JP2004221523A - Electrochemical capacitor and hybrid power source constituted of it - Google Patents

Electrochemical capacitor and hybrid power source constituted of it Download PDF

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Publication number
JP2004221523A
JP2004221523A JP2003165906A JP2003165906A JP2004221523A JP 2004221523 A JP2004221523 A JP 2004221523A JP 2003165906 A JP2003165906 A JP 2003165906A JP 2003165906 A JP2003165906 A JP 2003165906A JP 2004221523 A JP2004221523 A JP 2004221523A
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negative electrode
positive electrode
electrochemical capacitor
lithium
battery
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JP4833504B2 (en
Inventor
Hiroshi Abe
Mayumi Yamada
Naoto Yasuda
直人 安田
真由美 山田
浩史 阿部
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Hitachi Maxell Ltd
日立マクセル株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrochemical capacitor having a high capacity and excellent cycle characteristics, and provide a hybrid power source constituted of the electrochemical capacitor which is small in size, less in the occurrence of overcharge, has a high capacity, and is durable for a long-term use. <P>SOLUTION: The electrochemical capacitor is constituted of a positive electrode using a carbonaceous material capable of the absorption and desorption of an anion, a negative electrode, and an organic electrolyte solution containing lithium salt as an electrolyte. By using a lithium titanic oxide having a ramsdellite type crystal structure to a negative electrode to set a capacity ratio between the negative electrode and positive electrode at the negative electrode/the positive electrode of 1-7, the electrochemical capacitor is constructed. The hybrid power source is constituted by connecting the electrochemical capacitor and a battery in parallel. As the lithium titanic oxide having the ramsdellite type crystal structure, that expressed by a Li<SB>2</SB>Ti<SB>3</SB>O<SB>7</SB>is preferable, and as the ratio of the negative electrode/the positive electrode, that of the negative electrode/the positive electrode 1.5-5 is preferable. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrochemical capacitor and a hybrid power supply using the same as an element, and more particularly, to an organic electrolytic solution-based electrochemical having both a capacitance by an electric double layer and a redox capacity using lithium ions as an active material medium. The present invention relates to a capacitor and a hybrid power supply using the electrochemical capacitor and a battery together.
[0002]
[Prior art]
The electric double layer capacitor is obtained by increasing the capacity of a conventional capacitor using an electric double layer generated at an interface between an electrode and an electrolytic solution as an energy source. Therefore, energy can be taken in and out by rapid charge / discharge, and there is an advantage that a cycle deterioration hardly occurs because an oxidation-reduction reaction does not occur.
[0003]
However, an electric double layer capacitor cannot achieve a high energy density unlike a secondary battery because an oxidation-reduction reaction does not occur, whereas an energy density of a lithium ion battery is 100 Wh / kg or more. The current state is that the energy density of these materials is only about 1-2 Wh / kg.
[0004]
Therefore, instead of the conventional electric double layer capacitor having only the electric double layer capacitance, an electrochemical capacitor having a pseudo capacitance due to oxidation and reduction in addition to the electric double layer capacitor has been proposed. . This electrochemical capacitor utilizes an oxidation-reduction reaction in the vicinity of the electrode interface, that is, a two-dimensional oxidation-reduction reaction, and is originally distinguished from a battery utilizing a bulk-phase (three-dimensional) oxidation-reduction reaction. Things.
[0005]
As an electrode material of this electrochemical capacitor, an example using a metal oxide or a conductive polymer is famous. As the metal oxide, a noble metal such as Ru or Ir, or a transition metal has been studied. Among these metal oxides, in place of expensive noble metals, in recent years, as a transition metal electrochemical capacitor, which has been actively researched in recent years, from Telcordia, etc., activated carbon is used for the positive electrode, and the spinel type is used for the negative electrode. (See, for example, Non-Patent Document 1).
[0006]
[Non-patent document 1]
"An Asymmetric Hybrid Nonaqueous Energy Storage Cell," Glenn G. Amatucci, Journal of the Electrochemical Society, 148 (8) A930-A939 (2001)
[0007]
The electrochemical capacitor having such a configuration has an energy density of several tens of Wh / kg, which is lower than that of a lithium ion secondary battery exhibiting an energy density of 100 Wh / kg or more, but is lower than that of a capacitor (<1 Wh / kg). Has a high energy density.
[0008]
The present inventors have found that even if a spinel-type lithium titanium oxide having an average particle diameter of about 1.0 μm prepared by a relatively simple and inexpensive method is used, load characteristics similar to or higher than those of Non-Patent Document 1 are obtained. Although it was confirmed that it could be obtained, good characteristics as reported in the cycle characteristics could not be obtained.
[0009]
Therefore, the appearance of an electrochemical capacitor having a high capacity and excellent cycle characteristics has been demanded.
[0010]
In recent years, demand for mobile devices such as mobile phones, personal computers, digital cameras, and video cameras has been increasing year by year, and accordingly, at present, high performance, small size and light weight have been achieved. Since these mobile devices are portable devices, batteries are used as power supplies.
[0011]
In this mobile device, when a power is turned on or a shutter button is pressed with a camera, a large current flows instantaneously, at which time the battery voltage drops rapidly. Then, when the voltage drops to a certain specific battery voltage, the primary battery is replaced and the secondary battery is recharged.
[0012]
However, in many cases, about 50% of the capacity of the battery to be replaced or charged remains. This is because the voltage drop under a high load is large, and the battery must be replaced or recharged while having a remaining capacity at a low current.
[0013]
Therefore, in order to cope with an instantaneous high load fluctuation, a system using an electric double layer capacitor having good load characteristics together with a battery has been proposed. This electric double layer capacitor absorbs and desorbs cations and anions in an electrolytic solution onto the surface of a polarizable electrode such as activated carbon, and uses the resulting capacitance of the electric double layer as an energy source. Since no electrochemical redox reaction occurs, a large current can flow instantaneously. Therefore, if this electric double layer capacitor is connected in parallel to the battery, polarization due to load fluctuation can be suppressed.
[0014]
For example, J. Miller et al. Can adopt a system in which a battery and an electric double-layer capacitor are connected in parallel as a power source for the mobile device, thereby suppressing a voltage drop under a high load and extending the use time of the battery by five times. (For example, see Non-Patent Document 2).
[0015]
[Non-patent document 2]
5th Intl. Seminar on Double-Layer Capacitors and Similar Energy Storage Devices, S.M. P. Wolsky and N.W. See Marinec, eds. Florida Educational Seminars, BocaRation, Fla. (1995), p. 3 and 7
[0016]
However, an electric double layer capacitor cannot achieve a high energy density unlike a secondary battery because an oxidation-reduction reaction does not occur, and an energy density of a lithium ion battery is 100 Wh / kg or more, whereas an electric At present, the energy density of the multilayer capacitor is limited to about 1 to 2 Wh / kg.
[0017]
Therefore, instead of the conventional electric double layer capacitor having only the electric double layer capacitance, in addition to the electric double layer capacitor as described in Non-Patent Document 1, a pseudo capacitance due to oxidation-reduction It is conceivable to use an electrochemical capacitor having both of the above and a battery together.
[0018]
An electrochemical capacitor having such a configuration has an energy density of several tens of Wh / kg, which is lower than that of a lithium ion secondary battery exhibiting an energy density of 100 Wh / kg or more, but has a capacitor (<1 Wh / kg). However, as described above, good cycle characteristics are not always obtained, although the energy density is higher than that of an electric double layer capacitor (<2 Wh / kg).
[0019]
As a system using both a battery and a capacitor, for example, a system in which three electric double layer capacitors are connected to a two-series lithium ion battery has been proposed (see Patent Document 1).
[0020]
[Patent Document 1]
JP 2001-218381 A (page 1)
[0021]
In the combined use system of a battery and a capacitor described in Patent Document 1, the voltage of a fully charged lithium-ion battery is usually about 4.2 V in a single cell, so that the voltage is 8.4 V in two series, and an organic electrolyte is used. Since the maximum voltage of the electric double layer capacitor used is usually 2.5 V, it becomes 7.5 V in three series. That is, since the total maximum voltage of the battery is higher than that of the electric double layer capacitor, if the battery and the electric double layer capacitor are directly connected in parallel, the electric double layer capacitor becomes overcharged and the internal pressure due to decomposition of the electrolyte solution is increased. Rise and fever occur. Accordingly, in the combined system described in Patent Document 1, a protection circuit is incorporated to prevent overcharging of the electric double layer capacitor, and there is a problem that the cost is increased accordingly.
[0022]
Also, a system in which an electric double layer capacitor is connected to a lithium ion polymer battery to simplify a protection circuit has been proposed (for example, see Patent Document 2).
[0023]
[Patent Document 2]
JP-A-2000-013915 (page 1)
[0024]
However, in the combined system described in Patent Document 2, since a plurality of electric double layer capacitors are connected for the purpose of adjusting the voltage so that the electric double layer capacitor is not overcharged, there is a space problem. , Which hinders miniaturization.
[0025]
In addition, utilization of natural energy is strongly demanded from the viewpoint of environmental problems, and in particular, utilization of solar cells using solar energy is being actively promoted. For example, a system that stores energy generated by a solar cell in a battery has been proposed (for example, see Patent Document 3).
[0026]
[Patent Document 3]
JP-A-6-351174 (page 1)
[0027]
However, storage batteries have problems such as being unsuitable for rapid charging and being unable to withstand long-term use.Therefore, instead of a storage battery, an element that stores electric power generated by a solar cell in an electric double-layer capacitor is used. It has been proposed (for example, see Patent Document 4).
[0028]
[Patent Document 4]
JP-A-7-177683 (page 1)
[0029]
However, although the electric double layer capacitor has advantages such as a long service life and high-speed charging, it has a problem that the usage time is shortened and the application is restricted because the amount of stored power is significantly lower than that of the battery. there were.
[0030]
A road stud power supply has been proposed as an example of the use of a system using both a solar cell and an electric double layer capacitor as described above (see Patent Document 5).
[0031]
[Patent Document 5]
JP-A-8-232216 (page 1)
[0032]
In the combined system described in Patent Document 5, electric power generated by a solar cell is stored in an electric double layer capacitor in the daytime, and at night, power is supplied from the electric double layer capacitor to blink a light emitting diode. Road studs are generally required to have a durability of 5 to 7 years or more, and therefore, those having high durability, such as an electric double layer capacitor, are suitable as a storage power source.
[0033]
However, the operating voltage of the electric double layer capacitor is usually in the range of 0 to 2.5 V, but the output voltage of the solar cell and the working voltage of the light emitting diode in the road tacking application are often 2.8 to 3.3 V. Since the operating voltage of the electric double layer capacitor is higher than that of the electric double layer capacitor, it is usually necessary to provide a circuit for preventing the electric double layer capacitor from being overcharged and a circuit for boosting the electric double layer capacitor. Since a capacitor has an extremely small storage capacity as compared with a storage battery, a plurality of electric double layer capacitors must usually be used in parallel. That is, a photovoltaic power generation system combining a solar cell and a conventional electric double-layer capacitor has to mount a complicated circuit and many electric double-layer capacitors, and thus has a difficulty in reducing the size and weight.
[0034]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION It is a first object of the present invention to solve the above-described problems of the electrochemical capacitor, and to provide a high-capacity electrochemical capacitor having excellent cycle characteristics. A second object of the present invention is to provide a hybrid power supply that solves the problem of the power supply, is small in size, has a low risk of being overcharged, has a high capacity, has excellent cycle characteristics, and can withstand long-term use. And
[0035]
[Means for Solving the Problems]
The present inventors have conducted various studies to solve the above problems, and as a result, first, a positive electrode using a carbonaceous material capable of adsorbing and desorbing anions, a negative electrode, and an organic electrolytic solution containing a lithium salt as an electrolyte A lithium-titanium oxide having a ramsdellite-type crystal structure for the negative electrode, and the capacity ratio of the negative electrode to the positive electrode is set to negative electrode / positive electrode = 1 to 7, thereby achieving high capacity. And an electrochemical capacitor having excellent cycle characteristics was obtained, and the above first object was achieved.
[0036]
Further, the present inventors, the above-mentioned electrochemical capacitor, that is, a positive electrode using a carbonaceous material capable of absorbing and desorbing anions, and a negative electrode using a lithium-containing titanium oxide having a ramsdellite-type crystal structure, A battery is connected in parallel with an electrochemical capacitor in which an organic electrolytic solution containing a lithium salt is contained as an electrolyte and the capacity ratio of the negative electrode and the positive electrode is set to negative electrode / positive electrode = 1 to 7, and a battery is connected in parallel. Further, the present inventors have found that a hybrid power source which has a low risk of being overcharged, has a high capacity, has excellent cycle characteristics, and can be used for a long time can be obtained, and can achieve the second object.
[0037]
BEST MODE FOR CARRYING OUT THE INVENTION
First, in the present invention, an electrochemical capacitor that can achieve the first object will be described in detail. The electrochemical capacitor of the present invention is a capacitor having an electric double layer at an interface between an electrode and an organic electrolyte. And a redox capacity by an electrochemical oxidation-reduction reaction in one element, a hybrid electrochemical capacitor comprising a positive electrode using a carbonaceous material capable of adsorbing and desorbing anions. A negative electrode using a lithium titanium oxide having a ramsdellite type crystal structure capable of electrochemical insertion and desorption of lithium ions, and an organic electrolytic solution containing a lithium salt as an electrolyte; And the capacity ratio of the positive electrode to the negative electrode / positive electrode = 1 to 7.
[0038]
In the electrochemical capacitor of the present invention, the lithium titanium oxide used for the negative electrode has a ramsdellite-type crystal structure.2Ti3O7, Li4Ti5O12And the like, and in particular, the chemical formula Li2Ti3O7Is preferably represented by And this Li2Ti3O7In the case of the above, it is preferable that the d value of the main peak by the X-ray diffraction method using Cu as a target is 0.445 nm, 0.269 nm, 0.224 nm, and 0.177 nm (each ± 0.0002 nm).
[0039]
The lithium titanium oxide having a ramsdellite type crystal structure has a reduction potential of Li / Li+Starts at around 2.0 V and progresses with a gentle potential gradient up to around 0.5 V. In the oxidation reaction, the potential slightly rises and proceeds in the opposite direction. In contrast, even for the same lithium titanium oxide, the chemical formula Li4Ti5O12Lithium titanium oxide having a spinel-type crystal structure represented by the formula: Li / Li+Has a very flat charge / discharge curve at around 1.5V.
[0040]
When charging and discharging are performed using lithium titanium oxide for the negative electrode and activated carbon as the carbonaceous material for the positive electrode, the positive electrode undergoes adsorption and desorption of the anion of the lithium salt used as the electrolyte, and the negative electrode generates lithium ion. Intercalation occurs. At this time, when a lithium titanium oxide having a ramsdellite-type crystal structure is used for the negative electrode, the Li (lithium) potential at the time of charging is higher than when a lithium titanium oxide having a spinel-type crystal structure is used. On the other hand, since the potential difference between the positive electrode and the negative electrode is small, it is considered that the adsorption of anions proceeds more easily, and an electrochemical capacitor having characteristics suitable for a long cycle life can be obtained.
[0041]
The lithium titanium oxide having the ramsdellite-type crystal structure can be used regardless of the production method, for example, lithium hydroxide, lithium oxide, lithium nitrate, one selected from lithium carbonate, or After mixing a plurality of lithium compounds and titanium oxide, performing a heat treatment at a temperature from 1000 ° C. to about 1400 ° C., which is close to a temperature at which the lithium titanium oxide melts, and then pulverizing with an alumina ball mill or the like. Can be produced by a solid-phase method via At this time, the lithium titanium oxide preferably has an average particle diameter of 10 μm or less, particularly preferably has an average particle diameter of 0.01 μm or more, and particularly preferably has an average particle diameter of 0.01 to 1 μm. That is, when the average particle diameter of the lithium titanium oxide is 10 μm or less, it is possible to suppress a decrease in output characteristics due to a delay in diffusion of lithium ions into the particles due to the particles being too large. When the average particle diameter is 0.01 μm or more, it is possible to suppress a decrease in dispersibility due to agglomeration of particles at the time of electrode preparation and a decrease in workability due to the aggregation.
[0042]
In addition, the lithium titanium oxide having the ramsdellite-type crystal structure is obtained by synthesizing a lithium titanium oxide by a hydrolysis reaction, a dehydration condensation reaction, and a heat treatment using an organometallic compound as a starting material, in addition to the case using the solid phase method. Alternatively, it may be manufactured by a sol-gel method via a step of carrying out. According to the sol-gel method, the heat treatment temperature can be lower than in the case of the solid-phase method, which is advantageous in cost.
[0043]
In order to produce a negative electrode using the lithium titanium oxide having a ramsdellite-type crystal structure obtained as described above, for example, a conductive auxiliary to the lithium titanium oxide having the ramsdellite-type crystal structure and A binder such as polytetrafluoroethylene or polyvinylidene fluoride may be added and mixed, and the resulting negative electrode mixture may be formed by an appropriate means. For example, the negative electrode mixture is molded under pressure, or the negative electrode mixture is dispersed in a solvent to prepare a paste containing the negative electrode mixture (in this case, the binder is previously dissolved or dispersed in the solvent, The paste containing the negative electrode mixture may be applied to a current collector made of a metal foil or a metal net and dried to form a film-like negative electrode mixture layer. Then, the negative electrode can be manufactured by passing through a step of compressing as necessary. However, the method for manufacturing the negative electrode is not limited to the above-described method, but may be another method.
[0044]
The conductive agent is not particularly limited with respect to the material and shape, but is preferably a carbonaceous material. Specific examples thereof include, for example, carbon black, acetylene black, and Examples include shaped carbon, carbon fiber, natural graphite, and artificial graphite.
[0045]
In mixing and dispersing the lithium titanium oxide having the ramsdellite-type crystal structure with a conductive additive and a binder, any mixing means such as a stirrer, a ball mill, and ultrasonic dispersion can be employed. The temperature and time are not particularly limited, but, for example, it is preferable to perform mixing and dispersion at 0 to 40 ° C. for about 1 to 12 hours. The mixing ratio of the lithium titanium oxide having the ramsdellite-type crystal structure, the conductive additive, and the binder is preferably 80: 15: 5 to 50:30:20, particularly preferably 70:20:10 to 60 by mass ratio. : 25: 15 is preferred.
[0046]
In the present invention, the positive electrode is PF6 And BF4 A carbonaceous material capable of adsorbing and desorbing anions such as is used. As such a carbonaceous material, for example, activated carbon and single-walled carbon nanotube are preferable. When these carbonaceous materials are charged and discharged in an electrochemical cell, an electrochemical oxidation-reduction reaction of doping and undoping the anion species between carbon layers does not occur, but only adsorbs and desorbs anions between carbon layers. Thus, rapid anion transfer can be achieved. In addition, these carbonaceous materials have a linear change in the potential of charge and discharge as described above, and do not show a shoulder having a flat portion or a gentle slope in potential unlike materials used for active materials of batteries.
[0047]
The activated carbon has a specific surface area of 1000 m as measured by a BET specific surface area.2/ G or more is preferred. This is because the specific surface area of the carbonaceous material measured by the BET specific surface area is 1000 m.2This is because, by being / g or more, a decrease in capacitance due to the electric double layer generated at the interface between the carbonaceous material and the organic electrolyte can be suppressed.
[0048]
Further, the activated carbon has micropores having a diameter of less than 2 nm, mesopores having a diameter in the range of 2 to 50 nm, and macropores having a diameter of more than 50 nm, and the pore volume of the micropores is 0.5 cc / cm. g or more, the pore volume of the mesopores is 0.3 cc / g or more, the existence ratio of the pore volume of the micropores to the total pore volume is 50 to 75%, and the pore volume of the mesopores is Is preferably 25 to 50%. In addition, the proportion of the macropore pore volume to the total pore volume is preferably 3% or less, particularly preferably 1% or less, and particularly preferably close to 0%. The activated carbon preferably has an average particle size of 5 to 20 μm.
[0049]
Pores are defined by IUPAC as micropores with diameters smaller than 2 nm, mesopores with diameters of 2 to 50 nm, and macropores with diameters greater than 50 nm, but usually the majority of ions are in the mesopores. It is said to be adsorbed and desorbed, and it is said that those having a high mesopore pore volume are preferable as activated carbon for electrode of a capacitor.
[0050]
However, PF adsorbing and desorbing on activated carbon6 And BF4 Since the size of the anion is usually 1 nm or less, the anion should be able to move sufficiently within the pores of the micropores and be capable of being adsorbed. Therefore, the present inventors have developed micropores sufficiently, specifically, the pore volume of the micropores measured by a method using a mercury porosimeter is 0.5 cc / g or more, and the mesopores also developed. Specifically, the pore volume of the mesopores is 0.3 cc / g or more, and the ratio of the pore volume of the micropores to the total pore volume is 50 to 75%. It has been found that when activated carbon having an abundance ratio of 25% to 50% is used, a high capacitance can be obtained by adsorption and desorption of anions. This is presumably because the development of mesopores having a larger diameter than the micropores promoted the movement of anions and increased the amount of adsorption and desorption to the micropores.
[0051]
The particle diameter of the activated carbon is preferably 5 to 20 μm in average particle diameter for reasons such as shortening the ion movement distance and securing a large specific surface area. If the average particle size of the activated carbon is larger than 20 μm, the particle size may be too large and the ions may not be able to move to the inside of the particles rapidly. There is a possibility that the pores cannot be sufficiently developed.
[0052]
The activated carbon is not particularly limited with respect to the raw material, the production method, and the like. Usually, a coconut shell, petroleum coke, a phenol resin, or the like is used as a starting material, preferably a phenol resin is used as a starting material, and carbonized at about 600 to 800 ° C. Alternatively, it can be obtained by activation treatment with an aqueous alkali solution, preferably an aqueous alkali solution.
[0053]
In order to produce a positive electrode using the carbonaceous material, for example, the same conductive aid and binder as in the case of the negative electrode are added to the carbonaceous material and mixed, and the obtained positive electrode mixture is mixed with an appropriate means. What is necessary is just to shape | mold. For example, the positive electrode mixture is molded under pressure, or the positive electrode mixture is dispersed in a solvent to prepare a paste containing the positive electrode mixture (in this case, the binder is previously dissolved or dispersed in the solvent, The paste containing the positive electrode mixture may be applied to a current collector made of a metal foil, a metal net, or the like, and dried to form a positive electrode mixture layer in a film form. The positive electrode can be manufactured by passing through a step of compressing as necessary. However, the method for producing the positive electrode is not limited to the method described above, and may be another method.
[0054]
In producing an electrochemical capacitor, it is necessary that the capacity ratio between the negative electrode and the positive electrode is set to 1 to 7 for the negative electrode / positive electrode, and the negative electrode / positive electrode is preferably 1.5 to 5 for the negative electrode. That is, if the above capacity ratio is smaller than 1 or larger than 7, sufficient capacity and cycle characteristics cannot be obtained. Here, the capacity of the negative electrode and the capacity of the positive electrode are, for example, in a three-electrode or two-electrode electrochemical cell using metallic lithium as a counter electrode, the obtained capacity per each electrode mass and each electrode filled in the electrochemical capacitor. Can be known from the mass of However, the mass of the electrode means the mass of the electrode mixture, and does not include the mass of the current collector.
[0055]
In constituting the electrochemical capacitor of the present invention, an organic electrolyte prepared by dissolving an electrolyte in an organic solvent is used. The solvent of the organic electrolytic solution is not particularly limited, for example, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, cyclic esters such as ethylene glycol sulfite, and dimethyl carbonate, diethyl carbonate and the like Each of the chain esters can be used alone, or two or more kinds can be used in combination. As the electrolyte, for example, LiClO4, LiPF6, LiBF4, LiAsF6, LiSbF6, LiCF3SO3, LiCF3CO2, Li2C2F4(SO3)2, LiN (CF3SO2)2, LiC (CF3SO2)3, LiCnF2n + 1SO3Lithium salts such as (n ≧ 2) can be used alone or in combination of two or more. The concentration of the electrolyte in the electrolyte is not particularly limited, but is preferably about 0.3 to 2 mol / l, particularly preferably about 0.4 to 1.5 mol / l.
[0056]
The shape of the electrochemical capacitor of the present invention is not particularly limited, such as a cylindrical shape, a square shape, and a coin shape, and the manufacturing method thereof is not particularly limited. For example, when manufacturing a cylindrical electrochemical capacitor, the negative electrode and the positive electrode formed into a sheet shape are wound in a roll shape through a separator similar to those used for batteries and capacitors. A body may be prepared, the wound body may be filled in a cylindrical can with a bottom, the above-mentioned organic electrolyte solution may be injected, and the container may be sealed.
[0057]
The electrochemical capacitor of the present invention has a redox capacity due to the doping / dedoping function of lithium ions in the lithium titanium oxide of the negative electrode, and also has an interface between the carbonaceous material of the positive electrode and the organic electrolyte. In addition, the element has the capacitance of the electric double layer generated at the same time, that is, an element having both characteristics of a lithium ion battery and an electric double layer capacitor. Therefore, the electrochemical capacitor of the present invention is particularly suitable for a power supply of a device requiring a large instantaneous current and an energy capacity, or a power supply of an equipment requiring a long charge / discharge cycle life.
[0058]
Next, a hybrid power supply that achieves the second object in the present invention will be described. The hybrid power supply of the present invention is configured by connecting the electrochemical capacitor and a battery in parallel. At this time, the electrochemical capacitor of the present invention has an allowable charging voltage VEIs a high allowable charging voltage V of 2.5 to 3.5 VETherefore, under normal conditions, the electrochemical capacitor is less likely to be in an overcharged state, and thus is prevented from being in an overcharged state as occurs when a conventional electric double layer capacitor is used. It is not necessary to provide a protection circuit for the power supply or to connect two or more electric double layer capacitors in series, and the high capacity and excellent cycle characteristics of the electrochemical capacitor are maintained in the hybrid power supply. You can make use of it. Therefore, by using the electrochemical capacitor of the present invention, there is provided a hybrid power supply that is small in size, has a low risk of overcharging, has a high capacity, has excellent cycle characteristics, and can withstand long-term use. be able to.
[0059]
In the hybrid power supply of the present invention, the electrochemical capacitor is, as described above, a positive electrode using a carbonaceous material capable of absorbing and desorbing anions, and a negative electrode using a lithium-containing titanium oxide having a ramsdellite-type crystal structure. And an organic capacitor containing an organic electrolyte containing a lithium salt as an electrolyte, wherein the electric capacity ratio between the negative electrode and the positive electrode is negative electrode / positive electrode = 1 to 7, but in parallel with the electrochemical capacitor. A commonly used primary battery or secondary battery can be used as the battery to be connected, and a solar battery can also be used.
[0060]
Examples of the primary battery include a manganese battery, an alkaline battery, a nickel battery, and a lithium battery. Alkaline batteries, nickel batteries, and the like widely used in digital cameras and the like are usually used in two series, so that elements connected in parallel generally require a withstand voltage of 3.2 to 3.4 V. As described above, since the operating voltage range of the electric double layer capacitor is 0 to 2.5 V, in order to connect these batteries and one electric double layer capacitor in parallel, a circuit for preventing overcharging must be provided or an electric circuit must be provided. Although it is necessary to take measures such as connecting two or more double-layer capacitors in series, the electrochemical capacitor used in the hybrid power supply of the present invention exhibits an allowable charging voltage of 3.5 V at the maximum, so that only one capacitor is used. No complicated circuit for preventing charging is required.
[0061]
In addition, examples of the secondary battery connected in parallel with the electrochemical capacitor include a lead battery, a nickel cadmium battery, and a nickel metal hydride battery. These batteries may be used in more than one series, in which case the maximum voltage of the batteries may exceed 3V. In this case, if those batteries and one electric double layer capacitor having a withstand voltage of 2.5 V are connected in parallel, the electric double layer capacitor becomes overcharged. Therefore, it was necessary to provide a protection circuit or connect two or more electric double layer capacitors in series. However, the electrochemical capacitor used in the hybrid power supply of the present invention has a high withstand voltage, and only one is sufficient. No protection circuit is required.
[0062]
The configuration and output of the solar cell connected in parallel with the electrochemical capacitor are not particularly limited, and an amorphous solar cell, a crystalline silicon solar cell, and a dye-sensitized solar cell are preferably used. The number of modules is not particularly limited, and may be appropriately selected according to the use of devices to be operated.
[0063]
The hybrid power supply according to the present invention includes an allowable charging voltage V of the electrochemical capacitor.EIs 2.5 to 3.5 V, and the maximum voltage V of the battery isBIs 2.5 to 3.5 V, and VE≧ VBTo be satisfied. Where VBMeans the maximum voltage indicated by the battery during an open or closed circuit.
[0064]
Allowable charging voltage V of the electrochemical capacitorEIs adjusted by the type of the negative electrode active material, the capacity ratio between the positive electrode and the negative electrode, or the utilization rate of the capacity of the electrochemical capacitor. Allowable charging voltage V in the present inventionEThis means that when an electrochemical capacitor is loaded in a cylindrical can or the like, there is no external abnormality such as blistering or heat generation of the can, and the maximum charging voltage that does not cause extreme deterioration of electrochemical control such as capacity and cycle. means.
[0065]
The allowable charging voltage VEWhen a lithium-containing titanium oxide is used as the negative electrode active material, if the negative electrode side is set to less than 1 V with respect to the Li potential, there are problems such as structural destruction of the negative electrode active material. For example, about 4.5 V with respect to the lithium potential, the maximum value is 3.5 V.
[0066]
VE≧ VBIs not satisfied, that is, VBIs VEWhen a higher voltage is indicated, it is not preferable to directly connect the battery and the electrochemical capacitor in parallel because the electrochemical capacitor may be overcharged, possibly causing damage to the electrochemical capacitor.
[0067]
Therefore, in the present invention, when the electrochemical capacitor and the battery are connected in parallel to constitute a hybrid power supply, the allowable charging voltage VEOf the present invention having a maximum voltage V of 2.5 to 3.5 VBIs connected in parallel with one series, one parallel battery or more having a voltage of 2.5 to 3.5 V;E≧ VBIs satisfied, it is possible to provide a small and lightweight hybrid power supply that does not require a complicated protection circuit.
[0068]
Here, a structural example of the hybrid power supply of the present invention will be described with reference to FIGS. FIG. 1 shows an external appearance of a hybrid power supply in which an electrochemical capacitor and a battery are loaded in a pack 1 made of a plastic exterior material. The pack 1 has a capacitor storage section 2 for loading an electrochemical capacitor, a battery storage section 3 for loading a battery, and a battery storage lid 4 for inserting and removing a battery. FIG. 2 shows the contents of the hybrid power supply shown in FIG. 1, in which a laminated electrochemical capacitor 5 is built in the back of the pack, and two cylindrical batteries 6 are connected via a battery connector 7. They are connected in series or two in parallel. An external terminal 8 for electrically connecting to an external load is provided at the bottom of the pack. FIG. 3 shows a connection state between the electrochemical capacitor 5 and the battery 6 in two series. The electrochemical capacitor 5 and the battery 6 are connected in parallel via a positive terminal 9 and a negative terminal 10 in the pack. . Since the battery 6 can be put in and taken out of the pack 1, when the capacity of the battery is exhausted, it may be replaced with a new battery if it is a primary battery, or a dedicated charger if it is a secondary battery. The battery may be recharged and then loaded into the pack again for use. In the case of a secondary battery, the battery pack can be recharged with a charger and used.
[0069]
FIGS. 1 to 3 show an example using a laminated electrochemical capacitor and a cylindrical battery, but these may be rectangular or gum-shaped, and the shape is not limited. The number of batteries may be, for example, four in two series and two in parallel.
[0070]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples. In the following examples,% indicating the concentration of a solution or a dispersion is mass% unless otherwise specified, and Examples 1 to 3 and Comparative Examples 1 to 3 relate to electrochemical capacitors. Examples 4 to 6 and Comparative Examples 4 to 7 relate to a hybrid power supply.
[0071]
Example 1
Chemical formula Li2Ti3O7The average particle diameter by particle size distribution measurement using a laser diffraction / scattering method is 0.47 μm, and the specific surface area by nitrogen adsorption determined by a BET five-point method is 7.5 m.2/ G of lithium titanium oxide having a ramsdellite-type crystal structure, a negative electrode was prepared in the following procedure.
[0072]
First, a binder solution was prepared by dissolving 10 parts by mass of polyvinylidene fluoride as a binder in 23 parts by mass of an N-methyl-2-pyrrolidone solvent, and acetylene black and ketjen black, which were conductive assistants, were prepared in the binder solution. Was added to the mixture, and the mixture was dispersed beforehand for 5 hours with a stirrer. The liquid containing the conductive aid and the binder was mixed with 65 parts by mass of the lithium titanium oxide, and the mixture was dispersed with an ultrasonic homogenizer having an output of 150 W to prepare a paste containing a negative electrode mixture.
[0073]
The obtained negative electrode mixture-containing paste is applied on an aluminum foil having a thickness of 40 μm with an applicator at a clearance of 60 μm, and preliminarily dried on a hot plate at 100 ° C. for 20 minutes to form a negative electrode mixture layer. Was applied with a clearance of 100 μm using an applicator, and preliminarily dried on a hot plate at 100 ° C. for 20 minutes to form a negative electrode mixture layer. Further, after vacuum drying at 80 ° C. for 12 hours, the obtained electrode body was 1 ton / cm 22After pressing for 10 seconds, 3ton / cm2For 10 seconds to obtain a negative electrode.
[0074]
The thickness of the obtained negative electrode was 70 μm, and the formation amount of the negative electrode mixture layer (however, this refers to the formation amount of the negative electrode mixture layer per unit square centimeter; the same applies hereinafter) was 2.5 mg / cm on both sides.2Met. The area of one side is 2cm2The working electrode is a working electrode, metallic lithium is used as a counter electrode and a reference electrode, and 1.5 M LiPF is used as an electrolyte.6/ EC + DEC [LiPF in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC)6Of an electrolyte prepared by dissolving 1.5 mol / l in a three-electrode electrochemical cell at a charge / discharge voltage of 1 to 2.5 V and a current density of 0.5 mA / cm.2The capacity per unit mass of the negative electrode when the capacity was measured at 90 mAh / g. However, the mass of the negative electrode in the above description means the mass of the negative electrode mixture, and does not include the mass of the aluminum foil as the current collector.
[0075]
The pressed negative electrode was cut into a width of 24 mm and a length of 186 mm, and used as a negative electrode for forming an electrochemical capacitor. As a material of a positive electrode to be combined with the negative electrode, the specific surface area by a five-point method of BET specific surface area measurement was 1200 m.2/ G of activated carbon was prepared as shown below. First, polyvinylidene fluoride was dissolved in 23 parts by mass of N-methyl-2-pyrrolidone so as to have a concentration of 25%, and 15 parts by mass of acetylene black as a conductive aid was added to the solution and dispersed with a stirrer for 5 hours. The solution containing the conductive additive and the binder was mixed with 60 parts by mass of the activated carbon, and the mixture was dispersed with an ultrasonic homogenizer having an output of 150 W to prepare a paste containing a positive electrode mixture. The obtained positive electrode mixture-containing paste was applied on an aluminum foil having a thickness of 40 μm with a clearance of 140 μm using an applicator, and preliminarily dried on a hot plate at 100 ° C. for 20 minutes to form a positive electrode mixture layer. The mixture was applied to the back surface with a clearance of 220 μm using an applicator, and preliminarily dried on a hot plate at 100 ° C. for 20 minutes to form a positive electrode mixture layer. The obtained electrode body is 1 ton / cm2After pressing for 10 seconds, 3ton / cm2After pressing for 10 seconds to reduce the thickness to 0.13 mm, it was cut into a width of 24 mm and a length of 171 mm to obtain a positive electrode. The thickness of the positive electrode is 0.13 mm as described above, and the formation amount of the positive electrode mixture layer (however, the formation amount of the positive electrode mixture layer per unit square centimeter is also Means 2.5 mg / cm on both sides2Met.
[0076]
The positive electrode and the negative electrode prepared as described above are vacuum-dried at 120 ° C. for 3 days, and then wound in a dry atmosphere through two separators made of a microporous polyethylene film having a thickness of 25 μm and a width of 27 mm, and have a diameter of A roll of less than 10 mm was produced.
[0077]
After a rubber cap was attached to the above-mentioned wound body and dried at 80 ° C. for 12 hours, the composition was 1.5 M LiPF in an inert atmosphere.6/ EC + DEC [Literally mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC)6Was dissolved in 1.5 mol / l of an organic electrolyte solution], and the vacuum-opening was repeated three times to impregnate the wound body with the organic electrolyte solution. The amount of the organic electrolyte impregnated in the wound body in this way was 1.2 g.
[0078]
The wound body impregnated with the organic electrolyte was placed in a bottomed cylindrical can having an outer diameter of 10 mm and a height of 40 mm, and was sealed according to a conventional method to obtain an electrochemical capacitor. The capacity ratio of the negative electrode to the positive electrode of the cylindrical electrochemical capacitor thus produced was negative electrode / positive electrode = 3.0. Then, after the electrochemical capacitor was charged to 3.1 V at a constant current of 14.4 mA, a charge / discharge cycle of discharging to 1.0 V was repeated three times to perform a chemical conversion treatment.
[0079]
Example 2
The amount of the negative electrode mixture layer formed on the negative electrode was 1.3 mg / cm.2An electrochemical capacitor was produced and subjected to a chemical conversion treatment in the same manner as in Example 1, except that the capacity ratio between the negative electrode and the positive electrode was set to 1.5 for the negative electrode / positive electrode.
[0080]
Example 3
The amount of the negative electrode mixture layer formed on the negative electrode was 4.5 mg / cm2An electrochemical capacitor was prepared and subjected to a chemical conversion treatment in the same manner as in Example 1, except that the capacity ratio of the negative electrode to the positive electrode was set to 5.0 for the negative electrode / positive electrode.
[0081]
Comparative Example 1
0.4 mg / cm of the amount of the negative electrode mixture layer formed on the negative electrode2An electrochemical capacitor was produced and subjected to a chemical conversion treatment in the same manner as in Example 1 except that the capacity ratio between the negative electrode and the positive electrode was set to negative electrode / positive electrode = 0.5.
[0082]
Comparative Example 2
The amount of the negative electrode mixture layer formed on the negative electrode was 6.8 mg / cm.2An electrochemical capacitor was produced and subjected to a chemical conversion treatment in the same manner as in Example 1, except that the capacity ratio of the negative electrode to the positive electrode was set to 7.5 for the negative electrode / positive electrode.
[0083]
Comparative Example 3
Instead of the ramsdellite type lithium titanium oxide used in Example 1, the diffraction pattern by the X-ray diffraction method is represented by the chemical formula Li.4Ti5O12An electrochemical capacitor was produced and subjected to a chemical conversion treatment in the same manner as in Example 1, except that a lithium titanium oxide having a spinel type crystal structure belonging to.
[0084]
The cycle characteristics of the electrochemical capacitors of Examples 1 to 3 and Comparative Examples 1 to 3 after the chemical conversion treatment were evaluated. That is, for the electrochemical capacitors of Examples 1 to 3 and Comparative Examples 1 to 3 after the chemical conversion treatment, charge and discharge were repeated at a constant current of 72 mA under conditions of a charge cut voltage of 3.1 V and a discharge cut voltage of 1.0 V. Then, the cycle characteristics were evaluated. The cycle test was performed at 25 ° C., and the discharge capacity at the 1st cycle and the discharge capacity at the 10000th cycle were measured. The retention was determined.
[0085]
[0086]
Table 1 shows the capacity retention rates determined as described above, together with the capacity ratio between the negative electrode and the positive electrode, the crystal structure of the lithium titanium oxide of the negative electrode, and the discharge capacity at the first cycle.
[0087]
[Table 1]
[0088]
As shown in Table 1, the electrochemical capacitors of Examples 1 to 3 have a larger discharge capacity in the first cycle and a larger capacity retention rate in the 10,000 cycles than the electrochemical capacitors in Comparative Examples 1 to 3. , High capacity, and excellent cycle characteristics. That is, the electrochemical capacitors of Examples 1 to 3 in which a lithium titanium oxide having a ramsdellite type crystal structure was used for the negative electrode and the capacity ratio between the negative electrode and the positive electrode was in the range of negative electrode / positive electrode = 1 to 7 were high. Although the capacity and the cycle characteristics were excellent, even when lithium titanium oxide having the same crystal structure was used, the capacity ratio of the negative electrode to the positive electrode was less than the range of negative electrode / positive electrode = 1 to 7 in Comparative Examples 1 to 2. The electrochemical capacitors had smaller capacities and inferior cycle characteristics than the electrochemical capacitors of Examples 1 to 3.
[0089]
The electrochemical capacitor of Comparative Example 3 using lithium titanium oxide having a spinel-type crystal structure for the negative electrode even with the same lithium titanium oxide has a capacity close to that of the electrochemical capacitors of Examples 1 to 3. However, the cycle characteristics were significantly inferior to those of the electrochemical capacitors of Examples 1 to 3. In other words, even when the same lithium titanium oxide is used, when a lithium titanium oxide having a ramsdellite type crystal structure is used for the negative electrode, a lithium titanium oxide having a spinel type crystal structure is used for the negative electrode. In comparison, it was clear that an electrochemical capacitor having significantly improved cycle characteristics was obtained.
[0090]
As described above, according to the present invention, an electrochemical capacitor having high capacity and excellent cycle characteristics can be provided.
[0091]
Next, Examples 4 to 6 and Comparative Examples 4 to 7 relating to the hybrid power supply will be described.
[0092]
Example 4
Chemical formula Li2Ti3O7Is represented by, the average particle diameter by particle size distribution measurement using laser diffraction / scattering method is 0.6 μm, the main peak d value by X-ray diffraction method using Cu as a target is 0.445 nm, 0.269 nm, A dispersion aqueous solution containing 3 parts by mass of acetylene black and 70% of polytetrafluoroethylene was added to 60 parts by mass of lithium titanium oxide having 0.224 nm and 0.177 nm so that the polytetrafluoroethylene became 10 parts by mass. The resulting negative electrode mixture-containing paste was applied to both sides of an aluminum foil having a thickness of 15 μm and a width of 200 mm, and dried at 120 ° C. to form a negative electrode mixture layer.2To produce a negative electrode.
[0093]
The thickness of the obtained negative electrode was 70 μm, and the formation amount of the negative electrode mixture layer (however, the formation amount of the negative electrode mixture layer per unit square centimeter; the same applies hereinafter) was 7.8 mg / cm on both sides.2Met. The area of one side is 2cm2And the reference electrode is made of metallic lithium, and the organic electrolyte is 1.5 M LiPF6/ EC + DEC [LiPF in mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC)]6Of an organic electrolyte prepared by dissolving 1.5 mol / l] in a three-electrode electrochemical cell at a charge / discharge voltage of 1 to 2.5 V and a current density of 0.5 mA / cm.2The capacity per unit mass of the negative electrode when the capacity was measured was 100 mAh / g. However, the mass of the negative electrode in the above description means the mass of the negative electrode mixture, and does not include the mass of the aluminum foil as the current collector.
[0094]
Activated carbon having an average particle size of 15 μm obtained by carbonizing a phenol resin and activating in a potassium hydroxide aqueous solution was used for the positive electrode. The activated carbon has a BET specific surface area of 3200 m by nitrogen adsorption.2/ G, the pore volume of the micropore is 1.0 cc / g, the pore volume of the mesopore is 0.7 cc / g, and the existence ratio of the pore volume of the micropore to the total pore volume is 60 cc / g. %, The content ratio of the mesopore pore volume to the total pore volume was 39%.
[0095]
To 90 parts by mass of this activated carbon, 5 parts by mass of acetylene black was added, and a dispersion aqueous solution containing 70% of polytetrafluoroethylene was further added and kneaded so as to have 5 parts by mass of polytetrafluoroethylene, and the obtained positive electrode was kneaded. The mixture-containing paste was applied to both sides of a 15 μm-thick aluminum foil, dried at 120 ° C. to form a positive electrode mixture layer, and then 3 ton / cm2To produce a positive electrode.
[0096]
The thickness of the obtained positive electrode was 90 μm, and the formation amount of the positive electrode mixture layer was 2.0 mg / cm on both sides.2Met. The area of one side is 2cm2The working electrode was cut out so as to obtain a capacity, and the capacity was measured with a three-electrode electrochemical cell as in the case of the negative electrode. Charge cut voltage: 4.5 V, discharge cut voltage: 3 V, current density: 0.5 mA / cm2And the capacity per unit mass of the positive electrode was 80 mAh / g. However, the mass of the positive electrode in the above description means the mass of the positive electrode mixture, and does not include the mass of the aluminum foil as the current collector.
[0097]
The negative electrode was cut out to a width of 40 mm and a length of 320 mm, the positive electrode was cut out to a width of 40 mm and a length of 310 mm, and an aluminum tab was welded to the center of each to make them a negative electrode and a positive electrode for forming an electrochemical capacitor.
[0098]
The negative electrode and the positive electrode were wound via a separator made of a microporous polyethylene film having a thickness of 25 μm to obtain a wound body having a diameter of 9.5 mm and a length of 40 mm. The wound body was loaded in a cylindrical can having a diameter of 10 mm and a height of 45 mm. In a dry box in an argon gas atmosphere, LiPF was added to a mixed solvent obtained by mixing propylene carbonate and diethyl carbonate at a ratio of 1: 2 (volume ratio).6Was dissolved into the cylindrical can at a concentration of 1.5 mol / liter, and the open portion of the cylindrical can was closed with a sealing member made of butyl rubber having a thickness of 5 mm. The shape of the electrochemical capacitor was fabricated. The capacity ratio between the negative electrode and the positive electrode in this cylindrical electrochemical capacitor was negative electrode / positive electrode = 5.
[0099]
The electrochemical capacitor produced as described above was charged and discharged at a constant current of 30 mA under the conditions of a charge cut voltage of 3.5 V and a discharge cut voltage of 1.0 V, and the initial discharge capacity was measured. Obtained. The charge and discharge were repeated up to 10,000 cycles under the same charge and discharge conditions as above, and the discharge capacity at the 10,000th cycle was measured. The results are shown in Table 2 below.
[0100]
Next, the cylindrical electrochemical capacitor produced as described above was connected to a crystalline silicon solar cell module (output: 0.22 W, voltage: 3.3 V, size: 50 × 55 mm) formed by connecting six cells in series. A hybrid power supply was manufactured by connecting the power supply in parallel via electric wires.
[0101]
The solar cell of the hybrid power supply manufactured as described above was irradiated at a temperature of 80 ° C. for 1 hour under an illumination of 50,000 lux. Thereafter, the solar cell was covered with a black cloth so as not to generate more power, an external power supply was connected, a constant current discharge of 10 mA was performed, and the discharge cut voltage was 1 V, and the discharge capacity was measured. The obtained discharge capacity is shown in Table 3 below.
[0102]
The above operation was repeated until the capacity reached 60% of the initial discharge capacity, and the number of cycles that could be repeated was examined. The results are shown in Table 3 below.
[0103]
Example 5
A positive electrode was prepared in the same manner as in Example 4 except that a single-walled carbon nanotube having a diameter of 4 nm obtained by an arc discharge method was used in place of the activated carbon, and a cylinder was formed in the same manner as in Example 4 except that the positive electrode was used. The shape of the electrochemical capacitor was fabricated. The electric capacity of the positive electrode in this electrochemical capacitor was 80 mAh / g, and the formation amount of the positive electrode mixture layer was 5 mg / cm.2Where the capacity ratio between the negative electrode and the positive electrode was negative electrode / positive electrode = 2.
[0104]
The electrochemical capacitor produced as described above was charged and discharged at a constant current of 30 mA with a charge cut voltage of 3.5 V and a discharge cut voltage of 1.0 V. As a result, a discharge capacity of 40 mAh was obtained. The charge and discharge were repeated up to 10,000 cycles under the same charge and discharge conditions as above, and the discharge capacity at the 10,000th cycle was measured. The results are shown in Table 2 below.
[0105]
A hybrid power supply was prepared in the same manner as in Example 4 except that the above-mentioned electrochemical capacitor was used, and the discharge capacity of the hybrid power supply was measured in the same manner as in Example 4. % Was examined in the same manner as in Example 4. The results are shown in Table 3 below.
[0106]
Comparative Example 4
0.4 mg / cm of the amount of the negative electrode mixture layer formed on the negative electrode2An electrochemical capacitor was produced in the same manner as in Example 4, except that the capacity ratio of the negative electrode to the positive electrode was set to 0.5 for the negative electrode / positive electrode, and the electrochemical capacitor was charged and discharged in the same manner as in Example 4 to discharge. The capacity was measured, and the discharge capacity at the 10000th cycle was measured in the same manner as in Example 4. The results are shown in Table 2 below.
[0107]
A hybrid power supply was prepared in the same manner as in Example 4 except that the above-mentioned electrochemical capacitor was used, and the discharge capacity of the hybrid power supply was measured in the same manner as in Example 4. % Was examined in the same manner as in Example 4. The results are shown in Table 3 below.
[0108]
Comparative Example 5
The amount of the negative electrode mixture layer formed on the negative electrode was 6.8 mg / cm.2An electrochemical capacitor was manufactured in the same manner as in Example 4, except that the capacity ratio between the negative electrode and the positive electrode was set to 7.5 for the negative electrode / positive electrode, and the electrochemical capacitor was charged and discharged in the same manner as in Example 4 to discharge. The capacity was measured, and the discharge capacity at the 10000th cycle was measured in the same manner as in Example 4. Table 2 shows the results.
[0109]
A hybrid power supply was prepared in the same manner as in Example 4 except that the above-mentioned electrochemical capacitor was used, and the discharge capacity of the hybrid power supply was measured in the same manner as in Example 4. % Was examined in the same manner as in Example 4. Table 3 shows the results.
[0110]
[Table 2]
[0111]
[Table 3]
[0112]
As shown in Table 3, the hybrid power supplies of Examples 4 and 5 have a larger discharge capacity, a higher capacity, a larger number of cycles, and better cycle characteristics than the hybrid power supplies of Comparative Examples 4 and 5. , It can be used for a long time. This is because, as shown in Table 2, the electrochemical capacitors used for the hybrid power supplies of Examples 4 to 5 have higher capacity and cycle characteristics than the electrochemical capacitors used for the hybrid power supplies of Comparative Examples 4 to 5. It is based on excellence.
[0113]
Example 6
A negative electrode was prepared in the same manner as in Example 4, except that the negative electrode mixture-containing paste used in Example 4 was applied to one surface of an aluminum foil, and the positive electrode mixture-containing paste used in Example 4 was applied to one surface of the aluminum foil. A positive electrode was prepared in the same manner as in Example 4 except that the coating was performed.
[0114]
The obtained negative electrode and positive electrode were each cut out to a width of 20 mm and a length of 40 mm, and aluminum tabs were welded to the ends of the electrodes.
[0115]
A separator made of a 25-μm-thick polyethylene nonwoven fabric was interposed between the negative electrode and the positive electrode, and the resultant was loaded on an exterior material made of a laminate film having an aluminum foil as a core material. In a dry box in an argon gas atmosphere, the electrolytic solution used in Example 1 was vacuum-injected into the packaging material made of the above-mentioned laminated film, and welded with a heat sealer to produce a laminated electrochemical capacitor. The obtained electrochemical capacitor had a width of 30 mm, a length of 45 mm, and a thickness of 1 mm. The electrochemical capacitor was charged and discharged at a constant current of 10 mA at a charge voltage of 3.5 V and a discharge voltage of 1.0 V, and a discharge capacity of 2 mAh was obtained. Allowable charging voltage V of this electrochemical capacitorEWas 3.5V.
[0116]
Next, a hybrid power supply having the structure shown in FIG. 1 was manufactured using this electrochemical capacitor. That is, the electrochemical capacitor 5 and two AA alkaline batteries 6 were loaded into a polycarbonate pack 1 (width 32 mm, length 50 mm, thickness 17 mm). The two batteries are connected in series, and the maximum voltage V of the two batteries connected in series isB(Open circuit voltage) was 3.25V.
[0117]
An external electric load was connected to the hybrid power supply manufactured as described above to perform pulse discharge. In the pulse discharge mode, after a current of 300 mA was passed for 20 seconds, a pulse current of 1.5 A was passed for 2 seconds. This was defined as one cycle, and the cycle was repeated until the voltage of the hybrid power supply became 2.0 V. The hybrid power supply was set in a constant temperature bath at 23 ° C., and the number of cycles until the voltage reached 2.0 V was examined. Table 4 shows the results.
[0118]
Both batteries in the hybrid power supply after the above-described pulse discharge test could be taken out of the pack and could be replaced with new batteries.
[0119]
Comparative Example 6
No electrochemical capacitor was loaded, and pulse discharge was performed under the same conditions as in Example 6 using only the two series AA alkaline batteries contained in the pack of FIG. 1 as a power source until the voltage reached 2.0 V. Was examined for the number of cycles. Table 4 shows the results.
[0120]
Comparative Example 7
Activated carbon electrodes prepared as positive electrodes in Example 4 were used as both electrodes, and they were loaded in the same exterior material made of an aluminum laminated film as in Example 6. A mixed solvent of propylene carbonate and diethyl carbonate mixed at a ratio of 1: 2 (volume ratio) contains (C2H5)4NBF4Is dissolved in a concentration of 1.5 mol / liter into an exterior material made of the laminate film, vacuum-sealed, sealed, and laminated electric double layer capacitor (width 30 mm, length 45 mm, (Thickness: 1 mm). The electric double layer capacitor was charged and discharged with a constant current of 10 mA at a charge voltage of 2.5 V and a discharge voltage of 1.0 V, and a discharge capacity of 0.5 mAh was obtained. Allowable charging voltage V of this electric double layer capacitorEWas 2.5V.
[0121]
The maximum voltage V composed of this laminated electric double layer capacitor and two series AA alkaline batteries as in Example 4.BWas connected in parallel with a 3.25 V battery assembly to produce a hybrid power supply having the same structure as that of FIG. However, the maximum voltage V of the batteryBIs the allowable charging voltage V of the electric double layer capacitorEBecause it is higher, a protection circuit was attached to take measures to prevent the electric double layer capacitor from being overcharged. In this hybrid power supply, since a protection circuit was required, the size of the pack was 32 mm in width, 50 mm in length, and 20 mm in thickness, which was thicker than in the fourth embodiment. For this hybrid power supply, pulse discharge was performed in the same manner as in Example 4, and the number of pulse cycles was examined. Table 4 shows the results.
[0122]
[Table 4]
[0123]
As shown in Table 4, the cycle number of the hybrid power supply of Example 6 was larger than that of the single battery of Comparative Example 6. This is because the voltage of the battery drops sharply when a current of 1.5 A flows in the pulse discharge test in the battery of Comparative Example 6 alone, but the hybrid power supply of Example 6 significantly reduces the voltage drop due to polarization. It is considered that the number of pulse cycles increased.
[0124]
Further, the number of cycles of the hybrid power supply of Example 6 was larger than that of the hybrid power supply of Comparative Example 7 using the electric double layer capacitor. The large number of cycles means that the power supply can be used for a longer time. Particularly, in the hybrid power supply of Example 6, the electrochemical capacitor used in the configuration is the same as the hybrid power supply of Comparative Example 7. Since the capacity is larger and higher than that of the electric double layer capacitor used, it can be said that the capacitor is very useful in addition to the large number of cycles.
[0125]
【The invention's effect】
As described above, according to the present invention, an electrochemical capacitor having high capacity and excellent cycle characteristics can be provided. Further, according to the present invention, it is possible to provide a hybrid power supply that is small, has a low risk of being overcharged, has a high capacity, has excellent cycle characteristics, and can withstand long-term use.
[Brief description of the drawings]
FIG. 1 is a diagram showing an appearance of a hybrid power supply according to the present invention.
FIG. 2 is a view showing an arrangement of an electrochemical capacitor and a battery assembly of the hybrid power supply according to the present invention, and corresponds to the inner view of FIG. 1;
FIG. 3 is a diagram showing a connection state between an electrochemical capacitor of a hybrid power supply and a battery assembly according to the present invention.
[Explanation of symbols]
1 pack
2 Capacitor storage
3 Battery compartment
4 Battery cover
5 electrochemical capacitors
6 batteries
7 Battery connector
8 External terminals
9 Positive terminal
10 Negative electrode terminal

Claims (8)

  1. An electrochemical capacitor comprising a positive electrode using a carbonaceous material capable of adsorbing and desorbing anions, a negative electrode, and an organic electrolytic solution containing a lithium salt as an electrolyte, wherein the negative electrode has a ramsdellite type crystal structure. An electrochemical capacitor characterized by using a lithium titanium oxide having an electric capacity ratio of the negative electrode to the positive electrode of 1 to 7 for the negative electrode and the positive electrode.
  2. The electrochemical capacitor according to claim 1, wherein the lithium titanium oxide having a crystal structure of ramsdellite type, represented by the chemical formula Li 2 Ti 3 O 7.
  3. The carbonaceous material used for the positive electrode has micropores having a diameter of less than 2 nm, mesopores having a diameter in the range of 2 to 50 nm, and macropores having a diameter of more than 50 nm. 5 cc / g or more, the pore volume of the mesopores is 0.3 cc / g or more, and the existence ratio of the micropore pore volume to the total pore volume is 50 to 75%. The electrochemical capacitor according to claim 1 or 2, wherein activated carbon having an existing ratio of the pore volume of the mesopores to 25 to 50% and an average particle diameter of 5 to 20 µm.
  4. A positive electrode using a carbonaceous material capable of adsorbing and desorbing anions, a negative electrode using a lithium-containing titanium oxide having a ramsdellite-type crystal structure, and an organic electrolytic solution containing a lithium salt as an electrolyte, A hybrid power supply comprising: a battery connected in parallel with an electrochemical capacitor having an electric capacity ratio between the negative electrode and the positive electrode of 1 to 7;
  5. A positive electrode using a carbonaceous material capable of adsorbing and desorbing anions, a negative electrode using a lithium-containing titanium oxide having a ramsdellite-type crystal structure, and an organic electrolytic solution containing a lithium salt as an electrolyte, 5. The hybrid power source according to claim 4, wherein the battery connected in parallel with the electrochemical capacitor having the negative electrode / positive electrode having an electric capacity ratio of negative electrode / positive electrode = 1 to 7 is a solar cell.
  6. The hybrid power supply according to claim 4, wherein the lithium-containing titanium oxide having a ramsdellite type crystal structure is represented by a chemical formula of Li 2 Ti 3 O 7 .
  7. The carbonaceous material using the positive electrode has micropores having a diameter of less than 2 nm, mesopores having a diameter in the range of 2 to 50 nm, and macropores having a diameter of more than 50 nm, and the pore volume of the micropores is 0. 5 cc / g or more, the pore volume of the mesopores is 0.3 cc / g or more, and the existence ratio of the micropore pore volume to the total pore volume is 50 to 75%. The hybrid power supply according to any one of claims 4 to 6, wherein the activated carbon is an activated carbon having a pore volume ratio of mesopores of 25 to 50% with respect to the average particle diameter of 5 to 20 µm.
  8. A positive electrode using a carbonaceous material capable of adsorbing and desorbing anions, a negative electrode using a lithium-containing titanium oxide having a ramsdellite-type crystal structure, and an organic electrolytic solution containing a lithium salt as an electrolyte, the electric capacity ratio of the negative electrode and the positive electrode is a negative electrode / positive electrode = 1-7, an electrochemical capacitor permissible charging voltage V E is 2.5~3.5V, the maximum voltage V B 2.5 to 3 A hybrid power supply, comprising: a battery capable of being mounted and demounted in a range of 0.5 V, loaded in the same pack, and satisfying V E ≧ V B.
JP2003165906A 2002-11-22 2003-06-11 Electrochemical capacitor and hybrid power supply comprising the same Expired - Fee Related JP4833504B2 (en)

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