JP2004342595A - Electrode for electrochemical cell, and electrochemical cell using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrochemical cell in which the cycle life-span characteristic and high-speed charge and discharge characteristics are improved. <P>SOLUTION: In the electrochemical cell including a positive electrode containing a proton-conducting type compound as an electrode active material, a negative electrode containing the proton-conducting type compound as the electrode active material, and an electrolyte containing a proton source, an electrode containing an anion exchange resin is used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrochemical cell used for a power storage device such as a secondary battery and an electric double layer capacitor, and an electrode suitable for the electrochemical cell.

  A power storage device such as a secondary battery or a capacitor using a proton conductive polymer as an electrode active material has been proposed and put into practical use. FIG. 1 is a diagram showing a cross section of a conventional electrochemical cell.

  As shown in FIG. 1, a conventional electrochemical cell includes a positive electrode 3 and a negative electrode 4 each containing a proton conductive polymer or the like as an electrode active material, on a positive electrode current collector 1 and a negative electrode current collector 2. , And these are bonded together with the separator 5 interposed therebetween, and only protons function as charge carriers. An aqueous solution or a non-aqueous solution containing an electrolyte that gives protons is filled as an electrolytic solution, and is sealed with a gasket 6.

  The positive electrode 3 and the negative electrode 4 are prepared using an electrode material containing a dopant-added or dopant-free proton conductive polymer powder or the like as a main component, a conductive auxiliary agent, and a binder. As a method of forming the electrode, a method of filling the electrode material into a mold of a predetermined size and forming the electrode by a hot press machine (1), and forming a film of the slurry of the electrode material on the surface of the current collector by screen printing. There is a method (2) of drying this film to form an electrode. The positive electrode and the negative electrode thus formed are arranged to face each other with a separator interposed therebetween, thereby constituting an electrochemical cell.

  Examples of the proton conductive compound used as the electrode active material include polyaniline, polythiophene, polypyrrole, polyacetylene, poly-p-phenylene, polyphenylenevinylene, polyperinaphthalene, polyfuran, polyflurane, polythienylene, polypyridinediyl, polyisothianaphthene, Π-conjugated polymers such as polyquinoxaline, polypyridine, polypyrimidine, polyindole, polyaminoanthraquinone, polyimidazole and derivatives thereof, indole π-conjugated compounds such as indole trimer compounds, quinones such as benzoquinone, naphthoquinone and anthraquinone Compounds, quinone-based polymers such as polyanthraquinone, polynaphthoquinone, and polybenzoquinone (which can convert quinone oxygen into hydroxyl groups by conjugation); And a proton-conducting polymer obtained by copolymerization of two or more different monomers. By adding a dopant to these compounds, a redox pair is formed and conductivity is exhibited. These compounds are selectively used as a positive electrode and a negative electrode active material by appropriately adjusting the difference in the oxidation-reduction potential.

  As the electrolyte, an aqueous electrolyte comprising an acid aqueous solution and a non-aqueous electrolyte obtained by adding an electrolyte to an organic solvent are known. In the case of an electrode using a proton conductive compound, the former aqueous electrolyte is used. Are widely used because they can provide a particularly large-capacity electrochemical cell. As the acid, an organic acid or an inorganic acid is used.Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tetrafluoroboric acid, hexafluorophosphoric acid, and hexafluorosilicic acid. , Saturated monocarboxylic acid, aliphatic carboxylic acid, oxycarboxylic acid, p-toluenesulfonic acid, polyvinylsulfonic acid, lauric acid and the like.

In the electrochemical cell having such a configuration, when, for example, an indole trimer compound is used as the electrode active material, the electrochemical reaction expressed by the following reaction formula (1) between the electrode active material and ions contained in the electrolytic solution is performed. Energy is accumulated by a typical redox reaction. The first-stage reaction in the formula indicates a reaction due to doping. In the formula, X ⁻ represents a dopant ion, for example, a sulfate ion, a halide ion or the like, which imparts electrochemical activity by doping a proton conductive compound. The second-stage reaction shows an electrochemical reaction (electrode reaction) accompanied by adsorption and desorption of protons of the doped compound.

  The problem with the above reaction is that the reaction between the electrode active material and the anion occurs, whereby the electrode as a whole repeatedly swells and expands, leading to a decrease in the strength of the electrode over time. As a result, cracks and cracks occur in the electrodes, and the electron conductivity of the electrode active material is reduced. As a result, the internal resistance of the electrochemical cell is increased, and the cycle life characteristics may be reduced.

  To verify this, an electrode using an indole trimer compound as an electrode active material was prepared, and a charge / discharge cycle test was performed by cyclic voltammetry. This was performed for the purpose of verifying the effect of the number of reactions between the electrode active material and the ions in the electrolyte on the cycle life characteristics.

  In this test, a working electrode formed by applying a slurry in which a fiber of an electrode active material and an anion exchange resin were mixed on a conductive substrate and forming a film was used. A Pt electrode was used as a counter electrode, and an Ag / AgCl electrode was used as a reference electrode. In the test, constant current charging and discharging and constant current and constant voltage (constant voltage time: 12 hours) charging and discharging were respectively performed. The test temperature is 25 ° C.

  FIG. 2 is a graph showing the results of a constant current test (cycle test) and a constant current constant voltage test (constant voltage holding test). In this graph, the horizontal axis is plotted as the total test time, and the vertical axis is plotted as the remaining capacity. From this result, it is clear that repetition of charge / discharge has a greater effect on cycle life characteristics deterioration than constant voltage time. In other words, it can be said that the more the interaction between the electrode active material and the ions, the more the cycle life characteristics decrease.

  Furthermore, the results of tests performed separately have confirmed that an increase in temperature promotes a decrease in cycle life characteristics. Thus, it can be said that the interaction between the electrode active material and the ions in the electrolytic solution is one of the factors that greatly affect the cycle life characteristics.

  Also, in the electrochemical cell according to the prior art, there is room for improvement in the high-speed charge and discharge characteristics. FIG. 3 is a diagram showing measurement results of cyclic voltammetry when the voltage scanning speed is changed. Here, a trimer of 5-cyanoindole, which is an indole trimer compound shown in the above reaction formula, was used as the positive electrode active material.

  According to this result, by increasing the scanning speed, the peak separation was increased, and the appearance capacity was greatly reduced. Further, since the peak of the oxidation-reduction potential became broad, it was found that the reaction between the electrode active material and the ions was slow, indicating that the high-speed charge / discharge characteristics were insufficient.

  In addition to the above-described problems, an electrochemical cell laminate in which a basic element (hereinafter, referred to as a “unit cell”) having a structure including a pair of electrodes, a separator interposed therebetween, and an electrolyte as one unit (hereinafter referred to as “unit cell”) has Due to the deterioration of the balance, there is a problem that the battery characteristics are greatly reduced as compared with the unit cells. The cause of the deterioration of the voltage balance in the electrochemical cell stack may be a variation in the chemical reaction occurring in the unit cell.

  To verify this, the following electrochemical cell was fabricated and its charge / discharge characteristics were measured.

  5-Cyanoindole trimer as a positive electrode active material, vapor grown carbon (VGCF) as a conductive auxiliary, polyvinylidene fluoride (average molecular weight: 1100) as a binder, and a weight of 69/23/8 in the stated order. The mixture was weighed so as to obtain a ratio, and stirred and mixed with a blender. 10 mg of this mixed powder was weighed and stirred at room temperature for 5 minutes in 1 ml of DMF to obtain a slurry which was uniformly dispersed. This was formed into a film by a screen printing method on a current collector made of a conductive rubber, and then dried to obtain a positive electrode. Next, polyphenylquinoxaline as a negative electrode active material and ketjen black (EC-600JD) as a conductive auxiliary were weighed in the stated order so as to have a weight ratio of 75/25, followed by stirring and mixing with a blender. Then, using this mixture and m-cresol as a solvent, a negative electrode was prepared in the same manner as the positive electrode. A 20% by weight aqueous sulfuric acid solution was used as an electrolytic solution, and a 20-μm-thick polyolefin-based porous membrane was used as a separator. The surfaces on which the above-described positive electrode and negative electrode were formed were attached to each other with the separator interposed therebetween, impregnated with an electrolytic solution, and sealed with a gasket to obtain a unit cell.

  Five unit cells (Nos. 1 to 5) were prepared, and their charge / discharge characteristics were measured. As measurement conditions, the battery was charged at a temperature of 25 ° C. and a constant current and a constant voltage (CCCV, CV = 10 minutes) and completely discharged at a constant current (CC). 4 and 5 show a voltage change (voltage profile during constant current charging) and a voltage change with respect to discharge time (voltage profile during constant current discharging) with respect to the charging time, respectively. From this measurement result, it can be seen that the voltage profile varies between the unit cells even though they were manufactured under the same conditions.

  An electrochemical cell manufactured by stacking a plurality of unit cells having a variation in voltage profile at the time of charge and discharge and connecting them in series is, for example, a rated voltage of 6 V obtained by connecting five unit cells having a rated voltage of 1.2 V. In the case of the electrochemical cell laminate of (1), the following problem occurs. That is, since the unit cells constituting the electrochemical cell stacked body have different voltage profiles, some of the unit cells exceed the rated voltage of 1.2 V, and some of the unit cells fall below the rated voltage of 1.2 V. An overvoltage is applied to the unit cell exceeding the voltage. As a result, the electrolyte solution and the electrode active material tend to deteriorate, and as a result, the internal resistance of the unit cell increases, and the voltage that the unit cell bears during the charging process becomes higher than the voltage that other unit cells bear, and the battery characteristics deteriorate. Leads to deterioration. Then, it is considered that the difference between the unit cells in the voltage profile becomes remarkable as charging and discharging are repeated, and the cycle life is greatly reduced.

  On the other hand, a technique for improving the cycle life characteristics of a non-aqueous electrolyte secondary battery is disclosed in Japanese Patent Application Laid-Open No. 2000-195553. Patent Document 1 discloses a positive electrode using a composite oxide capable of inserting and extracting lithium ions as an electrode active material, a negative electrode using carbon powder capable of inserting and extracting lithium ions as an electrode active material, There is disclosed a technique for improving the cycle life characteristics at high temperature in a secondary battery using a non-aqueous electrolyte in which a salt is dissolved.

  This technique is characterized in that at least one of the positive electrode and the negative electrode contains at least one additive selected from the group consisting of a chelating agent, a polyimide resin, a chelating resin, an ion exchanger, and azoles and derivatives thereof.

  As the ion exchanger, any one that can form a chelate compound with manganese ions and that is insoluble in a non-aqueous electrolyte can be used, and a cation exchange type or amphoteric ion exchange type organic or inorganic exchange It states that the body can be used. By using such an ion exchanger, manganese ions eluted from the electrode active material on the positive electrode side can be captured and manganese deposition on the negative electrode can be suppressed, so that cycle life characteristics can be significantly improved. Is disclosed.

Patent Document 2 (Japanese Patent Application Laid-Open No. 2001-167995) discloses a gel electrolyte containing a matrix polymer, a nonaqueous solvent, a lithium inorganic salt, and a fiber made of an ion exchange resin as an electrolyte suitable for a lithium ion secondary battery. Is disclosed. And, it is disclosed that the lithium ion transport number and ionic conductivity can be improved by employing such an electrolyte.
JP-A-2000-195553 JP 2001-167795 A

  An object of the present invention is to provide an electrochemical cell having improved cycle life characteristics and high-speed charge / discharge characteristics, and an electrode suitable for such an electrochemical cell.

  The present invention includes the embodiments described in the following items (1) to (19).

  (1) A positive electrode containing a proton conductive compound as an electrode active material, a negative electrode containing a proton conductive compound as an electrode active material, and an electrode used in an electrochemical cell containing an electrolyte containing a proton source. And an electrode for an electrochemical cell comprising a proton conductive compound and an anion exchange resin.

  (2) The electrode for an electrochemical cell according to item 1, wherein the proton conductive compound is a compound that stores electrochemical energy by a redox reaction with ions of an electrolyte.

  (3) The electrode for an electrochemical cell according to item 1 or 2, wherein the anion exchange resin is fibrous.

  (4) The electrode for an electrochemical cell according to paragraph 1, 2 or 3, wherein the anion exchange resin is fibrous having a length of 10 mm or less and a major axis of 100 µm or less.

  (5) The electrode for an electrochemical cell according to any one of (1) to (4), wherein the anion exchange resin is a fiber made of polyvinyl alcohol having an anion exchange group.

  (6) The electrode for an electrochemical cell according to any one of (1) to (5), comprising 0.01 to 60% by weight of an anion exchange resin with respect to the electrode active material.

  (7) The electrode for an electrochemical cell according to any one of (1) to (6), wherein the electrolyte is an electrolyte containing an electrolyte that ionizes protons.

  (8) The electrode for an electrochemical cell according to any one of items 1 to 7, wherein the anion exchange resin is uniformly dispersed and contained in the electrode.

  (9) The electrode for an electrochemical cell according to any one of Items 1 to 7, wherein the anion exchange resin is contained in an electrode surface layer.

  (10) An electrochemical cell containing a positive electrode containing a proton conductive compound as an electrode active material, a negative electrode containing a proton conductive compound as an electrode active material, and an electrolyte containing a proton source, An electrochemical cell having the electrode according to any one of items 1 to 9 as at least one electrode.

  (11) An electrochemical cell including a positive electrode containing a proton conductive compound as an electrode active material, a negative electrode containing a proton conductive compound as an electrode active material, and an electrolyte containing a proton source. An electrochemical cell having the electrode according to any one of items 1 to 9 as an electrode.

  (12) The electrochemical cell according to (10) or (11), wherein the electrochemical cell can operate so that only protons are involved as charge carriers in the oxidation-reduction reaction of the active material of both electrodes accompanying charge and discharge.

  (13) The electrochemical cell according to (10), (11) or (12), wherein the electrolyte is an aqueous solution containing an acid.

(14) A power storage device provided with an electrochemical cell containing a positive electrode containing a proton conductive compound as an electrode active material, a negative electrode containing a proton conductive compound as an electrode active material, and an electrolyte containing a proton source. So,
The electrochemical cell has the electrode according to any one of claims 1 to 9 as the at least one electrode,
A power storage device in which a plurality of the electrochemical cells are electrically connected.

(15) A power storage device including an electrochemical cell containing a positive electrode containing a proton conductive compound as an electrode active material, a negative electrode containing a proton conductive compound as an electrode active material, and an electrolyte containing a proton source. So,
The electrochemical cell has the electrode according to any one of 1 to 9 as the positive electrode,
A power storage device in which a plurality of the electrochemical cells are electrically connected.

  (16) The power storage device according to (14) or (15), wherein the electrochemical cells are connected in series.

  (17) The power storage device according to item 16, wherein the electrochemical cells are stacked.

  (18) The power storage device according to any one of (14) to (17), wherein the electrochemical cell is operable such that only protons are involved as charge carriers in an oxidation-reduction reaction of an active material of both electrodes accompanying charge and discharge.

  (19) The power storage device according to any one of items 14 to 18, wherein the electrolyte of the electrochemical cell is an aqueous solution containing an acid.

  In the electrode for an electrochemical cell of the present invention, the anion exchange resin contained in the electrode captures the anion in the electrolytic solution, so that the reaction between the electrode active material and the anion as the dopant can be controlled. Therefore, it is possible to reduce the structural deterioration of the active material caused by the reaction between the electrochemical ions and the electrode active material.

  As a result, a decrease in the electron conductivity of the electrode active material can be prevented, and an increase in the internal resistance of the cell can be prevented, so that the cycle life characteristics are improved.

  Further, by containing an anion exchange resin, an ion exchange action is performed in the vicinity of the reaction site of the electrode active material, so that the reaction between the electrode active material and the ions becomes faster than in the related art.

  Furthermore, by using an anion exchange resin having excellent hydrophilicity, the water content of the anion exchange resin itself increases, and as a result, the amount of the electrolyte impregnated inside the electrode increases.

  As a result, the ion conductivity inside the electrode is improved, and the high-speed charge / discharge characteristics are improved.

  In addition, the anion exchange resin traps anions remaining on the electrode surface, which increase due to repetition of charge and discharge, and thus prevents an increase in electrode surface resistance and a decrease in ionic conductivity of the electrolyte. As a result, the cation transport number is maintained in the initial state, and as a result, an increase in the cell internal resistance is prevented, and the cycle life characteristics are improved.

  Further, the anion exchange resin contained in the electrode controls the doping / dedoping reaction of the anion with respect to the electrode active material, thereby reducing the variation of the voltage profile between the unit cells during charging and discharging. Thereby, the cycle life characteristic of the electrochemical cell in which the plurality of unit cells are connected is improved.

  As described above, according to the present invention, it is possible to provide an electrochemical cell having improved cycle life characteristics and rapid charge / discharge characteristics, and an electrode suitable for such an electrochemical cell.

  Hereinafter, preferred embodiments of the present invention will be described.

  The configuration of the electrode for an electrochemical cell according to the present invention contains a proton conductive compound and an anion exchange resin as an electrode active material, and optionally contains a conductive auxiliary material and a binder.

  Hereinafter, a case will be described in which an indole trimer compound is used as the electrode active material on the positive electrode side, and a quinoxaline-based polymer (polyphenylquinoxaline) is used as the electrode active material on the negative electrode side.

  First, a method for manufacturing the positive electrode will be described. For example, fibrous carbon having an average diameter of 150 nm and an average length of 10 to 20 μm (VGCF (trade name) manufactured by Showa Denko KK; And polyvinylidene fluoride (hereinafter referred to as PVDF) can be used as the binder.

  The electrode active material, fibrous carbon, and PVDF are weighed, for example, in the stated order at a weight ratio of 69/23/8, an anion exchange resin is added, and dry mixing is performed using a blender. The use amount of the anion exchange resin with respect to the electrode active material is preferably 0.01 to 60% by weight, and more preferably 0.1 to 30% by weight. A predetermined amount of each of the mixture and dimethylformamide (hereinafter, referred to as DMF) as a solvent is weighed, mixed, and stirred at room temperature for several minutes to obtain a uniformly dispersed slurry.

  Although DMF is used here, the material is not limited to DMF as long as it is an organic solvent in which a material that does not dissolve in the solvent used among the positive electrode materials is easily dispersed.

  After this slurry is formed into a film on a current collector by a screen printing method, the slurry is dried to obtain a positive electrode.

  The electrodes can be formed by a method using hot pressing as described in the description of the related art.

  Although the anion exchange resin is mixed with another electrode material before film formation here, the electrode may be formed by a method of providing an anion exchange resin layer on the electrode surface. As this method, an electrode material containing an electrode active material, a conductive auxiliary material, a binder and the like is molded, and a slurry in which an anion exchange resin is dispersed is applied to the surface of the obtained molded body, and dried. A method can be used in which the powder of the dried electrode material is placed in a molding die, the dried anion-exchange resin is placed thereon, and batch press molding is performed.

  The amount of the anion exchange resin used for the electrode active material can be preferably set appropriately within the above range, but the electrode obtained by mixing and dispersing the anion exchange resin in the electrode material, that is, the anion exchange resin Is uniformly dispersed in the electrode (Form A), the amount is preferably 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, and further preferably 0.1 to 10% by weight. preferable. On the other hand, in the case of an electrode obtained by applying or pressing an anion exchange resin on the surface of an electrode material, that is, an electrode containing an anion exchange resin only in the electrode surface layer (form B), the amount is preferably 1 to 60% by weight. -40% by weight is more preferable, and 1-30% by weight is further preferable.

  In the electrode form A, since the anion exchange resin is mixed and dispersed in the electrode material, the anion exchange resin can be present near the reaction site of the electrode active material, and as a result, the ion exchange efficiency is high. Therefore, even if a small amount of an anion exchange resin is added, a great improvement effect can be obtained.

  On the other hand, in the form B of the electrode, to obtain the same effect as in the form A, it is necessary to use a large amount of the anion exchange resin. However, as shown in Example 3, which will be described later, the amount is set to an appropriate amount. By doing so, a relatively large improvement effect can be obtained. In Form A, if an excess of an anion exchange resin is added in order to obtain a higher improvement effect, particularly when a highly hydrophilic anion exchange resin is used, the water content when the electrolyte is impregnated increases. This causes the electrodes to swell, making handling difficult in the manufacturing process and increasing the electrode resistance. In the embodiment B, a high improvement effect can be obtained while suppressing such a problem.

  Next, a method for manufacturing the negative electrode will be described. For example, Ketjen black can be used as the conductive auxiliary on the negative electrode side. Here, without using an anion exchange resin and a binder, the electrode active material and Ketjen Black are mixed in a weight ratio of, for example, 75/25 in the order described, and this mixture is used as a solvent using m-cresol. Into a slurry, and a film can be formed on the current collector by the same method as that for the positive electrode.

  The anion exchange resin used for the electrode for the electrochemical cell of the present invention is not particularly limited as long as it has a function of exchanging anions. Examples of the ion exchange group include a trimethylammonium group and a primary to tertiary amino group, and examples of the exchange ion form include —Cl and —OH.

  Examples of the base resin constituting the anion exchange resin include an acrylic resin, a polystyrene resin, a polyvinyl alcohol resin, a nylon resin, a polyester resin, a polystyrene-polyethylene composite resin, and a polystyrene-polypropylene composite resin, but are not necessarily limited thereto. Not something. Further, an anion exchange resin made of a conductive resin provided with conductivity by combining a conductive auxiliary material such as carbon particles with these resins can also be used.

  As the shape of the anion exchange resin, various shapes such as a granular shape and a fibrous shape can be used, but a fibrous shape is preferable.

  The reason why the fibrous anion exchange resin is preferable is that the specific surface area is very large and the ion exchange rate is very high. In the present invention, a high ion exchange rate is required in order to improve the rapid charge / discharge characteristics. Therefore, a fibrous anion exchange resin is preferable.

  The fiber length of the fibrous anion exchange resin is preferably 10 mm or less, and the major axis of the fiber is preferably 100 μm or less.

  In the case of an anion exchange fiber having a major fiber length of 100 μm or less, the ion exchange time to reach 80% of the theoretical ion exchange capacity is about 1/8 of the granular anion exchange resin having a particle size of 14 to 50 mesh. Has an exchange rate substantially equal to that of a granular anion exchange resin of 200 to 400 mesh.

  Since the smaller the fiber diameter and the shorter the fiber length, the larger the specific surface area, it is preferable to use fibers having the above-mentioned fiber diameter and fiber length. This also means that when the ion exchange fibers are dispersed in the electrode material, the ion exchange fibers can be more uniformly dispersed, and the anion exchange resin is uniformly distributed in the vicinity of each reaction site of the electrode active material in the vicinity thereof. Therefore, the efficiency of ion exchange is improved, the variation of the ion exchange reaction is reduced, and the effect of improving the battery characteristics can be further enhanced. In addition, the fiber length is preferably 0.1 mm or more, and the major axis of the fiber is preferably 1 μm or more from the viewpoint of availability, ease of preparation, and handling.

  When an aqueous electrolyte is used and an anion exchange resin having excellent hydrophilicity is used, the water content of the anion exchange resin itself increases, and as a result, the amount of the electrolyte impregnated inside the electrode increases. Thereby, the ionic conductivity inside the electrode is improved, and the high-speed charge / discharge characteristics are improved. Further, since the variation of the ion exchange reaction is reduced, the cycle life characteristics of the electrochemical cell in which a plurality of unit cells are connected is also improved.

  For example, as shown in FIG. 1, the electrochemical cell of the present invention is provided on a positive electrode 3 containing a proton conductive compound as an electrode active material provided on a positive electrode current collector 1, and provided on a negative electrode current collector 2. A negative electrode 4 containing a proton-conducting compound as an electrode active material is disposed to face each other with a separator 5 interposed therebetween.

  As an electrolyte, a solution containing an electrolyte for ionizing protons, preferably an aqueous solution, is contained, and is sealed by a gasket 6. Further, an anion exchange resin may be added to the electrolytic solution, but the effect of addition is small compared to the case where the anion exchange resin is directly contained in the electrode.

  As the separator 5, a conventionally used polyolefin-based porous membrane or a cation exchange membrane having a thickness of, for example, 10 to 50 μm can be used.

  The electrochemical cell of the present invention can have the electrode of the present invention containing an anion exchange resin as at least one of a positive electrode and a negative electrode, and has the positive electrode as a positive electrode from the viewpoint of improving battery characteristics. Is preferred.

  The electrochemical cell of the present invention has, as shown in FIG. 1, for example, a single elementary element (hereinafter, referred to as a “unit cell”) that includes a pair of electrodes, a separator interposed therebetween, and an electrolyte as one unit. Or a plurality of unit cells may be electrically connected. As the connection structure of the unit cells, a stacked structure in which a plurality of unit cells are stacked and electrically connected in series, a planar structure in which a plurality of unit cells are arranged on the same plane and electrically connected in series, Can be mentioned.

  As the laminated structure, for example, a structure in which the unit cells 7 shown in FIG. 1 are directly laminated and the pressing plates 8 are respectively laminated outside the unit cells at the upper and lower ends (FIG. 6), and on both upper and lower sides of each unit cell 7 A structure in which the pressure plates 8 are stacked and arranged, and the stacked plates are stacked (FIG. 7) is exemplified.

  The exterior shape of the electrochemical cell can be a conventionally used shape such as a coin type or a laminate type, and is not particularly limited.

  As an electrochemical cell in which the desired effect is more remarkably obtained, a cell capable of operating so that only protons act as charge carriers in a redox reaction in both electrodes accompanying charge and discharge, and more specifically, includes a proton source Containing an electrolyte, the proton concentration and operating voltage of the electrolyte are controlled so that it can operate so that only the adsorption and desorption of protons of the electrode active material is involved in electron transfer accompanying the oxidation-reduction reaction at both electrodes during charge and discharge. Are preferred.

  The reaction formula (1) shows a reaction of an indole trimer compound, which is one of the proton conductive compounds. The first-stage reaction shows a reaction by doping, and the second-stage reaction shows an electrochemical reaction (electrode reaction) accompanied by adsorption and desorption of protons of the doped compound. In an electrochemical cell that causes such an electrode reaction, only the absorption and desorption of protons are involved in the electron transfer involved in the oxidation-reduction reaction. Since the volume change is small and the cycle characteristics are excellent, and the proton mobility is high and the reaction is fast, the high rate characteristics are excellent, that is, the rapid charge and discharge characteristics are excellent.

  As described above, a proton conductive compound is used as the electrode active material in the present invention, and the proton conductive compound is an organic compound (polymer) capable of accumulating electrochemical energy by a redox reaction with electrolyte ions. ).

  As such a proton conductive compound, conventionally known compounds can be used.For example, polyaniline, polythiophene, polypyrrole, polyacetylene, poly-p-phenylene, polyphenylenevinylene, polyperinaphthalene, polyfuran, polyflurane, polythienylene, polythylene Π-conjugated polymers such as pyridinediyl, polyisothianaphthene, polyquinoxaline, polypyridine, polypyrimidine, polyindole, polyaminoanthraquinone, polyimidazole and derivatives thereof, indole-based conjugated compounds such as indole trimer compound, benzoquinone Quinone-based compounds such as naphthoquinone and anthraquinone, and quinone-based polymers such as polyanthraquinone, polynaphthoquinone, and polybenzoquinone (where quinone oxygen forms hydroxyl groups by conjugation) And a proton-conducting polymer obtained by copolymerization of two or more types of monomers that give the polymer. By doping these compounds, a redox pair is formed, and conductivity is exhibited. These compounds are selectively used as a positive electrode active material and a negative electrode active material by appropriately adjusting the difference in the oxidation-reduction potential.

  As the proton conductive compound, a π-conjugated compound or a π-conjugated polymer having a nitrogen atom, a quinone-based compound or a quinone-based polymer can be preferably used.

  Among these, an indole trimer compound is preferable as the positive electrode active material, and a quinoxaline-based polymer compound is preferable as the negative electrode active material.

  The indole trimer compound has a fused polycyclic structure having a six-membered ring composed of atoms at the 2- and 3-positions of three indole rings. The indole trimer compound can be prepared from one or more compounds selected from indole and indole derivatives or indoline and its derivatives by a known electrochemical or chemical method.

  Examples of such an indole trimer compound include those represented by the following chemical formula.

(Wherein R independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a nitro group, a phenyl group, a vinyl group, a halogen atom, an acyl group, a cyano group, an amino group, a trifluoromethyl group, a sulfonic acid group, A fluoromethylthio group, a carboxylic acid ester group, a sulfonic acid ester group, an alkoxyl group, an alkylthio group, an arylthio group, an alkyl group having 1 to 20 carbon atoms which may have these substituents, and having these substituents Represents an aryl group having 6 to 20 carbon atoms and a heterocyclic compound residue which may be present.)
In the above formula, examples of the halogen atom for R include fluorine, chlorine, bromine and iodine. In the formula, as the alkyl group for R, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl Group, n-heptyl group, n-octyl group and the like. In the formula, the acyl group of R is a substituent represented by -COX, and X includes the above-mentioned alkyl group. In the formula, the alkoxyl group of R is a substituent represented by -OX, and X includes the above-mentioned alkyl group. In the formula, examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthryl group. In the formula, the alkyl portion of the alkylthio group represented by R may be the above-mentioned alkyl group. In the formula, the aryl portion of the arylthio group for R can be the above-mentioned aryl group. In the formula, as the heterocyclic compound residue of R, a 3 to 10-membered ring group having 2 to 20 carbon atoms and 1 to 5 heteroatoms can be mentioned. As the hetero atom, oxygen, sulfur, Nitrogen.

  The quinoxaline-based polymer is a polymer having a unit having a quinoxaline skeleton, and a polymer having a quinoxaline skeleton represented by the following chemical formula can be used.

(R in the formula may be contained as a linking group in the main chain of the polymer or may be contained as a side chain group. In the formula, Rs are each independently a hydrogen atom, Hydroxyl group, amino group, carboxyl group, nitro group, phenyl group, vinyl group, halogen atom, acyl group, cyano group, trifluoromethyl group, sulfonyl group, sulfonic acid group, trifluoromethylthio group, alkoxyl group, alkylthio group, Arylthio group, carboxylic acid ester group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have these substituents, an alkyl group having 6 to 20 carbon atoms which may have these substituents An aryl group and a heterocyclic compound residue are shown.)
In the above formula, examples of the halogen atom for R include fluorine, chlorine, bromine and iodine. In the formula, as the alkyl group for R, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl Group, n-heptyl group, n-octyl group and the like. In the formula, the acyl group of R is a substituent represented by -COX, and X includes the above-mentioned alkyl group. In the formula, the alkoxyl group of R is a substituent represented by -OX, and X includes the above-mentioned alkyl group. In the formula, examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthryl group. In the formula, the alkyl portion of the alkylthio group represented by R may be the above-mentioned alkyl group. In the formula, the aryl portion of the arylthio group for R can be the above-mentioned aryl group. In the formula, as the heterocyclic compound residue of R, a 3 to 10-membered ring group having 2 to 20 carbon atoms and 1 to 5 heteroatoms can be mentioned. As the hetero atom, oxygen, sulfur, Nitrogen.

  As such a quinoxaline-based polymer, a polymer having a 2,2 '-(p-phenylene) diquinoxaline skeleton is preferable, and polyphenylquinoxaline represented by the following formula can be used. In addition, n in a formula shows a positive integer.

  An inorganic acid or an organic acid can be used as a proton source of an electrolyte containing a proton source (which can give a proton). For example, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tetrafluoroboric acid, Examples include fluorophosphoric acid and hexafluorosilicic acid, and examples of the organic acid include saturated monocarboxylic acid, aliphatic carboxylic acid, oxycarboxylic acid, p-toluenesulfonic acid, polyvinylsulfonic acid, and lauric acid. Among these electrolytes containing a proton source, an acid-containing aqueous solution is preferable, and a sulfuric acid aqueous solution is particularly preferable.

The proton concentration in the electrolyte solution containing the proton source is preferably at least 10 ^-3 mol / l, more preferably at least 10 ^-1 mol / l, from the viewpoint of the reactivity of the electrode material, and on the other hand, the activity of the electrode material is reduced or eluted. It is preferably 18 mol / l or less, more preferably 7 mol / l or less from the viewpoint of prevention of odor.

  Next, the present invention will be described in more detail with reference to examples of an electrochemical cell for a secondary battery. In addition, by appropriately setting the basic configuration of the above-described electrochemical cell, a configuration suitable for a capacitor can also be obtained.

(Example 1)
5-Cyanoindole trimer as a positive electrode active material, fibrous carbon as a conductive auxiliary material, and PVDF (average molecular weight: 1100) as a binder were weighed in the stated order so as to have a weight ratio of 69/23/8. Then, an anion exchange resin of 0.3% by weight with respect to the positive electrode active material was weighed, and stirred and mixed with a blender. As the anion exchange resin, a fiber having a trimethylammonium group as an ion exchange group, having an exchange ion form of -OH type polyvinyl alcohol, and having a fiber major axis of 60 µm (manufactured by Nichibi Corporation, IEF-SA (OH )) Was cut to a fiber length of 3 mm.

  10 mg of this mixed powder was weighed and stirred at room temperature for 5 minutes in 1 ml of DMF to obtain a slurry which was uniformly dispersed. This was formed into a film on the current collector by a screen printing method, and then dried to obtain a positive electrode having a thickness of 100 μm. This was cut into a predetermined shape and used.

  Next, polyphenylquinoxaline, which is a proton conductive polymer, was used as an electrode active material on the negative electrode side, and Ketjen Black (EC-600JD, manufactured by Ketjen Black International Co., Ltd.) was used as a conductive auxiliary on the negative electrode side. . These were weighed in the stated order at a weight ratio of 75/25 and stirred and mixed with a blender. Then, using m-cresol as a solvent, a negative electrode having a thickness of 100 μm was obtained in the same manner as the positive electrode. Here, the fibers of the anion exchange resin were not mixed on the negative electrode side.

  A 20 wt% sulfuric acid aqueous solution was used as an electrolytic solution, and the surfaces on which the positive electrode and the negative electrode were formed were attached to each other via a separator made of a polyolefin-based porous film having a thickness of 30 μm. A coin-shaped electrochemical cell having an outer diameter of 14 mm and having a cross section shown in FIG. 1 was obtained.

  The electrochemical cell thus prepared was subjected to a high-temperature cycle test. The conditions for the test are a temperature of 45 ° C., a charge / discharge rate of 10 C, and a charge / discharge cycle of 5000. The evaluation items are the initial appearance capacity and the remaining capacity after 5000 cycles.

(Example 2)
A mixed material for a positive electrode and a negative electrode was prepared in the same manner as in Example 1, and an electrochemical cell was prepared in the same manner as in Example 1, except that each electrode was formed by hot press molding. High temperature cycle characteristics were evaluated.

(Example 3)
In the same manner as in Example 1, a mixed material for the positive electrode (excluding the anion exchange resin) was prepared, and hot press molding was performed. The anion exchange resin used in Example 1 was formed on the surface of the molded body to a thickness of 20% by weight based on the 5-cyanoindole trimer to obtain a positive electrode. At the time of film formation, a predetermined amount of a slurry in which an anion exchange resin was dispersed was applied to the surface of the molded body, and dried.

  Further, a mixed material for a negative electrode was prepared in the same manner as in Example 1, and was subjected to hot press molding to obtain a negative electrode. Thereafter, an electrochemical cell was prepared in the same manner as in Example 1, and a high-temperature cycle test was performed.

(Example 4)
An electrochemical cell was prepared and subjected to a high-temperature cycle test in the same manner as in Example 3, except that the amount of the anion exchange resin was adjusted to 60% by weight based on the electrode active material on the positive electrode side.

(Example 5)
An electrochemical cell was prepared and subjected to a high-temperature cycle test in the same manner as in Example 1 except that the mixing amount of the anion exchange resin with respect to the electrode active material on the positive electrode side was changed to 6.5% by weight.

(Example 6)
An electrochemical cell was prepared and subjected to a high-temperature cycle test in the same manner as in Example 1, except that the mixing amount of the anion exchange resin with respect to the electrode active material on the positive electrode side was 0.005% by weight.

(Example 7)
An electrochemical cell was prepared and subjected to a high-temperature cycle test in the same manner as in Example 1 except that the length of the fiber of the anion exchange resin was changed to 0.5 mm.

(Example 8)
An anion exchange resin (ion exchange group: trimethylammonium group, exchange ion type: -OH type, manufactured by Toray Industries, Inc., trade name: IONEX, TIN-200) comprising a polystyrene-polyethylene composite fiber having a fiber major axis of 60 μm was used. An electrochemical cell was prepared and subjected to a high-temperature cycle test in the same manner as in Example 1, except that the cell was selected and the fiber length was cut to 3 mm.

(Example 9)
Anion exchange resin composed of conductive fibers obtained by introducing carbon into a base resin composed of nylon 6 (ion exchange group: trimethylammonium group, exchange ion type: -OH type, manufactured by Kanebo Co., Ltd., trade name: Vectron-961) An electrochemical cell was prepared and subjected to a high-temperature cycle test in the same manner as in Example 1 except for using.

(Example 10)
An electrochemical cell was prepared in the same manner as in Example 1 except that a granular weakly basic anion exchange resin having a particle size of 14 to 50 mesh (manufactured by Mitsubishi Chemical Corporation, Diaion (registered trademark) SA10A) was used. A cycle test was performed.

(Example 11)
An electrochemical cell was prepared in the same manner as in Example 1, except that the anion exchange resin used in Example 1 was mixed in both the positive electrode and the negative electrode with 0.3% by weight based on the electrode active material, respectively. A high temperature cycle test was performed.

(Example 12)
An electrochemical cell was prepared in the same manner as in Example 1, except that a granular strong basic anion exchange resin (manufactured by Dow Chemical Company, trade name: Dowex 1 × 8) having a particle size of 200 to 400 mesh was used. And a high temperature cycle test.

(Comparative Example 1)
An electrochemical cell was prepared and subjected to a high-temperature cycle test in the same manner as in Example 1 except that the anion exchange resin was not added to the electrode material.

  Table 1 summarizes the results of the high-temperature cycle tests performed on the electrochemical cells of Examples 1 to 12 and Comparative Example 1. The following is clear from the results in Table 1.

  In each of the examples, as compared with Comparative Example 1, both the initial capacity and the remaining capacity were large, and the results showed excellent high-temperature cycle characteristics, and the effect of the anion exchange resin was exhibited. In addition, despite the fact that the high-temperature cycle test was carried out at a higher current than usual, no remarkable decrease in the remaining capacity was observed, indicating that the high-speed charge / discharge characteristics were improved.

  Comparing Example 1 with Example 2, the initial capacity of Example 2 is larger than that of Example 2. This is because the electrode is formed by screen printing in Example 1, In Example 2, since the electrodes were formed by press molding, it is understood that the density of the electrodes was higher in Example 2 and the initial capacity was correspondingly increased.

  The third embodiment has a larger remaining capacity than the first embodiment. This is because the amount of the anion exchange resin used is as large as 20% by weight based on the electrode active material. On the other hand, in Example 6, since the amount of the anion exchange resin added was reduced to 0.005% by weight based on the electrode active material, the effect of the addition was obtained, but the improvement effect was small.

  In Example 3, the anion exchange resin was provided on the electrode surface by coating, whereas in Example 5, it was mixed in the electrode material. That is, when the anion exchange resin is excessively contained in the electrode material, the anion exchange resin itself does not function as an electrode active material, so that the effect of improving the characteristics is reduced.

  Further, when an anion exchange resin is provided on the electrode surface layer by coating, even if an excessive amount is used, it does not easily contribute to improvement in characteristics. This is clear from the comparison between the results of Example 4 and Example 3 in which the amount of the anion exchange resin used was 60% by weight.

  In Example 5, since the addition amount of the anion exchange resin was 6.5% by weight with respect to the electrode active material, which was larger than that in Example 1, the initial capacity was lower than that in Example 1. However, the decrease in the remaining capacity is further suppressed.

  In Example 7, both the initial capacity and the remaining capacity showed larger values than the other examples. It is understood that this is because the specific surface area of the anion exchange resin was increased by adjusting the length of the fibers of the anion exchange resin to 1/6 that of the other examples, and the effect of adding the fibers was increased. On the other hand, although no particular numerical value is shown, when an anion exchange resin fiber having a length exceeding 10 mm was used, the effect of improving the properties tended to decrease.

  In Example 8, a different anion exchange resin from that of Example 1 was used. Also in this case, the characteristics are almost the same as those in Example 1, indicating that a desired effect can be obtained with a suitable anion exchange resin.

  In Example 9, an anion exchange resin different from Example 1 and Example 8 was used. Also in this case, the same characteristics as those in Example 1 were obtained. This is thought to be due to the fact that, in addition to the anion exchange action, the resistivity of the electrode was lowered due to the conductivity of the anion exchange resin.

  In Example 10, a granular anion exchange resin was used. The test results are inferior to those using fibrous anion exchange resin. This is presumably because the granular form had a smaller specific surface area than the fibrous form, and the effect of adding the anion exchange resin was relatively low.

  Example 11 is different from the other examples in that an anion exchange resin was added to both the positive electrode and the negative electrode. The test results showed that the effect of improving the characteristics was lower than in Example 1 in which the anion exchange resin was not added to the negative electrode. From this, it is clear that the addition of the anion exchange resin to the positive electrode greatly contributes to the improvement of the characteristics.

  In Example 12, 200-400 mesh granular anion exchange resin was used, and almost the same effect as Example 1 using fibrous anion exchange resin was obtained.

(Example 13)
In the preparation of the positive electrode, FIG. 1 shows in the same manner as in Example 1 except that the content of the anion exchange resin with respect to the electrode active material was 10% by weight, and a 20 μm-thick polyolefin-based porous membrane was used as a separator. A unit cell having a cross-sectional structure was manufactured.

As shown in FIG. 6, five unit cells 7 were stacked and connected in series, and a pressing plate 8 was arranged at the upper and lower outermost portions of the stacked body. Then, a pressure of 5 kgf / cm ² (4.9 × 10 ⁵ Pa) was applied to the laminate through the pressurizing plate 8 and fixed by caulking to obtain an electrochemical cell laminate.

  The electrochemical cell laminate and the cell laminates of the following Examples and Comparative Examples were charged at a constant current and constant voltage (5 C, 1.2 V per unit cell) for 10 minutes in an environment of 25 ° C. At 5C), the battery was discharged until the depth of discharge reached 100%, and the charging and discharging were repeated to evaluate the battery characteristics. Table 2 shows the results. The initial capacity in the table is a relative value of the initial capacity of another cell stack when the initial capacity of the cell stack of Comparative Example 2 is 1. In addition, the cycle index in the table means that the number of cycles when the capacity after charge and discharge of the cell stack of Comparative Example 2 reaches 80% of the initial capacity is 1, and the charge of other cell stacks is 1. This is a relative value of the number of cycles when the capacity after discharge reaches 80% of the initial capacity.

  From these results, it is understood that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 14)
In the same manner as in Example 1, a mixed material for the positive electrode (excluding the anion exchange resin) was prepared, and hot press molding was performed. The anion exchange resin used in Example 1 was formed on the surface of the molded body to a thickness of 10% by weight with respect to the 5-cyanoindole trimer to obtain a positive electrode. At the time of film formation, a predetermined amount of a slurry in which an anion exchange resin was dispersed was applied to the surface of the molded body, and dried. Then, a negative electrode was produced in the same manner as in Example 1, and an electrochemical cell laminate was produced in the same manner as in Example 13.

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 15)
An electrochemical cell laminate was prepared in the same manner as in Example 13 except that a granular weakly basic anion exchange resin having a particle size of 14 to 50 mesh (manufactured by Mitsubishi Chemical Corporation, Diaion (registered trademark) SA10A) was used. .

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 16)
An electrochemical cell laminate was produced in the same manner as in Example 13, except that the content of the anion exchange resin with respect to the electrode active material on the positive electrode side was 0.005% by weight.

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 17)
An electrochemical cell laminate was produced in the same manner as in Example 14, except that the content of the anion exchange resin with respect to the electrode active material on the positive electrode side was changed to 60% by weight.

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 18)
An electrochemical cell laminate was produced in the same manner as in Example 13, except that the length of the fiber of the anion exchange resin was changed to 10 mm.

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 19)
An electrochemical cell laminate was produced in the same manner as in Example 13, except that the length of the fiber of the anion exchange resin was 1.5 mm.

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 20)
An anion exchange resin (ion exchange group: trimethylammonium group, exchange ion type: -OH type, manufactured by Toray Industries, Inc., trade name: IONEX, TIN-200) comprising a polystyrene-polyethylene composite fiber having a fiber major axis of 60 μm was used. An electrochemical cell laminate was prepared in the same manner as in Example 13 except that the fiber length was cut to 3 mm and used.

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 21)
As shown in FIG. 7, an electrochemical cell laminate was produced in the same manner as in Example 13, except that pressure plates were arranged on the upper and lower sides of each unit cell, and five pressure plates were laminated.

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 22)
An electrochemical cell laminate was produced in the same manner as in Example 13, except that ten unit cells were laminated.

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Example 23)
An electrochemical cell laminate was prepared in the same manner as in Example 13 except that a granular strong basic anion exchange resin having a particle size of 200 to 400 mesh (manufactured by Dow Chemical Company, trade name: Dowex 1 × 8) was used. Produced.

  From the results shown in Table 2, it can be seen that according to the present invention, the capacity and cycle life characteristics of the electrochemical cell laminate are improved.

(Comparative Example 2)
An electrochemical cell laminate was produced in the same manner as in Example 13, except that the anion exchange resin was not added to the electrode material. The reason why the initial capacity is smaller than that in Example 13 is considered that the voltage profile of each unit cell in the stacked body is different, so that some cells do not reach the rated voltage.

(Comparative Example 3)
An electrochemical cell laminate was produced in the same manner as in Comparative Example 2 except that ten unit cells were laminated.

(Comparative Example 4)
An electrochemical cell laminate was produced in the same manner as in Example 21, except that the anion exchange resin was not added to the electrode material.

The figure which shows the cross section of an electrochemical cell (unit cell). The graph which shows the result of a constant current test (cycle test) and a constant current constant voltage test (constant voltage holding test). The figure which shows the measurement result of the cyclic voltammetry at the time of changing a voltage scanning speed. 4 is a graph showing charging characteristics (voltage profile) of the electrochemical cell. 4 is a graph showing discharge characteristics (voltage profile) of the electrochemical cell. Sectional drawing of an electrochemical cell laminated body. Sectional drawing of an electrochemical cell laminated body.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 1 Positive electrode collector 2 Negative electrode collector 3 Positive electrode 4 Negative electrode 5 Separator 6 Gasket 7 Unit cell 8 Pressure plate

Claims (19)

  A positive electrode containing a proton conducting compound as an electrode active material, a negative electrode containing a proton conducting compound as an electrode active material, and an electrode used in an electrochemical cell containing an electrolyte containing a proton source, comprising: An electrode for an electrochemical cell containing a conductive compound and an anion exchange resin.   The electrode for an electrochemical cell according to claim 1, wherein the proton conductive compound is a compound that stores electrochemical energy by a redox reaction with ions of an electrolyte.   The electrode for an electrochemical cell according to claim 1 or 2, wherein the anion exchange resin is fibrous.   4. The electrode for an electrochemical cell according to claim 1, wherein the anion exchange resin is in a fibrous shape having a length of 10 mm or less and a long diameter of 100 μm or less. 5.   The electrode for an electrochemical cell according to any one of claims 1 to 4, wherein the anion exchange resin is a fiber made of polyvinyl alcohol having an anion exchange group.   The electrode for an electrochemical cell according to any one of claims 1 to 5, comprising 0.01 to 60% by weight of the anion exchange resin based on the electrode active material.   The electrode for an electrochemical cell according to any one of claims 1 to 6, wherein the electrolyte is an electrolyte containing an electrolyte that ionizes protons.   The electrode for an electrochemical cell according to any one of claims 1 to 7, wherein the anion exchange resin is uniformly dispersed and contained in the electrode.   The electrode for an electrochemical cell according to any one of claims 1 to 7, wherein the anion exchange resin is contained in an electrode surface layer.   A positive electrode containing a proton conductive compound as an electrode active material, a negative electrode containing a proton conductive compound as an electrode active material, and an electrochemical cell containing an electrolyte containing a proton source, wherein at least one of the above An electrochemical cell having the electrode according to any one of claims 1 to 9 as an electrode.   A positive electrode containing a proton conductive compound as an electrode active material, a negative electrode containing a proton conductive compound as an electrode active material, and an electrochemical cell containing an electrolyte containing a proton source. Item 10. An electrochemical cell having the electrode according to any one of items 1 to 9.   12. The electrochemical cell according to claim 10, wherein the electrochemical cell can operate so that only protons are involved as charge carriers in an oxidation-reduction reaction of an active material of both electrodes accompanying charge and discharge.   The electrochemical cell according to claim 10, 11 or 12, wherein the electrolyte is an aqueous solution containing an acid. A positive electrode containing a proton conducting compound as an electrode active material, a negative electrode containing a proton conducting compound as an electrode active material, and a power storage device including an electrochemical cell containing an electrolyte containing a proton source,
The electrochemical cell has the electrode according to any one of claims 1 to 9 as the at least one electrode,
A power storage device in which a plurality of the electrochemical cells are electrically connected. A positive electrode containing a proton conducting compound as an electrode active material, a negative electrode containing a proton conducting compound as an electrode active material, and a power storage device including an electrochemical cell containing an electrolyte containing a proton source,
The electrochemical cell has the electrode according to any one of claims 1 to 9 as the positive electrode,
A power storage device in which a plurality of the electrochemical cells are electrically connected.   The power storage device according to claim 14, wherein the electrochemical cells are connected in series.   The power storage device according to claim 16, wherein the electrochemical cells are stacked.   The power storage device according to any one of claims 14 to 17, wherein the electrochemical cell can operate such that only protons are involved as charge carriers in an oxidation-reduction reaction of an active material of both electrodes accompanying charge and discharge.   The power storage device according to any one of claims 14 to 18, wherein the electrolyte of the electrochemical cell is an aqueous solution containing an acid.

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