Battery

Abstract

To solve the problem in which a secondary battery using lithium has a risk of ignition.SOLUTION: A positive electrode 202, a negative electrode 203, and a separator 204 are housed between a first external terminal 205 located on the lower side and a second external terminal 206 located on the upper side. Portions of the first external terminal 205 and the second external terminal 206 are insulated by a gasket 207. The positive electrode 202 consists of a positive electrode current collector 221 located on an inner surface of the first external terminal 205 and connected to the positive electrode 202 and a positive electrode layer 222 provided on the surface of the positive electrode current collector 221 facing the separator 204. The negative electrode 203 consists of a negative electrode current collector 231 located on an inner surface of the second external terminal 206 and connected to the negative electrode 203 and a negative electrode 232 made of metallic lithium and provided on the surface of the negative electrode current collector 231 facing the separator 204. The separator 204 is impregnated in lithium perchlorate (LiClO4).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a capacitor battery and a secondary battery, and a method for manufacturing said battery. The capacitor battery and secondary battery of the present invention mainly use an aqueous perchlorate solution, a saturated aqueous perchlorate solution, or the like, as an electrolyte. [Background technology]

[0002] The most widely used lithium-ion secondary battery is the manganese lithium secondary battery (ML type), which uses a manganese composite oxide for the positive electrode and a lithium-aluminum alloy for the negative electrode. Patent Document 1 discloses a lithium ion secondary battery having features such as a positive electrode material for the lithium ion secondary battery. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2020-155223 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional lithium ion secondary batteries or sodium ion secondary batteries use an organic electrolyte solution, which poses the risk of fire. [Means for solving the problem]

[0005] The electromotive force of a secondary battery is governed by the redox reaction at the negative and positive electrodes. For example, in lithium-ion batteries, the electromotive force varies from 3 V or more to 3 V or less. This is because the reactions occurring at the negative and positive electrodes are different.

[0006] In the present invention, a saturated lithium perchlorate aqueous solution is used as the electrolyte for the capacitor battery. Since the aqueous solution of perchlorate has a wide potential window, it exhibits excellent properties as an electrolyte for a secondary battery.

[0007] The capacitor battery and secondary battery of the present invention use, as the electrolyte of the battery, an aqueous solution of any one of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), barium perchlorate (Ba(ClO4)2), and magnesium perchlorate (Mg(ClO4)2), or an aqueous solution of a mixture of these aqueous solutions. Note that each aqueous solution of perchloric acid is preferably a saturated aqueous solution of perchloric acid of 98% or more. At least the positive electrode is made of or formed from an iron complex, and at least one of the positive electrode and the negative electrode is coated with Fe2O3. Since the battery of the present invention has a capacitor structure, it is sometimes called an electric double layer capacitor battery.

[0008] In one embodiment of the present invention, a capacitor battery, secondary battery, etc., is constructed with a negative electrode made of graphite, or a mixture of activated carbon, or a mixture of graphite and activated carbon, and a positive electrode made of graphite, or a mixture of LiCoO2 (or a material that does not change structure when oxidized), or a mixture of graphite and LiCoO2.

[0009] A separator 204 is disposed between the positive electrode material 221 and the negative electrode material 231. The separator 204 is impregnated with an aqueous solution of lithium perchlorate (LiClO4). The positive electrode 205 and the negative electrode 206 are insulated by a gasket 207.

[0010] In one embodiment of the present invention, a capacitor battery, a secondary battery, or the like, has a positive electrode 205 and a negative electrode 206 formed on one substrate or film 301. An electrolyte solution 222 is disposed on the substrate or film 301, or the positive electrode 205 and the negative electrode 206 are immersed in the electrolyte solution 222.

[0011] A positive electrode material 221 and a negative electrode material 231 are disposed adjacent to each other on a substrate 301a and a substrate 301b. A positive electrode material 221 is disposed on the substrate 301b facing the positive electrode material 221 on the substrate 301a. A negative electrode material 231 is disposed on the substrate 301b facing the negative electrode material 231 on the substrate 301a. The surfaces of the positive electrode material 221 and the negative electrode material 231 are coated with Fe2O3. The space between the substrates 301a and 301b is sealed with a gasket 207, and is filled with an electrolyte 222 consisting of an aqueous solution of perchlorate.

[0012] The battery of the present invention comprises a negative electrode made of a mixture of graphite and activated carbon, a positive electrode containing lithium cobalt oxide, and an aqueous solution of lithium perchlorate filled between the positive electrode and the negative electrode.

[0013] The battery of the present invention includes a negative electrode made of a mixture of graphite and activated carbon, a positive electrode containing graphite and lithium cobalt oxide, and an aqueous lithium perchlorate solution filled between the positive electrode and the negative electrode, and the content ratio of the graphite in the positive electrode to the material mixed therewith is 1:0.8 to 1:1.5.

[0014] The battery of the present invention comprises a negative electrode made of a mixture of graphite and activated carbon, a positive electrode made of a low-spin iron(II) complex material, and an electrolyte filled between the positive electrode and the negative electrode, the electrolyte being any one of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), barium perchlorate (Ba(ClO4)2), and magnesium perchlorate (Mg(ClO4)2).

[0015] The low-spin iron(II) complex material is [Fe(phen)3] 2+ , [Fe(bipy)3] 2+ , [Fe(terpy)3] 2+ It is preferable that the above formula is any one of the formulas.

[0016] The battery of the present invention also comprises a negative electrode and a positive electrode made of a mixture of graphite and activated carbon, and an electrolyte filled between the positive electrode and the negative electrode, the electrolyte being any one of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), barium perchlorate (Ba(ClO4)2), and magnesium perchlorate (Mg(ClO4)2). At least one of the negative electrode and the positive electrode is preferably coated with Fe2O3. The negative electrode and the positive electrode are formed or arranged adjacent to each other on the same substrate, sheet or film, and are formed or arranged so that there is a step between the negative electrode and the positive electrode. Effect of the Invention

[0017] The capacitor battery, secondary battery, etc. of the present invention uses a saturated aqueous solution of perchlorate as the electrolyte, so there is no risk of fire. In addition, the conductivity of a saturated aqueous solution of perchlorate is about 10 times higher than that of an organic electrolyte, so it can store large amounts of power, can be charged quickly, and can obtain a high current capacity.

[0018] By using an aqueous electrolyte (perchlorate aqueous solution) in the capacitor battery, the conductivity of the battery is increased and there is no risk of fire. In addition, there is no need to use a dry room to remove moisture in the manufacturing process of the capacitor battery, which reduces the manufacturing equipment costs.

[0019] In the capacitor battery, secondary battery, etc. of the present invention, the positive electrode 205 and the negative electrode 206 are formed on one substrate or film 301, so that it is possible to configure a battery that does not use a separator 204. Therefore, there is no need to use a separator 204, and the positive electrode 205 and the negative electrode 206 are not short-circuited. [Brief description of the drawings]

[0020] [Figure 1] 1A and 1B are diagrams illustrating the configuration and an explanatory diagram of a capacitor battery and a secondary battery of the present invention. [Diagram 2] 1 is a perspective view and a partial cross-sectional view of a capacitor battery and a secondary battery of the present invention. [Diagram 3] FIG. 2 is an explanatory diagram of a cyclic voltammogram (CV) of a saturated aqueous perchlorate solution. [Figure 4] FIG. 2 is an explanatory diagram of a cyclic voltammogram (CV) and temperature change of a saturated aqueous lithium perchlorate solution. [Diagram 5] FIG. 2 is an explanatory diagram of a saturated aqueous lithium perchlorate solution and the conductivity of a saturated aqueous lithium perchlorate solution and its change with temperature. [Figure 6] FIG. 2 is an explanatory diagram illustrating the charge and discharge operations of a capacitor battery and a secondary battery according to the present invention. [Figure 7] FIG. 2 is an explanatory diagram illustrating the charge and discharge operations of a capacitor battery and a secondary battery according to the present invention. [Figure 8] FIG. 2 is an explanatory diagram illustrating the characteristics of a capacitor battery and a secondary battery according to the present invention. [Figure 9] FIG. 2 is an explanatory diagram illustrating the characteristics of a capacitor battery and a secondary battery according to the present invention. [Figure 10] FIG. 2 is an explanatory diagram illustrating the characteristics of a capacitor battery and a secondary battery according to the present invention. [Figure 11] FIG. 2 is an explanatory diagram illustrating the characteristics of a capacitor battery and a secondary battery according to the present invention. [Figure 12] 1A and 1B are configuration diagrams and explanatory diagrams of a capacitor battery and a secondary battery of the present invention; [Figure 13] 1A and 1B are configuration diagrams and explanatory diagrams of a capacitor battery and a secondary battery of the present invention; [Figure 14] 1A and 1B are configuration diagrams and explanatory diagrams of a capacitor battery and a secondary battery of the present invention; [Figure 15] 1A and 1B are configuration diagrams and explanatory diagrams of a capacitor battery and a secondary battery of the present invention; [Figure 16] 1A and 1B are configuration diagrams and explanatory diagrams of a capacitor battery and a secondary battery of the present invention; [Figure 17] 1A to 1C are explanatory diagrams illustrating a method for producing a capacitor battery and a secondary battery according to the present invention. [Figure 18] 1A to 1C are explanatory diagrams illustrating a method for producing a capacitor battery and a secondary battery according to the present invention. [Figure 19] 1A to 1C are explanatory diagrams illustrating a method for producing a capacitor battery and a secondary battery according to the present invention. [Figure 20] 1A to 1C are explanatory diagrams illustrating a method for producing a capacitor battery and a secondary battery according to the present invention. [Figure 21] 1A and 1B are configuration diagrams and explanatory diagrams of a capacitor battery and a secondary battery of the present invention; [Figure 22] 1A and 1B are configuration diagrams and explanatory diagrams of a capacitor battery and a secondary battery of the present invention; [Figure 23] 1A and 1B are configuration diagrams and explanatory diagrams of a capacitor battery and a secondary battery of the present invention; DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the capacitor battery and secondary battery of the present invention will be described with reference to the drawings.

[0022] In each drawing for explaining the embodiment of the invention, elements having the same function are given the same reference numerals, and the description thereof may be omitted. In addition, the embodiments of the present invention described in this specification may be combined in part or in whole with each other. In the drawings for explaining the embodiments of the invention, the drawings may be enlarged, reduced, or omitted in order to facilitate understanding and explanation and to facilitate illustration.

[0023] In the description or illustration of the embodiments of the present invention, the positive electrode and the negative electrode may be described or illustrated as a concept of a container or an electrode, or may be described as a concept of the electrode material to be used, or may be described as a concept including the container and the electrode material.

[0024] In charging an electric double layer capacitor, the adsorption of cations to the negative electrode is driven by electrostatic interactions between the negative electrode and cations. The storage capacity and charge / discharge rate are independent of temperature and are not affected by the conductivity of the electrolyte. In cases where ion diffusion in the bulk is essential, such as in secondary batteries, the storage capacity and charge / discharge rate are affected by temperature and the conductivity of the electrolyte. The electrical conductivity of the electrolyte is a dominant factor with respect to the internal resistance of the cell, and is therefore also an important factor in electric double layer capacitors.

[0025] Asymmetric capacitors behave differently from symmetric capacitors. When the negative electrode contains activated carbon or a substance with similar functions to activated carbon, positive ions are adsorbed onto its large surface, and electrons accumulate in the electrode to maintain electrical neutrality.

[0026] In a symmetric capacitor, activated carbon or a substance with a similar function to activated carbon is present in the positive electrode, so that anions are adsorbed onto the surface of the positive electrode, maintaining electrical neutrality, and positive holes are generated in the electrode.

[0027] In an asymmetric capacitor, if the positive electrode does not contain activated carbon or a substance with a similar function to activated carbon, it is impossible for anions to be adsorbed to the positive electrode in the same way as to the negative electrode. In order to maintain electrical neutrality between the negative and positive electrodes, the positive electrode must have a positive charge.

[0028] This means that the positive electrode is oxidized. Since there is no oxygen at the positive electrode and water does not decompose, the oxidation of the positive electrode means that electrons are extracted from the positive electrode, creating holes.

[0029] However, unlike a normal oxidation reaction, no substance (ion) is transferred; only electrons are transferred. This makes it a redox capacitor, since an oxidation reaction occurs at the positive electrode when the capacitor is charged.

[0030] When an iron(II) low-spin complex is present at the positive electrode, it becomes an iron(III) low-spin complex when oxidized. Both iron(II) and iron(III) low-spin complexes are octahedral complexes and undergo reversible oxidation-reduction reactions.

[0031] Between iron divalent and iron trivalent, the number of d electrons changes from 6 to 5, and when the two coexist in an aqueous solution, an electron exchange reaction occurs, causing the iron divalent to change to iron trivalent and the iron trivalent to change to iron divalent. The redox potential is 0.36 V for the hexacyanoiron(II) complex and 1.06 V for the tris-1,10-phenanthrolineiron(II) complex. When the applied voltage at the positive electrode exceeds the redox potential, the iron(II) complex is oxidized to the iron(III) complex, a reaction that is reversible and proceeds rapidly. Tris-1,10-phenanthroline iron(II) complex, [Fe(II)(phen)3] 2+ The oxidation-reduction reaction is shown below. 1,10-phenanthroline: phen [Fe(II)(phen)3] 2+ ←→ [Fe(III)(phen)3] 3+ + e -

[0032] Low-spin iron complexes maintain the octahedral structure in the II and III valences, with little change in structure. However, the counter ions (ClO4 - ) increases by one as it oxidizes. In other words, to maintain electrical neutrality, ClO4 - moves.

[0033] In an electric double layer capacitor that uses NaClO4 as the electrolyte, Na + From the viewpoint of neutralization of the whole cell, ClO4 from the negative electrode to the positive electrode - and Na transfer from the positive electrode to the negative electrode + The movement of is the same phenomenon.

[0034] When an iron(II) low-spin complex is mixed with the positive electrode, the iron(II) is oxidized to iron(III) when the applied voltage at the positive electrode exceeds the redox potential of the iron(II) complex. During discharge, iron(III) is reduced to iron(II). This means that the charge and discharge are accompanied by an oxidation-reduction reaction, making it a redox capacitor.

[0035] Although mixing high-spin iron(II) complexes with the positive electrode does not negate the redox effect, many high-spin iron(II) complexes are not as stable as low-spin complexes. It may be oxidized in air, so care must be taken when handling it. Iron(II) sulfate and iron(II) phosphate are stable, and iron(II) phosphate in particular is insoluble in water. As described above, the iron complex has a good oxidation-reduction effect. The present invention relates to a battery using the iron complex in the positive electrode.

[0036] The electrolyte is divided into the very vicinity of the electrode (Helmholtz layer) and the bulk diffusion layer. Localization of ions due to charging is restricted to the vicinity of the Helmholtz layer. At this time, cations remain solvated (hydrated in aqueous systems) and are adsorbed to the negative electrode.

[0037] When a saturated aqueous solution of sodium perchlorate is used as the electrolyte, the structure in which water is adsorbed on the electrode surface as shown in Fig. 7(b) is not rational, because in this aqueous solution, the water molecules are bound by the metal ions and there are almost no free water molecules. The cation is the counter ion (ClO4 - ) and are adsorbed onto the surface of the negative electrode, causing electrons to accumulate at the negative electrode to maintain electrical neutrality.

[0038] In the positive electrode, positively charged vacancies (holes) with the same charge as the electrons adsorbed to the negative electrode are generated. The adsorption of ions due to charging occurs near the Helmholtz layer and is not affected by diffusion in the bulk layer.

[0039] It is reasonable to consider that the adsorption of cations is caused by electrostatic interactions between the electrode and ions. Because, if the diffusion of ions is rate-limiting during charging and discharging, it must be affected by the conductivity and temperature of the electrolyte. In addition, the application of the statistical mechanical Boltzmann distribution to the ion distribution near the electrode is not supported because the Boltzmann distribution is a function of temperature.

[0040] In secondary batteries, the diffusion of ions in the bulk layer is essential because the redox reaction involves mass transfer. No matter how fast the redox reaction is, it is rate-limited by the diffusion rate and is therefore affected by the conductivity and temperature of the electrolyte.

[0041] In principle, the charging rate in a secondary battery is not faster than the diffusion rate. In an electric double layer capacitor, the charge and discharge rate is governed by the electrostatic interaction between the negative electrode and the cations, and the ionic radius and charge of the cations are important factors. A comparison is made between saturated LiClO4 and saturated NaClO4 aqueous solutions used as the electrolyte for an electric double layer capacitor.

[0042] The collector electrode is titanium foil, and the active material is a mixture of activated carbon and graphite. The active material is formed on the titanium using coating technology, printing technology, etc. Needless to say, other than titanium foil, other metal foils and metal plates such as stainless steel foil, iron foil, and silver foil can also be used.

[0043] The difference between the two capacitors is that the positive ions are Li + and Na + That's all. + Na + Although the ionic radius is smaller than that of Li, the hydration radius is + It is said that Na is large. + and Li + Both are classified as hard acids, and are expected to have strong electrostatic interactions with the negative electrode.

[0044] When ions are adsorbed on the electrode, they move with hydration, as shown in Figure 7(a). Here, the molar concentration of the saturated LiClO4 aqueous solution is 5.27m(mol / kg), and the molar concentration of the saturated NaClO4 aqueous solution is 17.1m.

[0045] Although the solubility of LiClO4 in water is not high, its potential window is the same as that of a saturated aqueous solution of NaClO4. +This is also evidence of the strong hydration power of the water. The binding of water is said to extend to the second coordination sphere. The conductivity of a saturated LiClO4 aqueous solution exceeds 200 mS / cm at 20°C, which is about twice as high as that of a saturated NaClO4 aqueous solution.

[0046] Figure 8 shows the relationship between the ratio of activated carbon and energy density when a saturated NaClO4 aqueous solution and a saturated LiClO4 aqueous solution are used as the electrolyte. In both electrolytes, the energy density increases in proportion to the ratio of activated carbon.

[0047] As shown in Fig. 8, the energy density value is slightly higher in the saturated NaClO4 solution than in the saturated LiClO4 solution. + The hydration radius of Na + This is probably due to the fact that it is larger.

[0048] Therefore, Na + Li + Therefore, the volume of the ion is smaller (Stokes radius is Na + and Li + are 1.84 and 2.38 Å, respectively), which results in more Na+ ions being adsorbed onto the electrode, resulting in a larger charge storage capacity.

[0049] In this case, the weight molar concentration of the saturated LiClO4 aqueous solution is relatively low at 5.27 m, but since the energy density and the activated carbon ratio are proportional, this means that the electrolyte is sufficiently concentrated.

[0050] The conductivity of saturated LiClO4 solution is twice as high as that of saturated NaClO4 solution, but the energy density of the former is lower than that of the latter, which supports the idea that the conductivity does not affect the storage capacity.

[0051] In an asymmetric capacitor, the situation is different from that of a symmetric electric double layer capacitor. In Figure 10, the negative electrode is a mixture of graphite (including acetylene black) and activated carbon, and the positive electrode is composed of only graphite (including acetylene black).

[0052] The cell voltage during charging is about 3V. The cut-off voltage during discharging is changed from 2.5V to 3.2V. There is a large difference between the cut-off voltages of 3.2V and 2.7V during discharging. It can be seen that the storage capacity is very low below the cut-off voltage of 2.7V. This means that at the positive electrode, the anion, ClO4 - This means that the electrode surface area on which the molecules are adsorbed is small, and holes are unlikely to be generated at the electrode.

[0053] However, at a cut-off voltage of 3.2V, the discharge curve changes completely and the energy density becomes 20Wh / kg. This can be explained as follows. When the applied voltage exceeds the threshold value at the positive electrode, the graphite is oxidized. When we say oxidation, there is no oxygen at the positive electrode and water does not decompose. In the end, electrons are pulled out of the graphite and holes are created. That is, the following oxidation reaction occurs at the positive electrode. C is graphite. C → C + + e - Although mass transfer is usually involved, here there is no mass transfer and only electron transfer occurs. Another form of asymmetric capacitor is shown in Figure 11. Carbon cloth coated with Fe2O3 provides an electrode with a large surface area, similar to activated carbon.

[0054] In Fig. 11(a), both the positive and negative electrodes are coated with Fe2O3. In Fig. 11(b), only the negative electrode is coated with Fe2O3. The positive electrode is made of carbon cloth only.

[0055] As shown in Figure 11(a), when carbon cloth coated with Fe2O3 is used as the negative and positive electrodes, an electric double layer capacitor that is comparable to activated carbon can be created. On the other hand, as shown in Figure 11(b), when the negative electrode is coated with Fe2O3 and only carbon cloth is used as the positive electrode, the storage capacity is drastically reduced. As in the embodiment of FIG. 11(a), it is preferable to use an electrode formed of carbon cloth or the like and coated with Fe2O3.

[0056] From the above results, it can be seen that the electric double layer capacitor is driven by the negative electrode, and if activated carbon or a substance having a similar function to activated carbon is present, ions are adsorbed thereto, and electrons accumulate at the negative electrode.

[0057] In the positive electrode, holes accumulate to maintain the electrical neutrality of the entire cell. In asymmetric capacitors, if the positive electrode does not contain activated carbon or a material with similar functions to activated carbon, the positive electrode may be oxidized. In this case, the energy density is as high as that of a symmetric electric double layer capacitor with activated carbon, and the discharge curve shows a plateau characteristic like a secondary battery.

[0058] As an additive to the positive electrode, we assume that the additive is an iron(II) low-spin complex. The same applies to transition metal complexes other than iron. As mentioned at the beginning, when an iron(II) low-spin complex is oxidized, it becomes an iron(III) low-spin complex.

[0059] The redox potential is 0.36 V for the hexacyanoiron(II) complex and 1.06 V for the tris(1,10-phenanthroline)iron(II) complex. When the applied voltage at the positive electrode exceeds the redox potential, the iron(II) complex is oxidized to the iron(III) complex.

[0060] This reaction is known to be reversible and rapid. Tris-1,10-phenanthroline iron(II) complex, [Fe(II)(phen)3] 2+ The oxidation-reduction reaction of is shown below. Here, phen: 1,10-phenanthroline. [Fe(II)(phen)3] 2+ ←→ [Fe(III)(phen)3] 3+ + e -

[0061] Low-spin iron complexes maintain the octahedral structure in the II and III valences, with little change in structure. However, the counter ions (ClO4 - ) increases by one as it oxidizes. In other words, as it charges, ClO4 is transferred from the negative electrode to the positive electrode to maintain electrical neutrality.- moves.

[0062] In an electric double layer capacitor, ions also move throughout the cell. For example, when NaClO4 is used as the electrolyte, Na + The difference with secondary batteries is that in electric double layer capacitors, the movement of ions is not the rate-limiting step. From the viewpoint of neutralization of the entire cell, ClO4 from the negative electrode to the positive electrode - and Na transfer from the positive electrode to the negative electrode + The movement of is the same phenomenon.

[0063] From the viewpoint of practical application of asymmetric capacitors, it is desirable that the oxidation reaction at the positive electrode due to charging occurs at a cell voltage of 2 to 2.5 V. There are many iron(II) low-spin complexes, so it is sufficient to select one that satisfies the above conditions. Low-spin iron(II) complexes include naturally occurring complexes: iron(II) porphyrin complexes can be isolated from mammalian blood. Assuming that general-purpose activated carbon or inexpensive metal compounds are used as the active material, the cut-off voltage is set to 2.5 to 2.7 V in consideration of long-term stability.

[0064] In Figure 9, when the ratio of graphite to activated carbon in the electrode is changed, the energy density increases in proportion to the ratio of activated carbon. This means that the ion concentration is high enough, and the adsorbed ion concentration increases with increasing activated carbon. In a mixture of graphite and activated carbon, the activated carbon content is limited to 70%, but in a mixture of activated carbon and acetylene black, the activated carbon content can be increased to 90%. In that case, the energy density exceeds 30Wh / kg. Based on the results so far, it has been shown that by using activated carbon as an electrode, an energy density of 30Wh / kg can be achieved in an aqueous electric double layer capacitor.

[0065] Hereinafter, the capacitor battery (electric double layer capacitor battery) of the present invention will be illustrated as being configured as a lithium ion secondary battery, and the structures of the capacitor battery and secondary battery according to the embodiment will be described with reference to the drawings. Fig. 1 is a cross-sectional view showing an example of a capacitor battery.

[0066] In Fig. 1, a coin-type lithium ion secondary battery is illustrated, but the technical idea of ​​the present invention is not limited to this. For example, it goes without saying that the battery may be cylindrical as shown in Fig. 2. Other examples include a film shape and a box shape.

[0067] 1, in a lithium ion secondary battery as an example of a capacitor battery of the present invention, a positive electrode material 221 is formed or disposed on a conductor forming a positive electrode 205. A negative electrode material 231 is formed or disposed on a conductor forming a negative electrode 206. A separator 204 is disposed between the positive electrode material 221 and the negative electrode material 231, and the separator 204 is filled, permeated, or impregnated with an electrolyte solution 222.

[0068] 1, a positive electrode terminal 202 is connected to the positive electrode 205, and a negative electrode terminal 203 is connected to the negative electrode 206. The positive electrode 205 and the negative electrode 206 are insulated from each other by a gasket 207.

[0069] The positive electrode is composed of a positive electrode material 221 located on and connected to the inner surface of the positive electrode 205, the negative electrode is disposed in a position facing the positive electrode material 221, and a separator 204 is disposed between the positive electrode and the negative electrode.

[0070] A material containing cobalt is used as the positive electrode material 221. For example, a mixture of graphite and lithium cobalt oxide (LiCoO2) may be used. The content ratio of the graphite to the mixed material is preferably in the range of 1:0.8 to 1:1.5.

[0071] Other examples include a mixture of graphite and cobalt (LiCoO2), a mixture of graphite and manganese (LiMn2O4), a mixture of graphite and nickel (LiNiO2), a mixture of graphite and iron phosphate (LiFePO4), and a mixture of graphite and iron oxide (Fe2O, Fe2O3). Carbon quantum dots (CQDs) are also examples. As described above, in addition to lithium cobalt oxide, lithium manganate, lithium iron phosphate, and the like can be used for the positive electrode.

[0072] As explained in Figure 11, at least one of the positive electrode and the negative electrode is coated with Fe2O3. Preferably, both the positive electrode and the negative electrode are coated with Fe2O3.

[0073] The mixture of LiCoO2 and the like may be any oxide as long as it does not undergo structural changes when oxidized. Note that it is not limited to graphite, and carbon materials such as graphite and coke can be used.

[0074] A mixture of graphite and a material using cobalt (LiCoO2) may be used. The content ratio of the graphite to the material to be mixed is preferably in the range of 1:0.8 to 1:1.5.

[0075] The material to be mixed with graphite is not limited to oxide materials. For example, a mixture of graphite and a material using an iron phenanthroline complex ([Fe(phen)3](ClO4)2) or a mixture of graphite and a material using an iron cyano complex (Li4[Fe(CN)6]) can be used.

[0076] The ligand of the iron(II) complex is not limited to phenanthroline, but may be one that forms a low-spin complex such as bipyridine. Other examples include a mixture of materials using graphite and nickel hydroxide (Ni(OH)2).

[0077] The negative electrode is composed of a negative electrode material 231 located and connected to the inner surface of the negative electrode 206. The negative electrode material 231 may be graphite (LiC6), hard carbon (LiC6), titanate (Li4Ti5O 12 ) and lithium titanate (LTO).

[0078] The separator 204 is impregnated with an aqueous solution of a perchlorate such as lithium perchlorate (LiClO4). The aqueous solution of the perchlorate is preferably a saturated aqueous solution of perchlorate, but there is no difference in performance or efficiency even if the aqueous solution is close to a saturated state. It is sufficient if the aqueous solution is 95% or more saturated. More preferably, it is sufficient if the aqueous solution is 98% or more saturated.

[0079] The negative electrode 206 is inserted into the positive electrode 205 with its bottom end and both side surfaces wrapped in a gasket 207 , and the negative electrode 206 is fixed to the positive electrode 205 by crimping, and is insulated from the negative electrode 206 and the positive electrode 205 by the gasket 207 .

[0080] Fig. 6 is an explanatory diagram for explaining the charging and discharging operation of the electric double layer capacitor battery of the present invention. In Fig. 6, Fig. 6(a) is an explanatory diagram for the operation when the electric double layer capacitor battery is being charged by a charger 101, and Fig. 6(b) is an explanatory diagram for the operation when the electric double layer capacitor battery is being discharged to a load device such as a mobile device 102.

[0081] Electric double layer capacitor batteries are generated by the localization of ions dissolved in the electrolyte. That is, when a voltage is applied to the solution, positive ions localize at the negative electrode and negative ions localize at the positive electrode. To maintain electrical neutrality, electrons are adsorbed at the negative electrode, and positively charged vacancies are created at the positive electrode.

[0082] As shown in Fig. 6(a), when a voltage is applied to a Li-ion battery, cobalt is partially oxidized from trivalent (LiCoO2) to tetravalent (CoO2) in the positive electrode, as shown in the formula below. Partial is expressed by x < 1. LiCoO2←→ Li (1-x) CoO2+ xLi + +xe - Positive electrode (Formula 1) 6xC + xLi + +xe - ←→ xC6Li negative electrode (Formula 2)

[0083] Meanwhile, at the negative electrode, lithium ions are intercalated into the graphite and partially reduced. In other words, the Li+ released at the positive electrode is reduced at the negative electrode to become C6Li.

[0084] At this time, the redox potential of the intercalated C6Li (C6Li / Li + =2.90) is the (Li / Li + =3.05). The potential at the positive electrode (reaction 1) is 0.90V, so adding (equation 1) and (equation 2) gives an electromotive force of 3.8V for the total reaction (battery). However, the electromotive force changes depending on the value of x. In fact, Toshiba's aqueous lithium-ion battery operates at 2.4V.

[0085] In electric double layer capacitor batteries that use graphite as the negative electrode, there is nothing to oxidize at the positive electrode, and positively charged vacancies are generated to maintain electrical neutrality. + is not reduced but simply localizes in the electrode.

[0086] If there is a substance that can be oxidized, such as LiCoO2, in the positive electrode, at a certain voltage (exceeding the electromotive force), the Li + intercalates into graphite to produce C6Li. + In this case, the same phenomenon occurs as in the negative electrode of a lithium-ion battery. In other words, the only difference between the lithium ion battery and the electric double layer capacitor battery of the present invention is the mixture of the positive electrode.

[0087] When a voltage is applied as shown in Figure 6(a), charging begins as the voltage rises. Initially, all charging is done by the electric double-layer capacitor battery. When the voltage exceeds 2V and a certain voltage (electromotive force), an oxidation-reduction reaction similar to that of a lithium-ion battery occurs. The cut-off voltage is set to 2.7V. This can be said to be a new concept of energy storage device that combines an oxidation-reduction reaction with an electric double-layer capacitor battery.

[0088] When a large current is applied, the redox reaction cannot keep up, and only the electric double-layer capacitor battery functions. When a small current is applied for a long time, the redox reaction occurs at a voltage that exceeds the electromotive force, and the overall energy density increases significantly.

[0089] For example, in the electric double layer capacitor battery we developed, the current density is 20mA / cm 2 , charge / discharge capacity 0.03mAh / cm 2 This means that the battery can be fully charged in 5.4 seconds with a coulombic efficiency of 0.03 mAh / cm 2 This means that a charging capacity of

[0090] In 5.4 seconds, the secondary battery (redox reaction) barely responds, and only the electric double layer capacitor functions during rapid charging. On the other hand, when charging for a long time at a low current density, for example when the current density is 1 / 10 or less, the secondary battery (redox reaction) begins to function.

[0091] At the negative electrode, Li + At the positive electrode, for example, LiCoO2 is partially oxidized to Li (1-x) It becomes CoO2. If [Fe(phen)3](ClO4)2 is present at the positive electrode, it is oxidized to [Fe(phen)3](ClO4)3. In other words, iron is oxidized from divalent to trivalent.

[0092] The above-mentioned power storage method is possible only with aqueous electrolytes with a wide potential window. If the potential window of the electrolyte is narrow, the applied voltage cannot be increased and the redox reaction does not occur. In other words, it does not function as a secondary battery. It is essentially different from the redox capacitors reported so far. Similarly, it can be done with organic electrolytes, but the storage capacity of an electric double layer capacitor with organic electrolytes is only a few percent of that of a secondary battery, which is almost within the margin of error.

[0093] Secondary batteries convert the redox reaction occurring at the negative and positive electrodes into electrical energy. The role of the electrolyte is to enable the movement of electrons and ions between the negative and positive electrodes.

[0094] A saturated aqueous solution of lithium perchlorate with a potential window of 3 V or more can be used as an electrolyte for lithium-ion batteries. Even if it is not saturated, a concentrated aqueous solution close to saturation has a wide potential window and can therefore be used as an electrolyte for secondary batteries.

[0095] In order to use a saturated aqueous perchlorate solution as the electrolyte for a secondary battery, since the potential window of an electrolyte is specific, it is necessary to select an electrolyte whose electromotive force of the secondary battery is smaller than the potential window of the electrolyte.

[0096] A solid electrolyte may be used for the separator 204. The solid electrolyte suppresses the movement of ions between the negative electrode and the positive electrode, and is applied independently to each electrode, i.e., the negative electrode and the positive electrode, so that the reduction potential at the negative electrode and the oxidation potential at the positive electrode can be suppressed low during charging.

[0097] This makes it possible to use an aqueous solution with a narrow potential window as the electrolyte. A saturated aqueous solution of lithium perchlorate has a wider potential window (3.2 V at 25°C) than other aqueous solutions, making it a preferable electrolyte.

[0098] The present invention has a wide potential window, and therefore can be used stably for a long period of time. In the sodium ion battery, a saturated aqueous sodium perchlorate solution can be used as the electrolyte.

[0099] Saturated perchlorate aqueous solutions include lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), barium perchlorate (Ba(ClO4)2), and magnesium perchlorate (Mg(ClO4)2). These saturated perchlorate aqueous solutions are used as electrolytes in secondary batteries.

[0100] In the embodiment of the present invention, a saturated aqueous solution of perchlorate is used as the electrolyte, but the electrolyte is not limited to saturated. Even if the aqueous solution of perchlorate is close to saturated, there is no significant difference in effect, capacity, and performance. Therefore, it goes without saying that an aqueous solution of perchlorate may be used.

[0101] 1, 2, etc. are perspective views and partial cross-sectional views of the electric double layer capacitor battery (secondary battery) of the present invention. This is an embodiment in which the electric double layer capacitor battery (secondary battery) of the present invention is configured in a cylindrical shape. In order to facilitate illustration, the positive electrode 205, the negative electrode 206, etc. are omitted. It goes without saying that the electric double layer capacitor battery (secondary battery) of the present invention can be configured in a wide variety of other shapes, such as a box shape or a plate shape.

[0102] As shown in Figures 1, 2, etc., the electric double layer capacitor battery (secondary battery) of the present invention is configured such that a positive electrode material 221, a negative electrode material 231, and a separator 204 are arranged in a container 107, and, if necessary, an insulating film 108 is disposed between the positive electrode material 221, the negative electrode material 231, the separator 204, etc. An electrolyte solution 222 is filled between the separator 204 , the positive electrode material 221 , and the negative electrode material 231 , and the electrolyte solution 222 is filled between the positive electrode material 221 and the negative electrode material 231 . Fig. 3 is an explanatory diagram of a cyclic voltammogram (CV) of a saturated aqueous solution of perchlorate. An Ag / AgCl electrode was used as the reference electrode. In the CV measurement shown in Figure 3, no current flows in the flat areas. This means that the water splitting reaction is not occurring. The flat areas are the potential windows.

[0103] The potential window is 3.2 V for saturated sodium perchlorate aqueous solution and saturated lithium perchlorate aqueous solution, and it can be seen that saturated magnesium perchlorate, saturated perchlorate aqueous solution, and saturated barium perchlorate aqueous solution also have a wide potential window (about 3 V).

[0104] This means that saturated aqueous solutions of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), barium perchlorate (Ba(ClO4)2) and magnesium perchlorate (Mg(ClO4)2) can be used as electrolytes in secondary batteries. As shown in Figure 3, saturated aqueous solutions of perchlorate salts have a wide potential window. Using these aqueous solutions as electrolytes makes it possible to operate at high applied voltages.

[0105] Figure 4 is an explanatory diagram of the cyclic voltammogram (CV) and temperature change of a saturated aqueous solution of lithium perchlorate. An Ag / AgCl electrode is used as the reference electrode. Since CV depends on temperature, the potential window also changes with temperature. It is 3.2 V at 25°C, but decreases to 3.0 V at 40°C and 2.8 V at 60°C.

[0106] In FIG. 4, the solution is saturated at 25°C. However, as the temperature rises, the solubility of lithium perchlorate increases, so at 40°C and 60°C, the solution is not saturated but is concentrated and close to saturated.

[0107] 4, a wide potential window is maintained at 40° C. and 60° C. In other words, even in a concentrated aqueous solution close to saturation, the potential window is wide, and it can be used as an electrolyte for secondary batteries.

[0108] Aqueous solutions other than lithium perchlorate (LiClO4) can also be used as the electrolyte, such as sodium perchlorate (NaClO4), magnesium perchlorate (Mg(ClO4)2), calcium perchlorate (Ca(ClO4)2), barium perchlorate (Ba(ClO4)2), or aluminum perchlorate (Al(ClO4)3). FIG. 5 is an explanatory diagram of the conductivity of a saturated aqueous lithium perchlorate solution and its temperature change. The conductivity of a saturated aqueous solution of lithium perchlorate is more than twice as high as that of a saturated aqueous solution of sodium perchlorate. In either case, the conductivity increases with increasing temperature.

[0109] In Figure 5, the horizontal axis of the graph is temperature, and the vertical axis is conductivity in millisiemens per centimeter (mS / cm). The conductivity of a lithium perchlorate (LiClO4) solution is about twice as high as that of a saturated NaClO4 solution, making the saturated LiClO4 solution an excellent electrolyte.

[0110] As a result of the above, when a saturated aqueous solution of lithium perchlorate (LiClO4) is used as the electrolyte, a maximum applied voltage of 3.2 V is possible at 25°C, and a voltage of 2.8 V is possible even at 60°C.

[0111] The conductivity of an aqueous solution of lithium perchlorate (LiClO4) is higher than that of an aqueous solution of sodium perchlorate (NaClO4), making it preferable as an electrolyte for electric double-layer capacitor batteries (secondary batteries).

[0112] Water forms large cluster-like structures through hydrogen bonds. These cluster structures weaken the bonds of water, narrowing the potential window as a result. Conversely, if it were independent H2O, it is assumed that the potential window would be wider. This is made possible by ultra-concentrated aqueous solutions.

[0113] The weight concentration of a saturated aqueous solution of sodium perchlorate is extremely high (17.1 mol / (1 kg of water) at 25°C), and it is estimated that the water cluster structure is almost completely destroyed.

[0114] A mixture of two or more saturated aqueous solutions selected from the above-mentioned saturated aqueous sodium perchlorate solution, saturated aqueous lithium perchlorate solution, saturated aqueous magnesium perchlorate solution, saturated aqueous calcium perchlorate solution, saturated aqueous barium perchlorate solution, saturated aqueous aluminum perchlorate solution, saturated aqueous magnesium sulfate solution, saturated aqueous potassium sulfate solution, and saturated aqueous sodium sulfate solution can also be used as the electrolyte.

[0115] The mixture is not limited to a combination of two saturated aqueous solutions, such as a mixture of a saturated aqueous solution of sodium perchlorate and a saturated aqueous solution of lithium perchlorate, but may also be a mixture of three or more saturated aqueous solutions, such as a mixture of a saturated aqueous solution of sodium perchlorate, a saturated aqueous solution of lithium perchlorate, and a saturated aqueous solution of barium perchlorate. Such a mixture does not necessarily have to contain an aqueous solution of lithium perchlorate, and a mixture of various combinations can be used as the electrolyte.

[0116] Although a saturated aqueous lithium perchlorate solution or a concentrated aqueous lithium perchlorate solution close to saturation is used as the electrolyte in the lithium ion battery, the use of a saturated aqueous sodium perchlorate solution as the electrolyte in the sodium ion battery, like the lithium ion battery, is also within the technical scope of the present invention.

[0117] Other embodiments of the present invention will be described below. Descriptions of matters or contents that are the same as or similar to matters previously described may be omitted. In addition, the embodiments described in this specification and the drawings may be combined in part or in whole.

[0118] 12 is a diagram illustrating the configuration of a battery according to another embodiment of the present invention. In the embodiment of FIG. 1 and FIG. 2, a negative electrode material 231 and a positive electrode material 221 are disposed in positions facing the separator 204.

[0119] In the embodiment of the present invention shown in Fig. 12, negative electrode materials 231 and positive electrode materials 221 are alternately arranged or formed adjacent to each other on a substrate or film (sheet) (hereinafter referred to as substrate (film)) 301a. An electrolyte solution 222 is filled around the negative electrode materials 231 and the positive electrode materials 221.

[0120] Moreover, positive electrode materials 221 and negative electrode materials 231 are alternately disposed or formed adjacent to each other on the substrate (film) 301b. The periphery of the positive electrode materials 221 and the negative electrode materials 231 is filled with an electrolyte solution 222.

[0121] A positive electrode material 221 of the substrate (film) 301b is disposed at a position facing the positive electrode material 221 of the substrate (film) 301a. A negative electrode material 231 of the substrate (film) 301b is disposed at a position facing the negative electrode material 231 of the substrate (film) 301a. A separator 204 is disposed between the substrate (film) 301a and the substrate (film) 301b, and the separator 204 is attached to a gasket 207. An electrolyte solution 222 is filled around the substrate (film) 301a, the substrate (film) 301b, and the separator 204.

[0122] A positive electrode material 221 of the substrate (film) 301b is arranged or formed at a position facing the positive electrode material 221 of the substrate (film) 301a, and a negative electrode material 231 of the substrate (film) 301b is arranged or formed at a position facing the negative electrode material 231 of the substrate (film) 301a. In FIG. 1, the separator 204 functions as an electrolytic membrane, but also has the function of preventing the negative electrode material 231 and the positive electrode material 221 from contacting each other.

[0123] In the embodiment of FIG. 12, the positive electrode material 221 of the substrate (film) 301b is disposed or formed at a position facing the positive electrode material 221 of the substrate (film) 301a, so that there is no separator 204a, and even if the positive electrode material 221 of the substrate (film) 301a and the positive electrode material 221 of the substrate (film) 301b come into contact with each other, no electrical short circuit occurs. In addition, since the battery is composed of the electrolyte 222 and the adjacent positive electrode material 221 and negative electrode material 231, the efficiency is good. The positive electrode material 221 of each substrate (film) 301 functions as a positive electrode, the negative electrode material 231 functions as a negative electrode, and the electrolyte solution 222 functions to form a battery.

[0124] The negative electrode material 231 and the positive electrode material 221 are disposed or formed on one side of the substrate (film) 301a and the substrate (film) 301d. The negative electrode material 231 and the positive electrode material 221 are disposed or formed on both sides of the substrate (film) 301b and the substrate (film) 301c.

[0125] Both ends of each substrate (film) 301 are sealed with gaskets 207, and each separator 204 (separator 204a, separator 204b, separator 204c) is disposed to prevent opposing electrode materials from contacting each other. Substrate (film) 301a, substrate (film) 301b, substrate (film) 301c, The substrate (film) 301 d is held in a container 107 . The power capacity can be increased by stacking multiple substrates (films) 301 .

[0126] Fig. 13 is a diagram showing the configuration and an explanatory diagram of a battery in another embodiment of the present invention. In Fig. 13, the negative electrode material 231 is coated with the negative electrode coating material 303, and the positive electrode material 221 is coated with the positive electrode coating material 302.

[0127] As explained in FIG. 11, when an electrode material made of or formed from carbon cloth or the like is coated with Fe2O3, it becomes an electrode with a large surface area like activated carbon. In Fig. 11(a), both the positive and negative electrodes are coated with Fe2O3, while in Fig. 11(b), only the negative electrode is coated with Fe2O3.

[0128] 13, by coating the positive electrode material 221 with an iron oxide material such as Fe2O3 as a positive electrode coating material 302 and coating the negative electrode material 231 with an iron oxide material such as Fe2O3 as a negative electrode coating material 303, an electrode with a large surface area like activated carbon is obtained, and the battery efficiency is improved. Note that the electrode may be coated with a coating material on either the positive electrode material 221 or the negative electrode material 231. As in the embodiment of FIG. 13, it is preferable to use electrodes formed of carbon cloth or the like and coated with Fe2O3.

[0129] As shown in Figures 12 and 13, by arranging electrodes of the same polarity at opposing positions, the battery functions even if the electrodes at opposing positions (for example, the positive electrode material 221 of the substrate (film) 301a and the positive electrode material 221 of the substrate (film) 301b) are positively charged. Therefore, the separator 204 used to prevent contact between the electrode materials is not necessary. It goes without saying that the separator 204 may also be used in the configuration of Figure 13. Figures 14 and 15 are configuration and explanatory diagrams of a battery etc. in another embodiment of the present invention. They mainly show a state in which the separator 204 is not configured or arranged.

[0130] 14 is an explanatory diagram of the arrangement of the positive electrode material 221 and the negative electrode material 231. The positive electrode material 221 and the negative electrode material 231 are formed in a comb-like shape and are arranged with a gap therebetween. A gasket 207 is arranged around the electrode materials, and an electrolyte 222 is filled inside the gasket 207. One end of the positive electrode material 221 is connected to an electrode terminal 304a for applying a positive potential, and one end of the negative electrode material 231 is connected to an electrode terminal 304b for applying a negative potential. A battery or the like is constituted by a positive electrode material 221 formed in a comb-like shape, a negative electrode material 231 formed in a comb-like shape, and a filled electrolyte solution 222.

[0131] By disposing or forming the positive electrode material 221 and the negative electrode material 231 adjacent to each other on the substrate (film) 301a, the separator 204 becomes unnecessary. By forming them in a comb-like shape, the area where the positive electrode material 221 and the negative electrode material 231 are adjacent to each other becomes large, and good current capacity can be realized.

[0132] In addition, in Figure 14 etc., the electrode material is illustrated as having a comb-like shape, but this is not limited to this, and any configuration may be used as long as the positive electrode material 221 and the negative electrode material 231 are arranged or formed so as to be adjacent to each other on one plane.

[0133] Fig. 15 is a cross-sectional view taken along line AA' in Fig. 14. Fig. 15(a) shows an embodiment in which a positive electrode material (positive electrode) and a negative electrode material (negative electrode) are formed or configured on substrate 301a. Fig. 15(b) shows an embodiment in which a positive electrode material (positive electrode) and a negative electrode material (negative electrode) are formed or configured on substrates 301a and 301b.

[0134] 15(a), a filling hole (inlet / outlet hole) 305 for the electrolyte 222 is formed in a substrate 301b. The electrolyte can be injected from the inlet / outlet hole 305a, and the electrolyte can be discharged from the inlet / outlet hole 305b. Therefore, the electrolyte 222 can be replaced.

[0135] The electrolyte 222 deteriorates with use of the battery. Therefore, it is preferable to replace the electrolyte 222 at a certain level. In addition, the electrolyte can be injected after assembling the substrate 301a and the substrate 301b with the gasket 207, which facilitates the manufacture of the battery.

[0136] Inlet and outlet holes 305 may be formed or disposed in both substrates 301a and 301b. In addition, inlet and outlet holes (not shown) for electrolyte 222 or the like may be formed in gasket 207, container 107, etc., and electrolyte 222 may be injected and poured out from these inlet and outlet holes (not shown). Alternatively, electrolyte 222 may be constantly injected from inlet and outlet hole 305a and poured out from inlet and outlet hole 305b, so that electrolyte 222 circulates.

[0137] 15(b) and the like, it is preferable to arrange the positive electrode material 221 of the substrate 301a and the positive electrode material 221 of the substrate 301b in opposing positions, and the negative electrode material 231 of the substrate 301a and the negative electrode material 231 of the substrate 301b in opposing positions. This is because there are few problems in the operation of the battery even if the substrates 301a and 301b are deformed by external pressure or the like, and the positive electrode material 221 of the substrate 301a comes into contact with the positive electrode material 221 of the substrate 301b, and also the negative electrode material 231 of the substrate 301a comes into contact with the negative electrode material 231 of the substrate 301b. 14 and 15 show a configuration in which a positive electrode material 221 and a negative electrode material 231 are disposed or formed adjacent to a substrate 301 on a flat surface.

[0138] 16 shows a configuration in which a step t is formed in a substrate 301a. The step t is produced by forming a protrusion 307. The protrusion 307 may be formed on the substrate 301a using a resin or the like, or may be formed by cutting the substrate 301a into a groove shape.

[0139] 16 shows an example in which the positive electrode material 221 is formed on the protruding portion 307, and the negative electrode material 231 is formed on the recessed portion 308. The positions of the positive electrode material 221 and the negative electrode material 231 may be reversed. For example, the negative electrode material 231 is formed on the protruding portion 307, and the positive electrode material 221 is formed on the recessed portion 308.

[0140] The step t is determined by the film thickness of the positive electrode material 221 and the negative electrode material 231. If the film thickness of the positive electrode material 221 or the negative electrode material 231 is a, the film is formed so as to satisfy the relationship t > a, and more preferably so as to satisfy the relationship 2t > a.

[0141] 16, a positive electrode material 221 and a negative electrode material 231 are formed on an uneven substrate 301a, and an electrolyte 222 is filled between substrates 301b and 301a. The positive electrode material 221, the negative electrode material 231, and the electrolyte 222 therebetween constitute a capacitor battery or the like. In the battery manufacturing method of the present invention, the positive electrode material 221 and the negative electrode material 231 are formed by a deposition technique and a sputtering technique.

[0142] Figures 17, 18, 19, and 20 are explanatory diagrams of the manufacturing method of the present invention for a battery, etc. Figure 17(a) is a plan view of a substrate 301a, and Figure 17(b) is a cross-sectional view taken along line AA' in Figure 17(a).

[0143] A step t is formed in the substrate 301a. The protrusion 307 may be formed by using a resin or the like on the substrate 301a. The recess 308 may be formed by cutting the substrate 301a into a groove shape.

[0144] 17(a), comb-shaped recesses 308 and protrusions 307 are formed on a substrate 301a, and an electrode terminal 304a for applying a negative voltage is disposed on one end of the recess 308, and an electrode terminal 304b for applying a positive voltage is disposed on one end of the recess 308. Note that the shape is not limited to the comb-shaped shape, and it is sufficient that at least one pair of protrusions 307 and recesses 308 is formed.

[0145] 18 shows an embodiment in which a film 306 is formed on a substrate 301a by a deposition technique (deposition film formation). Note that the technique is not limited to the deposition technique (deposition film formation), and sputtering film formation may also be used. Needless to say, the film 306 may also be formed or configured by using ion plating or chemical vapor deposition (CVD).

[0146] The deposition material 309 (positive electrode material 221, negative electrode material 231) is evaporated from the evaporation source, and the film 306 on the substrate 301a arranged above is deposited. The film 306a becomes the positive electrode material 221, and the film 306b becomes the negative electrode material 231.

[0147] The positive electrode material 221 and the negative electrode material 231 are formed from the same deposition material 309, but due to the step t, the deposited film 306 is "cut at the film step" and separated into a deposited film 306a and a deposited film 306b.

[0148] The deposited film 306a formed on the convex portion 307 becomes the positive electrode material 221, and the deposited film 306b formed on the concave portion 308 becomes the negative electrode material 231. Therefore, in one deposition process, the positive electrode material 221 and the negative electrode material 231 can be formed or configured simultaneously due to the step t. In addition, the step t allows the positive electrode material 221 and the negative electrode material 231 to be formed in a comb-like shape as shown in FIG. 17(a). In addition, the electrode terminals 304a and 304b can be formed of the deposited material 309.

[0149] As described with reference to FIG. 11 etc., when the positive electrode material 221 and the negative electrode material 231 are coated with iron oxide (for example, Fe2O3), after forming the deposited film 306 (deposited film 306a, deposited film 306b), iron oxide (for example, Fe2O3) is used as the deposited material 309 to form iron oxide (for example, Fe2O3) on the deposited film 306 (deposited film 306a, deposited film 306b). The deposition material 309 for the electrode terminals 304a and 304b is preferably formed into a plated film by a plating technique such as Ni plating or Cu plating.

[0150] The embodiment of the manufacturing method of the present invention shown in Fig. 18 is an embodiment in which the positive electrode material 221 and the negative electrode material 231 are formed of the same material. The manufacturing method of the present invention shown in Fig. 19 is an embodiment in which the positive electrode material 221 and the negative electrode material 231 are formed of different materials. In order to change or modify the forming materials of the positive electrode material 221 and the negative electrode material 231, a deposition mask 310 is used.

[0151] As shown in FIG. 19(a), a deposition mask 310a having openings in the recesses 308 is placed under the substrate 301a. The deposition material 309 passes through the openings of the deposition mask 310a and is deposited as a deposition film 306b on the recesses 308 of the substrate 301a. The deposition film 306b becomes the negative electrode material 231. The deposition mask 310a may be placed in the opposite manner. A deposition mask 310a having openings in the protrusions 307 is placed under the substrate 301a. The deposition material 309 passes through the openings of the deposition mask 310a and is deposited as a deposition film 306b on the protrusions 307 of the substrate 301a.

[0152] 19(b), a deposition mask 310b having openings at the convex portions 307 is placed under the substrate 301a. The deposition material 309 passes through the openings of the deposition mask 310b and is deposited as a deposition film 306a on the convex portions 307 of the substrate 301a. The deposition film 306a becomes the positive electrode material 221. The deposition mask 306 may be positioned in the opposite direction to that described above.

[0153] In the embodiment of FIG. 19, by using a deposition mask 310a used for forming the positive electrode material 221 and a deposition mask 310b used for forming the negative electrode material 231, the positive electrode material 221 and the negative electrode material 231 can be formed of different materials.

[0154] As shown in Fig. 20, when one of the positive electrode material 221 and the negative electrode material 231 is formed and the electrode material is coated with iron oxide (e.g., Fe2O3) as described in Fig. 11 etc., a deposition film 306 (deposited film 306a or 306b) is formed. Next, iron oxide (e.g., Fe2O3) is used as the deposition material 309 to form iron oxide (e.g., Fe2O3) on the deposition film 306 (deposited film 306a or 306b). In order to form one of the positive electrode material 221 and the negative electrode material 231, a deposition mask 310 is used.

[0155] 20(a), a deposition mask 310 having openings in recesses 308 is placed under the substrate 301. The deposition material 309 passes through the openings of the deposition mask 310 and is deposited as a deposition film 306b on the recesses 308 of the substrate 301a. The position of the deposition mask 310 may be reversed. A deposition mask 310 having openings in protrusions 307 is placed under the substrate 301. The deposition material 309 passes through the openings of the deposition mask 310 and is deposited as a deposition film 306b on the protrusions 307 of the substrate 301a.

[0156] As shown in FIG. 20(b), no deposition mask 310 is used, and iron oxide (for example, Fe2O3) is used as the deposition material 309 to form iron oxide (for example, Fe2O3) on the deposition film 306b.

[0157] 20, a deposition mask 310 is used to form the negative electrode material 231. Also, iron oxide (for example, Fe2O3) can be formed so as to cover the entire substrate 301a.

[0158] The above embodiment is an embodiment in which the positive electrode material 221 and the negative electrode material 231 are arranged in a comb-like shape. The present invention is not limited to this. For example, as shown in FIG. 21, they may be formed in a spiral or helical shape. In other words, the present invention may have any configuration or structure as long as a positive electrode made of the positive electrode material 221 and a negative electrode made of the negative electrode material 231 are formed adjacent to one substrate or film, and the electrolyte solution 222 is filled between the positive electrode material 221 and the negative electrode material 231.

[0159] In the above embodiment, the adjacent positive electrode made of the positive electrode material 221 and the negative electrode made of the negative electrode material 231 are fixed in position, but the present invention is not limited to this.

[0160] Fig. 22 is a diagram showing the configuration and an explanatory diagram of a battery of the present invention. In Fig. 22, a positive electrode made of a positive electrode material 221 is arranged in a container 107 so as to be cylindrical about a center position C and rotatable in an L direction. Also, a negative electrode made of a negative electrode material 231 is arranged in the container 107 so as to be cylindrical about a center position C and rotatable in an R direction. An electrolyte 222 is filled in the container 107.

[0161] The positive electrode made of the positive electrode material 221 rotates around a central position C, and the negative electrode made of the negative electrode material 231 rotates around a central position C. With the rotation, the positional relationship between the positive electrode and the negative electrode changes, and the electrolyte solution 222 is agitated.

[0162] 22, as shown in FIG. 15(a), a filling hole (inlet / outlet hole) 305 (not shown) for the electrolyte 222 may be formed or disposed in the container 107. The electrolyte can be injected and discharged from the inlet / outlet hole 305. Therefore, the electrolyte 222 can be replaced. The state of charge or discharge may be monitored, and the flow rate or movement of the electrolyte may be changed or adjusted according to the state of charge or discharge. By injecting and discharging the electrolyte through the inlet / outlet hole 305, the electrolyte can be moved and stirred, and the charging and discharging conditions can be improved.

[0163] In Fig. 22, the positive electrode made of the positive electrode material 221 is arranged and configured so as to be rotatable in the L direction, and the negative electrode made of the negative electrode material 231 is arranged and configured so as to be rotatable in the R direction, but this is not limited thereto. The rotation direction of the positive electrode made of the positive electrode material 221 and the rotation direction of the negative electrode material 231 may be the same. The rotation direction of the positive electrode made of the positive electrode material 221 and the rotation direction of the negative electrode material 231 may be synchronized and rotated while maintaining the positional relationship. By maintaining the positional relationship, the charging or discharging state of the battery can be made constant, and the electrolyte can be stirred.

[0164] The above items are also applicable to other embodiments. In addition, it is not limited to rotation, and for example, in the embodiment of FIG. 21, it may be rotated about the center O. In addition, it is not limited to rotation, and it may be vibrated. For example, in the embodiment of FIG. 16, the electrolyte can be stirred by moving or vibrating the substrate (film, sheet) 301a in the vertical or horizontal direction. The vibration may be vibration or movement by ultrasonic waves or the like.

[0165] In the embodiment of the present invention, electrodes or electrode materials of the same polarity are arranged at opposing positions, but the present invention is not limited to this. Electrodes or electrode materials of different polarities may be arranged at opposing positions.

[0166] In the above embodiment, a gap or a step is formed or configured between the negative electrode or negative electrode material 231 and the positive electrode or positive electrode material 221, and the electrolyte 222 is filled therein, but the present invention is not limited to this. An insulating film or an insulating wall made of an insulating material (not shown) may be formed or disposed between the negative electrode material 231 and the positive electrode material 221.

[0167] The negative electrode material 231 and the positive electrode material 221 may be patterned or separated by an etching method or the like, or may be formed separately by a printing method. The negative electrode material 231 and the positive electrode material 221 may be formed as one electrode, and a laser or the like may be irradiated between the negative electrode material 231 and the positive electrode material 221 to separate the negative electrode material 231 and the positive electrode material 221.

[0168] In the above embodiment, a gap or a step is formed or configured between the negative electrode or negative electrode material 231 and the positive electrode or positive electrode material 221, and the electrolyte 222 is filled therein, but the present invention is not limited to this.

[0169] Fig. 23 is a diagram showing the structure and explanation of a battery in another embodiment of the present invention. In Fig. 23, an insulating film or insulating wall made of an insulating material 312 is formed or placed between an anode material 231 and a cathode material 221. By forming or placing the insulating material 312, there is no electrolyte between the anode material 231 and the cathode material 221, and the electric field strength between the anode material 231 and the cathode material 221 becomes uniform.

[0170] The only purpose of the separator 204 is to prevent the positive and negative electrodes from shorting out. If the separator had the function of preventing shorting out, it would not be necessary to have the separator 204. However, if the internal resistance is determined by the conductivity of the electrolyte, it is better to have a shorter distance between the positive and negative electrodes.

[0171] As shown in Figure 23, by arranging the insulating material 312, the effective distance between the positive and negative electrodes can be shortened. If a short circuit occurs (if the resistance becomes abnormally small), the part is automatically removed, and the entire battery will function without any problems. The insulating material 312 may be SiO2, SiN x Examples of the material include inorganic materials such as TiO2 and SiON, and organic materials such as polyethylene, polyester and polypropylene.

[0172] The insulating material 312 may be a wall-shaped insulating wall, or may be an isolation film or isolation wall that provides isolation or an isolation gap between adjacent electrodes so that the electric field strength between the electrodes is uniform or there is no electric field concentration.

[0173] The negative electrode material 231 and the positive electrode material 221 may be patterned and separated by an etching method or the like, or may be formed separately by a printing method. The negative electrode material 231 and the positive electrode material 221 may be formed as one electrode, and a laser or the like may be irradiated between the negative electrode material 231 and the positive electrode material 221 to separate the negative electrode material 231 and the positive electrode material 221. It goes without saying that the configuration and form of the insulating material 312 etc. in FIG. 23 can be applied to other embodiments of the present invention.

[0174] The capacitor battery of the present invention not only functions as a capacitor, but also as a secondary battery or has secondary battery-like functions. When a voltage is applied, charging begins as the voltage rises. Initially, it is all due to the electric double layer capacitor. When a certain voltage (electromotive force) is exceeded, an oxidation-reduction reaction similar to that of a lithium-ion battery occurs. In other words, it is a new concept of an electricity storage device that combines an oxidation-reduction reaction with an electric double layer capacitor. Therefore, it has both the functions, configurations, and structures of high-speed charging and discharging and secondary battery-like voltage generation. [Industrial Applicability]

[0175] The electric double layer capacitor battery of the present invention is capable of rapid charging and discharging as compared to a conventional secondary battery. Electric double layer capacitor batteries, which have excellent high output characteristics, are expected to be applied in various fields, such as the storage of new energy.

[0176] Aqueous electric double layer capacitor batteries (secondary batteries) that use aqueous electrolytes have high electrical conductivity, excellent electrolyte dissociation and ion mobility, and are highly safe because the solvent is water, are non-volatile, easy to manage moisture, and are low cost. They also have high-speed charge and discharge functions. The electric double layer capacitor battery (secondary battery) of the present invention can overcome the limitations of water electrolysis, and is expected to be used in a variety of fields. [Explanation of symbols]

[0177] 101 Charger 102 Load 107 Container 108 Insulating film 202 Positive terminal 203 Negative terminal 204 Separator 205 Positive electrode 206 Negative electrode 207 Gasket 222 Electrolyte 221 Positive electrode materials 231 Anode Materials 301 Substrates (films, sheets) 302 Positive electrode coating material 303 Anode coating material 304 Electrode terminal 305 Entrance / Exit Hole 306 Membrane 307 Convex 308 Recess 309 Evaporation materials 310 Metal Mask 312 Insulating materials (insulating walls, partition walls)

Claims

1. A container; a negative electrode containing at least one of graphite, activated carbon, and acetylene black disposed in the container; The iron low-spin complex and lithium cobalt oxide (LiCoO 2 ) a positive electrode containing at least one material; A battery comprising an aqueous solution of lithium perchlorate in a saturated state of 95% or more filled between the positive electrode and the negative electrode.

2. A container; a negative electrode containing at least one of graphite, activated carbon, and acetylene black disposed in the container; Lithium cobalt oxide (LiCoO 2 a positive electrode containing A battery comprising an aqueous solution of lithium perchlorate in a saturated state of 95% or more filled between the positive electrode and the negative electrode.

3. The material of the positive electrode is graphite and lithium cobalt oxide (LiCoO 2 ), wherein the graphite and the lithium cobalt oxide (LiCoO 2 3. The battery according to claim 1, wherein the content ratio of the cation exchange resin and the cation exchange resin is in the range of 1:0.8 to 1:1.

5.

4. The iron low-spin complex is an iron(II) porphyrin, [Fe(phen) 3 ] 2+ , [Fe(bipy) 3 ] 2+ , [Fe(terpy) 3 ] 2+ 2. The battery according to claim 1, wherein the battery is any one of the following:

5. At least one of the positive and negative electrodes has a surface of Fe 2 O 3 3. The battery according to claim 1, further comprising a coating of

6. 3. The battery according to claim 1, wherein the negative electrode and the positive electrode are formed or disposed adjacent to each other on the same substrate, sheet or film.

7. The negative electrode includes a first negative electrode and a second negative electrode, The positive electrode includes a first positive electrode and a second positive electrode, the first negative electrode and the first positive electrode are formed or disposed on a first substrate or a first sheet or a first film; the second negative electrode and the second positive electrode are formed or disposed on a second substrate or a second sheet or a second film; The first substrate, the first sheet, or the first film and the second substrate, the second sheet, or the second film are disposed facing each other; The first negative electrode and the second negative electrode are disposed in opposing positions, 3. The battery according to claim 1, wherein the second positive electrode and the second positive electrode are disposed in opposing positions.

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