JP2015012625A - Power unit for electrically-driven equipment as well as electric heating equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent non-bulky power unit for electrically-driven equipment as well as electric heating equipment, improved in safety.SOLUTION: A power unit for electrically-driven equipment as well as electric heating equipment, includes a circuit in which a conductive polymer battery 1 that is a high power-density battery, and a high capacity-density lithium ion secondary battery 2, are connected in parallel. Power is supplied to electrically-driven equipment or electric heating equipment by the conductive polymer battery 1. When a state of charge (SOC) in the conductive polymer battery 1 becomes lower than a preset predetermined value, the conductive polymer battery 1 is charged by using the high capacity-density lithium ion secondary battery 2.

Description

  The present invention relates to a power supply device for electric / electric heating equipment used for driving electric / electric heating equipment.

  In recent years, it has been proposed to use a combination of two different types of batteries as a power supply device for a motor or the like that requires high output and high capacity, such as an electric vehicle or a power tool.

  These power supply devices use a high-power density battery that can supply a large output (a large current) in a short time for driving a motor or the like, and cannot supply a large output. The battery is characterized in that a high (high power capacity) battery is used as a charging battery when the charge amount of the high power density type battery is reduced. Hereinafter, the former is referred to as “high power density type battery”, and the latter is referred to as “high capacity density type battery”. The output density is represented by the output per unit weight of the battery [W / kg], and the capacity density is represented by the capacity per unit weight of the battery [Ah / kg]. In the above expression, “large output” and “large capacity” are relative values when two different types of batteries (a high output density type battery and a high capacity density type battery) are compared.

  At present, as the high power density type battery and the high capacity density type battery of such a power supply device, those using lithium ion secondary batteries are mainly used (see Patent Documents 1 to 3). In other words, even for batteries using the same lithium ion, by adjusting various parameters such as the type of active material and the thickness of the active material layer, both high power density battery types and high capacity density battery types can be obtained. Therefore, both battery characteristics can be adjusted in a well-balanced manner, and the power supply device having the desired characteristics can be obtained relatively easily.

Japanese Patent Laid-Open No. 11-332023 JP 2013-59161 A JP2013-85413A

  However, the lithium ion secondary battery may be heated due to an extreme overcharge or overdischarge, resulting in heat generation. The lithium ion secondary battery includes a plurality of safety devices to prevent the runaway. And the heat_generation | fever becomes especially large when using a lithium ion secondary battery as a high output density type battery by which high output is requested | required.

  Therefore, in order to increase the safety of power supply devices mounted on electric vehicles, electric tools, etc., it is also considered to replace lithium ion secondary batteries used as high power density type batteries with, for example, electric double layer capacitor type batteries. ing. However, since the electric capacity of the electric double layer capacitor type battery is an order of magnitude smaller than that of the lithium ion secondary battery, if an electric capacity comparable to that of the lithium ion secondary battery is obtained, the battery is There is a problem that it becomes very bulky and cannot be mounted on a compact electric vehicle or power tool. Conversely, if an electric double layer capacitor type battery having a small volume and a small electric capacity is used, it is necessary to repeatedly charge from the high capacity density type battery combined therewith, so that the life of the high capacity density type battery is reduced. There is a problem that a short period of time is used, and the use period of the entire power supply apparatus becomes short.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide an excellent power supply device for electric / electric heating equipment that has high safety and is not bulky.

  In order to achieve the above object, the present invention is a power supply device for driving an electric / electric heating device, comprising a circuit in which a high power density type battery and a high capacity density type battery are connected in parallel. A conductive polymer type battery is used as the output density type battery, power is supplied to the electric / electric heating device by the conductive polymer type battery, and the charge amount (SOC) of the conductive polymer type battery is preset. The gist of the present invention is a power supply device for an electric / electric heating device in which the conductive polymer type battery is charged by using the high capacity density type battery when the value is lower than a predetermined value.

  That is, the present inventors have conducted extensive research to develop a power supply device for electric / electric heating equipment that is safe and excellent. As a result, the conductive polymer type battery is used as a high output density type electric power supply device for electric / electric heating equipment. When used as a battery, the inventors have found that the life as a power supply device is prolonged due to high safety, high capacity, high output, and high cycle characteristics of the conductive polymer battery, and the present invention has been achieved.

  According to the present invention, since the conductive polymer type battery that has not been used for such applications in the past is used as the high capacity density type battery in the power supply device for electric / electric heating equipment, the conductive polymer type battery described above is used. The high capacity, high output, and high cycle characteristics of the high power density type battery that is comparable to or better than the power supply for electric / thermal equipment using a lithium ion secondary battery, is safe and has a long battery life. It is possible to provide a long and excellent power supply device for electric / electric heating equipment.

  In the present invention, in particular, when at least one electrode of the conductive polymer type battery has a conductive polymer and an anionic material fixed in the electrode, the conductive polymer type battery is rocked. It has a chair-type mechanism, which is preferable because it exhibits better 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. , It means that the anionic material is fixed and does not move, so that the cation moves, and the conductive polymer type battery using this has a rocking chair type mechanism. To do.

  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, a conductive polymer is preferable. The performance of the type battery is further improved and becomes more preferable.

  In the present invention, when the conductive polymer is polyaniline, the electrochemical capacity of the polyaniline is large, and the performance of the conductive polymer battery is further improved, which is particularly preferable.

It is explanatory drawing which shows the structure of the power supply device for electric / electric heating equipment of this invention. (A) is a graph which shows the discharge rate characteristic of the conductive polymer type battery used for the Example of this invention, (b) is a graph which shows the charging / discharging cycle characteristic of the said conductive polymer type battery. It is a graph which shows the simulation data of the battery life in the Example and comparative example of this invention. It is explanatory drawing which shows the structure of the comparative example used for the said simulation data.

  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 power supply apparatus for electric / electric heating equipment of the present invention is an apparatus used as a power source for driving various electric equipments and electric heating equipment. As the electric equipment, an automobile driving motor mounted on an electric vehicle is used. And various drive motors. In addition, electric vehicles equipped with these motors, electric tools (grinders, drills, etc.), ventilation fans, blowers, fans, submersible pumps, pumps, refrigerators, freezers, vacuum cleaners, winches, onboard hoists, conveyors, compressors, Examples include hydraulic machines. On the other hand, examples of the electric heating device include an electric heater, a rice cooker, a kettle, a dryer, and an iron. These electric / electric heating devices need to be driven at a high output at the same time as the power is turned on, and it is optimal to use the power supply device for electric / electric heating devices of the present invention.

  The power supply device for electric / electric heating equipment of the present invention (hereinafter sometimes abbreviated as “power supply device”) for driving such electric / electric heating equipment has a configuration as shown in FIG. That is, this power supply device is provided with a conductive polymer type battery 1 as a high output density type battery for supplying electric power to an electric / electric heating device such as a motor, and the conductive polymer type battery 1 is charged. For this purpose, a high capacity density type lithium ion secondary battery 2 is provided. The conductive polymer type battery 1 and the high capacity density type lithium ion secondary battery 2 are respectively connected to a controller 5 via SOC (State Of Charge) detectors 3 and 4, and further via a power control device 6. Connected in parallel. The conductive polymer type battery 2 is connected to a load 8 such as a motor via an inverter 7 so as to supply AC power to the load 8.

  When the charge amount of the conductive polymer type battery 1 decreases and becomes lower than the charge amount preset in the controller 5, the controller 5 and the power control device 6 cause the high capacity density type lithium. The conductive polymer battery 1 is charged using the ion secondary battery 2. Moreover, when the charge amount of the high capacity density type lithium ion secondary battery 2 is decreased by repeating the charge and becomes lower than a preset charge amount value, the controller 5 causes the high capacity density type battery to be charged. The lithium ion secondary battery 2 is charged using an external power source (not shown). An upper limit value of the charge amount for ending these charging operations is also set in the controller 5 in advance.

  According to this power supply device, the conductive polymer type battery 1 used as the high power density type battery can have a high output comparable to that of the electric double layer capacitor type battery, has good cycle characteristics, and has a single SOH (State). Of Health: [Deterioration of full charge capacity at the time of degradation / initial full charge capacity], an indicator of battery deterioration, generally 75% is regarded as a standard for disposal), and has a feature that the decrease is small The capacity is also relatively large. Therefore, it is not necessary to frequently charge from the high capacity density type lithium ion secondary battery 2, the SOH drop of the high capacity density type lithium ion secondary battery 2 can be suppressed, and the life of the entire power supply device can be reduced. Can be extended.

  In addition, the conductive polymer type battery 1 is stable and safe due to the property that the conductivity decreases due to heat, overcharge and overdischarge, and runs away even if it receives heat from the surroundings other than the power supply device. Hard to do. Therefore, it can be used with peace of mind as a drive for an electric vehicle, a power tool or the like, or as a drive for an electric heating apparatus that handles heat.

  In the above power supply device, the conductive polymer type battery 1 used as a high power density type battery does not necessarily need to supply only power to the load 8 such as a motor. It can also be set so as to fulfill a function of charging the lithium ion secondary battery 2.

  Further, in the above power supply device, if the conductive polymer type battery 1 and the high capacity density type lithium ion secondary battery 2 are set in parallel and perform the function as the power supply device, the other settings are as follows. The configuration is not limited to that shown in FIG. The high capacity density type battery used for charging the conductive polymer type battery 1 is not limited to the lithium ion secondary battery, and different types of batteries may be used.

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

  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 battery 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 battery 1 used in the present invention will be described in more detail. For example, the conductive polymer battery 1 includes an electrolyte layer, and a positive electrode and a negative electrode provided opposite to each other, and in this example, in this example, A positive electrode sheet having an active material and a solid containing the conductive polymer and its dopant is used for the positive electrode.

  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 considered that it is also involved in the improvement of characteristics as 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, the conductive polymer type battery 1 having an excellent weight output density may not be obtained. On the other hand, the amount of the anionic material relative to the conductive polymer is not sufficient. If the amount is too large, the weight of the positive electrode due to the increase in the weight of the components other than the positive electrode active material may result in failure to obtain a conductive polymer type battery 1 having a high weight energy density when the weight of the entire battery is taken into consideration. There is.

  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.

  The electrolyte layer used in the conductive polymer type battery 1 is preferably a sheet formed by impregnating a separator with an electrolytic solution or a sheet formed of a solid electrolyte, for example. 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.

  Further, when a separator is used in the conductive polymer type battery 1, the separator can prevent an electrical short circuit between the positive electrode and the negative electrode disposed opposite to each other with the separator interposed therebetween. Insulating porous sheets that are stable, have high ion permeability, and have some 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.

  Further, in the conductive polymer type battery 1, a material that can insert and desorb base metal ions and 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 battery 1 using these materials, for example in inert gas atmosphere, such as an ultra high purity argon gas, in a glove box.

  The conductive polymer battery 1 used in the present invention thus obtained is not only excellent in weight output density and cycle characteristics as in an electric double layer capacitor, but also in the weight energy density of a conventional electric double layer capacitor. Has a much higher gravimetric energy density. And it is much safer than the lithium ion secondary battery conventionally used as a high power density type battery. Therefore, when used as a high power density battery in a power supply device for electric / electric heating equipment, an excellent power supply device that is safe and has a long battery life can be obtained.

  The reason why the conductive polymer type battery 1 has such a high capacity is that the cation transfer type rocking chair type battery that requires a small amount of electrolyte and the anion transfer type reserve type battery that has excellent output characteristics. This is considered to be due to the combination of both excellent properties.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to the following 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 type battery 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. In addition, the obtained discharge energy density is converted into a value per battery weight, and the unit is “Wh / kg” (the same applies to FIG. 2B below).

  As can be seen from FIG. 2 (a), this conductive polymer type battery has an energy density of 399 Wh / kg to 164 Wh / kg even though the current value is changed 500 times from 0.2 C to 100 C. However, since the original capacity is large, the high energy density of 150 Wh / kg or more is maintained.

  Therefore, it can be seen that this conductive polymer battery has very excellent output characteristics. Incidentally, the capacity density of the conventional lithium ion secondary battery, which is generally known, is significantly reduced from a rate of about 3C.

  Further, the discharge energy density was measured when the conductive polymer type battery 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 battery maintains 88% of the initial weight energy density even at the 1000th cycle. And even if the number of cycles is 5000, 100 Wh / kg is maintained, and the cycle characteristics are much better than the conventional lithium ion secondary battery.

  Five conductive polymer batteries (laminated sheet type cell: electrode effective area 12cm x 12cm, 5 layers, 1.0Wh / 1 cell) prepared in the above manner are arranged in series to make 18V specification, high output It was set as the conductive polymer type battery used as a density type battery. Then, the conductive polymer type battery and four high-capacity density type lithium ion secondary batteries (3.0 Ah / 1 cell) are arranged in series to obtain an 18V specification, and an electric / electric heating device having a configuration as shown in FIG. A power supply device was prepared. And when this was mounted on an electric tool (cordless electric screwdriver, 18 V, maximum torque 150 N · m) and used as a power source for driving the motor, it could be used satisfactorily.

  Assuming a power supply device in which the conductive polymer type battery and the high capacity density type lithium ion secondary battery are combined at a volume ratio of 1: 1 (capacity ratio of 25:75), the high capacity density type lithium ion secondary battery is used. The change in SOH when power was continuously supplied while charging the conductive polymer type battery using the secondary battery was simulated and converted into data based on the SOH change of each battery alone. The result is shown as a line segment A in FIG. For reference, the SOH change of the conductive polymer type battery used is shown as a line segment a1, and the SOH change of the high capacity density type lithium ion secondary battery is shown as a line segment a2.

[Comparative Example 1]
Further, as a comparative example, in the power supply device having the configuration shown in FIG. 1, a high power density type battery using an electric double layer capacitor instead of the conductive polymer type battery was assumed. The configuration is shown in FIG. As in the above embodiment, the electric double layer capacitor and the high capacity density type lithium ion secondary battery are combined at a volume ratio of 1: 1 (capacity ratio of 5:95), and the high capacity density type lithium ion secondary battery is combined. The change in SOH when power was continuously supplied while charging the electric double layer capacitor using a battery was simulated and converted into data based on the change in SOH of each battery alone. The result is shown as a line segment B in FIG. For reference, the SOH change of the used electric double layer capacitor is shown as a line segment b1, and the SOH change of the high capacity density type lithium ion secondary battery is shown as a line segment b2.

  This simulation is based on the following concept. That is, since the conductive polymer battery has good cycle characteristics, the decrease in SOH alone is small. In addition, since the capacity is relatively large, it is not necessary to frequently be charged from a high capacity density type lithium ion secondary battery, and therefore, a decrease in SOH of the high capacity density type lithium ion secondary battery is suppressed. As a result, as shown by a line segment A in FIG. 3, the SOH reduction of the entire combination battery is suppressed. Therefore, the lifetime of the combined battery as a whole (elapsed time until SOH becomes 75% or less: TA) becomes very long.

  On the other hand, since the high-power electric double layer capacitor has a small electric capacity, charging from a high capacity density type lithium ion secondary battery is frequently required. For this reason, SOH of a high capacity density lithium ion secondary battery will fall rapidly, and SOH of the whole combination battery will be controlled. Therefore, the lifetime of the combined battery as a whole (elapsed time until SOH becomes 75% or less: TB) is significantly shorter than that of the TA.

  From the above, it can be seen that the power supply device of Example 1 has a longer battery life and is practically superior to the power supply device of Comparative Example 1 using an electric double layer capacitor.

  The present invention can be widely used as a power supply device for electric / electric heating equipment for driving electric / electric heating equipment.

DESCRIPTION OF SYMBOLS 1 Conductive polymer type battery 2 High capacity density type lithium ion secondary battery 3, 4 SOC detector 5 Controller 8 Load

Claims (5)

  A power supply device for driving electric / electric heating equipment, comprising a circuit in which a high power density type battery and a high capacity density type battery are connected in parallel, and a conductive polymer type battery as the high power density type battery. When the electric power is supplied to the electric / electric heating device by the conductive polymer type battery, and the charge amount (SOC) of the conductive polymer type battery becomes lower than a predetermined value, the high capacity density type battery A power supply device for an electric / electric heating device, characterized in that the conductive polymer type battery is charged using a battery.   The power supply device for electric / electric heating equipment according to claim 1, wherein at least one electrode of the conductive polymer type battery has a conductive polymer and an anionic material fixed in the electrode.   The power supply device for electric / electric heating equipment according to claim 2, wherein the anionic material is a polymer anion.   The power supply device for electric / electric heating equipment according to claim 3, wherein the polymer anion is polycarboxylic acid.   The power supply device for electric / electric heating equipment according to any one of claims 1 to 4, wherein the conductive polymer is polyaniline.

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