Abstract:
The purpose of this invention is to provide a repeatedly chargeable and dischargeable quantum battery that is available for a long period of time without an aging change. The quantum battery is charged by causing an n-type metal oxide semiconductor to have a photo-exited structural change, thereby the electrode of quantum battery is prevented from being oxide and a price reduction and stable operation are possible. The repeatedly usable quantum battery is constituted by laminating; a first metal electrode having an oxidation preventing function, charging layer in which an energy level is formed in the band gap by causing an n-type metal oxide semiconductor covered with an insulating material to have a photo-exited structure change and electrons are trapped at the energy level; p-type metal oxide semiconductor layer; and a second metal electrode having the oxidation preventing function, the electrodes are passive metal layers formed of metals having passive characteristics.

Description:
TECHNICAL FIELD 
     The present invention relates to an electrode for a quantum battery based on an operation principle in which a new energy level is formed in a band gap through the photo-excited structural change of a metal oxide caused by ultraviolet irradiation, and electrons are trapped in the energy level in the band gap, thereby charging a battery. 
     BACKGROUND ART 
     Secondary batteries have been widely distributed for mobile terminals such as mobile phones and notebook computers and electric vehicles, and are repeatedly used through charging and discharging. In secondary batteries of the related art, electrodes were deteriorated from the repetitive charging and discharging of large power and large capacitance, and furthermore, the characteristics of the batteries were also degraded from deterioration over time, deterioration caused by the oxidization of electrodes, and the like, thereby hindering the extension of the service life. 
     Particularly, regarding the oxidization of electrodes, there is an essential problem depending on the charging principles of individual secondary batteries. 
     In a lithium battery, a metal oxide containing lithium is used as the positive electrode, on the other hand, a material capable of storing and releasing lithium such as carbon is used as the negative electrode, and the materials are impregnated with an electrolytic solution made up of a lithium salt capable of dissociating ions and an organic solvent capable of dissolving the lithium salt. As an electrode for the above-described lithium battery, a carbon electrode made of graphite powder improved for high performance and an increase in capacitance has been disclosed (for example, refer to PTL 1, 2 or the like). 
     In addition, there is another proposal that, in a non-aqueous electrolytic solution secondary battery provided with a negative electrode containing silicone as a negative electrode active material, a positive electrode containing a positive electrode active material and a non-aqueous electrolytic solution, an additive suppressing the oxidization of silicone during the operation of the battery is contained in the negative electrode or on the surface of the negative electrode, and a film-forming agent for forming a film on the surface of the negative electrode in the non-aqueous electrolytic solution is contained (for example, refer to PTL 3 or the like). 
     In addition, in a polymer electrolyte fuel battery, a cell in which a solid polymer film is interposed between separator pieces is used as a unit cell and a number of cells are stacked, and, since the separator pinching the solid polymer film is required to have favorable conductivity and low contact resistance, a graphite separator has thus far been used. However, since the graphite separator is brittle, instead of graphite, stainless steel is used as the separator, the surfaces of a steel sheet are coated with passivation films formed of an oxide or hydroxide of Cr, Mo, Fe or the like that is a component of stainless steel, and the anti-corrosion effect for the basic steel is obtained from the barrier effect of the passivation film (for example, refer to PTL 4, 5 or the like). 
     As described above, a variety of countermeasures have been proposed regarding the oxidization of electrodes in individual secondary batteries from the viewpoint of the principles of battery functions and structural aspects. 
     CITATION LIST 
     Patent Literature 
     
         
         PTL 1: JP-A-2002-124256 
         PTL 2: JP-A-11-73964 
         PTL 3: JP-A-2006-286314 
         PTL 4: JP-A-2007-27032 
         PTL 5: JP-A-2009-167486 
       
    
     SUMMARY OF INVENTION 
     Technical Problem 
     The invention describes a quantum battery that is a secondary battery configured by laminating a first conductive electrode, a charging layer that forms an energy level in the band gap through a photo-excited structural change of an n-type metal oxide semiconductor coated with an insulating substance, thereby trapping electrons, a p-type semiconductor layer and a second conductive electrode (PCT/JP2010/067643). 
     The quantum battery is structured to have the laminated charging layer and the p-type semiconductor layer pinched from both sides using the electrodes, and a metallic material is used as the electrode material. In the above-described laminate structure, when the charging layer is formed on one electrode or when the other electrode is formed on the p-type semiconductor layer, there is a problem in that the metal electrode is oxidized due to heat generated in a thermal process during the manufacturing of the battery, the adhesion with the charging layer or the p-type metal oxide semiconductor layer is decreased, and, in a case in which the adhesion is significantly decreased, the electrode is peeled off. 
     An object of the invention is to solve the problem of the electrode that is peeled off in a thermal process during the manufacturing of the battery in a quantum battery being charged by forming an electron-trapping level in the band gap through a photo-excited structural change of an n-type metal oxide semiconductor and trapping electrons in the trapping level, and to provide a quantum battery that is available for a long period of time. 
     Solution to Problem 
     A quantum battery according to the invention is constituted of a first metal electrode; a charging layer that forms an energy level in a band gap through a photo-excited structural change of an n-type metal oxide semiconductor coated with an insulating substance so as to trap electrons; a p-type metal oxide semiconductor layer; and a second metal electrode, 
     either the first metal electrode or the second metal electrode is a metal electrode having an oxidation preventing function. 
     Each of the first metal electrode and the second metal electrode may be a metal electrode having an oxidation preventing function. 
     The metal electrode having an oxidation preventing function is a passive metal layer having passivation characteristics. It is also possible to provide a plurality of passive metal layers. 
     In addition, either the first metal electrode or the second metal electrode may be a metal electrode configured by laminating a metal electrode made up of conductive metal layers and a metal electrode having an oxidation preventing function, and each of the first metal electrode and the second metal electrode may be a metal electrode configured by laminating a metal electrode made up of conductive metal layers and a metal electrode having an oxidation preventing function. 
     Even in this case, the metal electrode having an oxidation preventing function is a passive metal layer having passivation characteristics, and the passive metal layer may be a plurality of passive metal layers. 
     In the quantum battery, nickel oxide or copper aluminum oxide is an effective material for a p-type metal oxide semiconductor, but it is also possible to use a p-type semiconductor made of other materials. 
     In addition, the n-type metal oxide semiconductor in the charging layer is made of a material that is any one of stannic oxide, titanium dioxide and zinc oxide or a combination thereof, and is a complex having a charging function obtained through the photo-excited structural change caused by ultraviolet irradiation. The insulating substance coating the n-type metal oxide semiconductor is an insulating resin or an inorganic insulator. 
     A metallic material for the passive metal layer is at least any one of chromium, nickel, titanium and molybdenum. Furthermore, the metallic material for the passive metal layer may be an alloy containing at least any one of chromium, nickel, titanium and molybdenum. Furthermore, the metallic material for the passive metal layer may be an alloy containing at least copper and any one of chromium, nickel, titanium and molybdenum. 
     In the quantum battery, it is possible to use copper as the metallic material for the conductive metal layer and to use a flexible insulating sheet as a substrate. 
     Advantageous Effects of Invention 
     According to the quantum battery of the invention, it is possible to provide a stable quantum battery in which a problem of the peeling of an electrode due to the oxidation of a metal electrode in a thermal process during the manufacturing of the quantum battery is prevented, and the oxidation of the electrode due to changes over time is suppressed, thereby preventing deterioration or peeling, and enabling the repetition of charging and discharging over a long period of time. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         FIG. 1  is a view illustrating a configuration of a repeatedly chargeable and dischargeable quantum battery according to the invention. 
         FIG. 2  is a view describing a charging layer in the quantum battery according to the invention. 
         FIG. 3  is a band view describing a new energy level formed due to a photo-excited structural change. 
         FIG. 4  is a view describing the behavior of electrons caused by a photo-excited structural change. 
         FIG. 5  is a band view describing a charging and discharging function of a secondary battery to which the invention is applied. 
         FIG. 6  is an explanatory view of the quantum battery into which an n-type metal oxide semiconductor layer is inserted. 
         FIG. 7  is an explanatory view of the quantum battery in which a metallic material having passivation characteristics is used only for a second electrode. 
         FIG. 8  is an explanatory view of the quantum battery in which a metallic material having passivation characteristics is used only for the second electrode, and a substrate is provided on a first electrode side. 
         FIG. 9  is an explanatory view of the quantum battery in which a metallic material having passivation characteristics is used only for a first electrode. 
         FIG. 10  is an explanatory view of the quantum battery in which a metallic material having passivation characteristics is used only for the first electrode, and the substrate is provided on a second electrode side. 
         FIG. 11  is an explanatory view of the quantum battery in which the first electrode and the second electrode are provided with a laminate structure of a conductive metal layer with conductivity and a passive metal layer having passivation characteristics. 
         FIG. 12  is an explanatory view of the quantum battery in which the first electrode and the second electrode are provided with a laminate structure of the passive metal layer having passivation characteristics. 
         FIG. 13  is an explanatory view of the quantum battery in which the first electrode and the second electrode are provided with a laminate structure having the conductive metal layer with conductivity interposed between the passive metal layers having passivation characteristics. 
         FIG. 14  is an explanatory view of the quantum battery in which the first electrode is a metal layer having passivation characteristics, and the second electrode is provided with a laminate structure having the conductive metal layer with conductivity interposed between the passive metal layers having passivation characteristics. 
         FIG. 15  is an explanatory view of the quantum battery in which the substrate is provided on the first electrode side, and the second electrode is provided with a laminate structure having the conductive metal layer with conductivity interposed between the passive metal layers having passivation characteristics. 
         FIG. 16  is an example of the quantum battery carried out using a metal layer having passivation characteristics. 
         FIG. 17  is an example of the quantum battery carried out using an alloy layer of a metal having passivation characteristics. 
     
    
    
     DESCRIPTION OF EMBODIMENTS 
     The invention describes a quantum battery used as a secondary battery based on a new charging principle in which a photo-excitation structure-changing technique is employed for a charging layer, and a metal layer having passivation characteristics is provided to prevent deterioration caused by the oxidation of an electrode in a thermal process during the manufacturing of the battery or changes over time. 
       FIG. 1  is a view illustrating a cross-sectional structure of a repeatedly chargeable and dischargeable quantum battery  10  according to the invention. In  FIG. 1 , the quantum battery  10  has a configuration in which a conductive first electrode  12  for which a metallic material having passivation characteristics is used, a charging layer  14  charging energy, a p-type metal oxide semiconductor layer  16 , and a conductive second electrode  18  for which, similarly to the first electrode  12 , a metallic material having passivation characteristics is used are laminated. 
     Functionally, the first electrode  12  and the second electrode  18  may be formed of a conductive film, and examples of a highly conductive metal that can be used include copper, a copper alloy, nickel, aluminum, silver, gold, zinc, tin and the like. Among the above-described metals, copper is cheap and suitable for a material for the electrode. In some embodiments, the first electrode  12  and the second electrode  18  are opaque to ultraviolet light. 
     However, generally, copper forms a copper I oxide film when left to stand in the atmospheric environment, and forms basic copper carbonate in a high humidity. Furthermore, there is a case in which copper is oxidized due to sulfur oxide in the air so as to form copper sulfide or copper sulfate. Therefore, in a case in which the function of copper as an electrode deteriorates significantly, copper peels off. While there might be a difference in the degree of oxidation, other metallic materials also have a problem of oxidation, and the oxidation significantly shortens the service life. Particularly, in the present quantum battery  10 , there is a problem in that the first electrode  12  may be oxidized while forming the charging layer  14 . 
     As means for solving the above-described problem, it is effective to add an anti-oxidization function to the metal electrode, and therefore, in a case in which the electrode is constituted of a metallic material, a material having passivation characteristics is applied, thereby preventing the oxidation in a thermal process during the manufacturing of the battery and extending the service life of the battery, which is the core of the invention. 
     Passivity refers to a state in which metal corrodes at an extremely low speed although the metal belongs to a base (active) electromotive series, and is a property considered as the basis of the corrosion resistance of a metallic material. A metal that is significantly polarized due to a slight anode current is passivated when behaving similarly to a very electrochemically-noble (inactive) metal. In this case, an oxide film that is a corrosion product becomes protective, and provides corrosion resistance. 
     The corrosion area can be investigated using an anode polarization curve in which a potential is applied to an electrode in the positive direction so as to cause an oxidation reaction. In a case in which the potential is low, the current increases along with the potential. When the potential exceeds a certain value, the current decreases abruptly, remains constant across a certain potential range, and then increases again. The potential range in which the current increases for the first time is called an active range, the potential range in which the current is held at a low value is called a passivity range, and the potential range in which the current increases again is called a transpassivity range. In the passivity range, the protective performance is high, and a several nanometer-thick passive oxide film is formed. 
     As is evident from an anode curve, in the passivity range, the current decreases, that is, the conductivity is impaired, but it is common to protect an electrode from the contact with the atmosphere, and the electrode is oxidized only locally. Therefore, a quantum battery becomes possible which prevents the deterioration of an electrode by suppressing oxidation to a local extent, and can be used for a long period of time in spite of repetitive charging and discharging. 
     Specific examples of a metallic material having passivation characteristics include chromium, nickel, titanium, molybdenum and the like, and the metallic material may be an alloy containing at least one of chromium, nickel, titanium and molybdenum. 
       FIG. 2  is a view describing the charging layer in the quantum battery to which the invention is applied. In  FIG. 2 , the charging layer  14  is provided with a structure in which silicone is used as an insulating film  22 , titanium dioxide is used as an n-type metal oxide semiconductor  20 , atomized titanium dioxide is coated with silicone, and loaded into the charging layer  14 . When irradiated with ultraviolet rays so as to cause a photo-excited structural change, titanium dioxide obtains a function of storing energy. 
     Examples of a material for the n-type metal oxide semiconductor  20  used in the charging layer  14  include titanium dioxide, stannic oxide and zinc oxide, and the material is manufactured by decomposing an aliphatic acid salt of a metal. Therefore, an aliphatic acid that can turn into a metal oxide through combustion in an oxidizing atmosphere is used as the aliphatic acid salt of a metal. When a material having passivation characteristics is used as the metal electrode, it is possible to prevent oxidation caused by combustion. 
     For the insulating film  22 , mineral oil, magnesium oxide (MgO) or silicon dioxide (SiO 2 ) may be used as an inorganic insulating material in addition to silicone, and an insulating resin may be a thermoplastic resin such as polyethylene or polypropylene or a thermosetting resin such as a phenol resin or an amino resin. 
     In the charging layer  14 , a substance irradiated with ultraviolet rays forms a new energy level through a photo-excited structural change. The photo-excited structural change refers to a phenomenon of a change of the lattice distance in a substance excited by the irradiation of light, and the n-type metal oxide semiconductor  20  that is an amorphous metal oxide has a property of causing a photo-excited structural change. A state of a new energy level formed by the photo-excited structural change in the charging layer  14  in a case in which titanium dioxide is used as the n-type metal oxide semiconductor  20  and silicone is used as a material for the insulating film will be described below using a band view. 
       FIGS. 3(A) and 3(B)  are band views describing a state of a new energy level  44  formed due to the photo-excited structural change in a case in which silicone  34  is present as the insulating film  22  between a metal of copper  30  as the first electrode  12  and titanium dioxide  32  as the n-type metal oxide semiconductor  20 . As a result of the photo-excited structural change phenomenon, the new energy level  44  is formed in a band gap of the n-type metal oxide semiconductor  20 . In a conduction band  36 , a barrier is present due to an insulating layer formed of the silicone  34 . 
       FIG. 3(A)  illustrates a state in which an ultraviolet ray  38  is irradiated in a case in which the insulating layer formed of the silicone  34  is present between the titanium dioxide  32  and the copper  30 . When the ultraviolet ray  38  is irradiated on the titanium dioxide  32  coated with the insulating layer, an electron  42  present in a valence band  40  of the titanium dioxide  32  is excited to the conduction band  36 . In the vicinity of an interface with the copper  30 , the electron  42  passes through the insulating layer of the silicone  34  at a certain probability, and temporarily moves into the copper  30 . The photo-excited structural change of titanium dioxide  32  occurs while the electron  42  is absent, and the interatomic distance changes at a portion at which the electron  42  in the valence band  40  is removed. At this time, the energy level  44  moves into a band gap within the Fermi level  46 . 
       FIG. 3(B)  illustrates a state in which the above-described phenomenon has repeatedly occurred while the ultraviolet ray  38  is irradiated, and a number of energy levels  44  are formed in the band gap. However, the electron  42  that is supposed to be trapped in the energy level  44  is excited by the ultraviolet ray  38  and moves into the copper  30 . The energy level  44  in an electron-absent band gap generated as described above remains even after the ultraviolet irradiation ends. 
     The role of the silicone  34  as the insulating layer is to produce a barrier between the copper  30  and the titanium dioxide  32  so as to allow the energy level  44  to be formed in the electron-absent band gap after the excited electron  42  passes through the barrier using a tunnel effect. The electron  42  moved into the copper  30  remains in the copper  30  due to a charged potential in the vicinity of the silicone  34 . 
       FIG. 4  is a view schematically expressing a state of the electrons  42  moved into the copper  30  due to the photo-excited structural change of the titanium dioxide  32  coated with the silicone  34  caused by the irradiation of ultraviolet rays. The electrons  42  pass through the barrier formed of the silicone  34  using the tunnel effect, move into the copper  30 , and remain in the copper due to a weak trapping force generated by the potential of the silicone  34 . 
     As a secondary battery, the p-type metal oxide semiconductor layer  16  is laminated on the charging layer  14  so as to form a blocking layer, and the second electrode  18  is provided on the blocking layer. A principle of the secondary battery having the above-described structure will be described using the band view in  FIG. 5 . 
       FIG. 5(A)  is a band view in a case in which, in the quantum battery  10  constituted of nickel oxide  50  that is interposed between the copper  30  configuring the first electrode  12  and copper  48  configuring the second electrode  18  and functions as the silicone  34  and the titanium dioxide  32  in the charging layer  14  and the p-type metal oxide semiconductor layer  16 , a negative voltage is applied to the copper  48  configuring the second electrode  18 , and the copper  30  configuring the first electrode  12  is grounded so as to be set to 0 V. 
     When a bias electric field (−) is applied to the titanium dioxide  32  having the energy level  44  in the band gap, the electrons  42  in the copper  30  pass through (tunneling) the barrier formed of the silicone  34 , and move into the titanium dioxide  32 . The moved electrons  42  are blocked by the nickel oxide  50  from further moving into the copper  48 , and thus are trapped in the energy level  44  present in the band gap of the titanium dioxide  32 , whereby energy is stored. That is, a charged state in which the charging layer  14  is filled with the electrons  42  is obtained. This state is maintained even after the application of the bias electric field is stopped, and thus the quantum battery functions as a secondary battery. 
       FIG. 5(B)  is a band view of a case in which a load (not illustrated) is connected to the copper  30  and the copper  48  and the quantum battery is discharged. The electrons  42  trapped in the band gap turn into free electrons in the conduction band  36 . The free electrons move into the copper  30  and then flow into the load. The above-described phenomenon is the output state of energy, that is, a discharging state. In addition, in the end, all electrons  42  move away from the energy level  44  in the band gap, and the entire energy is consumed. 
     As described above, when voltage is applied from outside to the energy level formed in the band gap of the titanium dioxide so as to form an electric field and load electrons, and a load is connected to the electrodes, energy is extracted by releasing the electrons, and the quantum battery functions as a battery. The quantum battery can be used as a secondary battery by repeating the above-described phenomenon. What has been described above is the principle of a basic quantum battery to which the invention is applied. 
     Thus far, a principle of a basic secondary battery has been described, and, in principle, since the electrons  42  move into the first electrode  12  through the insulating film  22  using the tunnel effect, and remain in the first electrode, the adhesion between the charging layer  14  and the first electrode  12  becomes extremely important. Therefore, it becomes necessary to prevent the degradation of the adhesion caused by the oxidization of the electrodes caused by the thermal process during the manufacturing of the battery and changes over time. 
     For the above-described reason, deterioration from the oxidation of the electrode has a large influence on the quantum battery to which the invention is applied, and, when a metal having passivation characteristics is used to form the electrode so as to suppress the deterioration of the electrode to partial surface oxidation, it is possible to prevent the oxidation caused by the thermal process during the manufacturing of the battery or changes over time and to extend the service life of the quantum battery. 
     Since the second electrode  18  is laminated on the p-type metal oxide semiconductor layer  16 , there is no serious problem with the adhesion with the first electrode  12 , but the influence of the deterioration of the electrode is still a critical problem to the second electrode  18  as well. 
     Therefore, to the second electrode  18  as well, an electrode constituted using a metallic material having passivation characteristics becomes effective means for the adhesion during the manufacturing and the extension of the service life of the quantum battery  10  to which the invention is applied. 
       FIG. 6  illustrates a case in which the invention is applied to a quantum battery  54  having an n-type metal oxide semiconductor layer  56  interposed between the first electrode  12  and the charging layer  14 . 
     While the titanium dioxide  32  in the charging layer  14  is surrounded by the insulating film formed of the silicone  34 , the film is not always uniform, and there is a case in which the titanium dioxide  32  comes into direct contact with the electrode through portions on which the film is not formed. In such a case, the electrons  42  are injected into the titanium dioxide  32  through recombination, the energy level  44  is not formed in the band gap, and the charging capacitance decreases. Therefore, to suppress the decrease in the charging capacitance and to produce a higher-performance secondary battery, a titanium dioxide thin layer is formed between the first electrode  12  and the charging layer  14  as an n-type metal oxide semiconductor layer  56  as illustrated in  FIG. 6 . The titanium dioxide thin layer functions as an insulating layer, contributes to performance improvement, furthermore, rarely causes characteristic variations of an element, and has an effective structure for the stability in the manufacturing line and the improvement of yield. 
     It is also possible to apply the invention to the quantum battery  54  having the n-type metal oxide semiconductor layer  56  formed between the first electrode  12  and the charging layer  14 , and then an effect that suppresses the deterioration of the electrode even after repetitive charging and discharging is exhibited. 
     Thus far, a case in which the invention in which the electrodes having passivation characteristics are used is applied to the first electrode and the second electrode has been described, but the invention exhibits the same effect even when applied to only one electrode. 
       FIG. 7  illustrates an example of a quantum battery  60  in which a metallic material having passivation characteristics is used only for the second electrode  18 . In this case, it is possible to provide a structure in which the oxidation of the electrode is suppressed by providing a substrate  64  on the first electrode  12  for which a metallic material having no passivation characteristics is used as in a quantum battery  62  illustrated in  FIG. 8 . 
       FIG. 9  illustrates a quantum battery  68  in which a metallic material having passivation characteristics is used as the first electrode  12 , and  FIG. 10  illustrates an example of a quantum battery  70  in which the substrate  64  is provided on the second electrode  18 . 
     In this example, a case in which a metallic material having passivation characteristics is used as the first electrode  12  and the second electrode  18  has been described, but it is possible to make the first electrode  12  and the second electrode  18  in a laminated structure of a conductive metal layer having conductivity and a passive metal layer having passivation characteristics. 
       FIG. 11  illustrates a quantum battery  72  in which the first electrode  12  and the second electrode  18  have a laminated structure. In  FIG. 11 , the first electrode  12  has a laminated structure of a first conductive metal layer  74  and a first passive metal layer  76 . The first passive metal layer  76  is provided on the charging layer  14 . Similarly, the second electrode  18  also has a laminated structure of a second conductive metal layer  80  and a second passive metal layer  78 , and the second passive metal layer  78  is provided on the p-type metal oxide semiconductor layer  16 . 
     For the first passive metal layer  76  and the second passive metal layer  78 , the same metallic material as the material used as the electrodes as the metallic material having passivation characteristics can be used. That is, the metallic material is chromium, nickel, titanium, molybdenum or the like, and may be an alloy containing at least one of chromium, nickel, titanium, molybdenum and the like. 
       FIG. 12  illustrates a quantum battery  82  in which the first electrode  12  and the second electrode  18  have a laminated structure, the first conductive metal layer  74  and the second conductive metal layer  80  illustrated in  FIG. 11  are made of a metallic material having passivation characteristics so as to form a third passive metal layer  84  and a fourth passive metal layer  86 . Since the electrodes have a laminated structure of a metallic material having passivation characteristics, it is possible to further improve the effect to prevent the oxidation of the electrodes. 
     In this case, the metallic material having passivation characteristics is chromium, nickel, titanium, molybdenum or the like, and any alloy containing at least one of chromium, nickel, titanium, molybdenum and the like is used. Here, the first passive metal layer  76 , the second passive metal layer  78 , the third passive metal layer  84  and the fourth passive metal layer  86  do not need to be made of the same metallic material, and can be made of a variety of combinations of the metallic materials having passivation characteristics, and also may be made of a plurality of the passive metal layers. 
     In addition, a variety of combinations are possible in which one electrode has a laminated structure of metallic materials having passivation characteristics and the other electrode has a single layer, or only one electrode has a laminated structure of metallic materials having passivation characteristics, and one example will be described below. 
       FIG. 13  illustrates an example of a quantum battery  88  having a structure obtained by laminating a third passive metal layer  84  and a fourth passive metal layer  86  respectively on the first conductive metal layer  74  and the second conductive metal layer  80  of the quantum battery  82  in  FIG. 12 . 
       FIG. 14  illustrates an example of a quantum battery  90  in which the first electrode  12  is constituted of a metallic material having passivation and the second electrode  18  is a laminate of the second passive metal layer  78 , the second conductive metal layer  80  and the fourth passive metal layer  86 . 
       FIG. 15  illustrates an example of a quantum battery  92  in which only the second electrode  18  has a laminated structure of the second passive metal layer  78 , the second conductive metal layer  80  and the fourth passive metal layer  86 , and the substrate  64  is provided on the first electrode  12 . 
     Next, an example of an actually-prototyped quantum battery will be described. 
     Example 1 
       FIG. 16  illustrates an example of a quantum battery  100  prototyped on a glass substrate according to the invention using a polyimide film  94  as the substrate  64 . 
     The polyimide film  94  is 4 μm-thick, and a 50 nm-thick chromium film  96  having passivation characteristics and a 300 nm-thick copper layer  30  are laminated on the polyimide film. Furthermore, a 50 nm-thick chromium layer  96  is laminated. When manufacturing the above-described charging layer  14 , approximately 300° C. heat is generated in the manufacturing process. 
     At this phase, an ultraviolet ray  38  is irradiated on the charging layer  14  so as to cause a photo-excited structural change of titanium dioxide  32  and form a new energy level  44 . 
     After that, a 150 nm-thick nickel oxide film  50  is formed, and a 50 nm-thick chromium film  96  and a 300 nm-thick copper film  48  are laminated, thereby completing a quantum battery  100 . 
     When manufacturing the quantum battery  100 , it is possible to use a gas-phase film-forming method such as sputtering, ion plating, electronic beam deposition, vacuum deposition or chemical deposition as a method for forming the respective layers. In addition, a metal electrode can be formed using an electrolytic plating method, a non-electrolytic plating method or the like. 
     Example 2 
       FIG. 17  is an example of a quantum battery  102  prototyped using an alloy as a metallic material. 
     The polyimide film  94  is 4 μm-thick, and a 50 nm-thick chromium film  96  having passivation characteristics and, similarly, a 300 nm-thick aluminum copper alloy film  104  having passivation characteristics are laminated on the polyimide film. Furthermore, a 50 nm-thick chromium film  96  is laminated, and a 50 nm-thick titanium dioxide film  32  is laminated on the chromium film as the n-type metal oxide semiconductor layer. Next, a 1000 nm or more-thick film of titanium dioxide  32  miniaturized and coated with silicone  34  is laminated so as to produce a charging layer  14 . In this case as well, similarly to Example 1, approximately 300° C. heat is generated in the manufacturing process when manufacturing the above-described charging layer  14 . 
     Furthermore, similarly to Example 1, an ultraviolet ray is irradiated on the charging layer  14  so as to cause a photo-excited structural change of titanium dioxide, thereby forming a new energy level. 
     After that, a 150 nm-thick nickel oxide film  50  and a 50 nm-thick chromium film  96  are laminated, and a 300 nm-thick aluminum copper alloy film  104  is laminated, thereby completing a quantum battery  102 . 
     Both in Examples 1 and 2, there were no electrodes oxidized in the thermal process during the manufacturing of the batteries, quantum batteries maintaining favorable charging and discharging repetition characteristics over a long period of time were obtained, and the effect to prevent the oxidation of the electrode could be confirmed. 
     Thus far, the embodiment of the invention has been described, and the invention can be modified as appropriate as long as the object and advantages of the invention are not impaired, and furthermore, the invention is not limited to the embodiment. 
     REFERENCE SIGNS LIST 
     
         
         
           
               10 ,  54 ,  60 ,  62 ,  68 ,  70 ,  72 ,  82 ,  88 ,  90 ,  92 ,  100 ,  102  quantum battery 
               12  first electrode 
               14  charging layer 
               16  p-type metal oxide semiconductor layer 
               18  second electrode 
               20  n-type metal oxide semiconductor 
               22  insulating film 
               30 ,  48  copper 
               32  titanium dioxide 
               34  silicone 
               36  conduction band 
               38  ultraviolet ray 
               40  valence band 
               42  electron 
               44  energy level 
               46  fermi level 
               50  nickel oxide 
               64  substrate 
               74  first conductive metal layer 
               76  first passive metal layer 
               78  second passive metal layer 
               80  second conductive metal layer 
               84  third passive metal layer 
               86  fourth passive metal layer 
               94  polyimide film 
               96  chromium 
               104  aluminum copper alloy