in volatilizes and a void is formed in the positive electrode active material phase. However, in the method for producing a positive electrode body of the present invention, the void portion is crushed when the positive electrode body is subjected to pressure treatment, so that the lithium ion conductivity of the positive electrode body is hardly lowered due to the void portion.

  In addition, if a porous current collector is used as in the production method of the present invention, the movement of the positive electrode active material particles is constrained in the void space that is a constricted space. Stress easily acts on the active material particles, and voids generated in the positive electrode active material phase are easily crushed. Moreover, since the amount of oxygen on the surface of the porous current collector is 3.1% by mass or less, the high rate discharge characteristics of the positive electrode body obtained by the production method of the present invention are excellent. In addition, since it serves as a skeleton that retains the shape of the positive electrode body after the pressure treatment, a void portion that is once crushed in the positive electrode active material phase is hardly formed.

  The resin used in the present invention may be arbitrarily selected as long as it is a material that is thermally decomposed at a temperature lower than the melting point of the metal constituting the porous current collector. For example, there are polyurethane, polypropylene, polyethylene and the like. Among these, urethane foam is preferable as the resin of the present invention because it has a high porosity and is easily pyrolyzed. The resin preferably has a porosity of 80% to 98% and a pore diameter of about 50 μm to 500 μm. The resin preferably has a communication hole. Thereby, a porous body current collector without closed pores is obtained.

(8) In the method for producing a positive electrode body of the present invention, the pressure treatment is preferably performed in the range of 100 to 1000 MPa.

  If pressurization is performed within this pressure range, the active material particles can be reliably plastically deformed. In addition, by pressurizing in this pressure range, almost all voids formed in the positive electrode active material phase can be crushed, so a dense positive electrode active material phase, that is, a positive electrode active material phase having a high discharge capacity per volume can be obtained. Can be formed.

(9) The non-aqueous electrolyte battery of the present invention is a non-aqueous electrolyte battery including a positive electrode body manufactured by the manufacturing method of the present invention as described above.

By setting it as a nonaqueous electrolyte battery provided with the positive electrode body manufactured with the manufacturing method of such an invention, it can be set as what has large discharge capacity and was excellent in cycling characteristics and high rate discharge characteristics. In addition, the nonaqueous electrolyte battery here includes both a primary battery and a secondary battery. In any case, the discharge characteristics are excellent.

By using the positive electrode body of the present invention produced by the method for producing the positive electrode body of the present invention, a battery having a large discharge capacity and excellent cycle characteristics and high rate discharge characteristics can be produced.

It is a schematic longitudinal cross-sectional view of a lithium ion battery (nonaqueous electrolyte battery) provided with the positive electrode body of this invention. It is a schematic diagram which shows typically the SEM photograph of the positive electrode active material phase with which the positive electrode body of this invention is equipped. It is the schematic diagram which showed the manufacturing process of the porous body electrical power collector 34 used for the positive electrode body of this invention. (A) shows a part of cross section of resin 31 which has a communicating hole. (B) shows a state where the metal layer 32 is formed on the surface of the resin 31 (metal layer coating resin 33). (C) shows the porous current collector 34 after the resin 31 disappears from the metal layer coating resin 33. 5 is a schematic diagram for explaining a decomposition process of the metal layer coating resin 33 in the molten salt 41. FIG. It is a cross-sectional SEM photograph of the porous electrical power collector which consists of aluminum used for the positive electrode body of this invention. It is a figure which shows the EDX analysis result of the porous electrical power collector which consists of aluminum used for the positive electrode body of this invention.

Hereinafter, an example in which the positive electrode body of the present invention is applied to a nonaqueous electrolyte battery will be described in detail. In addition, this invention is not necessarily limited to the following embodiment, In the range which does not deviate from the summary of this invention, it can change suitably.
<Overall configuration of nonaqueous electrolyte battery>

  FIG. 1 is a schematic longitudinal sectional view of a lithium ion battery (nonaqueous electrolyte battery). The lithium ion battery 100 includes a positive electrode layer 10, a negative electrode layer 20, and an electrolyte layer 30 disposed between the electrode layers 10 and 20. The positive electrode layer 10 includes a porous positive electrode current collector (porous current collector) 11 having pores, and a positive electrode active material phase 12 formed in the voids. The negative electrode layer 20 includes a negative electrode current collector 21 and a negative electrode active material layer 22.

  And this invention positive electrode body is utilized as the positive electrode layer 10 among the said battery structures. In the battery 100 as shown in FIG. 1, a known configuration can be used for the configuration other than the positive electrode layer 10 (that is, the positive electrode body of the present invention). Therefore, in the following description, it demonstrates centering around a positive electrode body.

<Method for producing positive electrode body>
The positive electrode body of the present invention is manufactured by a method including the following steps [1] to [6].
[1] A step of preparing an alkoxide solution in which a metal alkoxide or a hydrolyzate of metal alkoxide, which becomes a lithium ion conductive solid electrolyte by condensation polymerization, is dissolved in a solvent.
[2] A step of preparing a raw material sol by mixing active material particles in the alkoxide solution.
[3] Forming a metal layer on the surface of the resin having communication holes, and thermally decomposing the resin while maintaining the metal layer at a base potential lower than the standard electrode potential of the metal while the resin is immersed in a molten salt To obtain a porous current collector made of a metal.
[4] A step of filling the pores of the porous current collector with the raw material sol.
[5] A metal alkoxide or a hydrolyzate of metal alkoxide contained in the raw material sol is subjected to heat treatment to form a solid electrolyte, whereby a positive electrode active material phase in which active material particles are solidified with a solid electrolyte is formed in the pores. Forming step.
[6] A step of pressurizing the positive electrode active material phase and plastically deforming each particle so that a part of the contour line between adjacent particles in the positive electrode active material phase is along the solid electrolyte.

≪Process 1≫
Examples of the lithium ion conductive solid electrolyte include LiNbO ₃ , Li ₄ TiO ₁₂ , and LiTaO ₃ . The metal alkoxide to produce a solid electrolyte such as finally the by polycondensation, for example, preferably a combination of ethoxy lithium (LiOC ₂ H ₅₎ and pentaethoxyniobium _{(Nb (OC 2 H 5)} 5) If these are hydrolyzed and polycondensed, LiNbO ₃ is produced. In addition, to produce Li ₄ Ti ₅ O ₁₂ , for example, LiOC ₂ H ₅ and Ti (OC ₄ H ₉ ) ₄ can be used as the metal alkoxide. To produce LiTaO ₃ , for example, LiOC ₂ H ₅ and Ta (OC ₂ H ₅ ) ₅ can be used. On the other hand, as the hydrolyzate of metal alkoxide, a product obtained by hydrolyzing the metal alkoxide can be used.

  As a solvent for the alkoxide solution, when the solute is a metal alkoxide, for example, an alcohol solvent such as ethyl alcohol or methyl alcohol can be used. When the solute is a hydrolyzate of metal alkoxide, an aqueous solvent can be used, or a mixed solvent of an alcohol solvent and an aqueous solvent can be used.

  The concentration of the solute in the alkoxide solution is not particularly limited, but is preferably 5 to 30 mol / ml. The advantage of the concentration within this range will be described in the description of step 2 described later.

≪Process 2≫
Lithium-containing oxides can be used as positive electrode active material particles to be mixed with the alkoxide solution in preparing the raw material sol. As the lithium-containing oxide, a substance that can be represented by LiαO ₂ or Liβ ₂ O ₄ in a chemical formula is preferable (provided that α and β include at least one of Co, Mn, and Ni). Specifically, lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium cobalt nickelate (LiCo _0.3 Ni _0.7 O ₂ ), lithium manganate (LiMn ₂ O ₄ ), etc. It is done. Further, lithium titanate (Li ₄ Ti ₅ O ₁₂ ), lithium manganate compound (LiM _y Mn _{2 -y} O ₄ ; M = Cr, Co, Ni), lithium iron phosphate and its compound (LiFePO ₄ , LiFe _0. Transition metal oxide materials such as olivine compounds which are ₅ Mn _0.5 PO ₄ ). In addition, sulfide chalcogenides such as TiS ₂ , V ₂ S ₃ , FeS, FeS ₂ , LiMS _X (M is a transition metal such as Mo, Ti, Cu, Fe, Ni, or Sb, Sn, Pb). , TiO ₂ , Cr ₃ O ₈ , V ₂ O ₅ , MnO _{2, and the} like, and lithium metal oxides having a skeleton made of a metal oxide. The raw material sol may contain a conductive aid such as acetylene black.

  The concentration of the positive electrode active material particles in the raw material sol obtained by mixing the positive electrode active material particles in the alkoxide solution depends on the amount of the positive electrode active material in the positive electrode body to be produced and the solute (metal alkoxide or its hydrolyzate) in the alkoxide solution. What is necessary is just to select suitably by a density | concentration, However, It is preferable to set it as the range of about 5-50 g / ml in general. Here, when the concentration of the solute in the alkoxide solution in Step 1 is 5 to 30 mol / ml, the viscosity of the alkoxide solution is approximately 200 to 500 mPa · s. In this case, when the active material particles are mixed in the alkoxide solution in the present step 2, the active material particles can be easily dispersed uniformly in the raw material sol.

≪Process 3≫
Step 3 will be described with reference to FIG.

<< Step 3-1 >>
FIG. 3A is an enlarged schematic view showing a part of a cross section of a resin having communication holes, and shows a state in which holes are formed using the resin 31 as a skeleton. Here, as resin which has a communicating hole, foamed resin or the nonwoven fabric which entangled the fiber is used. As the material of the foamed resin, any resin can be selected as long as it can be decomposed at a temperature lower than the melting point of the metal constituting the metal layer formed on the surface. For example, there are polyurethane, polypropylene, polyethylene and the like. The porosity of the foamed resin is preferably 80% to 98%. The pore diameter of the foamed resin is preferably 50 μm to 500 μm. Urethane foam has a high porosity, high pore connectivity and high uniformity in pore diameter, and is excellent in thermal decomposability. Therefore, it is preferable to use urethane foam.

  Next, a metal layer 32 is formed on the surface of the resin 31 having communication holes, thereby obtaining a resin coated with the metal layer (FIG. 3B). Thereafter, when the resin 31 is thermally decomposed and disappeared from the metal layer coating resin 33, a metal porous body 34 in which only the metal layer 32 remains is obtained (FIG. 3C).

  As a method for forming a metal layer on the surface of the resin, (i) a vapor deposition method typified by a vacuum deposition method, a sputtering method or plasma CVD, (ii) a plating method, or (iii) an aluminum paste coating method is used. It is preferable.

  Regarding (i): In the vacuum vapor deposition method, a metal layer can be formed by melting and evaporating a metal and attaching it to the surface of a resin having communication holes. In the sputtering method, a metal layer can be formed by attaching a metal vaporized by plasma irradiation to a target metal to the surface of a resin having a communication hole. In the plasma CVD method, a metal layer can be formed by applying a high frequency to a metal as a raw material to form a plasma and attaching it to the surface of a resin having a communication hole.

About (ii): When forming an aluminum layer as a metal layer, it is preferable to perform molten salt electroplating which plating aluminum in molten salt. In this case, it is preferable to plate aluminum in a molten salt after conducting the conductive treatment on the surface of the resin. The molten salt used here may be the same as or different from the molten salt 41 used in steps 3-2 to 3-3 described later. For example, molten salts such as potassium chloride, aluminum chloride, and sodium chloride are preferred. Alternatively, a binary or multicomponent salt of AlCl ₃ —XCl (X: alkali metal) may be used and used as a eutectic molten salt. The eutectic molten salt is preferable because the melting temperature is lowered. This molten salt needs to contain at least aluminum ions.

  Regarding (iii): When applying a metal paste to the surface of the resin, the metal paste is, for example, a mixture of a metal powder, a binder (binder resin) and an organic solvent. Specifically, after applying the metal paste to the surface of the resin, heating is performed to eliminate the organic solvent and the binder resin, and the metal contained in the metal paste is sintered. Heating at the time of sintering may be performed in one step or in multiple steps. For example, the metal paste may be sintered at the same time as the decomposition of the foamed resin by applying the metal paste and heating at a low temperature to make the organic solvent disappear, and then immersing in molten salt and heating. The aluminum paste is preferably sintered in a non-oxidizing atmosphere.

<< Step 3-2 >>
Next, as shown in FIG. 4, the metal layer coating resin 33 and the positive electrode 42 are immersed in the molten salt 41, and the metal layer 32 is kept at a base potential lower than the standard electrode potential of the metal. Thereby, the oxidation of the metal layer 32 is suppressed. The potential at which the metal layer is to be maintained is baser than the standard electrode potential of the metal and nobler than the reduction potential of the cations in the molten salt. Here, the positive electrode 42 can be appropriately selected as long as it shows insolubility in the molten salt. For example, platinum, titanium, or the like is used.

<< Step 3-3 >>
In this state, when the molten salt 41 is heated above the decomposition temperature of the resin 31, only the resin 31 constituting the metal layer coating resin 33 is decomposed and disappears. As a result, a porous metal body 34 is obtained. When this is used for an electrode of a nonaqueous electrolyte battery and has a current collecting function, it is called a porous current collector.

  In this case, in order to prevent melting of the metal, the heating temperature needs to be lower than the melting point of the metal. For example, when selecting aluminum as a metal layer, it heats at 660 degrees C or less which is melting | fusing point of aluminum.

  The preferable value of the porosity (total ratio of all the holes occupied in the current collector) in the porous current collector is 90 to 98% by volume, and more preferably 95 to 98% by volume. A current collector with such a porosity can secure a sufficient current collecting area and can be filled with a raw material sol containing an amount required for a high-power battery.

≪Process 4≫
In Step 4, in order to fill the pores of the porous current collector with the raw material sol prepared in Step 2 described above, for example, the porous current collector is immersed in the raw material sol in the vacuum container, It may be evacuated. In this way, the raw material sol can be impregnated without leaving the pores of the porous current collector.

  In addition, as a method for filling the raw material sol into the porous current collector, a dip filling method or a coating method (for example, roll coating method, applicator coating method, electrostatic coating method, powder coating method, spraying method) Coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor blade coating method, wire bar coating method, knife coater coating method, blade coating method, screen printing method, etc.) .

≪Process 5≫
In order to hydrolyze and polycondensate metal alkoxide, or to polycondensate metal alkoxide hydrolyzate into a solid electrolyte, heat treatment may be performed. The heat treatment conditions are preferably 200 to 300 ° C. × 0.5 to 6 hours. When the solid electrolyte is generated at this temperature, the positive electrode current collector is not softened by heat and its strength is not reduced, and the positive electrode active material contained in the raw material sol is not decomposed. In addition, according to the heat treatment under this condition, the solid electrolyte tends to have an amorphous structure. Among solid electrolytes, LiNbO ₃ , LiTaO _{3, and the} like are superior in lithium ion conductivity in the amorphous structure than in the crystalline structure.

  By this step 5, a positive electrode body in which a positive electrode active material phase is formed so as to fill the pores of the porous current collector is produced. The active material particles in the positive electrode active material phase at the time when Step 5 is completed are in a state where they are in point contact with each other, and the lithium ion conductivity between the particles is low. Moreover, since it is such a state, the average distance of the clearance gap between particles is long. Lithium ion conductive solid electrolyte is arranged in the gaps between the particles, so that lithium ion conduction can be ensured, but if the average distance is long, the lithium ion conductivity of the whole positive electrode active material phase becomes low. End up. Moreover, voids formed by volatilization of the solvent of the raw material sol are generated in the positive electrode active material phase.

<< Step 6 >>
In order to pressurize the positive electrode body in which the positive electrode active material phase is formed in the pores of the porous current collector, the positive electrode body may be compressed from both sides. Specifically, pressure is applied in a direction in which the front surface and the back surface of the positive electrode body approach each other. By this pressurization, plastic deformation is performed so that some of the adjacent positive electrode active material particles in the positive electrode active material phase are along each other. At the same time, voids generated in the positive electrode active material phase in step 5 are also crushed and disappear. Here, since the positive electrode body of the present invention uses a porous current collector made of metal, the current collector serves as a skeleton, and the shape of the positive electrode body deformed by pressurization is maintained. .

  The pressure for the pressure treatment is preferably in the range of 100 to 1000 MPa. If pressure is applied within this range, the particles can be plastically deformed regardless of the type of active material particles, and voids can be almost eliminated.

<Positive electrode body>
The positive electrode body obtained through the above steps includes a positive electrode current collector made of metal and a positive electrode active material phase provided on one surface side of the positive electrode current collector. Further, the positive electrode active material phase has a group of particles of the positive electrode active material and a solid electrolyte that hardens the group of particles. And the state of the particle group in the positive electrode active material phase of this invention positive electrode body is as showing in FIG.

  FIG. 2 is a diagram schematically showing a cross section of the positive electrode active material phase provided in the positive electrode body of the battery A in Examples to be described later. As shown in FIG. 2, among the combinations of adjacent positive electrode active material particles 1 included in the positive electrode active material phase 12, there is a combination in which some of the contour lines are aligned. More specifically, there exists a combination of particles in which a pair of adjacent active material particles occupy 30% or more of the total length of the contour line of at least one of the pair of particles. Furthermore, the combination of particles in which a part of the contour lines of each other occupies 30% or more of all the combinations. Part of the contour line between the adjacent active material particles 1 is aligned with each other because the particles 1 are plastically deformed by compressing the positive electrode body so as to be sandwiched from both sides (see step 6 in the above manufacturing method). . Normally, each prepared particle has a different external shape, so if the particle is simply solidified with a solid electrolyte and is not pressurized (or if the pressure is weak), it is a small part of the contour line between the particles. Are rarely along each other. Even if a part of the contour line may be along, it is 5% or less of the contour line.

  The fact that the active material particles are plastically deformed can be confirmed by measuring a specific physical quantity in addition to visually confirming as described above. For example, using X-ray diffraction, it was confirmed that the peak of the active material particles in the pressurized positive electrode body was deviated from the peak of the active material particles as a raw material, thereby introducing strain into the active material particles. That is, it can be confirmed that the active material particles are plastically deformed.

<Battery configuration other than positive electrode layer>
≪Negative electrode layer≫
As described above, the negative electrode layer includes the negative electrode active material layer and the negative electrode current collector. The negative electrode active material layer is a layer made of a negative electrode active material such as Li, Si, In, or an alloy thereof. The negative electrode current collector is a layer made of a metal such as Al, Ni, or Fe, or an alloy thereof. However, depending on the selection of the negative electrode active material, the negative electrode active material layer itself can also serve as a current collector. In that case, the negative electrode current collector can be omitted.

≪Electrolyte layer≫
The electrolyte layer can be a sulfide solid electrolyte such as Li ₂ S—P ₂ S ₅ or an oxide solid electrolyte such as Li—P—O—N. The sulfide-based solid electrolyte may be composed only of lithium, phosphorus, and sulfur, and may further include other substances such as O, Al, B, Si, and Ge. The sulfide-based solid electrolyte can be obtained by a known method. For example, lithium sulfide (Li ₂ S) and diphosphorus pentasulfide (P ₂ S ₅ ) as raw materials are mixed in a ratio of 50:50 to 80:20, and then melted and rapidly cooled (melt quenching method). Or a mechanical milling process (MM process). The sulfide-based solid electrolyte obtained by these is amorphous. You may use it in this amorphous state, and also you may use it, after heat-processing and making it a crystalline sulfide type solid electrolyte.

The electrolyte layer can also be a non-aqueous organic electrolytic solution in which a lithium ion conductive material such as LiPF ₆ is dissolved in an organic solvent. In the case of an organic electrolytic solution, a separator (for example, polypropylene, polyethylene, etc.) that insulates both is disposed between the positive electrode layer and the negative electrode layer.

≪Others≫
When the electrolyte layer is a sulfide-based solid electrolyte, resistance may occur at the interface between the electrolyte layer and the positive electrode active material phase. Therefore, it is preferable to provide a buffer layer between the solid electrolyte layer and the positive electrode active material phase in order to reduce the interface resistance. As the buffer layer, a lithium-containing oxide (for example, LiNbO ₃ or the like) can be used.

  As an Example of this invention, the result of having evaluated this invention first using the battery A, the battery B, the battery C, the battery D, and the battery E by a solid electrolyte type lithium ion secondary battery is shown. Then, the result of having evaluated this invention using the battery F and the battery G by an electrolyte type lithium ion secondary battery is shown.

<Battery A>
<< Manufacture of Aluminum Porous Body >> A porous aluminum body was manufactured as a porous metal body. A polyurethane foam having a porosity of 97% and a pore diameter of about 300 μm was prepared as the resin. This was cut into 20 mm squares. An aluminum layer was formed on the surface of the polyurethane foam by vacuum deposition. As a result of SEM observation of the thickness of the aluminum layer, the thickness was 15 μm. Subsequently, the polyurethane foam having an aluminum layer formed on the surface is immersed in a LiCl—KCl eutectic molten salt at a temperature of 500 ° C., and the aluminum layer has a potential of −1 V with respect to the standard electrode potential of aluminum. For 30 minutes. At this time, bubbles were generated in the molten salt. This is presumed that the decomposition reaction of polyurethane occurs. The obtained porous aluminum body was cooled to room temperature in the air, and then washed with water to remove the molten salt. Thus, a porous current collector (aluminum porous body) used for battery A was obtained.

  An SEM photograph of the porous current collector (aluminum porous body) of Battery A is shown in FIG. From FIG. 5, it was found that the aluminum porous body has communication holes but no closed pores, and that the porosity is high. The surface of the porous current collector (aluminum porous body) of Battery A was subjected to EDX analysis at an acceleration voltage of 15 kV. The result is shown in FIG. Almost no oxygen peak was observed. Therefore, it was found that the oxygen content of the aluminum porous body was below the EDX detection limit (3.1 mass%). The apparatus used in this analysis was “EDAX Phoenix” manufactured by EDAX, and its model was HIT22 136-2.5.

<< Preparation of Positive Electrode >> After equimolar amounts of cobalt carbonate (CoCO ₃ ) powder and lithium carbonate (Li ₂ CO ₃ ) powder were mixed, the mixture was fired at 900 ° C. for 6 hours to obtain LiCoO ₂ powder. The average particle size (50% particle size) of the LiCoO ₂ powder was 10 μm.

Next, an alkoxide solution in which an equimolar mixture of ethoxylithium (LiOC ₂ H ₅ ) and pentaethoxyniobium (Nb (OC ₂ H ₅ ) ₅ ) was dissolved in an ethanol solvent was prepared. The content ratio of the equimolar mixture in the alkoxide solution was 15 mol / ml. The viscosity of the alkoxide solution was 200 mPa · s. A raw material sol was produced by mixing 100 g of LiCoO ₂ powder with 6 ml of the produced alkoxide solution. That is, the content ratio of LiCoO ₃ was 16.7 g / ml.

  A porous current collector (aluminum porous body) was immersed in the produced raw material sol and stored in a vacuum container, and the entire vacuum container was evacuated to 50 kPa. By this immersion and evacuation, the raw material sol was impregnated in the pores of the porous current collector (aluminum porous body). The porous collector had an average thickness of 100 μm and a porosity of 95% by volume.

Thereafter, the porous current collector filled with the raw material sol is heated in the atmosphere at 75 ° C. for 1 hour to remove the ethanol solvent contained in the raw material sol and hydrolyze / condense ethoxylithium and pentaethoxyniobium. And changed to LiNbO ₃ . As a result, a positive electrode body having a positive electrode active material phase fixed in a state where the particle groups of the positive electrode active material were dispersed almost uniformly in the solid electrolyte in the pores of the porous current collector was formed.

  Finally, the positive electrode body was pressed at 500 MPa so as to be sandwiched from both sides, thereby completing the positive electrode body of the present invention.

  When the cross section of the produced positive electrode was observed with a scanning electron microscope, it was observed that the positive electrode active material phase was formed so as to fill the pores of the porous current collector.

  FIG. 2 schematically shows an SEM photograph in a cross section of the positive electrode active material phase of the positive electrode body manufactured under the above conditions. When the state of the positive electrode active material particles 1 in the positive electrode active material phase 12 shown in FIG. 2 is observed in more detail, the active material particles 1 are plastically deformed, and some of the contour lines of the adjacent particles 1 are aligned with each other. It was. Further, the solid electrolyte 2 that hardens the positive electrode active material particles 1 was a homogeneous phase substantially free of grain boundaries. Further, in the observed visual field, no void portion was confirmed in the positive electrode active material phase 12. The area ratio of the solid electrolyte 2 in the cross section of the positive electrode active material phase 12 was about 3%, and the distance between adjacent particles 1 was almost 500 nm or less.

<< Production of Lithium Ion Battery >> Next, a lithium ion battery as a nonaqueous electrolyte battery was produced using the produced positive electrode body. First, each of the produced positive electrodes was used as a substrate, and a buffer layer made of LiNbO ₃ and having an average thickness of 10 nm was formed on one surface side by an excimer laser ablation method. The buffer layer lowers the resistance between the positive electrode layer 10 (more precisely, the positive electrode active material phase 12 exposed on one surface side of the positive electrode layer 10) and the solid electrolyte layer 30. A solid electrolyte layer 30 made of Li ₂ S + P ₂ S ₅ and having an average thickness of 10 μm was formed on the buffer layer by an excimer laser ablation method. Finally, a negative electrode active material phase 22 made of Li and having an average thickness of 4 μm was formed on the electrolyte layer 30 by a resistance heating method. Since the negative electrode active material phase 22 also serves as a current collector, the negative electrode current collector 21 was not provided.

<Battery B>
A lithium ion battery was prepared in the same manner as battery A, except that a nickel porous body was used as the porous current collector. Here, nickel cermet (registered trademark of Sumitomo Electric Industries, Ltd.), which is a Ni foam metal, was used as the nickel porous body. This nickel porous body had an average thickness of 100 μm and a porosity of 95% by volume. Further, as a result of EDX analysis of the surface of the porous current collector (nickel porous body) of the battery B with an acceleration voltage of 15 kV, the oxygen content of the nickel porous body is below the EDX detection limit (3.1 mass%). I found out.

<Battery C>
A lithium ion battery was produced in the same manner as battery A, except that a positive electrode body completed without forming pressure after forming a positive electrode active material phase in the pores of the aluminum porous body produced by battery A was used. did.

  When the state of the positive electrode active material particles in the positive electrode active material phase provided in the positive electrode body of the battery C was observed, the active material particles were not plastically deformed and the adjacent particles were in point contact. In addition, voids thought to be generated by volatilizing the solvent of the alkoxide solution were formed in the positive electrode active material phase. The area ratio of the solid electrolyte in the cross section of the positive electrode active material phase was about 3%. Moreover, since the pressurization process was not performed, most of the distance between adjacent particles was 1000 nm or more.

<Battery D>
A foamed urethane resin having a pore diameter of 200 μm to 500 μm, a porosity of 97%, and a thickness of 2.0 mm was prepared. This foamed urethane resin was placed in a vacuum deposition apparatus. An aluminum film was deposited on the surface of the foamed urethane resin by a vacuum deposition method in which aluminum metal was melted and evaporated by laser irradiation. Thereafter, the foamed urethane resin was thermally decomposed and removed by heat treatment at 550 ° C. in the atmosphere. Thereby, a porous current collector (aluminum porous body) of the battery D was obtained. The surface of the aluminum porous body of the battery D was subjected to EDX analysis at an acceleration voltage of 15 kV by the same method as in the case of the battery A. As a result, an oxygen peak was observed, and it was found that the amount of oxygen on the surface of the porous current collector (aluminum porous body) of battery D exceeded at least 3.1 mass%. This is because the surface of the porous current collector (aluminum porous body) was oxidized during the heat treatment.

  A battery D was produced in the same manner as the battery A, except that the porous current collector (aluminum porous body) used for the battery D was used.

<Battery E>
A battery of battery E was produced using a positive electrode body including a positive electrode active material layer made of a sintered body. The positive electrode body in the battery E was obtained by first preparing a positive electrode active material layer made of a sintered body and depositing a positive electrode current collector on one surface of the active material layer by a vapor phase method. The thicknesses of the active material layer and the current collector in the positive electrode body were each made equal to the volume of the porous current collector and the volume of the positive electrode active material phase when converted to volume. The battery configuration other than this positive electrode was the same as that of battery A.

<Performance evaluation of batteries A to E>
About the produced batteries A, B, C, D, and E, the discharge capacity (mAh / cm ² ) when charged to 4.2 V at a constant current of 0.05 mA and discharged at 3 V was measured. Also, the internal resistance of the battery was determined from the voltage drop at the start of discharge. Furthermore, the capacity maintenance rate (%) of each battery was measured. The capacity maintenance ratio is obtained by dividing the discharge capacity at the 100th cycle by the maximum discharge capacity in 100 cycles. The results of these measurements are shown in Table 1.

  As shown in Table 1, battery A had lower internal resistance, higher discharge capacity, and better cycle characteristics than battery C. Since the difference between the two batteries is whether the active material particles in the positive electrode active material phase are plastically deformed, it is clear that it is important to compress the positive electrode body until the active material particles are plastically deformed. became. Moreover, when the result of the battery B was considered, it was found that the same effect can be obtained even when the porous current collector is made of nickel.

  Battery A using a porous current collector having a surface oxygen content of 3.1% by mass or less has a higher discharge capacity than battery D having a surface oxygen content of more than 3.1% by mass. In particular, the discharge capacity was not decreased during high rate discharge (at 0.25 mA discharge). Furthermore, the battery A was superior in all of internal resistance, discharge capacity, and cycle characteristics as compared with the battery E using the positive electrode body made of a sintered body.

  Next, the battery F and the battery G using an organic electrolyte lithium ion secondary battery were evaluated by the following methods.

<Battery F>
As the positive electrode of the battery F, a positive electrode manufactured by the same method as the method of manufacturing the positive electrode of the battery A was used. As in the case of the battery A, a buffer layer having an average thickness of 10 nm made of LiNbO ₃ was formed on one surface side of the positive electrode body by an excimer laser ablation method. Next, a separator made of a microporous film having an average thickness of 20 μm and a negative electrode body made of a Li—Al alloy having an average thickness of 100 μm were prepared.

The above positive electrode body and negative electrode body were laminated through a separator, and finally, 1M-LiPF ₆ / EC: DEC (1: 1) was injected as an organic electrolyte. Thereby, the battery F was created.

<Battery G>
As the positive electrode of the battery G, a positive electrode body manufactured by the same method as that for manufacturing the positive electrode body of the battery B was prepared. Next, a separator made of a microporous film having an average thickness of 20 μm and a negative electrode body made of a Li—Al alloy having an average thickness of 100 μm were prepared.

The above positive electrode body and negative electrode body were laminated through a separator, and finally, 1M-LiPF ₆ / EC: DEC (1: 1) was injected as an organic electrolyte. Thereby, the battery G was created.

<Performance evaluation of batteries F and G>
A cycle test was performed on the battery F and the battery G. The conditions for the cycle test were as follows so that the potential of the positive electrode body was noble.
Charge: Constant current charge up to 4.4V at 0.03mA Discharge: Constant current discharge up to 3.0V at 0.03mA

  As a result, in the lithium ion secondary battery using the organic electrolyte, the battery F using the positive electrode current collector made of aluminum was superior to the battery G using the positive electrode current collector made of nickel. Specifically, the number of cycles until the discharge capacity is reduced to 50% of the initial discharge capacity was 1000 cycles in the battery F, and 750 cycles in the battery G. As described above, in the case of the 4.4V charge cycle test, which is a somewhat severe condition for the electrolyte-based lithium ion secondary battery, the battery using aluminum as the positive electrode current collector is more nickel than the positive electrode current collector. It was better than the battery to do.

The positive electrode body of the present invention produced by the method of manufacturing the positive electrode body of the present invention can be suitably used as a positive electrode layer of a nonaqueous electrolyte battery used for a power source of a portable device or an electric vehicle.

100 Lithium ion battery (non-aqueous electrolyte battery)
DESCRIPTION OF SYMBOLS 10 Positive electrode layer 11 Porous current collector 12 Positive electrode active material phase 20 Negative electrode layer 21 Negative electrode current collector 22 Negative electrode active material layer 30 Electrolyte layer 1 Positive electrode active material particle 2 Solid electrolyte 31 Resin 32 Metal layer 33 Metal layer covering resin 34 Porous Metal body (porous current collector)
41 Molten salt 42 Positive electrode

Claims (9)

A positive electrode body for a non-aqueous electrolyte battery comprising a porous current collector made of a metal and a positive electrode active material phase carried in the pores of the porous current collector,
The positive electrode active material phase has a group of particles of the positive electrode active material and a solid electrolyte that hardens these particle groups, and a part of the contour line between adjacent particles is along the solid electrolyte. ,
The positive electrode body for a nonaqueous electrolyte battery, wherein the amount of oxygen on the surface of the porous current collector in contact with the positive electrode active material phase is 3.1% by mass or less.   The positive electrode body for a nonaqueous electrolyte battery according to claim 1, wherein the porous current collector is made of aluminum.   The positive electrode body for a nonaqueous electrolyte battery according to claim 1, wherein the skeleton of the porous current collector is a hollow fiber shape. A positive electrode body for a non-aqueous electrolyte battery comprising a porous current collector made of a metal and a positive electrode active material phase carried in the pores of the porous current collector,
The positive electrode active material phase has a group of particles of the positive electrode active material and a solid electrolyte that hardens these particle groups, and a part of the contour line between adjacent particles is along the solid electrolyte. ,
The porous current collector has communication holes, no closed pores,
The positive electrode body for a non-aqueous electrolyte battery, wherein the porous current collector is made of only aluminum.   5. The positive electrode body for a non-aqueous electrolyte battery according to claim 1, wherein an area ratio of the solid electrolyte in an arbitrary cross section of the positive electrode active material phase is 20% or less.   The nonaqueous electrolyte battery according to claim 1, 2, 3, 4, or 5, wherein a porosity, which is a ratio occupied by a pore portion in the porous current collector, is 90 to 98% by volume. Positive electrode body. A method for producing a positive electrode body for a nonaqueous electrolyte battery, comprising:
A step of preparing an alkoxide solution in which a metal alkoxide or a hydrolyzate of metal alkoxide that becomes a lithium ion conductive solid electrolyte by condensation polymerization is dissolved in a solvent;
Mixing a positive electrode active material particle in the alkoxide solution to produce a raw material sol;
By thermally decomposing the resin while forming a metal layer on the surface of the resin having communication holes and maintaining the metal layer at a base potential lower than the standard electrode potential of the metal while the resin is immersed in a molten salt Obtaining a porous current collector made of metal;
Filling the raw material sol into the pores of the porous current collector;
By forming a solid electrolyte by polycondensation of the metal alkoxide or metal alkoxide hydrolyzate contained in the raw material sol by heat treatment, a positive electrode active material phase formed by solidifying the active material particles with the solid electrolyte is formed in the pores. Process,
Pressurizing the positive electrode active material phase, and plastically deforming each particle such that a part of the contour line between adjacent particles in the positive electrode active material phase passes along the solid electrolyte, and
The manufacturing method of the positive electrode body characterized by the above-mentioned.   The method for producing a positive electrode body for a non-aqueous electrolyte battery according to claim 7, wherein the pressure treatment is performed in a range of 100 to 1000 MPa.   A nonaqueous electrolyte battery comprising a positive electrode body produced by the production method according to claim 7 or 8.