JP2015029398A - Power supply device, mobile device arranged by use thereof, and battery-type electric vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a superior power supply device which is high in safety and longer in battery life and which can be charged at high speed.SOLUTION: A power supply device comprises: a conductive polymer type battery 1; a high-capacity density type lithium ion secondary battery 2; SOC detectors 3 and 4 for detecting the battery residual of each of the batteries 1 and 2; a controller 5; and a power output part for outputting power to a load 8. The charging from an external power source is performed on the conductive polymer type battery 1 preferentially. The power output to the power output part is performed from the high-capacity density type lithium ion secondary battery 2 preferentially. The high-capacity density type lithium ion secondary battery 2 is charged by the conductive polymer type battery 1.

Description

  The present invention relates to a power supply device, a mobile device using the power supply device, and a battery-powered electric vehicle. More specifically, the present invention relates to a power supply device for supplying power to a mobile device, a battery-powered electric vehicle, or the like.

  In recent years, portable electric / electronic devices (hereinafter referred to as “mobile devices”) such as laptop computers, mobile phones such as smartphones, personal digital assistants (PDAs), digital cameras, digital video cameras, and portable audio devices. (Generic name) is very popular. As a power source for driving such a mobile device, a secondary battery (also referred to as a chemical secondary battery) such as a lithium ion battery is used, and a commercial power source previously installed in a home or office is used. And can be used while being repeatedly charged.

  And in such a secondary battery, the one of a large capacity type has appeared one after another, and the larger the capacity, the longer the time that can be used with one charge, and carry it as a portable tool. Easy to use. However, the larger the capacity, the longer it takes to charge. For example, it may take 30 minutes to several hours to charge up to 80% of the capacity (full charge). There is a problem that the inside cannot be moved from a place where the power source is provided and the convenience is deteriorated.

  Therefore, in order to further shorten the charging time in the power supply device such as the mobile device described above, two different types of batteries, that is, a small electric capacity but a short time charge / discharge to supply a large output (large current). Combined with a high power density type battery that can be used and a battery that cannot supply a large output but has a high electric capacity density (high power capacity) and that requires a relatively long charge / discharge time. It has been studied to preferentially charge a high power density type battery having a high speed. 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.

  As an example of combining such a high power density type battery and a high capacity density type battery, for example, a high power density type battery type lithium ion secondary battery and a high capacity density type battery type lithium ion secondary battery (See Patent Document 1). This battery can be used as a standby power source capable of high-speed charging by using the above-described high-power density battery type lithium ion secondary battery as a charging battery.

  There is also a power supply device using a capacitor type storage battery such as an electric double layer capacitor as a high power density type battery and a lithium ion secondary battery as a high capacity density type battery (see Patent Document 2). In this device, the charging time as the whole power supply device can be shortened by preferentially performing the charging / discharging operation by the capacitor type storage battery.

International Publication No. 2010/095292 JP 2002-95174 A

  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. The heat generation becomes particularly large when a lithium ion secondary battery is used as a high output density type battery that requires high output, so that this can be applied to mobile devices that are susceptible to external impacts. It is not preferable to install and use it.

  On the other hand, recently, measures for seriously solving the problems of air pollution and global warming have been studied, and one of them is battery-powered electric vehicles such as hybrid cars and electric cars. Already put into practical use. Lithium ion secondary batteries have been put into practical use as these main batteries.

  However, a battery for a battery-powered electric vehicle is required to have a high output density especially during rapid charging or acceleration by regenerative braking. A lithium ion secondary battery has a large amount of electricity, but the output density is high as described above. There is a problem that it is low.

  Therefore, electric double layer capacitors have attracted attention as high power density type batteries. However, a high power density type battery using an electric double layer capacitor is safer than a lithium ion secondary battery, but its electric capacity is an order of magnitude smaller than that of the lithium ion secondary battery. If you try to obtain an electric capacity comparable to that of a secondary battery, the battery will become bulky, and its size and electric capacity will make it suitable for mounting on compact mobile devices and battery-powered electric vehicles that require large electric capacity. Capacity is limited.

  In general, a secondary battery deteriorates when charging and discharging are repeated. As an index indicating the deterioration of the battery, there is SOH (State Of Health). SOH is represented by the ratio of the full charge capacity (Ah) at the time of deterioration to the initial full charge capacity (Ah: ampere hour). It is said that if the SOH is low, it is better to replace it (generally 75%). However, when two types of batteries are combined, if one battery is charged and discharged frequently, The SOH of the battery decreases quickly. For this reason, even if the other battery can still be used, there is a problem that it is uneconomical due to a situation in which the entire power supply device must be disposed of.

  The present invention has been made in view of such circumstances, and an excellent power supply device that can be charged at high speed, has high safety, and has a long battery life, a mobile device using the power supply device, and a battery-powered electric vehicle. The purpose is to provide.

  In order to achieve the above object, the present invention provides a first battery with a fast charge / discharge rate, a second battery with a slow charge / discharge rate, and a first battery level detection circuit for detecting the battery level of the first battery. And a second battery remaining amount detection circuit that detects the remaining amount of the second battery, and an output unit that outputs the power to the load by connecting the output unit of the first battery and the output unit of the second battery together. A conductive polymer type battery is used as the first battery, and a high capacity density type battery is used as the second battery, and charging from an external power supply has priority over the first battery. Power output to the power output unit is performed preferentially from the second battery, and the first battery remaining amount detection circuit and the second battery remaining amount detection circuit. Depending on the output of the second battery by discharging from the first battery to the second battery. There is a first aspect a power supply adapted to be charged. The second gist is a mobile device and a battery-powered electric vehicle using the power supply device.

  That is, the present inventors conducted extensive research to develop a safe and excellent power supply device. As a result, a conductive polymer type battery having a high charge / discharge rate, a high capacity density type battery having a low charge / discharge rate, and In combination, the conductive polymer type battery is preferentially used for charging from an external power source, and the high capacity density type battery is charged from the conductive polymer type battery when carrying or moving. In addition to high safety and high-speed charging, it has been found that the above-mentioned conductive polymer battery has a high capacity, high output, and high cycle characteristics, so that the life of the power supply device can be extended, and the present invention has been achieved. did.

  According to the present invention, as a high power density type battery for charging in a power supply device, a conductive polymer type battery that has not been used for such applications in the past is used. With this, a sufficient amount of charge can be obtained, and this can be removed from the charging device and used safely. Moreover, due to the high capacity, high output, and high cycle characteristics of the above conductive polymer type battery, the battery life of the conductive polymer type battery and the other high capacity density type battery combined therewith becomes longer, and the power supply device as a whole Long life and economical. Furthermore, the safety of high power density batteries is high.

  In the present invention, the distinction between “slow charge / discharge rate” and “fast charge / discharge rate” is a relative distinction when two types of different batteries are compared.

  In the present invention, in particular, when at least one electrode of the conductive polymer battery has a conductive polymer and an anionic material fixed in the electrode, the conductive polymer 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 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 charge rate characteristic of the said conductive polymer type battery. It is a graph which shows the charging / discharging cycling characteristics of the said conductive polymer type battery. It is a graph which shows the charge rate characteristic of the lithium ion secondary battery shown for a comparison. 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. It is explanatory drawing for demonstrating the convenience of the mobile device using the power supply device of this invention. It is explanatory drawing of the mobile device which used the lithium ion secondary battery independently as a power supply device shown for a comparison. It is explanatory drawing which shows the structure at the time of charging the power supply device of this invention with a non-contact charge system.

  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 of the present invention is an apparatus used as a power supply for driving various mobile devices, battery-powered electric vehicles, and the like. Examples of the mobile device include a notebook computer, a mobile phone such as a smartphone, a personal digital assistant (PDA), a digital camera, a digital video camera, and a portable audio device. In addition, the battery-powered electric vehicle (hereinafter sometimes referred to as “electric vehicle”) means a vehicle that includes electric power obtained from one or more rechargeable batteries as part of mobility. used. 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. . In these mobile devices and electric vehicles, it is desirable to charge a sufficient amount for carrying or moving in as short a time as possible, and it is optimal to use the power supply device of the present invention.

  The power supply device of the present invention for driving such mobile devices, electric vehicles, and the like has a configuration as shown in, for example, the power supply device 9 of FIG. In the power supply device 9, the conversion unit 6 provided therein converts the power obtained from the external power supply 10 into power suitable for charging, and the converted power is charged / discharged from the second battery having a slow charge / discharge speed. It is preferentially transmitted to the first battery having a high speed and charged there. As the first battery having a high charge / discharge rate, a conductive polymer battery 1 is provided. In addition, a high capacity density type lithium ion secondary battery 2 is provided as a second battery having a slow charge / discharge rate for outputting electric power when the mobile device is carried and used by an electric vehicle. ing.

  The conductive polymer type battery 1 and the high capacity density type lithium ion secondary battery 2 are connected to the controller 5 via SOC (State Of Charge) detectors 3 and 4, respectively, and further via the converter 7. Connected in parallel. In addition, the conductive polymer type battery 1 and the high capacity density type lithium ion secondary battery 2 are connected to a load (mobile device) via a conversion unit 7 (corresponding to the “power output unit” of the present invention) connected thereto. Or an electric vehicle or the like) 8 to supply power to the load 8.

  The converter 6 converts the power obtained from the external power source 10 in various ways and outputs it to at least one of the first battery and the second battery. For example, the power is converted into a power output suitable for charging the battery, or the control is converted into a voltage suitable for power storage. Especially, it is preferable that the said conversion part 6 has a rectification function which rectifies | straightens an alternating voltage and converts it into a direct voltage, and a voltage control function which controls a voltage.

  The conversion unit 6 may include, for example, an oscillator, a power amplifier, a filter, a matching circuit, an inverter, a converter, a switching circuit, a protection 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.

  When the charge amount of the high-capacity density type lithium ion secondary battery 2 decreases and becomes lower than the charge amount preset in the controller 5, the controller 5 and the conversion unit 7 cause the conductivity to be reduced. The polymer type battery 1 is used to charge the high capacity density type lithium ion secondary battery 2. Further, when the charge amount of the conductive polymer type battery 1 is reduced by repeating the charging, the conductive polymer type battery 1 is charged using the external power source 10 each time. .

  The converter 7 has a switching circuit so that it can be controlled and converted to power / voltage suitable for the load, or the high capacity density type lithium ion secondary battery 2 can be charged from the conductive polymer type battery 1. May be. That is, the conversion unit 7 may include, for example, an oscillator, a power amplifier, a filter, a matching circuit, an inverter, a converter, a switching circuit, a protection circuit, and the like, similar to the conversion unit 6.

  In this power supply device 9, the conductive polymer type battery 1 used as a battery for charging from the external power source 10 has an extremely fast charge / discharge rate as compared with the high capacity density type lithium ion secondary battery 2, and has good cycle characteristics. The characteristic is that the decrease in SOH (State Of Health: [full charge capacity at the time of deterioration / full charge capacity at the initial stage] alone, an indicator of battery deterioration, generally 75% is regarded as a standard for disposal) is small. Therefore, the power supply device 9 can perform charging from the external power supply 10 at a stretch in a very short time, and is excellent in a sense of security when being carried or moved. The high capacity density type lithium ion secondary battery 2 in which SOH is likely to be lowered when charging and discharging are repeated is mainly discharged (output to the load 8), and the conductive polymer type battery 1 when the SOC is considerably lowered. Therefore, the number of times of charging is small, and the decrease in SOH as the whole power supply device 9 is suppressed. Therefore, the life of the power supply device 9 is extended, which is economical.

  In addition, the conductive polymer type battery 1 itself is stable and safe due to the property that the conductivity decreases due to heat, overcharge and overdischarge, and even if it receives heat from the surroundings other than the power supply device 9. Hard to runaway. Therefore, it becomes safe for high-speed charging, and devices equipped with this, such as mobile devices and electric vehicles, can be used more safely.

  In the above power supply device, the conductive polymer type battery 1 does not necessarily need to charge only the high capacity density type lithium ion secondary battery 2, and in some cases, the discharge causes the load to the load 8. It can also be set to fulfill the function of supplementing the output.

  Further, in the power supply device 9, the conductive polymer type battery 1 and the high capacity density type lithium ion secondary battery 2 are combined, and the conductive polymer type battery 1 is mainly charged from the external power source 10 as described above. As long as the function of charging the high-capacity lithium ion secondary battery 2 is achieved when carrying or moving, other settings are not limited to the configuration shown in FIG. The high capacity density type battery that receives the charge from the conductive polymer type battery 1 is not limited to the lithium ion secondary battery, and different types of batteries may be used.

  Further, in the power supply device 9, a circuit or the like combining the conductive polymer type battery 1 and the high capacity density type lithium ion secondary battery 2 is assembled as one device. For example, the conductive polymer type for charging is used. The battery 1 and a circuit therefor may be assembled as a single unit, which may be removably attached to a power supply device 9 such as a mobile device or an electric vehicle. According to this configuration, when charging the conductive polymer battery 1 from the external power source 10, it is not necessary to connect the entire device such as a mobile device or an electric vehicle to the external power source 10, and the unit of the conductive polymer battery 1 Only the external power source 10 can be connected, and the charging operation can be performed more easily.

  The conductive polymer type battery 1 used for the power supply device 9 refers to a secondary battery having an electrode containing a conductive polymer, and the main component of the active material of the electrode is made of a conductive polymer. Here, the main component means a component that occupies the majority of the whole, and includes the case where the whole consists of only the main component. The conductive polymer battery 1 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, in particular, 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.

  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 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, based on 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. 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 above-described positive electrode, electrolyte layer, negative electrode, and the like, the conductive polymer battery 1 can use a current collector. The current collector is not particularly limited as long as it has good conductivity and stability, but a metal foil or mesh such as nickel, aluminum, stainless steel or copper is preferably used, and a stainless steel material is preferably used. Furthermore, when the negative electrode is a metal, the negative electrode itself may also serve as a current collector.

  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. Therefore, when the conductive polymer battery 1 is used as a battery for fast charging from the external power supply 10 in a power supply device such as a mobile device or an electric vehicle, 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 and high output and can be charged at high speed is that a rocking chair type battery that is a cation transfer type battery that requires a small amount of electrolyte and an output. This is considered to be due to the fact that the anion migration type reserve battery having excellent characteristics has both excellent characteristics.

<Non-contact charging system>
Next, in order to enable non-contact charging, the power supply device of the present invention may further include a receiving antenna that receives power supplied from an external power supply. In other words, as described above, the power supply device of the present invention includes the first battery having a high charge / discharge rate, the second battery having a low charge / discharge rate, and the first battery for detecting the remaining battery level of the first battery. The remaining amount detection circuit, the second remaining battery level detection circuit for detecting the remaining amount of the second battery, and the output unit of the first battery and the output unit of the second battery are connected together to generate power to the load However, in addition to these, a power receiving unit that receives power supplied from an external power source may be provided.

  The power supply device to which the receiving antenna is added is charged by, for example, a non-contact charging system shown in FIG. At the time of charging, power supplied from the external power source 10 is transmitted from the transmitting antenna 11 in the power transmitting device 13 (charging device) to the receiving antenna 12 (for example, configured by a coil) by induction of AC power by electromagnetic coupling. Is done. Then, the converter 6 converts the power transmitted to the receiving antenna 12 into power suitable for charging, and the converted power is converted into the conductive polymer type battery 1 and the high capacity density type lithium ion secondary battery 2. Is transmitted to and stored in at least one of them.

  That is, in the non-contact charging system, by placing the power supply device 9 ′ near the power transmission device 13 having the transmission antenna 11, the reception antenna 12 in the power supply device 9 ′ and the transmission antenna 11 in the power transmission device 13 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 11 and the receiving antenna 12 within the near field.

  The transmission antenna 11 has a function of transmitting power, while the reception antenna 12 has a function of transmitting the power transmitted from the transmission antenna 11 to the power storage device via the converter 6 as necessary. It is what you have.

  The transmission antenna 11 and the reception antenna 12 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 6 converts the power transmitted from the receiving antenna 12 in various ways and outputs it to at least one of the conductive polymer type battery 1 and the high capacity density type lithium ion secondary battery 2. For example, the electric power output suitable for charging the conductive polymer type battery 1 or the high capacity density type lithium ion secondary battery 2 is converted, or the control output is converted to a voltage suitable for power storage. Especially, it is preferable that the said conversion part 6 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.

  Further, the converter 6 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 power transmission device 13 includes a transmission antenna 11 therein and is connected to an AC or DC power source. When the transmitting antenna 11 and the receiving antenna 12 are electromagnetically coupled during charging, charging can be performed without a contact.

  Examples of the system using the power supply device 9 'as described above include a mobile device such as a mobile phone, a battery-powered electric vehicle, and the like. This will be described in order below.

<Mobile phone>
Next, a non-contact charging system for a mobile phone using the power supply device 9 ′ will be described. A mobile phone using the power supply device 9 ′ includes a receiving antenna 12 that receives power supplied from the outside, a conductive polymer type battery 1 connected to the receiving antenna 12, and a high capacity density type lithium ion secondary battery. Since it is provided with at least one of 2, simply placing it in the near field of the transmitting antenna 11, such as placing it on a power transmission device 13 (so-called charger), which will be described next, can charge a large capacity in a short time. become able to.

  Since the power supply device 9 ′ of the present invention can receive power supply using electromagnetic energy as a medium, for example, the following is assumed as a specific usage scene.

  First, even when a mobile phone equipped with the power supply device 9 ′ of the present invention is carried and the user goes out for a long time, it is not necessary to carry a charging device. In other words, a charging device that supplies the aforementioned electromagnetic energy to any place on the go (for example, a predetermined place or position that is not related to public or private, such as a coffee shop table, an office desk on the go, an airplane or a train on the move) No) is provided, so that it is possible to receive power supply without worrying about the contact terminal type.

<Electric car>
A non-contact charging system for a battery-powered electric vehicle (hereinafter sometimes abbreviated as “electric vehicle”) using the power supply device 9 ′ will be described below.

  The battery of the electric vehicle can be configured with a wireless or non-contact power supply device 9 'with respect to other parts of the vehicle, so that not only can the battery be charged in a non-contact manner, but the battery can be replaced easily and reliably. There are several advantages with regard to safety, mechanical wear, and safety.

  In a contactless charging system for an electric vehicle, the vehicle is parked on a contactless charging base (corresponding to “power transmission device 13” in FIG. 9) that includes a transmission antenna 11 and is connected to an AC or DC power source. As a result, the receiving antenna 12 in the power supply device 9 ′ of the electric vehicle and the transmitting antenna 11 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 11 and the receiving antenna 12 within the near field.

  In order to properly align the transmission antenna 11 and the reception antenna 12 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.

[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. Further, the charging efficiency (%) at the charging rate was calculated. 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.

  These results are shown in FIGS. 2 (a) and 2 (b). The obtained discharge energy density is converted into a value per battery weight, and the unit is “Wh / kg” (the same applies to the following figures).

  As can be seen from FIGS. 2 (a) and 2 (b), this conductive polymer type battery has a discharge energy density of 399 Wh / kg, although the current value was changed 500 times from 0.2 C to 100 C. To 164 Wh / kg, it is only reduced to about 41%, and since the original capacity is large, a high energy density of 150 Wh / kg or more is maintained. Therefore, it can be seen that this conductive polymer battery has very high output characteristics.

  Further, this conductive polymer type battery exhibits a very high charging efficiency (%) with respect to the rate characteristics, and also exhibits a capacity of 80% or more with respect to the 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 high-speed charging / discharging is possible. Yes.

  Furthermore, the discharge energy density when the conductive polymer type battery 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 result is shown in FIG. As can be seen from this figure, 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.

  For comparison, a lithium ion secondary battery using lithium cobaltate as a positive electrode active material was produced instead of the conductive polymer battery, and the charge efficiency was measured in the same manner as described above. The result is shown in FIG. As can be seen from this figure, the lithium ion secondary battery can be charged for a short time because its charged capacity is drastically reduced at a charge rate exceeding 2C.

  Next, the conductive polymer type battery (sheet type on the laminate: 5 layers of electrode effective area 6 cm × 6 cm, 250 mAh / 1 cell) prepared as described above is arranged and used for charging from an external power source. Made a conductive polymer battery. Then, by combining this conductive polymer type battery and a high capacity density type lithium ion secondary battery (250 mAh / 1 cell), a power device for a mobile device having a configuration as shown in FIG. 1 was produced. When this product was mounted on a mobile phone and used as a drive power source, it was possible to charge SOC 50% at high speed in 3 minutes, and it was possible to carry it with peace of mind.

  In addition, assuming the power supply device which combined the said conductive polymer type battery and the high capacity | capacitance density type lithium ion secondary battery by the volume ratio 2: 1 (capacity ratio 50:50), the said conductive polymer type battery is used. The change in SOH when power was continuously supplied to the mobile device while charging the high capacity density type lithium ion 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 Comparative Example 1, it was assumed that the power supply apparatus having the configuration shown in FIG. 1 uses an electric double layer capacitor instead of the conductive polymer type battery for charging from an external power source. 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 2: 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. On the other hand, the high capacity density type lithium ion secondary battery is mainly discharged only when it is used, and only when the SOC is considerably lowered, charging from the conductive polymer type battery is required. Therefore, the decrease in SOH of the high capacity density type lithium ion secondary battery is suppressed. As a result, a decrease in SOH of the entire combined 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, in Comparative Example 1, since the electric double layer capacitor has good cycle characteristics, the decrease in SOH alone is small. However, when this electric double layer capacitor is used for charging a high capacity density type lithium ion secondary battery, the electric capacity of the electric double layer capacitor is smaller than that of the conductive polymer type battery. The number of times the ion secondary battery is charged is more frequent than when a conductive polymer battery is used. For this reason, a decrease in SOH of the high capacity density type lithium ion secondary battery is inevitable, and as a result, a decrease in SOH of the combined battery as a whole cannot be suppressed to a great extent. 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, the power supply device combining the conductive polymer type battery and the high capacity density type lithium ion secondary battery in Example 1 described above includes the electric double layer capacitor and the high capacity density type lithium ion secondary battery. It can be seen that the battery life is long and practically superior to the power supply device of Comparative Example 1 used.

  In addition, since the mobile device equipped with the power supply device of Example 1 can be charged from an external power source at a high speed by the conductive polymer type battery (50% charge is possible in 3 minutes), for example, As shown in FIG. 7, the mobile device is first carried for 1 hour in a state where 50% of the charge is charged in a conductive polymer type battery for 3 minutes, and the charged conductive polymer type battery is charged during that time. The high-capacity density type lithium ion secondary battery for driving is charged, and power is supplied to the mobile device from the high capacity density type lithium ion secondary battery as necessary. After 1 hour, if the conductive polymer battery is charged again for 3 minutes by an external power source, the battery can be fully charged as a whole if there is no power consumption during that time. In addition, even if there is some power consumption, 50% can be charged in a very short time of 3 minutes. Can be secured. Therefore, it is possible to carry the mobile device with peace of mind without being aware of the danger of “when the battery will run out”.

  On the other hand, conventional mobile devices equipped with a power supply device using a single high-capacity lithium ion secondary battery that requires one hour to fully charge, for example, cannot be charged in a short time on the go, If it is intended to be carried after being fully charged, as shown in FIG. 8, it takes 1 hour to charge and cannot be carried during that time. Therefore, it can be seen that the time during which the mobile device can be freely carried is limited, and the convenience is significantly inferior to that using the power supply device of the first embodiment.

  Moreover, the same effect as the said Example was acquired also in the electric vehicle, and the same tendency as the said Example was seen even when the non-contact charge system was used.

  The present invention can be widely used as a power supply device capable of high-speed charging.

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 (8)

A first battery with a fast charge / discharge rate, a second battery with a slow charge / discharge rate, a first battery remaining amount detection circuit for detecting the remaining amount of the first battery, and a remaining amount of the second battery. A second battery remaining amount detection circuit, and a power output unit that is connected to the output unit of the first battery and the output unit of the second battery and outputs power to the load,
A conductive polymer type battery is used as the first battery, and a high capacity density type battery is used as the second battery.
Charging from an external power source is preferentially performed on the first battery, and power output to the power output unit is preferentially performed from the second battery. The second battery is charged by discharging from the first battery to the second battery according to the outputs of the remaining battery level detection circuit and the second battery level detection circuit. Power supply.   The power supply device according to claim 1, wherein at least one electrode of the conductive polymer type battery includes a conductive polymer and an anionic material fixed in the electrode.   The power supply device according to claim 2, wherein the anionic material is a polymer anion.   The power supply device according to claim 3, wherein the polymer anion is a polycarboxylic acid.   The power supply device according to claim 1, wherein the conductive polymer is polyaniline. Furthermore, a power supply device comprising a receiving antenna for receiving power supplied from an external power source,
The power supply device according to any one of claims 1 to 5, wherein at least one of the first battery and the second battery is connected to the reception antenna and stores power received by the reception antenna.   A mobile device comprising the power supply device according to any one of claims 1 to 6.   A battery-powered electric vehicle comprising the power supply device according to any one of claims 1 to 6.

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