JP2015026507A - Power storage device, and portable phone and battery type electric car using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a power storage device, and a portable phone and a battery type electric car having the same, capable of achieving charging of high capacity that has not been obtained by a non-contact charging system in a short time.SOLUTION: The power storage device 1 includes a receiving antenna 4 that receives electric power supplied from the outside and a power storage device 2 connected with the receiving antenna 4. The power storage device 2 has an electrode including conductive polymer. By electromagnetically coupling a transmission antenna 5 in a transmission apparatus 6 and the receiving antenna 4 at charging, the power storage device 2 is charged in a non-contact manner.

Description

  The present invention relates to a power storage device, a mobile phone using the power storage device, and a battery-powered electric vehicle, and a power storage device capable of charging a large capacity in a short time in a non-contact charging system and a mobile phone using the same The present invention relates to a telephone and a battery type electric vehicle.

  Conventionally, problems caused by a charging device for charging a power storage device such as a secondary battery used as a power source of a mobile phone and the like and an electrical contact existing between the power storage device (for example, an electronic contact In the case of contamination, there is a problem that charging becomes impossible and charging cannot be performed. In order to solve this, a power supply system for portable electronic devices based on a non-contact charging method that can be charged without a contact with a charging device has been proposed (see Patent Document 1). This is a non-contact type power supply system that eliminates metal contacts and transmits and charges power by an induction coil, and has already been widely commercialized.

  Recently, it has become more important to improve the usability of the mobile phone body and the charging device set, and an easy operation type that can be charged by simply placing it has been strongly desired ( Patent Document 2).

  In the power supply system for portable electronic devices disclosed in Patent Document 1, a nickel cadmium battery is used as an electricity storage device. In recent years, a lithium ion secondary battery that is smaller and lighter and has a larger electricity storage capacity than a nickel cadmium battery as an electricity storage device. Is mainly used.

JP 2003-244855 A JP 2006-311712 A Special table 2013-528043 gazette

  However, the lithium ion secondary battery is an electricity storage device that obtains electric energy by an electrochemical reaction, and has a significant problem that the output density is low because the speed of the electrochemical reaction is low. Rapid charge / discharge is difficult due to high internal resistance. In addition, since the specific gravity of the positive electrode active material is large, there is still room for improvement in the capacity density per unit weight, and in addition, since the electrode and the electrolytic solution deteriorate due to the electrochemical reaction associated with charge and discharge, generally the life, That is, the cycle characteristics are not good.

  On the other hand, recently, measures to seriously solve the problem of air pollution and global warming have been studied, and as one of them, hybrid vehicles and electric vehicles have already been put into practical use. In this stage, it is proposed to charge the power storage device with a wireless charging system (hereinafter also referred to as “non-contact charging method”) (see Patent Document 3). Lithium ion secondary batteries have been put into practical use as these main power storage devices.

  However, power storage devices for hybrid vehicles and electric vehicles are particularly demanded for high power density during rapid charging and acceleration by regenerative braking.Lithium ion secondary batteries have a high power storage capacity. There is a problem that the power density is low.

  Therefore, electric double layer capacitors have attracted attention. An electric double layer capacitor usually uses a polarizable electrode formed of a conductive porous carbon material having a large specific surface area such as powdered activated carbon or fibrous activated carbon, and exhibits physical adsorption characteristics of supporting electrolyte ions in the electrolyte. It is a device that uses and stores electricity. For this reason, the electric double layer capacitor has a high output density, can be rapidly charged, and has a remarkably long life.

  However, on the other hand, the electric double layer capacitor has a very small storage capacity. For example, an electric double layer capacitor is said to have a volume energy density of about 1/50 to 1/20 compared to a lithium ion secondary battery. For this reason, there is a problem in practical use as a power storage device for a hybrid vehicle or an electric vehicle.

  The present invention has been made in view of such circumstances, and a power storage device capable of charging in a short time a large capacity in a non-contact charging method, a mobile phone using the same, and a battery-powered electric vehicle The purpose is to provide.

  In order to achieve the above object, the present invention includes a receiving antenna that receives electric power supplied from the outside, and an electric storage device connected to the receiving antenna, and the electric storage device includes an electrode containing a conductive polymer. A power storage device having the first feature is described.

  And this invention makes it 2nd summary to be a mobile telephone using the electrical storage apparatus which is said 1st summary, and similarly battery-type electricity which uses electrical storage device which is said 1st summary The third point is that it is an automobile.

  That is, the present inventors have conducted intensive research in order to obtain a power storage device that has an unprecedented battery performance. As a result, when an electricity storage device having an electrode containing a conductive polymer is used as an electricity storage device of an electricity storage device, the high capacity, high output, and high cycle characteristics of the electricity storage device having an electrode containing the conductive polymer are contactless charging. Enables stable power supply even at times. For this reason, the inventors have found that large-capacity charging that is unthinkable with conventional non-contact charging is possible in a short time, and reached the present invention.

  The power storage device of the present invention includes a reception antenna that receives power supplied from the outside and a power storage device connected to the reception antenna, and the power storage device includes an electrode containing a conductive polymer. In addition, since the battery capacity of the electricity storage device is large and the charging speed is fast, large-capacity charging that is not possible in the past in the non-contact charging method is possible in a short time.

  Furthermore, when the electrode including the conductive polymer further includes an anionic material, an electric device using the power storage device has further cycle characteristics and a charging speed.

  Furthermore, in the case of a mobile phone or a battery-type electric vehicle using the above power storage device, a mobile phone or a battery-type electric vehicle capable of charging a large capacity in a short time by a non-contact charging method can be obtained. . This is an effect that has been desired for many years in power storage devices such as mobile phones and battery-powered electric vehicles that require simple quick charging of electric capacity.

It is a block block diagram of the electrical storage apparatus of this invention. It is sectional drawing which shows the structure of the electrical storage device in this invention. It is a graph which shows the charging / discharging cycle characteristic of the electrical storage device in this invention. It is a graph which shows the discharge rate characteristic of the electrical storage device in this invention. It is a graph which shows the charging efficiency of a conductive polymer type battery and a lithium ion secondary battery. It is a graph which shows the charge or discharge characteristic with respect to SOC (State Of Charge) of the electrical storage device in an Example (use of a conductive polymer type battery) and a comparative example (use of a lithium ion secondary battery). It is a graph which shows the discharge or charge resistance value with respect to SOC (State Of Charge) of the electrical storage device in an Example (use a conductive polymer type battery) and a comparative example (use a lithium ion secondary battery).

  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.

  A power storage device according to the present invention includes a receiving antenna that receives power supplied from the outside and a power storage device connected to the receiving antenna, and the power storage device includes an electrode including a conductive polymer. To do. For example, as shown in FIG. 1, a power storage device 1 according to the present invention includes a power storage device 2 and a reception antenna 4, and the transmission antenna 5 in the power transmission device 6 and the reception antenna 4 are electromagnetically coupled during charging. Thus, the power storage device 2 and the power transmission device 6 are configured to charge the power storage device 2 by a so-called non-contact charging method in which there is no electrical circuit connection.

  The power storage device 2 incorporated in the power storage device 1 has at least a main active material of the positive electrode made of a conductive polymer, and has high capacity, high output, and high cycle characteristics. Details of the electricity storage device 2 will be described next.

<About the electricity storage device 2>
The configuration of the electricity storage device 2 will be described in more detail. For example, as shown in FIG. 2, the storage device 2 includes an electrolyte layer 13, and a positive electrode 12 and a negative electrode 14 that are provided to face each other. The conductive polymer is used as the main active material.

  As described above, the electrode containing the conductive polymer can be used for both the positive electrode 12 and the negative electrode 14 of the electricity storage device 2, but is particularly preferably used as the positive electrode 12. Hereinafter, the case where the electrode containing a conductive polymer is used as the positive electrode 12 will be described.

  As described above, the positive electrode 12 of the electricity storage device 2 is composed of a positive electrode forming material containing a conductive polymer. The positive electrode 12 is usually composed of a composite having a positive electrode active material layer composed of such a positive electrode forming material on a current collector, and is preferably used as a positive electrode sheet. Hereinafter, the positive electrode forming material and the like will be described in order.

[Conductive polymer]
In the present invention, a conductive polymer means that an ionic species is inserted into or desorbed from a polymer in order to compensate for a change in charge generated or lost by an oxidation reaction or reduction reaction of the polymer main chain. Refers to a group of polymers in which the conductivity of the polymer itself changes. In such a polymer, a state in which an ionic species is inserted into the polymer and has high conductivity is referred to as a doped state, and a state in which the ionic species is detached from the polymer and the conductivity is low is referred to as a dedope 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 dedope state), such a polymer is reversibly conductive again by the oxidation-reduction reaction. Thus, the insulating polymer in the dedope state is also included in the category of the conductive polymer in the present invention.

  Accordingly, one of the preferred conductive polymers in the present invention is a dopant containing 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 the present invention, another preferable conductive polymer is a polymer in a dedope state obtained by dedoping the conductive polymer.

  Examples of the polymer constituting the conductive polymer include polypyrrole, polyaniline, polythiophene, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyphenylene oxide, polyazulene, poly (3,4-ethylenedioxythiophene), Polyacene and the like and various derivatives thereof are used. Among these, in the present invention, one of the preferable polymers is at least one selected from polyaniline and derivatives thereof because the obtained conductive polymer has a large capacity per unit weight.

  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. Here, as the derivative of aniline, at least a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group is present at a position other than the 4-position of aniline. What has one can be illustrated. 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- Mention may be made of m-substituted anilines such as methoxyaniline, m-ethoxyaniline and m-phenylaniline.

  However, according to the present invention, even if it has a substituent at the 4-position, p-phenylaminoaniline gives polyaniline by oxidative polymerization, so that it can be suitably used exceptionally as an aniline derivative.

  The polypyrrole refers to a polymer obtained by chemical oxidative polymerization or electrolytic oxidative polymerization of pyrrole, 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 Those having at least one group can be exemplified. 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”. In the present invention, 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.

  In the electricity storage device 2 used in the present invention, it is preferable that at least one of the electrodes, for example, the positive electrode 12 has the conductive polymer and the anionic material.

[Anionic material]
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, at least one selected from polycarboxylic acids and metal salts 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.

  The metal salt of the polycarboxylic acid is at least one selected from an alkali metal salt and an alkaline earth metal salt, and the alkali metal salt is preferably a lithium salt or a sodium salt, and the alkaline earth metal salt Preferably, it is a magnesium salt or a calcium salt.

  In the electricity storage device 2, when at least one selected from the polycarboxylic acid and a metal salt thereof is used for the positive electrode 12 together with the conductive polymer, at least one selected from the polycarboxylic acid and the metal salt is a binder. On the other hand, it also functions as a dopant for the conductive polymer of the positive electrode 12, has a rocking chair type mechanism, and is considered to be involved in improving the characteristics of the electricity storage device 2.

  At least one selected from such polycarboxylic acids and metal salts thereof is usually 1 to 100 parts by weight, preferably 2 to 50 parts by weight, most preferably 5 parts per 100 parts by weight of the conductive polymer. Used in the range of ˜30 parts by weight. When the amount of at least one selected from the polycarboxylic acid and the metal salt thereof with respect to the conductive polymer is too small, it tends to be difficult to obtain the electricity storage device 2 having excellent weight output density, while the polycarboxylic acid with respect to the conductive polymer is difficult to obtain. When the amount of at least one selected from an acid and a metal salt thereof is too large, when the weight of the entire battery is taken into account due to an increase in the weight of the positive electrode 12 due to an increase in the weight of a member other than the positive electrode active material, the weight is high. There is a tendency that it is difficult to obtain a non-electric storage device of energy density.

  As the positive electrode forming material, together with the conductive polymer and the anionic material, a binder other than the anionic material, a conductive auxiliary agent, and the like can be appropriately blended as necessary.

  The conductive auxiliary agent may be any conductive material whose properties do not change depending on the potential applied during the discharge of the electricity storage device 2, and examples thereof include conductive carbon materials and metal materials. Among them, acetylene black, ketjen Conductive carbon black such as black, and fibrous carbon materials such as carbon fiber and carbon nanotube are preferably used. Particularly preferred is conductive carbon black.

  It is preferable that the said conductive support agent is 1-30 weight part with respect to 100 weight part of said conductive polymers, More preferably, it is 4-20 weight part, Especially preferably, it is 8-18 weight part. When the blending amount of the conductive aid is within this range, the shape and characteristics as the active material can be prepared without abnormality, and the rate characteristics can be effectively improved.

  Examples of the binder other than the anionic material include vinylidene fluoride.

  The positive electrode 12 is composed of a composite sheet having a current collector layer including a solid positive electrode active material containing a conductive polymer and a conductive auxiliary agent appropriately blended as necessary. The layer containing the active material and the conductive assistant is solid and porous.

  The positive electrode 12 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, the said conductive polymer powder and the said anionic material (with the conductive support agent etc. used as needed) on a collector It can be obtained as a composite sheet having a uniform positive electrode active material layer.

  The positive electrode 12 is preferably formed in a porous sheet. The thickness of the positive electrode sheet is preferably 1 to 1000 μm, and more preferably 10 to 700 μm.

  The thickness of the positive electrode 12 is measured by using a standard dial gauge (Ozaki Mfg. Co., Ltd.) whose tip shape is a flat plate with a diameter of 5 mm, and obtaining the average of 10 measured values with respect to the surface of the positive electrode 12. can get.

  Further, the porosity of the positive electrode 12 is preferably 20 to 80%, more preferably 40 to 60%. In addition, the said porosity is a value calculated | required by following formula (1), and the following "apparent volume of an electrode" is "the thickness which remove | excluded the collector thickness from the electrode surface area x electrode thickness." "Means. On the other hand, the “true volume of the electrode” below refers to “the volume of the electrode forming material excluding the current collector”. Specifically, the average density of the entire electrode forming material is calculated using the constituent weight ratio of the electrode forming material and the true density of each constituent material, and the total weight of the electrode forming material is divided by this average density. Is required.

[Equation 1]
Electrode porosity (%) = {(Apparent volume of electrode−True volume of electrode) / Apparent volume of electrode} × 100 (1)

  Moreover, it is preferable that the average value of the hole diameter of the micropore formed in the said positive electrode is 0.1-10 micrometers, More preferably, it is the range of 0.5-5 micrometers. In addition, the said hole diameter is measured using Shimadzu Corp. micromeritex pore content measuring device autopore 9520 type, for example.

[About electricity storage device 2]
Here, as described above, FIG. 2 shows an example of the electricity storage device 2, which includes the electrolyte layer 13, and the positive electrode 12 and the negative electrode 14 provided to face each other with the electrolyte layer 13 interposed therebetween. In addition, 11 is a collector for positive electrodes, and 15 is a collector for negative electrodes. FIG. 2 schematically shows the structure of the electricity storage device 2, and the thickness of each layer is different from the actual one.

  Moreover, although the electrolyte layer 13 is comprised with electrolyte, the sheet | seat which makes a separator impregnate an electrolyte solution and the sheet | seat which consists of solid electrolytes are used preferably, for example. The sheet made of the solid electrolyte itself also serves as a separator. Here, a solution in which an electrolyte is dissolved in a solvent may be referred to as an “electrolytic solution”.

  Examples of the electrolyte include base metal ions and appropriate counter ions, for example, sulfonate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroarsenic ions, bis (trifluoromethanesulfonyl). A combination of imide ion, bis (pentafluoroethanesulfonyl) imide ion, halogen ion and the like is preferably used.

  The base metal is a metal having an ionization tendency larger than that of hydrogen and easily oxidized in the air (when heated), and includes alkali metals, 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 ) _{2 and the} like.

  As the solvent constituting the electrolytic solution, for example, at least one nonaqueous solvent such as carbonates, nitriles, amides, ethers, that is, 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. These may be used alone or in combination of two or more.

  In the present invention, the separator can be used in various modes. As the separator, it is possible to prevent an electrical short circuit between the positive electrode 12 and the negative electrode 14 that are arranged to face each other across the separator. Furthermore, the separator is electrochemically stable and has a large ion permeability. Any insulating porous sheet having a certain degree of mechanical strength may be used. Accordingly, as the separator, for example, a porous porous sheet made of a resin such as paper, nonwoven fabric, polypropylene, polyethylene, or polyimide is preferably used. These may be used alone or in combination of two or more.

  Further, as described above, when a separator impregnated with an electrolytic solution is used as the electrolyte layer 13, the same electrolyte as that described above is used as the electrolyte constituting the electrolytic solution.

  The negative electrode 14 preferably contains at least one of a base metal and a material capable of inserting and releasing base metal ions. 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. . A preferable electricity storage device in the present invention is a lithium secondary battery, and lithium can be mentioned as a preferable base metal. Moreover, lithium ions can be given as more preferable base metal ions. As the material capable of inserting / extracting the base metal ions, a carbon material is preferably used, but silicon, tin and the like can also be used. In the present invention, “use” means not only the case where only the forming material is used, but also the case where the forming material is used in combination with another forming material. Is used at less than 50% by weight of the forming material.

  In addition to the positive electrode 12, the electrolyte layer 13, the negative electrode 14, and the like, the power storage device 2 can use the current collectors 11 and 15. The current collectors 11 and 15 are not particularly limited as long as they have good conductivity and stability, but metal foils and meshes such as nickel, aluminum, stainless steel, and copper are preferably used, and stainless steel materials are preferably used. It is done. Furthermore, when the negative electrode 14 is a metal, the negative electrode itself may also serve as a current collector.

  The electricity storage device 2 is formed in various shapes such as a laminate cell, a porous sheet type, a sheet type, a square type, a cylindrical type, and a button type.

  In addition, it is preferable to assemble the said electrical storage device 2 in inert gas atmosphere, such as an ultra-high purity argon gas, in a glove box.

  The electrical storage device 2 obtained in this way is not only excellent in weight output density and cycle characteristics like an electric double layer capacitor, but also has a weight energy density much higher than that of a conventional electric double layer capacitor. Have. Therefore, in the non-contact charging type power storage device, it is not necessary to combine an electric double layer capacitor and a lithium ion secondary battery or the like separately from the capacitor, and an excellent power storage device 1 is obtained only by using the power storage device alone. be able to.

  Note that the reason why the electricity storage device 2 has such a high capacity is that the amount of electrolyte solution is a cation migration type that is a cation migration type, and a rocking chair type electricity storage device that has excellent output characteristics. This is thought to be due to the combination of both excellent characteristics of the device.

<About power storage device>
And the electrical storage apparatus 1 provided with the said electrical storage device 2 is electrically stored by the non-contact charge system demonstrated below. At the time of charging, charging power supplied as electromagnetic energy from the power transmission device 6 shown in FIG. 1 is received from the transmission antenna 5 in the power transmission device 6 by AC power induction by electromagnetic coupling (for example, constituted by a coil). Is transmitted). The converter 3 converts the power transmitted to the receiving antenna 4 into power suitable for charging, and the converted power is transmitted to the power storage device 2 and stored in the power storage device 2. .

  That is, in the non-contact charging system, by placing the power storage device 1 near the power transmission device 6 having the transmission antenna 5, the reception antenna 4 in the power storage device 1 and the transmission antenna 5 in the power transmission device 6 are aligned, As a result, near-field coupling is generated and efficient energy transmission is possible. This is because a coupling mode can occur between the transmitting antenna 5 and the receiving antenna 4 within the near field.

  The transmitting antenna 5 has a function of transmitting power, while the receiving antenna 4 has a function of transmitting the power transmitted from the transmitting antenna 5 to the power storage device via the conversion unit 3 as necessary.

  The transmitting antenna 5 and the receiving antenna 4 may be configured as “loop” antennas, and more specifically, may be configured as a multi-turn loop antenna. This loop antenna is sometimes referred to as a “magnetic” antenna. The loop antenna may be configured to include a physical core such as an air core or a ferrite core. The air core loop antenna may place other elements in the core region. A physical core antenna is more preferable because a stronger electromagnetic field can occur.

  The converter 3 performs various conversions on the power transmitted from the receiving antenna 4 and outputs it to the power storage device 2. For example, the power storage device 2 is converted into a power output suitable for charging, or the control conversion is performed to a voltage suitable for power storage. Especially, it is preferable that the said conversion part 3 has a rectification function which rectifies | straightens alternating current power and converts it into direct-current power, and a voltage control function which controls a voltage.

  The conversion unit 3 may include, for example, an oscillator, a power amplifier, a filter, a matching circuit for efficiently coupling with a transmission / reception antenna, an inverter, a converter, a switching circuit, and the like.

  The oscillator is configured to generate a desired frequency, and this frequency may be adjusted according to an adjustment signal. Further, the signal of the oscillator may be amplified by a power amplifier with an amplification amount corresponding to the matching signal. The filter and matching circuit may be included to filter out harmonics and other unwanted frequencies, or to match the impedance of the power conversion module to the transmit / receive antenna.

  The power transmission device 6 includes a transmission antenna 5 and an AC or DC power source therein. When the transmitting antenna 5 and the receiving antenna 4 are electromagnetically coupled during charging, charging can be performed without a contact.

  Examples of the system using the power storage device 1 as described above include a mobile phone and a battery-type electric vehicle. This will be described in order below.

<Mobile phone>
Next, a non-contact charging system for mobile phones using the power storage device 1 will be described. Since the mobile phone using the power storage device 1 includes the receiving antenna 4 that receives power supplied from the outside and the power storage device 2 connected to the receiving antenna 4, the power transmitting device 6 ( Simply placing it in the near field of the transmitting antenna 5 such as placing it on a so-called charging device) makes it possible to charge a large amount of capacity in a short time.

  Since the power storage device 1 of the present invention can receive power supply using electromagnetic energy as a medium, a specific usage scene is assumed as follows, for example.

  First, even when the mobile phone equipped with the power storage device 1 of the present invention is carried and the user goes out for a long time, it is not necessary to carry the charging device. In other words, a charging device that supplies the electromagnetic energy (not shown) described above to any place on the go (for example, a predetermined place or position not related to public or private, such as a table in a coffee shop, an office desk on the go, an airplane or train on the move) Therefore, it is possible to receive power supply without worrying about the contact terminal type (model).

<Electric car>
Next, a non-contact charging system for a battery-type electric vehicle (hereinafter sometimes abbreviated as “electric vehicle”) using the power storage device 1 will be described.

  The electric vehicle is used in the sense of a vehicle that includes power derived from one or more rechargeable electrochemical cells as part of its mobility. For example, it may be a hybrid electric vehicle including an in-vehicle charging device that charges the vehicle using the energy obtained from the deceleration of the vehicle and a conventional motor, or all the movement capability may be extracted from the electric power. .

  Since the battery of the electric vehicle can be constituted by the wireless or non-contact power storage device 1 with respect to other parts of the vehicle, not only can the battery be charged in a non-contact manner, but also the battery can be replaced easily and reliability. There can be several advantages regarding mechanical wear, and safety.

  In a contactless charging system for an electric vehicle, the electric vehicle is parked on a contactless charging base (corresponding to the power transmission device 6 in FIG. 1) having a transmission antenna 5 and an AC or DC power source. The receiving antenna 4 in the power storage device 1 and the transmitting antenna 5 in the charging base are aligned. As a result, near-field coupling occurs, and efficient energy transmission becomes possible. This is because a coupling mode can occur between the transmitting antenna 5 and the receiving antenna 4 within the near field.

  In order to properly align the transmitting antenna 5 and the receiving antenna 4 in the electric vehicle non-contact charging system, the electric vehicle is properly positioned in the parking space, and the antenna is positioned after the electric vehicle is positioned in the parking space. This can be realized by finely adjusting the position.

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

  First, when manufacturing the power storage device of the present invention, a power storage device used for the power storage device was prepared and prepared.

[For Examples]
(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. Suction filtration was performed with two filter papers (manufactured by Advantech) to obtain a powder. 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-pressing 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%. In addition, the porosity was computed 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 in a stainless steel HS cell (manufactured by Hosen Co., Ltd.) for an electricity storage device experiment. 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.

  Various tests were conducted according to the following criteria using the obtained electricity storage device (hereinafter sometimes referred to as “conductive polymer battery”).

<Cycle characteristics>
The discharge energy density when the conductive polymer battery obtained above was discharged up to 5000 times at a high discharge rate of 8.3 C was measured, 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 measurement results are shown in FIG. As can be seen from FIG. 3, this conductive polymer type battery maintains 88% of the initial discharge energy density even at the 1000th cycle. And even if the number of cycles is 5000, it is maintained at 100 Wh / kg and has remarkably superior cycle characteristics as compared with conventional lithium ion secondary batteries.

<Discharge energy density>
Moreover, about the obtained conductive polymer type | mold battery, the charging / discharging rate was changed from 0.2C to 500C, and the discharge energy density was measured. The measurement apparatus and measurement conditions were the same as the above cycle characteristics.

  The measurement results are shown in FIG. In addition, the obtained discharge energy density is converted into a value per battery weight, and the unit is “Wh / kg”.

  As can be seen from FIG. 4, this conductive polymer type battery has a discharge energy density of about 399 Wh / kg to 164 Wh / kg, although the current value is changed 500 times from 0.2 C to 100 C. Since the capacity is only 41% and the original capacity is large, a high energy density of 150 Wh / kg or more is maintained even at 100C. Therefore, it can be seen that this conductive polymer battery has very high discharge characteristics.

<Charging efficiency (%)>
Further, under the same measurement apparatus and measurement conditions as those described above, the charging efficiency (%) at the charging rate of the conductive polymer battery was calculated, and the result is shown in FIG. From FIG. 5, this conductive polymer type battery shows very high charging efficiency (%) with respect to the rate characteristics, and shows a capacity of 80% or more with respect to full charge even at a charging rate of 20C. By the way, being able to fully charge at a charging rate of 20 C means that charging / discharging is completed in 1/20 hours, that is, 3 minutes, indicating that extremely short time rapid charging / discharging is possible. .

  For comparison, a lithium ion secondary battery using lithium cobaltate as a positive electrode active material having the same effective area was prepared instead of the conductive polymer battery, and the charging efficiency was measured. .

  The measurement results of the lithium ion secondary battery are also shown in FIG. As can be seen from FIG. 5, it is understood that the lithium ion secondary battery cannot be charged in a short time because its charged capacity is drastically decreased at a charging rate exceeding 2C.

〔Example〕
Next, using the obtained positive electrode sheet, a conductive polymer type battery (electrode effective area 10 cm × 10 cm, design electric energy 100 mWh / 1 cell) of a laminated sheet type cell was prepared. did. Then, using the battery for this example, a power storage device as an example was manufactured, and a power transmission device corresponding to the power storage device was manufactured. Note that the distance between the transmission antenna in the power transmission device and the reception antenna in the power storage device was 5 mm.

[Comparative Example]
Further, instead of the conductive polymer type battery which is the laminated sheet type cell, a general-purpose lithium ion secondary battery having the same effective area (positive electrode: lithium cobaltate, negative electrode: graphite, design power 200 mWh / 1 cell) In the same manner as in the above example, a power storage device as a comparative example was manufactured and a power transmission device corresponding to the power storage device was manufactured.

  The examples and comparative examples thus obtained were actually measured according to the following criteria.

<Energy and charging efficiency>
In the power storage devices of the above examples and comparative examples, when the built-in power storage device is discharged once, it is placed in a state where it can be contactlessly charged on the power transmission device, 10W contactless charging is performed for 36 seconds, and discharge is performed at 0.2C The results of the amount of power (mWh) and the charging efficiency (%) are shown in Table 1 below.

  From the results of Table 1 above, even in non-contact charging in a short time of 36 seconds, the charging efficiency in the example was significantly higher than that in the comparative example. This is considered to be due to the excellent charging performance of the conductive polymer type battery used in the examples.

<Discharge or charge characteristics, discharge or charge resistance value>
In the power storage devices of the above examples and comparative examples, the discharge or charge characteristics with respect to the SOC of the power storage device incorporated therein were measured, and the discharge or charge resistance value with respect to the SOC was measured. The result of the discharge or charge characteristic is shown in FIG. 6, and the result of the discharge or charge resistance value is shown in FIG.

  6 and 7, the electricity storage device (conductive polymer type battery) in the example has a lower discharge / charge resistance value than the electricity storage device (lithium ion secondary battery) in the comparative example. The charging characteristics were excellent. In particular, it can be considered from FIG. 6 that the charging characteristics of the electricity storage device in the example are remarkably excellent when the SOC is in the range of 5% to 70%, and this enables non-contact charging in a short time.

  Since the power storage device of the present invention includes the power storage device having excellent cycle characteristics, energy density, and charging efficiency as described above, it is possible to charge a very large capacity in a short time in a non-contact charging method. I understand that

  In addition, since the power storage device of the present invention can achieve the above-described effects, the cycle characteristics and energy of a mobile phone and an electric vehicle using the power storage device are also higher than those of the conventional lithium ion secondary battery. A dramatic improvement in density and charging efficiency can be obtained.

  INDUSTRIAL APPLICABILITY The present invention can be widely used as a power storage device for mobile phones and electric vehicles where non-contact quick charging is desired.

DESCRIPTION OF SYMBOLS 1 Power storage device 2 Power storage device 3 Converter 4 Reception antenna 5 Transmission antenna 6 Power transmission device 11 Current collector for positive electrode 12 Positive electrode 13 Electrolyte layer 14 Negative electrode 15 Current collector for negative electrode

Claims (4)

A receiving antenna for receiving power supplied from the outside;
A power storage device connected to the receiving antenna,
A power storage device, wherein the power storage device includes an electrode including a conductive polymer.   The power storage device according to claim 1, wherein the electrode including the conductive polymer further includes an anionic material.   A mobile phone comprising the power storage device according to claim 1 or 2.   A battery-powered electric vehicle comprising the power storage device according to claim 1 or 2.

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