JP4024568B2 - Electrochemical power storage device and method for manufacturing the same - Google Patents

Description

【００８４】
以上に説明したとおり本発明実施例１−３は、比較例１−２に比べていずれも重量あたりの静電容量が高い電極材料とすることができ、高容量の電気化学蓄電デバイスとすることができた。
【００８５】
【発明の効果】
以上のように本発明は、種々の活性炭、例えば電気二重層容量も大きく発現する比表面積が大きいものや官能基濃度が高いものにおいてもより効率よく遷移金属酸化物または遷移金属水酸化物を担持させた電極材料を作製し、さらに残存ハロゲン含有率を下げることにより高容量かつ長寿命である電気化学蓄電デバイスを作製することができる。
【図面の簡単な説明】
【図１】本発明の一実施形態における電気化学蓄電デバイスの構造断面図。
【図２】本発明の実施例１における熱分析結果を示すチャート。
【図３】本発明の実施例１におけるＸ線解析結果を示すチャート。
【図４】本発明の実施例1に示した酸化ルテニウムまたは水酸化ルテニウムが吸着した活性炭繊維電極と比較例１の吸着処理をしていない活性炭繊維電極のサイクリックボルタンメトリ測定結果である。
【符号の説明】
１ 正極集電体
２ 正極活性炭
３ 負極集電体
４ 負極活性炭
５ イオン透過性セパレータ
６ 絶縁性ゴム[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrochemical storage device having a high energy density and a long lifetime, and a method for manufacturing the same.
[0002]
[Prior art]
Conventionally, there are an electric double layer capacitor and a secondary battery as typical electrochemical storage devices, and they are already used in the market utilizing their respective characteristics.
[0003]
The electric double layer capacitor has a higher output density than a secondary battery, has a long life, and is used for a backup power source or the like that requires high reliability.
[0004]
On the other hand, the secondary battery has a higher energy density than the electric double layer capacitor and is the most typical electric energy storage device, but its life is shorter than that of the electric double layer capacitor and needs to be replaced after a certain period of use. Has the disadvantage of being.
[0005]
The difference between these two characteristics is due to the electrical energy storage mechanism. In an electric double layer capacitor, an electrochemical reaction does not occur between the electrode and the electrolyte, and the ions contained in the electrolyte during charging and discharging. Just move.
[0006]
Therefore, the electric double layer capacitor is less likely to be deteriorated than the secondary battery, and the ion moving speed is fast. Therefore, the electric double layer capacitor has a long life and a high output density.
[0007]
On the other hand, in a secondary battery, since an electrochemical reaction between an electrode and an electrolytic solution is used, deterioration occurs due to charging / discharging, a chemical reaction rate is slow, a life is short, and an output density is relatively small.
[0008]
However, since the secondary battery stores energy in the form of chemical energy, the secondary battery has a higher energy density than an electric double layer capacitor that can store energy only at the interface between the electrode and the electrolyte.
[0009]
On the other hand, in recent years, an electrochemical capacitor has been proposed which has both high output density and long life, which are characteristics of an electric double layer capacitor, and high energy density, which is a characteristic of a secondary battery.
[0010]
As a typical electrode material used in the electrochemical capacitor, there is a material using a transition metal compound such as ruthenium oxide.
[0011]
However, although the theoretical energy density of ruthenium oxide is high, there is a problem that the effective energy density when the device is manufactured as a prototype is low because of its low conductivity.
[0012]
As a means for solving this, the method described in JP-A-11 (1999) -354389, that is, using ruthenium chloride as a starting material, this is adsorbed on activated carbon fine particles and subjected to heat treatment in air at 470 ° C. for 40 minutes. Thus, a method for producing ruthenium oxide has been proposed. According to the present invention, since the conductivity is improved, the conventional problem is solved, and at the same time, since the ruthenium chloride solution can be reused, the use efficiency of ruthenium can be increased, thereby reducing the cost.
[0013]
Furthermore, Japanese Patent Laid-Open No. 2000-36441 also proposes a method in which ruthenium oxide is not formed as a final product, but ruthenium chloride is adsorbed and then an alkali neutralization treatment is performed to obtain ruthenium hydroxide as a final product. Yes.
[0014]
However, in the conventional method in which ruthenium chloride is used as a starting material and heat treatment is performed and ruthenium oxide is supported on the activated carbon fine particles, the following two problems exist.
[0015]
The first problem is the limit of energy density due to the limitation of the activated carbon to be supported.
[0016]
In general, many transition metal compounds containing ruthenium chloride have high oxidation ability, while activated carbon fine particles generally have a characteristic of being easily oxidized.
[0017]
Actually, the inventors of the present invention used various activated carbons to adsorb ruthenium chloride and then heat-treated by the method described in JP-A-11 (1999) -354389. In particular, activated carbon having a large specific surface area and a high functional group concentration. In the system using, activated carbon burned before ruthenium oxide was produced, and they could not be used as an electrode material.
[0018]
If the heat treatment time is extremely shortened, combustion can be controlled to some extent, but in that case, most of the ruthenium chloride adsorbed in the finer pores is not converted to ruthenium oxide, so the capacity density is improved. It will be disturbed.
[0019]
On the other hand, as an advantage of using activated carbon with a high functional group concentration, the electric double layer capacity on the surface on which ruthenium oxide is not completely supported can also be used as an energy density, so even with activated carbon having a large specific surface area and a high functional group concentration, it is high. The need to efficiently support the transition metal oxide at the combustion temperature is a problem.
[0020]
The second problem is the problem of reliability due to residual halogen compounds. After loading, dissolution of unvaporized chlorine ions remaining on the activated carbon in the electrolyte causes various adverse effects such as erosion to the case and deterioration of reliability such as deterioration of capacity life test. This problem similarly occurs in a process in which ruthenium chloride is alkali-neutralized to form ruthenium hydroxide without performing heat treatment.
[0021]
[Problems to be solved by the invention]
In order to solve the above-described conventional problems, the present invention eliminates contamination of halide ions as much as possible, and efficiently produces an electrode material carrying a transition metal oxide or transition metal hydroxide, thereby achieving a high capacity. An object of the present invention is to provide an electrochemical storage device having a long life and a method for producing the same.
[0022]
[Means for Solving the Problems]
To achieve the above object, an electrochemical electricity storage device of the present invention includes a pair of electrodes, a separator interposed between the pair of electrodes, and an electrolyte solution impregnated in the electrodes and the separator. The electrode is formed by adsorbing at least one selected from ruthenium nitrate and a solution in which ruthenium nitrate is dissolved on the carbon-based material and performing an addition treatment, thereby at least ruthenium oxide or ruthenium hydroxide is added to the carbon-based material. It is characterized by being an electrode carried on the substrate.
[0023]
Next, a method for manufacturing an electrochemical storage device according to the present invention includes manufacturing a electrochemical storage device including a pair of electrodes, a separator interposed between the pair of electrodes, and an electrolyte solution impregnated in the electrodes and the separator. In the method, the electrode is subjected to an addition treatment by adsorbing at least one selected from a transition metal nitrate compound and a solution in which the transition metal nitrate compound is dissolved in a carbon-based material, thereby at least a transition metal oxide or a transition. When the metal hydroxide is supported on the carbon-based material and formed , the addition treatment is immersion in an alkaline aqueous solution .
Another method of manufacturing an electrochemical storage device of the present invention is to manufacture an electrochemical storage device including a pair of electrodes, a separator interposed between the pair of electrodes, and an electrolyte solution impregnated in the electrode and the separator. In the method, the electrode is subjected to an addition treatment by adsorbing at least one selected from a transition metal nitrate compound and a solution in which the transition metal nitrate compound is dissolved in a carbon-based material, thereby at least a transition metal oxide or a transition. When the metal hydroxide is formed on the carbon-based material, the addition treatment is a heat treatment in a range of 150 ° C. or higher and 750 ° C. or lower.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
There are two methods for producing an oxide or hydroxide using a transition metal nitrate compound as a starting material: a heat treatment method at a temperature at which activated carbon does not burn or an alkali neutralization method at which activated carbon does not burn at all.
[0025]
If the transition metal oxide or transition metal hydroxide is supported on activated carbon having a large specific surface area and a high functional group concentration using these means, only the capacity increase caused by the transition metal oxide or the transition metal hydroxide is achieved. In addition, since the electric double layer capacity caused by the activated carbon increases, the electrochemical storage device using the electrode material exhibits a high capacity component.
[0026]
In particular, in the heat treatment method, nitrate ions present in transition metal nitrate compounds serve as a supply source of oxygen atoms, and transition metal oxides can be generated and supported on electrode activated carbon even in an inert atmosphere where no oxygen atoms are present. In addition, by using a nitric acid compound as a starting material in both the heat treatment method and the alkali neutralization method, the residual halogen content in the electrode material can be lowered, so that high reliability can be guaranteed.
[0027]
Therefore, in this invention, it is preferable not to contain the halide other than being inevitably mixed in the electrode material. More specifically, since it cannot be denied that halides of the order of 10 ppm are inevitably mixed, it is preferable to suppress contamination to 20 ppm or less.
[0028]
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0029]
FIG. 1 shows a cross-sectional view of an electrochemical storage device of an embodiment claimed in the present invention. This electrochemical storage device has an ion permeable separator 5 interposed between a positive electrode activated carbon 2 located on the positive electrode current collector 1 and a negative electrode activated carbon 4 located on the negative electrode current collector 3, and the positive electrode current collector 1 and The negative electrode current collector 3 is electrically insulated by an insulating rubber 6.
[0030]
At least one of these positive electrode activated carbon 2 and negative electrode activated carbon 4 contains a transition metal oxide or transition metal hydroxide represented by ruthenium oxide, and the valence of these oxides or hydroxides changes continuously. As a result, electrochemical energy is accumulated. Therefore, it is desirable to increase the energy density to contain more transition metal oxide per activated carbon surface area, but if the transition metal oxide is contained so as to cover the activated carbon surface, the electric bismuth formed on the activated carbon surface. Since the multi-layer capacity cannot be used, it is desirable to limit the carbon content to 0.01 to 30% by weight. Moreover, if the activated carbon used is a porous activated carbon having a specific surface area of 500 m ² / g or more and 4000 m ² / g or less, the effect of the present invention can be obtained. In particular, fibrous activated carbon is preferable.
[0031]
In the present invention, it is considered that the effects of the invention are particularly large among the transition metals, especially Ru, V, Cr, Mn, Mo, W and Group VIII elements (Fe, Co, Tc, Rh, Re, Os, Ir, Ni, Pd). It is done. For example, in terms of a transition metal nitrate compound, at least one selected from ruthenium nitrate, vanadium nitrate, tungsten nitrate, molybdenum nitrate, chromium nitrate, manganese nitrate, iron nitrate, rhodium nitrate, osmium nitrate, and iridium nitrate is preferable.
[0032]
In order to support ruthenium oxide or ruthenium hydroxide on the electrode activated carbon using ruthenium as a transition metal, the inventors conducted experiments using ruthenium nitrate as a starting material. The following three methods are conceivable as methods for supporting ruthenium oxide or ruthenium hydroxide on activated carbon using ruthenium nitrate as a starting material.
[0033]
First, after immersing activated carbon in a ruthenium nitrate aqueous solution, the extracted activated carbon is dried and heat-treated in a nitrogen atmosphere. By performing this heat treatment, nitrate ions present in the ruthenium nitrate serve as a supply source of oxygen atoms, and ruthenium oxide can be generated and supported on the electrode activated carbon even in a nitrogen atmosphere in which no oxygen atoms are present. This reaction is considered to be represented by the following chemical formula (1).
[0034]
Ru (NO ₃ ) ₃ → (1-n) Ru (NO ₃ ) ₃ + nRuO ₂ + 3nNO _x (where x = 7/3) (1)
Second, after immersing activated carbon in an aqueous ruthenium nitrate solution, the extracted activated carbon is dried and heat treatment is performed by adding oxygen or water vapor in an inert gas atmosphere.
By performing this heat treatment, the added oxygen or water vapor becomes a supply source of oxygen atoms, and ruthenium oxide can be generated and supported on the electrode activated carbon. However, since the combustion temperature of the activated carbon is determined by the gas partial pressure of the added oxygen or water vapor, it is necessary to determine the gas partial pressure according to the type of activated carbon in order to prevent the activated carbon from burning. The higher the reactivity of activated carbon, the lower the partial pressure of oxygen or water vapor, but the higher the partial pressure of oxygen or water vapor, the shorter the heat treatment time. In particular, when 0 to 30% by volume of oxygen is supplied to the inert gas, a heat treatment at 150 to 750 ° C. is necessary. However, since the combustion temperature of the activated carbon decreases as the oxygen content increases, a low temperature heat treatment is necessary.
[0035]
This reaction is considered to be represented by the following chemical formula (2) when oxygen is added.
[0036]
Ru (NO ₃ ) ₃ + xO ₂ → RuO ₂ + 3NO _y (where y = (2x + 7) / 3) (2)
Third, the activated carbon is immersed in an aqueous ruthenium nitrate solution, and an aqueous NaOH solution is slowly dropped. As the alkaline aqueous solution used for this alkali neutralization treatment, an aqueous solution of KOH, NaHCO ₃ , Na ₂ CO ₃ , NH ₄ OH can be used in addition to NaOH. It is preferably not large.
[0037]
The concentration of the alkaline substance in the alkaline aqueous solution is preferably in the range of 0.001 to 10N, and more preferably in the range of 0.01 to 4N.
[0038]
Ruthenium hydroxide is produced by this alkali neutralization treatment, and the activated carbon adsorbed by the ruthenium hydroxide is washed with water to remove residual sodium ions and nitrate ions, and then dried at 110 ° C. Ruthenium oxide or ruthenium hydroxide can be produced and supported on the electrode activated carbon.
[0039]
The first and second methods listed above require at least a heat treatment temperature of 400 ° C. or higher, but the third alkali neutralization method can be performed at a low temperature, so ruthenium oxidation is performed even on activated carbon with many functional groups. There is an advantage that it can form a ruthenium hydroxide.
[0040]
This reaction is considered to be represented by the following chemical formula (3).
[0041]
Ru (OH) ₃ → RuO ₂ + H ₂ O (3)
However, the chemical reaction formulas described above are merely examples, and the present invention is not limited thereby.
[0042]
By the method described above, more ruthenium oxide or ruthenium hydroxide is formed on the activated carbon than before, so that a device having a high energy density can be achieved and the residual halogen content in the electrode material can be reduced. The life can be extended because it can be lowered.
[0043]
As described above, the present invention supports transition metal oxides or transition metal hydroxides more efficiently even in various activated carbons, for example, those having large electric double layer capacity and large specific surface areas and high functional group concentrations. An electrochemical power storage device having a high capacity and a long life can be produced by producing the electrode material thus produced and further reducing the residual halogen content.
[0044]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to a following example.
[0045]
Example 1
In Example 1, the measurement of the capacitance of a sample in which ruthenium nitrate is adsorbed on activated carbon fibers and heat-treated in a nitrogen atmosphere will be described below.
[0046]
5 g of activated carbon fiber (Kynol, product No. “# 5092”) with a specific surface area of 1500 m ² / g is immersed in 50 ml of ruthenium nitrate solution (Tanaka Kikinzoku Co., Ltd., ruthenium content 50 g / L) and impregnated under vacuum It was made to rest later.
[0047]
After one day and night, the supernatant of the aqueous solution changed from a dark brown solution to a lighter brown color, indicating that ruthenium nitrate was adsorbed in the activated carbon fiber.
[0048]
The adsorbed activated carbon fiber is taken out and dried at 110 ° C, then heated from room temperature to 600 ° C at a heating rate of 300 ° C / hr in a nitrogen atmosphere, and then cooled to room temperature at a cooling rate of 1200 ° C / hr. went.
[0049]
By this heat treatment, ruthenium nitrate adsorbed on the activated carbon fiber was changed to ruthenium oxide or ruthenium hydroxide.
[0050]
Wrapped with 0.1362 g of activated carbon fiber heat treated after adsorption and 0.2823 g of activated carbon fiber (product No. "# 5092" manufactured by Kynol, Inc.) as a counter electrode, each immersed in 30 wt% dilute sulfuric acid aqueous solution and impregnated under vacuum went.
[0051]
As shown by the TG (thermogravimetry) curve of Example 1 shown in FIG. 2, the activated carbon fibers are burned in the heat treatment at 750 ° C. or higher, so that the temperature does not exceed 750 ° C. in the heat treatment in the nitrogen atmosphere. It is necessary to heat-treat. In FIG. 2, DTA indicates a differential thermal analysis, and DTG indicates a differential thermogravimetry curve. From the DTA and DTG curves, it is necessary to perform heat treatment at a temperature not exceeding 750 ° C. in heat treatment in a nitrogen atmosphere.
[0052]
Further, the activated carbon fibers after heat treatment obtained in this Example 1 shows the results of X-ray analysis in Figure 3, the generation of RuO ₂ adsorbed on the activated carbon fibers after the heat treatment was confirmed.
[0053]
Next, a 30 wt% dilute sulfuric acid aqueous solution as the electrolyte, a silver-silver chloride electrode as the reference electrode, and a three-electrode cyclic voltammogram method as the measurement method using an activated carbon fiber electrode adsorbed with ruthenium oxide or ruthenium hydroxide. The capacity was evaluated.
[0054]
The results of cyclic voltammetry measurements performed at a voltage sweep rate of 0.25 mV / sec in Example 1 and Comparative Example 1 are shown in FIG. 4, but the same measurement was performed in the subsequent Comparative Examples and Examples. At that time, the amount of current when the working electrode potential was swept from -0.2 to +0.8 V with respect to Ag / Ag ⁺ reference electrode was integrated with a coulomb meter and evaluated by converting it per sample weight. The method is common to all the embodiments described below, and only the capacitance per weight will be described below.
[0055]
As a result of the above evaluation, the capacitance per weight was 283.80 F / g for the activated carbon fiber electrode adsorbed with ruthenium oxide as shown in Table 1, and the capacitance of the activated carbon fiber electrode of Comparative Example 1 was 283.80 F / g. It was 1.32 times that of 215.26 F / g and 1.14 times that of 248.26 F / g of the sample using ruthenium chloride as Comparative Example 2 as a starting material.
[0056]
(Example 2)
In this Example 2, the capacitance measurement of a sample in which ruthenium nitrate is adsorbed on activated carbon fiber and heat-treated in a mixed gas atmosphere having a nitrogen: oxygen partial pressure ratio of 90:10 will be described below.
[0057]
5 g of activated carbon fiber (Kynol, product No. “# 5092”) with a specific surface area of 1500 m ² / g is immersed in 50 ml of ruthenium nitrate solution (Tanaka Kikinzoku Co., Ltd., ruthenium content 50 g / L) and impregnated under vacuum It was made to rest later.
[0058]
After one day and night, the supernatant of the aqueous solution changed from a dark brown solution to a lighter brown color, indicating that ruthenium nitrate was adsorbed in the activated carbon fiber.
[0059]
The adsorbed activated carbon fiber is taken out and dried at 110 ° C, then the temperature is raised from room temperature to 520 ° C at a heating rate of 300 ° C / hr in a mixed gas atmosphere with a nitrogen: oxygen partial pressure ratio of 90:10, and then a cooling rate of 1200 A heat treatment for cooling to room temperature at a temperature of ° C / hr was performed.
[0060]
By this heat treatment, ruthenium nitrate adsorbed on the activated carbon fiber was changed to ruthenium oxide or ruthenium hydroxide.
[0061]
A platinum wire was wound around 0.1823 g of activated carbon fiber heat treated after adsorption and 0.2823 g of activated carbon fiber (product No. "# 5092" manufactured by Kynol, Inc.) as a counter electrode, and each was immersed in a 30 wt% dilute sulfuric acid solution and impregnated under vacuum. went.
[0062]
Next, a 30 wt% dilute sulfuric acid aqueous solution as the electrolyte, a silver-silver chloride electrode as the reference electrode, and a three-electrode cyclic voltammogram method as the measurement method using an activated carbon fiber electrode adsorbed with ruthenium oxide or ruthenium hydroxide. The capacity was evaluated.
[0063]
As a result of the above evaluation, the capacitance per weight was 415.95 F / g for the activated carbon fiber electrode on which this ruthenium oxide or ruthenium hydroxide was adsorbed as shown in (Table 1). It showed 1.93 times compared with 215.26 F / g of the activated carbon fiber electrode, and 1.68 times compared with 248.26 F / g of the sample using ruthenium chloride as a starting material in Comparative Example 2.
[0064]
(Example 3)
In the third embodiment, the capacitance measurement of a sample obtained by adsorbing ruthenium nitrate on activated carbon fiber and performing an alkali neutralization treatment will be described below.
[0065]
5 g of activated carbon fiber (Kynol, product No. “# 5092”) with a specific surface area of 1500 m ² / g is immersed in 50 ml of ruthenium nitrate solution (Tanaka Kikinzoku Co., Ltd., ruthenium content 50 g / L) and impregnated under vacuum It was made to rest later.
[0066]
After one day and night, the supernatant of the aqueous solution changed from a dark brown solution to a lighter brown color, indicating that ruthenium nitrate was adsorbed in the activated carbon fiber.
[0067]
After dropping a sodium hydroxide aqueous solution into this solution, the activated carbon fiber was taken out and washed with water to remove residual sodium ions and nitrate ions, and then dried in a drier at 110 ° C.
[0068]
A platinum wire is wrapped around 0.2823g of activated carbon fiber (Kynol, product No. "# 5092") counteracted by 0.1372g of activated carbon fiber after adsorption of ruthenium oxide treated with alkali, and immersed in 30wt% dilute sulfuric acid aqueous solution. Impregnation was performed under vacuum.
[0069]
Next, a 30 wt% dilute sulfuric acid aqueous solution as the electrolyte, a silver-silver chloride electrode as the reference electrode, and a three-electrode cyclic voltammogram method as the measurement method using an activated carbon fiber electrode adsorbed with ruthenium oxide or ruthenium hydroxide. The capacity was evaluated.
[0070]
As a result of the above evaluation, the capacitance per weight was 385.37 F / g in the activated carbon fiber electrode on which this ruthenium oxide or ruthenium hydroxide was adsorbed as shown in (Table 1). It was 1.79 times higher than 215.26 F / g of the activated carbon fiber electrode, and 1.55 times higher than 248.26 F / g of the sample using ruthenium chloride as a starting material in Comparative Example 2.
[0071]
(Comparative Example 1)
In this comparative example, the capacitance measurement of the activated carbon fiber will be described below.
[0072]
Wrapped platinum wire around 0.0803g of activated carbon fiber (Kynol, product No. "# 5092") not treated with adsorption, and 0.2823g of activated carbon fiber (Kynol, product No. "# 5092") used as a counter electrode Were immersed in a 30 wt% dilute sulfuric acid aqueous solution and impregnated under vacuum.
[0073]
Next, the capacitance of the activated carbon fiber electrode that was not adsorbed using the 30 vol% dilute sulfuric acid aqueous solution as the electrolyte, the silver-silver chloride electrode as the reference electrode, and the three electrodes as the measurement method using the cyclic voltamgram method was evaluated. did.
[0074]
The results of this evaluation are shown in Table 1. The capacitance per weight of the activated carbon fiber electrode not subjected to the adsorption treatment in Comparative Example 1 was 215.26 F / g.
[0075]
(Comparative Example 2)
In this comparative example 2, the capacitance measurement of a sample in which ruthenium chloride is adsorbed on activated carbon fibers and heat-treated in a nitrogen atmosphere will be described below.
[0076]
Dissolve 0.25 g of ruthenium chloride in 50 ml of distilled water to prepare a dark red aqueous solution, and immerse 5 g of activated carbon fiber (product number “# 5092”, manufactured by Kynol, Inc.) with a specific surface area of 1500 m ² / g in the solution. And allowed to settle after impregnation under vacuum.
[0077]
After one day and night, the supernatant of the aqueous solution changed from a dark red aqueous solution to a lighter red, indicating that ruthenium chloride was adsorbed in the activated carbon fiber.
[0078]
The adsorbed activated carbon fiber is taken out and dried at 110 ° C, then heated from room temperature to 600 ° C at a heating rate of 300 ° C / hr in a nitrogen atmosphere, and then cooled to room temperature at a cooling rate of 1200 ° C / hr. went.
[0079]
By this heat treatment, ruthenium chloride adsorbed on the activated carbon fiber was changed to ruthenium oxide or ruthenium hydroxide.
[0080]
Wrapped with platinum wire 0.1374g heat treated after adsorption and 0.2823g activated carbon fiber (product No. "# 5092" manufactured by Kynol, Inc.) as a counter electrode, immersed in 30wt% dilute sulfuric acid aqueous solution and impregnated under vacuum went.
[0081]
Next, a 30 wt% dilute sulfuric acid aqueous solution as the electrolyte, a silver-silver chloride electrode as the reference electrode, and a three-electrode cyclic voltammogram method as the measurement method using an activated carbon fiber electrode adsorbed with ruthenium oxide or ruthenium hydroxide. The capacity was evaluated.
[0082]
As a result of the above evaluation, the capacitance per weight was 248.26 F / g for the activated carbon fiber electrode on which this ruthenium oxide or ruthenium hydroxide was adsorbed as shown in (Table 1). It was 1.15 times that of 215.26 F / g of the activated carbon fiber electrode.
[0083]
[Table 1]

[0084]
As described above, Example 1-3 of the present invention can be an electrode material having a higher capacitance per weight than Comparative Example 1-2, and can be a high-capacity electrochemical storage device. I was able to.
[0085]
【The invention's effect】
As described above, the present invention supports transition metal oxides or transition metal hydroxides more efficiently even in various activated carbons, for example, those having a large specific surface area and a high functional group concentration, which also have a large electric double layer capacity. An electrochemical power storage device having a high capacity and a long life can be produced by producing the electrode material thus produced and further reducing the residual halogen content.
[Brief description of the drawings]
FIG. 1 is a structural cross-sectional view of an electrochemical storage device according to an embodiment of the present invention.
FIG. 2 is a chart showing the results of thermal analysis in Example 1 of the present invention.
FIG. 3 is a chart showing X-ray analysis results in Example 1 of the present invention.
4 is a result of cyclic voltammetry measurement of the activated carbon fiber electrode adsorbed with ruthenium oxide or ruthenium hydroxide shown in Example 1 of the present invention and the activated carbon fiber electrode not subjected to the adsorption treatment of Comparative Example 1. FIG.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Positive electrode collector 2 Positive electrode activated carbon 3 Negative electrode collector 4 Negative electrode activated carbon 5 Ion permeable separator 6 Insulating rubber

Claims (19)

An electrochemical energy storage device comprising a pair of electrodes, a separator interposed between the pair of electrodes, and an electrolyte solution impregnated in the electrodes and the separator,
An electrode in which at least ruthenium oxide or ruthenium hydroxide is supported on the carbon-based material by adsorbing at least one selected from ruthenium nitrate and a solution in which ruthenium nitrate is dissolved on the carbon-based material and performing an addition treatment. An electrochemical electricity storage device characterized by the above.   The electrochemical storage device according to claim 1, wherein the additional treatment is a heat treatment.   The electrochemical storage device according to claim 1, wherein the addition treatment is immersion in an alkaline aqueous solution. The electrochemical storage device according to claim 1, wherein the carbon material is a porous coal having a specific surface area of 500 m ² / g or more and 4000 m ² / g or less.   The electrochemical storage device according to claim 1, wherein the carbon material is activated carbon fiber.   2. The electrochemical storage device according to claim 1, wherein no halide is added in the form of an oxide or hydroxide in the electrode material.   The electrochemical storage device according to claim 1, wherein the halide in the electrode material is less than 20 ppm.   The electrochemical storage device according to claim 1, wherein the amount of ruthenium nitrate supported is in the range of 0.01 mass% to 30 mass%. A method for producing an electrochemical storage device comprising a pair of electrodes, a separator interposed between the pair of electrodes, and an electrolyte solution impregnated in the electrodes and the separator,
The electrode is subjected to an addition treatment by adsorbing at least one selected from a transition metal nitrate compound and a solution in which the transition metal nitrate compound is dissolved to a carbonaceous material, so that at least a transition metal oxide or a transition metal hydroxide is obtained. In carrying and forming on the carbon-based material ,
The method for producing an electrochemical storage device, wherein the additional treatment is immersion in an alkaline aqueous solution .   The transition metal nitrate compound is at least one selected from ruthenium nitrate, vanadium nitrate, tungsten nitrate, molybdenum nitrate, chromium nitrate, manganese nitrate, iron nitrate, rhodium nitrate, osmium nitrate, iridium nitrate, cobalt nitrate, nickel nitrate and palladium nitrate. A method for producing an electrochemical storage device according to claim 9.   The method for producing an electrochemical storage device according to claim 9, wherein the carbon material is activated carbon fiber. The method for producing an electrochemical storage device according to claim 9, wherein the carbon material is a porous coal having a specific surface area of 500 m ² / g or more and 4000 m ² / g or less.   The method for manufacturing an electrochemical storage device according to claim 9, wherein no halide is added in the form of an oxide or hydroxide in the electrode material.   The method for manufacturing an electrochemical storage device according to claim 9, wherein the halide in the electrode material is less than 20 ppm. The method for producing an electrochemical storage device according to claim 9 , wherein the alkaline aqueous solution is at least one alkaline aqueous solution selected from NaOH, KOH, NaHCO ₃ , Na ₂ CO ₃ and NH ₄ OH. The method for producing an electrochemical storage device according to claim 15 , wherein the concentration of the alkaline substance in the alkaline aqueous solution is in the range of 0.001 to 10N.   The method for producing an electrochemical storage device according to claim 9, wherein free sodium ions and nitrate ions are removed by washing after immersion in an alkaline aqueous solution. A method for producing an electrochemical storage device comprising a pair of electrodes, a separator interposed between the pair of electrodes, and an electrolyte solution impregnated in the electrodes and the separator,
The electrode is subjected to an addition treatment by adsorbing at least one selected from a transition metal nitrate compound and a solution in which the transition metal nitrate compound is dissolved to a carbonaceous material, so that at least a transition metal oxide or a transition metal hydroxide is obtained. In carrying and forming on the carbon-based material,
The method for producing an electrochemical storage device, wherein the additional treatment is a heat treatment in a range of 150 ° C. or higher and 750 ° C. or lower . In the heat treatment, oxygen gas is 0 or more and 30 vol. The method for producing an electrochemical storage device according to claim 18 , wherein the method is under an inert gas atmosphere of not more than%.

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