JP2012186160A - Battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a structure for effectively using a novel metal porous body, such as an aluminum porous body, having a three-dimensional mesh structure, in a battery electrode.SOLUTION: In a secondary battery, at least one metal selected from the group consisting of an alkali metal, an alkali earth metal and aluminum is used for a negative electrode and an oxide or a sulfide, or a mixture thereof is used as a positive electrode active material. The battery uses an aluminum porous body having a three-dimensional mesh structure as a positive electrode collector. The aluminum porous body is preferably an aluminum skeleton with a substantially triangular prism shape, having a three-dimensional mesh-like structure and a cavity inside thereof, while a positive electrode active material is supported on a hole in a mesh.

Description

  The present invention relates to a battery using a metal porous body as a current collector.

  Metal porous bodies having a three-dimensional network structure are used in various fields such as various filters, catalyst carriers, and battery electrodes. For example, cermet made of nickel (manufactured by Sumitomo Electric Industries, Ltd .: registered trademark) is used as an electrode material for batteries such as nickel metal hydride batteries and nickel cadmium batteries. Celmet is a metal porous body having continuous air holes, and has a feature of high porosity (90% or more) compared to other porous bodies such as a metal nonwoven fabric. This can be obtained by forming a nickel layer on the surface of the porous resin skeleton having continuous air holes such as urethane foam, then heat-treating it to decompose the foamed resin molding, and further reducing the nickel. The formation of the nickel layer is performed by depositing nickel by electroplating after applying carbon powder or the like to the surface of the skeleton of the foamed resin molded body and conducting a conductive treatment.

  On the other hand, in a battery application, for example, aluminum is used as a positive electrode of a lithium ion battery in which an active material such as lithium cobaltate is applied to the surface of an aluminum foil. In order to improve the capacity of the positive electrode, it is conceivable that aluminum is made porous to increase the surface area and the aluminum is filled with an active material. This is because the active material can be used even if the electrode is thickened, and the active material utilization rate per unit area is improved.

  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 2 discloses a manufacturing method thereof. That is, “a film made of a metal that forms a eutectic alloy below the melting point of Al is formed on the framework of a foamed resin having a three-dimensional network structure by a vapor phase method such as a plating method, vapor deposition method, sputtering method, or CVD method. After that, the foamed resin formed with the above film is impregnated and coated with a paste mainly composed of Al powder, a binder and an organic solvent, and then heat-treated at a temperature of 550 ° C. to 750 ° C. in a non-oxidizing atmosphere. A “metal porous body manufacturing method” is disclosed.

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

  Although a plan to use an aluminum porous body as a battery electrode instead of an aluminum foil has been studied, there has been a problem in adopting any conventional aluminum porous body as a current collector for a battery electrode. Among the porous aluminum bodies, the aluminum foam has closed pores due to the characteristics of the production method, and therefore, even if the surface area is increased by foaming, the entire surface cannot be used effectively. In addition, the aluminum porous body described in Patent Document 2 described above has a problem that a metal that forms a eutectic alloy with aluminum must be included in addition to aluminum.

  The present invention has been made in view of such problems. An object of the present invention is to provide a structure for effectively utilizing a new aluminum porous body under development by the inventors of the present invention for a battery electrode as described later.

  The present inventors have intensively developed an aluminum structure having a three-dimensional network structure that can be widely used for battery applications including lithium ion secondary batteries. In the manufacturing process of the aluminum structure, the surface of a sheet-like foamed body such as urethane or melamine having a three-dimensional network structure is made conductive, and after the surface is subjected to aluminum plating, the urethane is removed.

  1st invention of this application uses the 1 type of metal chosen from the group which consists of an alkali metal, alkaline-earth metal, and aluminum for a negative electrode, and uses the oxide or sulfide, or these mixtures as a positive electrode active material. A battery using a porous aluminum body having a three-dimensional network structure as a positive electrode current collector (claim 1). The negative electrode metal may be any one of sodium, magnesium, calcium, and aluminum.

  By using the above-mentioned porous aluminum body as the positive electrode current collector of such a battery, the battery achieves a larger capacity than before, or improves the current collecting performance by shortening the distance between the current collector and the active material, etc. As a result, the performance desired to be improved can be realized.

  The porous aluminum body is composed of an aluminum skeleton configured in a three-dimensional network, and the aluminum skeleton is preferably a substantially triangular prism skeleton having a cavity inside. Such an aluminum porous body can be obtained by forming an aluminum layer on the surface of a skeleton of a porous resin having continuous ventilation holes such as foamed urethane, and then decomposing the foamed resin molded body by heat treatment. Formation of the aluminum layer is performed by depositing aluminum by electroplating after applying carbon powder or the like to the surface of the skeleton of the foamed resin molded body and conducting a conductive treatment. It is characterized by a high porosity (90% or more) compared to other porous bodies. In addition, since it has a cavity inside the skeleton, it is possible to support an active material in the cavity and to pass an electrolytic solution inside the cavity, thereby contributing to an improvement in battery performance.

  It is preferable to support the positive electrode active material in the pores in the network of such an aluminum porous body. Such a porous body has a high porosity, which is the ratio of the pores in the network, and by supporting an active material in the pores, a battery having a large capacity and excellent charge / discharge characteristics can be obtained. .

  According to the present invention, a battery in which a metal porous body is effectively used as a battery electrode can be obtained.

It is a schematic diagram explaining the fundamental structure of the battery by this invention. It is a figure which shows the structural example of the aluminum porous body used for this invention. It is a figure explaining the manufacturing process example of the aluminum porous body used for this invention. It is a cross-sectional schematic diagram explaining the example of a manufacturing process of the aluminum porous body used for this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. As an aluminum porous body, an aluminum structure having a three-dimensional network structure having a skeleton structure similar to that of nickel cermet (Celmet is a registered trademark) is specifically shown. In addition, this invention is not limited to this, It is shown by the claim, and it is intended that all the changes within the meaning and range equivalent to a claim are included.

(Battery configuration)
FIG. 1 is a diagram illustrating a basic configuration example of a battery according to the present invention. The overall configuration of the battery is as follows: a negative electrode composed of a negative electrode current collector 1 and a negative electrode active material layer 2, a separator 4 holding an electrolytic solution 3 in a void portion, and a positive electrode active material 5 as a positive electrode current collector 6 (aluminum cermet). The positive electrodes held in the hole portions are sequentially laminated. The storage container, the lead electrode, and the like are of course necessary as a normal battery structure, but are not illustrated or described here. Further, the electrolytic solution 3 is also retained in the negative electrode and the positive electrode.

  The negative electrode current collector 1 is not particularly limited as long as it has conductivity, and examples thereof include copper, stainless steel, nickel, carbon, and the like, and materials suitable for individual active materials can be used. . The negative electrode current collector can also have a porous structure.

  The positive electrode and the negative electrode are partitioned by a separator 4 having a hole capable of holding the electrolytic solution and the electrolytic solution 3. As the separator 4 having a function of electrically separating the positive electrode and the negative electrode, for example, a porous film containing polyethylene, polypropylene, polyvinylidene fluoride (PVdF), or the like, or a nonwoven fabric made of cellulose, etc. Available.

  The positive electrode current collector 6 is a porous aluminum body having a three-dimensional network structure, and has a positive electrode layer including the positive electrode active material 5 inside the network structure. The positive electrode layer is formed by fixing the positive electrode active material 5 with a binder or the like, and is formed by filling the skeleton structure of the positive electrode current collector.

  In the above, one kind of negative electrode metal selected from the group consisting of alkali metal, alkaline earth metal and aluminum is used for the negative electrode, and oxide, sulfide or a mixture thereof is used as the positive electrode active material.

  FIG. 2 shows an enlarged photograph of an example of an aluminum porous body having a three-dimensional network structure that can be preferably used in the present invention. A network structure having large pores is formed by three-dimensionally connecting substantially triangular prism-shaped hollow skeletons. As a typical size, a hole surrounded by a skeleton has a diameter of about several tens of μm to about 500 μm, and the skeleton has a side of several tens of μm and forms a hollow substantially triangular prism.

  Since such a positive electrode current collector has a large surface area, the contact area between the positive electrode current collector 6 and the positive electrode active material 5 can be extremely increased by adopting a configuration in which the positive electrode active material 5 is held inside the skeleton structure. And it becomes possible to take in electrolyte effectively by having a moderate gap | interval of about 10 to 30%, without the void | hole between mesh | networks being filled with a positive electrode active material.

  Since the porous aluminum body used in the present invention has cavities inside the skeleton, it is more preferable that the electrolytic solution is supplied to the inside of the positive electrode through the cavities. The skeleton can also be provided with a portion where the inside and the outside communicate with each other through a terminal portion or a pinhole on the skeleton wall surface. The electrolytic solution that has passed through the inside in such a portion reaches the positive electrode layer and can function as an active material.

(Manufacture of aluminum porous body)
Hereinafter, a process for producing an aluminum porous body as a specific example of the metal porous body will be described as a representative example with reference to the drawings as appropriate.

(Aluminum structure manufacturing process)
FIG. 3 is a flowchart showing the manufacturing process of the aluminum structure. FIG. 4 schematically shows a state in which an aluminum structure is formed using a resin molded body as a core material corresponding to the flowchart. The flow of the entire manufacturing process will be described with reference to both drawings. First, preparation 101 of the base resin molded body is performed. FIG. 4A is an enlarged schematic view in which the surface of a foamed resin molded body having continuous air holes is enlarged as an example of the base resin molded body. The pores are formed with the foamed resin molded body 11 as a skeleton. Next, the surface 102 of the resin molded body is made conductive. By this step, as shown in FIG. 4B, a thin conductive layer 12 made of a conductor is formed on the surface of the resin molded body 11. Subsequently, aluminum plating 103 in molten salt is performed to form an aluminum plating layer 13 on the surface of the resin molded body on which the conductive layer is formed (FIG. 4C). Thus, an aluminum structure in which the aluminum plating layer 13 is formed on the surface using the base resin molded body as a base material is obtained. Further, the removal 104 of the base resin molded body may be performed. An aluminum structure (porous body) in which only the metal layer remains can be obtained by disassembling and disappearing the foamed resin molded body 11 (FIG. 4D). Hereinafter, each step will be described in order.

(Preparation of porous resin molding)
A porous resin molded body having a three-dimensional network structure and continuous air holes is prepared. Arbitrary resin can be selected as a raw material of a porous resin molding. Examples of the material include foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene. Although described as a foamed resin molded article, a resin molded article having an arbitrary shape can be selected as long as it has continuous pores (continuous vent holes). For example, what has a shape like a nonwoven fabric entangled with a fibrous resin can be used instead of the foamed resin molded article. The foamed resin molded body preferably has a porosity of 80% to 98% and a cell diameter of 50 μm to 500 μm. Foamed urethane and foamed melamine can be preferably used as a foamed resin molded article because they have high porosity, have pore connectivity and are excellent in thermal decomposability. Urethane foam is preferable in terms of pore uniformity and availability, and foamed urethane is preferable in that a cell having a small cell diameter can be obtained.

  The porous resin molded body often has residues such as foaming agents and unreacted monomers in the foam production process, and it is preferable to perform a washing treatment for the subsequent steps. The resin molded body forms a three-dimensional network as a skeleton, thereby forming continuous pores as a whole. The urethane skeleton has a substantially triangular shape in a cross section perpendicular to the extending direction. Here, the porosity is defined by the following equation.

Porosity = (1− (weight of porous material [g] / (volume of porous material [cm ³ ] × material density))) × 100 [%]
In addition, the cell diameter is enlarged as the surface of the resin molded body with a micrograph, and the number of pores per inch (25.4 mm) is counted as the number of cells, and the average cell diameter = 25.4 mm / number of cells is average. Find the correct value.

(Electrically conductive resin molding surface)
In order to perform electroplating, the surface of the foamed resin is subjected to a conductive treatment in advance. There is no particular limitation as long as the treatment can provide a conductive layer on the surface of the foamed resin, electroless plating of a conductive metal such as nickel, vapor deposition and sputtering of aluminum, or conductive particles such as carbon. Arbitrary methods, such as application | coating of the conductive paint containing this, can be selected. As an example of the conductive treatment, a method of conducting the conductive treatment by sputtering of aluminum and a method of conducting the conductive treatment of the surface of the foamed resin using carbon as conductive particles will be described below.

-Aluminum sputtering-
The sputtering treatment using aluminum is not limited as long as aluminum is the target, and may be performed according to a conventional method. For example, after attaching a foamed resin to the substrate holder, while applying an inert gas, a DC voltage is applied between the holder and the target (aluminum) to cause the ionized inert gas to collide with the aluminum. The aluminum particles sputtered off are deposited on the foamed resin surface to form an aluminum sputtered film. The sputtering process is preferably performed at a temperature at which the foamed resin does not dissolve. Specifically, the sputtering process may be performed at about 100 to 200 ° C, preferably about 120 to 180 ° C.

-Carbon coating-
Prepare carbon paint as conductive paint. The suspension as the conductive paint preferably contains carbon particles, a binder, a dispersant and a dispersion medium. In order to uniformly apply the conductive particles, the suspension needs to maintain a uniform suspension state. For this reason, it is preferable that the suspension is maintained at 20 ° C to 40 ° C. The reason for this is that when the temperature of the suspension is below 20 ° C., the uniform suspension state collapses, and only the binder forms a layer on the surface of the skeleton that forms the network structure of the synthetic resin molding. Because it does. In this case, the applied carbon particle layer is easy to peel off, and it is difficult to form a metal plating that is firmly adhered. On the other hand, when the temperature of the suspension exceeds 40 ° C., the amount of evaporation of the dispersant is large, and the suspension is concentrated as the coating treatment time elapses, and the amount of carbon applied tends to fluctuate. The particle size of the carbon particles is 0.01 to 5 μm, preferably 0.01 to 0.05 μm. If the particle size is large, the pores of the porous resin molded body may be clogged or smooth plating may be hindered. If the particle size is too small, it is difficult to ensure sufficient conductivity.

  The carbon particles can be applied to the porous resin molded body by immersing the target resin molded body in the suspension and performing squeezing and drying. As an example of a practical manufacturing process, a long sheet-like strip-shaped resin having a three-dimensional network structure is continuously drawn out from a supply bobbin and immersed in a suspension in a tank. The strip-shaped resin immersed in the suspension is squeezed with a squeeze roll, and excess suspension is squeezed out. Subsequently, the belt-shaped resin is wound on a winding bobbin after the dispersion medium of the suspension is removed by hot air injection or the like from a hot air nozzle and sufficiently dried. The temperature of the hot air is preferably in the range of 40 ° C to 80 ° C. When such an apparatus is used, the conductive treatment can be performed automatically and continuously, and a skeleton having a network structure without clogging and having a uniform conductive layer is formed. The metal plating in the next process can be performed smoothly.

(Formation of aluminum layer: Molten salt plating)
Next, electrolytic plating is performed in a molten salt to form an aluminum plating layer on the surface of the resin molded body. By performing aluminum plating in a molten salt bath, a uniformly thick aluminum layer can be formed on the surface of a complicated skeleton structure, such as a porous resin body having a three-dimensional network structure. A direct current is applied in a molten salt using a resin molded body having a conductive surface as a cathode and aluminum having a purity of 99.0% as an anode. As the molten salt, an organic molten salt that is a eutectic salt of an organic halide and an aluminum halide, or an inorganic molten salt that is a eutectic salt of an alkali metal halide and an aluminum halide can be used. Use of an organic molten salt bath that melts at a relatively low temperature is preferable because plating can be performed without decomposing the resin molded body as a base material. As the organic halide, imidazolium salt, pyridinium salt and the like can be used. Specifically, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) are preferable. Since the molten salt deteriorates when moisture or oxygen is mixed in the molten salt, the plating is preferably performed in an atmosphere of an inert gas such as nitrogen or argon and in a sealed environment.

As the molten salt bath, a molten salt bath containing nitrogen is preferable, and among them, an imidazolium salt bath is preferably used. When a salt that melts at a high temperature is used as the molten salt, the resin is dissolved or decomposed in the molten salt faster than the growth of the plating layer, and the plating layer cannot be formed on the surface of the resin molded body. The imidazolium salt bath can be used without affecting the resin even at a relatively low temperature. As the imidazolium salt, a salt containing an imidazolium cation having an alkyl group at the 1,3-position is preferably used. Particularly, aluminum chloride + 1-ethyl-3-methylimidazolium chloride (AlCl ₃ + EMIC) molten salt is stable. Is most preferably used because it is high and difficult to decompose. Plating onto foamed urethane resin or foamed melamine resin is possible, and the temperature of the molten salt bath is 10 ° C to 60 ° C, preferably 25 ° C to 45 ° C. The lower the temperature, the narrower the current density range that can be plated, and the more difficult it is to plate on the entire porous body surface. At a high temperature of 60 ° C. or higher, a problem that the shape of the base resin is impaired tends to occur.

In molten salt aluminum plating on metal surfaces, it has been reported that additives such as xylene, benzene, toluene and 1,10-phenanthroline are added to AlCl ₃ -EMIC for the purpose of improving the smoothness of the plating surface. The present inventors have found that, in particular, when aluminum plating is performed on a porous resin body having a three-dimensional network structure, the addition of 1,10-phenanthroline has a specific effect on the formation of the aluminum structure. That is, the first feature that the aluminum skeleton forming the porous body is not easily broken and the second feature that uniform plating with a small difference in plating thickness between the surface portion and the inside of the porous body can be obtained. It is.

  Due to the above-mentioned two characteristics that the plating is hard to break and the plating thickness is uniform inside and outside, when the finished aluminum porous body is pressed, a porous body in which the entire skeleton is hardly broken and is pressed uniformly can be obtained. When an aluminum porous body is used as an electrode material for a battery or the like, the electrode is filled with an electrode active material and the density is increased by pressing, and the skeleton easily breaks during the active material filling process or pressing. It is extremely effective in applications.

  From the above, it is preferable to add an organic solvent to the molten salt bath, and 1,10-phenanthroline is particularly preferably used. The amount added to the plating bath is preferably 0.25 to 7 g / L. If it is 0.25 g / L or less, plating with poor smoothness is brittle, and the effect of reducing the difference in thickness between the surface layer and the inside is difficult to obtain. On the other hand, if it is 7 g / L or more, the plating efficiency is lowered and it is difficult to obtain a predetermined plating thickness.

On the other hand, an inorganic salt bath can be used as the molten salt as long as the resin is not dissolved. The inorganic salt bath is typically a two-component or multi-component salt of AlCl ₃ -XCl (X: alkali metal). Such an inorganic salt bath generally has a higher melting temperature than an organic salt bath such as an imidazolium salt bath, but is less restricted by environmental conditions such as moisture and oxygen, and can be put into practical use at a low cost overall. . When the resin is a foamed melamine resin, it can be used at a higher temperature than the foamed urethane resin, and an inorganic salt bath at 60 ° C. to 150 ° C. is used.

  The aluminum structure which has a resin molding as a frame | skeleton core by the above process is obtained. Depending on applications such as various filters and catalyst carriers, the resin and metal composite may be used as they are, but the resin is removed when used as a porous metal body without resin due to restrictions on the use environment. In the present invention, the resin is removed by decomposition in a molten salt described below so that oxidation of aluminum does not occur.

(Resin removal: treatment with molten salt)
Decomposition in the molten salt is carried out by the following method. A resin molded body having an aluminum plating layer formed on the surface is immersed in a molten salt, and the foamed resin molded body is removed by heating while applying a negative potential (potential lower than the standard electrode potential of aluminum) to the aluminum layer. When a negative potential is applied while being immersed in the molten salt, the foamed resin molded product can be decomposed without oxidizing aluminum. The heating temperature can be appropriately selected according to the type of the foamed resin molded body. When the resin molding is urethane, decomposition takes place at about 380 ° C., so the temperature of the molten salt bath needs to be 380 ° C. or higher. However, in order not to melt aluminum, the melting point of the aluminum (660 ° C.) or lower is required. It is necessary to process at temperature. A preferable temperature range is 500 ° C. or more and 600 ° C. or less. The amount of negative potential to be applied is on the minus side of the reduction potential of aluminum and on the plus side of the reduction potential of cations in the molten salt. By such a method, an aluminum porous body having continuous air holes, a thin oxide layer on the surface, and a small amount of oxygen can be obtained.

As the molten salt used for the decomposition of the resin, a salt of an alkali metal or alkaline earth metal halide that makes the electrode potential of aluminum base can be used. Specifically, it is preferable to include one or more selected from the group consisting of lithium chloride (LiCl), potassium chloride (KCl), sodium chloride (NaCl), and aluminum chloride (AlCl ₃ ). By such a method, an aluminum porous body having continuous air holes, a thin oxide layer on the surface and a small amount of oxygen can be obtained.

(Formation of conductive layer)
Hereinafter, a production example of the aluminum porous body will be specifically described. As the foamed resin molded body, a urethane foam having a thickness of 1 mm, a porosity of 95%, and a pore number (cell number) of about 50 per inch was prepared and cut into 100 mm × 30 mm squares. By immersing the urethane foam in a carbon suspension and drying, a conductive layer having carbon particles attached to the entire surface was formed. The components of the suspension include graphite + carbon black 25%, and include a resin binder, a penetrating agent, and an antifoaming agent. The particle size of carbon black was 0.5 μm.

(Molten salt plating)
A urethane foam with a conductive layer formed on the surface is used as a workpiece, set in a jig having a power supply function, and then placed in a glove box with an argon atmosphere and low moisture (dew point -30 ° C or lower), and melted at a temperature of 40 ° C. I was immersed in a salt aluminum plating bath (33mol% EMIC-67mol% AlCl 3). The jig on which the workpiece was set was connected to the cathode side of the rectifier, and a counter electrode aluminum plate (purity 99.99%) was connected to the anode side. An aluminum structure in which an aluminum plating layer having a weight of 150 g / m ² was formed on the surface of the urethane foam was obtained by plating by applying a direct current having a current density of 3.6 A / dm ² for 90 minutes. Stirring was performed with a stirrer using a Teflon (registered trademark) rotor. Here, the current density is a value calculated by the apparent area of the urethane foam.

  A sample of the skeleton portion of the obtained porous aluminum body was sampled, and cut and observed in a cross section perpendicular to the extending direction of the skeleton. The cross section has a substantially triangular shape, which reflects the structure of the urethane foam as the core material.

(Disassembly of foamed resin molding)
The aluminum structure was immersed in a LiCl—KCl eutectic molten salt at a temperature of 500 ° C., and a negative potential of −1 V was applied for 30 minutes. Bubbles were generated in the molten salt due to the decomposition reaction of the polyurethane. Then, after cooling to room temperature in the atmosphere, the molten salt was removed by washing with water to obtain a porous aluminum body from which the resin was removed. An enlarged photograph of the obtained aluminum porous body is shown in FIG. The porous aluminum body had continuous air holes, and the porosity was as high as that of the urethane foam having the core material.

  When the obtained aluminum porous body was dissolved in aqua regia and measured with an ICP (inductively coupled plasma) emission spectrometer, the aluminum purity was 98.5% by mass. Moreover, it was 1.4 mass% when carbon content was measured by the high frequency induction heating furnace combustion-infrared absorption method of JIS-G1211. Furthermore, as a result of EDX analysis of the surface with an acceleration voltage of 15 kV, almost no oxygen peak was observed, and it was confirmed that the oxygen content of the aluminum porous body was below the EDX detection limit (3.1 mass%).

(Example of secondary battery formation)
Hereinafter, the structural example of the secondary battery concerning this invention is shown. Each of the above-mentioned aluminum porous bodies is used as a positive electrode current collector to apply and carry a positive electrode material to constitute a battery.
<Sodium (Na) secondary battery>
Negative electrode; Na
Positive electrode; NaFePO ₄
Electrolyte solution; NaFSA-KFSA (FSA; bisfluorosulfonylamide)
<Magnesium (Mg) secondary battery>
Negative electrode: Mg
Positive electrode; V ₂ O ₅
Electrolyte solution: Ether solution of Grignard reagent RMgX (R = alkyl group, aryl group, X = Cl, or Br) THF solution of Mg [Al (C ₂ H ₅ ) (C ₄ H ₉ ) Cl ₂ ] ₂ < Calcium (Ca) Secondary Battery>
Negative electrode; Ca
Positive electrode; CaMn ₂ O ₄ / MoS ₂
Electrolytic solution; a solution obtained by dissolving Ca (ClO ₄ ) ₂ , Ca ₂ [Fe (CN) ₆ ] and the like in an aprotic polar solvent (for example, THF (tetrahydrofuran)) <Aluminum (Al) secondary battery>
Negative electrode: Al
Positive electrode; FeS ₂
Electrolytic solution: AlCl ₃ -NaCl-KCl mixed molten salt (drive at 100 ° C.)

DESCRIPTION OF SYMBOLS 1 Negative electrode collector 2 Negative electrode active material layer 3 Electrolyte solution 4 Separator 5 Positive electrode active material 6 Positive electrode collector 10 Battery 11 Foamed resin molding 12 Conductive layer 13 Aluminum plating layer

Claims (4)

  A secondary battery using one kind of negative electrode metal selected from the group consisting of alkali metals, alkaline earth metals and aluminum as a negative electrode, and using an oxide or sulfide or a mixture thereof as a positive electrode active material, A battery using a porous aluminum body having a structure as a positive electrode current collector.   The battery according to claim 1, wherein the porous aluminum body includes an aluminum skeleton configured in a three-dimensional network, and the aluminum skeleton is a substantially triangular prism skeleton having a cavity inside.   3. The battery according to claim 1, wherein a positive electrode active material is supported in pores in the mesh of the aluminum porous body.   The battery according to claim 1, wherein the negative electrode metal is any one of sodium, magnesium, calcium, and aluminum.