JP2015011764A - Uninterruptible power supply device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an uninterruptible power supply device capable of stably supplying an AC power even at an instantaneous power failure or at voltage reduction of an AC power supply, and that has a long life like a lead accumulator battery.SOLUTION: An uninterruptible power supply device comprises: a conductive polymer type power storage device 1; and a high-capacity uninterruptible power supply part 2 connected with an AC power supply and the conductive polymer type power storage device 1, supplying an AC power to a high-capacity load 3 or a low-capacity load 4, and performing charge and discharge of the conductive polymer type power storage device 1. The AC power from the AC power supply is supplied to the high-capacity load 3 by the high-capacity uninterruptible power supply part 2. At voltage reduction or at an instantaneous power failure of the AC power supply, the conductive polymer type power storage device 1 is discharged to maintain the supply of the AC power.

Description

  The present invention relates to an uninterruptible power supply that is set so that the supply of AC power to a load is maintained even when the voltage of an AC power supply drops or a power failure occurs.

  An uninterruptible power supply (UPS) supplies stable AC power to a load by switching to a backup power source without interruption in the event of a voltage drop in the AC power source or a power failure.

  Conventionally, a lead storage battery has been mainly used as a storage medium serving as such a backup power source. When using lead-acid batteries, the backup time is determined by the capacity of the storage battery. Long backups are possible. However, when a storage battery is used for the uninterruptible power supply, frequent backup is performed at the time of a power failure or a voltage drop of the AC power supply. Therefore, the storage battery is repeatedly charged and discharged, and the life of the storage battery is shortened.

  It has also been proposed to use an electric double layer capacitor as a power storage medium. The electric double layer capacitor can flow a large discharge current in a short time. Even if the AC power supply is repeatedly charged and discharged frequently during an instantaneous power failure or instantaneous voltage drop, there is no problem in the life of the electric double layer capacitor. However, when an electric double layer capacitor is used for an uninterruptible power supply, the electric storage capacity of the electric double layer capacitor is very small compared to a storage battery, and backup of only a few seconds, that is, only a very short time backup is possible. There is. Moreover, it is expensive compared with a storage battery. For this reason, an uninterruptible power supply using an electric double layer capacitor is not realistic for a load such as a computer that requires long-time backup.

  Therefore, in order to solve the above-mentioned problem, an uninterruptible power supply device that combines an electric double layer capacitor and a storage battery for supplementing its short backup characteristic has been proposed (see Patent Document 1). As shown in FIG. 4, this uninterruptible power supply device includes an electric double layer capacitor 10 and a storage battery 11 such as a lead storage battery, and is connected to an AC power source and the electric double layer capacitor 10 to increase the first AC power. A large-capacity uninterruptible power supply unit 12 that supplies the capacitive load 14 and charges and discharges the electric double layer capacitor 10 is provided. The small-capacity uninterruptible power supply unit 13 connected to the output side of the large-capacity uninterruptible power supply unit 12 and the storage battery 11 to supply the second AC power to the small-capacity load 15 and to charge and discharge the storage battery 11. have.

  The uninterruptible power supply unit is configured to discharge the electric double layer capacitor 10 in the large-capacity uninterruptible power supply unit 12 to discharge the large-capacity load 14 and the small-capacity uninterruptible power supply unit when the AC power supply is instantaneously interrupted or the voltage drops. 13 is supplied with the first AC power. When the voltage across the electric double layer capacitor 10 becomes equal to or less than the specified value before the end of discharge, a signal before the end of discharge is sent to the small-capacity uninterruptible power supply unit 13, and the small-capacity uninterruptible power supply unit 13 ends the discharge. The storage battery 11 is discharged based on the previous signal, and the second AC power is supplied to the small capacity load 15.

  Similarly, various uninterruptible power supply devices combining an electric double layer capacitor and a storage battery have been proposed (see Patent Documents 2 and 3).

JP 2010-016997 A JP 2010-016996 A JP 2010-016995 A

  However, since these uninterruptible power supply devices combine two types of power storage devices, there is a problem that the circuit system becomes complicated and the number of parts increases, requiring time and labor for assembly and maintenance. In addition, there is a possibility that a trouble that the switching between these two types of power storage devices does not work well may occur, and it cannot be said that reliability for long-time backup is sufficiently ensured.

  The present invention has been made in view of such circumstances, and can supply AC power stably even during an instantaneous power failure or voltage drop of an AC power source, and has a long life like a lead-acid battery. An object is to provide an uninterruptible power supply.

  In order to achieve the above object, the present invention provides an uninterruptible power supply set to maintain the supply of alternating current power to a load even when the voltage of the alternating current power supply is reduced or during a power failure. An uninterruptible power supply unit that is connected to an AC power source and a conductive polymer storage device and supplies AC power to a load and charges and discharges the conductive polymer storage device. An uninterruptible power supply that supplies AC power to the load by supplying AC power from the AC power source to the load and discharging the conductive polymer type energy storage device when the voltage of the AC power source drops or when a power failure occurs Is the gist.

  That is, the present inventors have conducted intensive research to develop an unprecedented excellent uninterruptible power supply, and as a result, when the conductive polymer type electric storage device is used as a storage battery of the uninterruptible power supply, the conductive polymer The high capacity, high output, and high cycle characteristics of the power storage device enable stable AC power supply in the event of an instantaneous power failure or instantaneous voltage drop of the uninterruptible power supply, and it is necessary to combine two types of power storage devices as before As a result, the present invention was reached.

  According to the present invention, since a conductive polymer type energy storage device that has never been used for such applications has been used as a storage battery of an uninterruptible power supply device, the high capacity, high Due to the output and high cycle characteristics, stable AC power can be supplied in the event of an instantaneous power failure or voltage drop of the AC power supply. And since this stable AC power supply is achieved simply by incorporating a conductive polymer type electricity storage device alone, there is no need to combine an electric double layer capacitor and a lead storage battery as in the conventional case, and the circuit system is simple. Therefore, it becomes difficult to cause a problem. In addition, since the total number of parts can be reduced, there is an advantage that the assembly and maintenance of the apparatus are simple. Moreover, the conductive polymer electricity storage device has the advantage that it has a low safety and is highly resistant to thermal runaway because it has a low oxygen content and its conductivity decreases due to heat, overcharge, and overdischarge.

  In the present invention, in particular, when at least one electrode of the conductive polymer type electricity storage device has a conductive polymer and an anionic material fixed in the electrode, the conductive polymer type electricity storage device. Has a rocking chair type mechanism, which is preferable because it exhibits more excellent cycle characteristics.

  Here, the “anionic material fixed in the electrode” refers to a material in which the anionic material is formed as a composite together with other electrode forming materials and is fixed in the composite. This means that the anionic material is fixed and does not move, so that the cation moves, and thus the electricity storage device using the same has a rocking chair type mechanism.

  In the present invention, it is preferable that the anionic material is a polymer anion because the polymer anion also functions as a binder for the electrode forming material. In particular, when the polymer anion is a polycarboxylic acid, The performance is further improved and it becomes more preferable.

  In the present invention, it is particularly preferable that the conductive polymer is polyaniline because the electrochemical capacity of polyaniline is large and the performance of the electricity storage device is further improved.

It is explanatory drawing which shows the structure of the uninterruptible power supply device of this invention. It is a graph which shows the discharge rate characteristic of the conductive polymer type electrical storage device used for the Example of this invention. It is a graph which shows the charge / discharge cycle characteristic of the said conductive polymer type electrical storage device. It is explanatory drawing which shows the structure of an example of the conventional uninterruptible power supply.

  Hereinafter, embodiments of the present invention will be described in detail. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description.

  First, the uninterruptible power supply apparatus of the present invention uses a conductive polymer type power storage device as a backup power storage device. For example, as shown in FIG. And a large-capacity uninterruptible power supply unit 2 connected to an AC power supply (not shown) and the conductive polymer power storage device 1. The large-capacity uninterruptible power supply unit 2 supplies alternating-current power to the large-capacity load 3 or the small-capacity load 4 and charges and discharges the conductive polymer power storage device 1.

  According to the uninterruptible power supply, normally, the large-capacity uninterruptible power supply unit 2 supplies alternating-current power from the alternating-current power supply to the large-capacity load 3, and when the voltage of the alternating-current power supply drops or a power failure occurs, By discharging the device 1, AC power can be supplied to the large-capacity load 3 without interruption. Further, when the power failure or voltage drop does not recover even after a predetermined time has elapsed, the large-capacity load 3 is switched to the small-capacity load 4 to cope with the supply of AC power for a long time. it can.

  Note that the control of the above operation is performed by an electric or electronic control means (not shown) provided separately. In the above example, the load can be switched between the large-capacity load 3 and the small-capacity load 4, but power is supplied to a single load. It doesn't matter.

  The conductive polymer power storage device 1 used in the uninterruptible power supply device has a high capacity, high output, and high cycle characteristics, at least the main active material of the positive electrode is made of a conductive polymer.

  The conductive polymer means that the ionic species are inserted into or removed from the polymer in order to compensate for a change in charge generated or lost by the oxidation reaction or reduction reaction of the polymer main chain. In such a polymer, the ionic species is inserted into the polymer and the state of high conductivity is called the “dope state”, and the ionic species leave the polymer and become conductive. A state with low properties is called a “dedoped state”. Even if a polymer having conductivity loses conductivity due to an oxidation reaction or a reduction reaction and becomes insulating (that is, in a dedoped state), such a polymer becomes conductive again reversibly by the oxidation-reduction reaction. Therefore, the insulating polymer in the dedope state is also included in the category of the conductive polymer in the present invention.

  Therefore, in the present invention, one of the preferred conductive polymers is a dopant of at least one proton acid anion selected from inorganic acid anions, aliphatic sulfonate anions, aromatic sulfonate anions, polymer sulfonate anions and polyvinyl sulfate anions. As a polymer. In addition, another preferred conductive polymer in the present invention is a polymer in a dedope state obtained by dedoping the conductive polymer.

  Examples of the polymer constituting such a conductive polymer include polyaniline, polypyrrole, polythiophene, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyphenylene oxide, polyazulene, poly (3,4-ethylenedioxythiophene). ), Polyacene and the like, and various derivatives thereof. Of these, at least one polymer selected from polyaniline or polypyrrole having a large electric capacity per unit weight and derivatives thereof is particularly preferable.

  The polyaniline means a polymer obtained by electrolytic polymerization or chemical oxidative polymerization of aniline, and the polyaniline derivative means a polymer obtained by electrolytic polymerization or chemical oxidative polymerization of an aniline derivative. In addition, as the derivative of aniline, at least one substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group or the like is present at a position other than the 4-position of aniline. Can be exemplified. Preferable specific examples include, for example, o-substituted anilines such as o-methylaniline, o-ethylaniline, o-phenylaniline, o-methoxyaniline, o-ethoxyaniline, m-methylaniline, m-ethylaniline, m- Examples thereof include m-substituted anilines such as methoxyaniline, m-ethoxyaniline and m-phenylaniline.

  However, even if it is an aniline derivative having a substituent at the 4-position, p-phenylaminoaniline gives polyaniline by oxidative polymerization, and therefore can be preferably used as an aniline derivative exceptionally.

  The polypyrrole refers to a polymer obtained by subjecting pyrrole to chemical oxidative polymerization or electrolytic oxidative polymerization, and the polypyrrole derivative refers to a polymer obtained by chemical oxidative polymerization or electrolytic oxidative polymerization of a pyrrole derivative. Here, as a derivative of pyrrole, substitution of alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, alkylaryl group, arylalkyl group, alkoxyalkyl group, etc. at positions other than 2-position and 5-position of pyrrole Examples having at least one group can be given. Preferred specific examples include, for example, 3-methylpyrrole, 3-ethylpyrrole, 3-ethenylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-phenylpyrrole, 3-phenoxypyrrole, 3-p-tolylpyrrole, 3-benzylpyrrole, 3-methoxymethylpyrrole, 3-p-fluorophenylpyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-diethenylpyrrole, 3,4-dimethoxypyrrole, 3, 4-diethoxypyrrole, 3,4-diphenylpyrrole, 3,4-diphenoxypyrrole, 3,4-di (p-toluyl) pyrrole, 3,4-dibenzylpyrrole, 3,4-dimethoxymethylpyrrole, 3 , 4-di (p-fluorophenyl) pyrrole and the like.

  In the present invention, unless otherwise specified, “aniline or a derivative thereof” is simply referred to as “aniline”, and “at least one selected from polyaniline and its derivatives” is simply referred to as “polyaniline”. Similarly, unless otherwise specified, “pyrrole or a derivative thereof” is simply referred to as “pyrrole”, and “at least one selected from polypyrrole and its derivatives” is simply referred to as “polypyrrole”. Therefore, even when the polymer constituting the conductive polymer is obtained from an aniline derivative or a pyrrole derivative, it may be referred to as “conductive polyaniline” or “conductive polypyrrole”, respectively.

  And in order to obtain the said conductive polymer in a dope state, it is suitable to make a dopant coexist at the time of the chemical oxidation polymerization or electrolytic oxidation polymerization of the monomer which can form the said conductive polymer.

  Moreover, it is preferable that the electroconductive polymer type electrical storage device 1 used by this invention has at least one electrode, for example, a positive electrode, which has the said electroconductive polymer and the anionic material fixed in the electrode.

  Specific examples of the anionic material include a polymer anion, an anion compound having a relatively large molecular weight, an anion compound having a low solubility in an electrolyte solution, and the polymer anion also functions as a binder for an electrode forming material. Therefore, it is more preferably used.

  As such a polymer anion, an active material compound having a carboxyl group in the molecule, particularly a polycarboxylic acid or a metal salt thereof is preferably used. Specific examples of the polycarboxylic acid include polyacrylic acid, polymethacrylic acid, polyvinylbenzoic acid, polyallylbenzoic acid, polymethallylbenzoic acid, polymaleic acid, polyfumaric acid, polyglutamic acid and polyaspartic acid, alginic acid, carboxymethylcellulose, and polymers thereof. These are at least one selected from a copolymer containing at least two types of repeating units. In addition, the said copolymer shall contain a graft copolymer.

  Specific examples of the metal salt of the polycarboxylic acid include at least one selected from an alkali metal salt and an alkaline earth metal salt. The alkali metal salt is preferably a lithium salt or a sodium salt. As the metal salt, a magnesium salt or a calcium salt is preferable.

  The configuration of the conductive polymer type electricity storage device 1 used in the present invention will be described in more detail. For example, the conductive polymer type electricity storage device 1 includes an electrolyte layer, and a positive electrode and a negative electrode that are provided to face each other. Then, it is the structure which used the positive electrode sheet which has the active material for the positive electrode and the solid containing the said conductive polymer and its dopant.

  Each of the positive electrode and the negative electrode is provided with a current collector, and an active material such as a conductive polymer is integrally fixed to the current collector. As such a current collector, a metal foil or mesh such as nickel, aluminum, stainless steel or copper is preferably used.

  The positive electrode sheet used for the positive electrode can be obtained, for example, as follows. That is, first, an anionic material such as polycarboxylic acid is dissolved or dispersed in water, and a conductive polymer powder and, if necessary, a conductive assistant such as conductive carbon black are added thereto. Is sufficiently dispersed to prepare a highly viscous paste having a solution viscosity (30 ° C., manufactured by Thermo Scientific, viscoelasticity measuring apparatus HAAKE Rheoless 600 viscometer) of about 0.05 to 50 Pa · s. And after apply | coating this on a collector, by evaporating water, from the said conductive polymer powder and the said anionic material (with the conductive support agent used as needed) on a collector It can be obtained as a composite sheet having a uniform positive electrode active material layer.

  The conductive auxiliary agent is excellent in conductivity, is effective for reducing the electrical resistance between the active materials of the battery, and is a conductive material whose properties do not change depending on the potential applied during charging and discharging of the battery. Is desirable. Usually, conductive carbon black as described above, for example, acetylene black, ketjen black, and the like, and fibrous carbon materials such as carbon fiber, carbon nanotube, and carbon nanofiber are used.

  The anionic material is not limited by theory, but has a function as a binder in the production of the positive electrode, and also functions as a dopant for the conductive polymer of the positive electrode. It is thought that it is concerned also in the improvement of the characteristic as the device 1.

  The anionic material is preferably used, for example, in an amount of 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, and most preferably 5 to 30 parts by weight with respect to 100 parts by weight of the conductive polymer. If the amount of the anionic material relative to the conductive polymer is too small, it may be impossible to obtain an electricity storage device excellent in weight output density, while if the amount of the anionic material relative to the conductive polymer is too large, Due to the increase in the weight of the positive electrode due to the increase in the weight of components other than the positive electrode active material, there is a possibility that an energy storage device having a high weight energy density cannot be obtained when the weight of the entire battery is taken into consideration.

  Moreover, although the positive electrode active material layer of the said positive electrode sheet is formed as a porous layer, it is desirable that the porosity is 35 to 80% of range.

The “void ratio” can be calculated by the following [Formula 1].
[Formula 1]
Porosity P (%) of positive electrode active material layer of positive electrode sheet = ((ST−V) / ST) × 100

Here, S is the area (cm ² ) of the positive electrode sheet, T is the thickness (cm) of the positive electrode sheet excluding the thickness of the current collector, and V is the volume (cm ³ ) of the positive electrode sheet excluding the current collector. . The volume of the positive electrode sheet excluding the current collector is calculated using the weight ratio of the material constituting the positive electrode sheet and the true density value of each material to calculate the average density of the entire material constituting the positive electrode sheet, This is obtained by dividing the total weight of the materials constituting the positive electrode sheet by this average density.

  And the electrolyte layer used for the said conductive polymer type electrical storage device 1 preferably uses, for example, a sheet obtained by impregnating a separator with an electrolytic solution or a sheet made of a solid electrolyte. The sheet made of the solid electrolyte itself also serves as a separator.

  Examples of the electrolyte that constitutes the electrolytic solution for impregnating the separator and the electrode as described above include, for example, base metal ions and appropriate counter ions, for example, sulfonate ions, perchlorate ions, tetrafluoro ions. A combination of borate ion, hexafluorophosphate ion, hexafluoroarsenic ion, bis (trifluoromethanesulfonyl) imide ion, bis (pentafluoroethanesulfonyl) imide ion, halogen ion, etc. is preferably used.

  The “base metal” refers to a metal that has a higher ionization tendency than hydrogen and is easily oxidized in the air (when heated), such as an alkali metal such as lithium, sodium and potassium, and magnesium and calcium. These include alkaline earth metals, aluminum, zinc, lead and the like.

Therefore, specific examples of such an electrolyte include LiCF ₃ SO ₃ , LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAsF ₆ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ LiCl, NaCF ₃ SO ₃ , NaClO ₄ , NaBF ₄ , NaPF ₆ , NaAsF ₆ , Ca (CF ₃ SO ₃ ) ₂ , Ca (ClO ₄ ) ₂ , Ca (BF ₄ ) ₂ , Ca (PF ₆ ) ₂ , Ca (AsF) ₆ ) You can raise _2nd .

  And as a solvent which comprises electrolyte solution, at least 1 type of nonaqueous solvents, such as carbonates, nitriles, amides, ethers, ie, an organic solvent, is used. Specific examples of such an organic solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, N, N'-dimethylacetamide, N-methyl-2- Examples include pyrrolidone, dimethoxyethane, diethoxyethane, and γ-butyrolactone.

  Moreover, in the said conductive polymer type electrical storage device 1, when using a separator, the separator can prevent the electrical short circuit between the positive electrode and negative electrode which are arrange | positioned on both sides of this, Any insulating porous sheet that is chemically stable, has a large ion permeability, and has a certain degree of mechanical strength may be used. Therefore, for example, a porous film made of a resin such as paper, nonwoven fabric, polypropylene, polyethylene, or polyimide is preferably used.

  Furthermore, in the conductive polymer electricity storage device 1, a base metal or a material that can insert and desorb base metal ions during oxidation and reduction is preferably used for the negative electrode. Examples of the base metal include alkali metals such as metal lithium and metal sodium, and alkaline earth metals such as metal magnesium and metal calcium, and examples of the base metal ion include ions of the base metal. . In addition, as a material that can insert and desorb the base metal ions, a carbon material is preferably used, but silicon, tin, and the like can also be used.

  And it is preferable to assemble the said conductive polymer type electrical storage device 1 using these materials, for example in an inert gas atmosphere, such as an ultra high purity argon gas, in a glove box.

  Thus obtained conductive polymer type electricity storage device 1 used in the present invention is not only excellent in weight output density and cycle characteristics as in an electric double layer capacitor, but also in the weight energy of a conventional electric double layer capacitor. It has a gravimetric energy density much higher than the density. Therefore, in the uninterruptible power supply, there is no need to combine an electric double layer capacitor with a small-capacity lead storage battery or the like, as in the prior art, as shown in FIG. An excellent uninterruptible power supply can be obtained.

  The conductive polymer type electricity storage device 1 has such a high capacity because of the rocking chair type electricity storage device that is a cation transfer type that requires a small amount of electrolyte and an anion transfer type that has excellent output characteristics. This is considered to be due to the fact that the reserve-type electricity storage device has both excellent characteristics.

  The uninterruptible power supply using the conductive polymer power storage device 1 has a simple circuit system and is less prone to problems, and the total number of parts can be reduced. It has the advantage of being simple. In addition, the conductive polymer electricity storage device 1 has the advantage that it has a low safety and is highly resistant to thermal runaway because it has a low oxygen content and its conductivity is reduced by heat, overcharge, and overdischarge.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.

[Example 1]
(Production of conductive polyaniline powder using tetrafluoroborate anion as dopant)
To a glass beaker with a capacity of 138 g of ion-exchanged water, 84.0 g (0.402 mol) of a 42 wt. While stirring, 10.0 g (0.107 mol) of aniline was added thereto. Initially when aniline was added to tetrafluoroboric acid aqueous solution, aniline was dispersed as oily droplets in tetrafluoroboric acid aqueous solution, but then dissolved in water within a few minutes, and uniform and transparent aniline aqueous solution It became. The aniline aqueous solution thus obtained was cooled to −4 ° C. or lower using a low-temperature thermostatic bath.

  Next, 11.63 g (0.134 mol) of manganese dioxide powder (reagent grade 1 manufactured by Wako Pure Chemical Industries, Ltd.) as an oxidizing agent is added little by little to the aniline aqueous solution, and the temperature of the mixture in the beaker is -1 ° C. Not to exceed. Thus, by adding an oxidizing agent to the aniline aqueous solution, the aniline aqueous solution immediately turned black-green. Thereafter, when stirring was continued for a while, a black-green solid started to be formed.

Thus, after adding an oxidizing agent over 80 minutes, it stirred for 100 minutes, cooling the reaction mixture containing the produced | generated reaction product. Thereafter, using a Buchner funnel and a suction bottle, the obtained solid was No. The powder was obtained by suction filtration with 2 filter papers. This powder was stirred and washed in a tetrafluoroboric acid aqueous solution of about 2 mol / dm ³ using a magnetic stirrer, then stirred and washed several times with acetone, and this was filtered under reduced pressure. The obtained powder was vacuum-dried at room temperature for 10 hours to obtain 12.5 g of conductive polyaniline having a tetrafluoroborate anion as a dopant as a bright green powder.

(Conductivity of conductive polyaniline powder)
After pulverizing 130 mg of the conductive polyaniline powder in a smoked mortar, vacuum-pressure molding was performed for 10 minutes under a pressure of 300 MPa using a KBr tablet molding machine for infrared spectrum measurement, and a conductive polyaniline disk having a thickness of 720 μm was formed. Obtained. The electrical conductivity of this disk (measured by a 4-terminal method conductivity measurement by the Van der Pau method) was 19.5 S / cm.

(Production of positive electrode sheet containing conductive polyaniline powder)
0.1 g of polyacrylic acid (weight average molecular weight 1,000,000 manufactured by Wako Pure Chemical Industries, Ltd.) was added to 3.9 g of ion-exchanged water, and allowed to stand overnight to swell. Then, it processed for 1 minute using the ultrasonic homogenizer, and it was made to melt | dissolve, and obtained the polyacrylic acid aqueous solution 4g of 2.5 weight% density | concentration uniformly.

  After mixing 0.8 g of the above conductive polyaniline powder with 0.1 g of conductive carbon black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.), this was added to 4 g of the 2.5 wt% polyacrylic acid aqueous solution, and a spatula was added. After kneading well, dispersion treatment was performed for 1 minute with an ultrasonic homogenizer to obtain a paste having fluidity. This paste was further defoamed using a vacuum suction bell and a rotary pump.

  Etching aluminum foil for electric double layer capacitor (Hosen) using a tabletop automatic coating device (manufactured by Tester Sangyo Co., Ltd.) using a doctor blade type applicator with a micrometer at a coating speed of 10 mm / sec. 30 CB). Subsequently, after leaving at room temperature for 45 minutes, it dried on the hotplate with a temperature of 100 degreeC. Thereafter, using a vacuum press machine (KVHC manufactured by Kitagawa Seiki Co., Ltd.), it was sandwiched between 15 cm square stainless steel plates and pressed at a temperature of 140 ° C. and a pressure of 1.49 MPa for 5 minutes to obtain a composite sheet.

  In this composite sheet, the porosity of the positive electrode active material composed of polyacrylic acid, conductive polyaniline powder, and conductive carbon black was 55%. The porosity was calculated by the above-mentioned [Formula 1]. At this time, the true density of the material used was 1.2 for polyaniline, 2.0 for acetylene black (Denka black), and 1.18 for polyacrylic acid. Using these values, the average density of the entire material was determined. Asked.

Next, the composite sheet is punched into a disk shape with a punching jig having a punching blade with a diameter of 15.95 mm to form a positive electrode sheet, and metal lithium (coin-type metal lithium manufactured by Honjo Metal Co., Ltd.) is used as the negative electrode. A non-woven fabric (manufactured by Hosen Co., Ltd., porosity 68%: TF40-50) is used as a separator. These were assembled into a stainless steel HS cell (manufactured by Hosen Co., Ltd.) for non-aqueous electrolyte secondary battery experiments. The positive electrode sheet and the separator were vacuum-dried at 100 ° C. for 5 hours in a vacuum dryer before being assembled to the HS cell. As the electrolytic solution, an ethylene carbonate / dimethyl carbonate solution (manufactured by Kishida Chemical Co., Ltd.) of lithium tetrafluoroborate (LiBF ₄ ) having a concentration of 1 mol / dm ³ was used. The assembly was performed in a glove box having a dew point of −100 ° C. in an ultrahigh purity argon gas atmosphere.

  With respect to the conductive polymer electricity storage device thus obtained, the charge / discharge rate was changed from 0.2 C to 100 C, and the discharge energy density was measured. The measurement was performed in a constant current-constant voltage charge / constant current discharge mode using a battery charging / discharging device (SD8 manufactured by Hokuto Denko). That is, when the charge end voltage is 3.8 V and the voltage reaches 3.8 V by constant current charging, the constant voltage charging of 3.8 V is 20% of the current value during constant current charging. After that, constant current discharge was performed up to a final discharge voltage of 2.0V.

  The result is shown in FIG. This characteristic value is converted per net weight of the positive electrode active material, that is, conductive polyaniline having a tetrafluoroborate anion as a dopant (the same applies to FIG. 3 below).

  As can be seen from FIG. 2, this conductive polymer type electricity storage device has an energy density of about 399 mWh / g to 164 mWh / g, even though the current value is changed 500 times from 0.2 C to 100 C. Since the original capacity is large, the high energy density of 150 mWh / g or more is maintained.

  Therefore, it can be seen that this conductive polymer type electricity storage device has a high weight output density and excellent cycle characteristics like an electric double layer capacitor, and also has a much higher weight energy density than an electric double layer capacitor. .

  Further, the discharge energy density was measured when the conductive polymer electricity storage device was discharged up to 5000 times at a high discharge rate of 8.3 C, and the cycle characteristics were examined. The measurement was performed using a battery charging / discharging device (SD8 manufactured by Hokuto Denko Co., Ltd.). The end-of-charge voltage was set to 3.8 V. After the voltage reached 3.8 V by constant current charging, the constant voltage charging of 3.8 V was applied to the current. This was performed until the value reached 20% of the current value at the time of constant current charge, and then constant current discharge was performed up to a discharge end voltage of 3.0V.

  The result is shown in FIG. As can be seen from this figure, this conductive polymer type electricity storage device maintains 88% of the initial weight energy density even at the 1000th cycle. And even if the number of cycles is 5000, 100 mWh / g is maintained, and the cycle characteristics are remarkably superior to those of ordinary power storage devices.

  An uninterruptible power supply having the configuration shown in FIG. 1 was produced using a conductive polymer power storage device having the above characteristics. And it was used as a power source for a home computer, intentionally created a power outage state, and tested as to whether or not the power supply could be maintained without interruption for 5 minutes of power outage for 5 minutes at 1 hour intervals. In all the times, the power supply by the discharge of the conductive polymer electricity storage device was satisfactorily performed without interruption of the power supply. Also, even when one power outage was set for a long time of 5 hours, the power supply was maintained without causing any problems during that time.

  The present invention can be widely used as an uninterruptible power supply that maintains the supply of AC power to a load even when the voltage of the AC power supply drops or during a power failure.

1 Conductive polymer type electricity storage device 2 Large capacity uninterruptible power supply 3 Large capacity load 4 Small capacity load

Claims (5)

An uninterruptible power supply set to maintain the supply of AC power to the load even when the voltage of the AC power supply drops or a power failure occurs,
A conductive polymer type electricity storage device; and an uninterruptible power supply connected to the AC power source and the conductive polymer type electricity storage device to supply AC power to a load and charge and discharge the conductive polymer type electricity storage device; The uninterruptible power supply unit supplies AC power from the AC power source to the load, and when the voltage of the AC power source drops or a power failure occurs, the conductive polymer type electricity storage device is discharged to supply AC power to the load. An uninterruptible power supply.   The uninterruptible power supply according to claim 1, wherein at least one electrode of the conductive polymer type electricity storage device includes a conductive polymer and an anionic material fixed in the electrode.   The uninterruptible power supply according to claim 2, wherein the anionic material is a polymer anion.   The uninterruptible power supply according to claim 3, wherein the polymer anion is polycarboxylic acid.   The uninterruptible power supply according to any one of claims 1 to 4, wherein the conductive polymer is polyaniline.

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