JP7229472B2 - Ultracapacitor materials and ultracapacitors - Google Patents

Description

The present invention relates to ultracapacitor materials and ultracapacitors.

Capacitors are originally electronic components that store and discharge electric charge (electrical energy) through electrostatic capacitance. It plays the role of an element, noise filter, etc., and is an indispensable part for electronic equipment. In recent years, high-performance IT products such as mobile phones and micro-storage devices and batteries for electric vehicles have rapidly evolved, and there is an increasing demand for capacitors that are smaller, have a larger capacity, and have advanced functions such as memories. In particular, there is a demand for products that are suitable for a smart grid (next-generation power grid) society that is compatible with green innovation (low carbonization) to prevent global warming. For example, the market for capacitors in automobiles, IT equipment, energy-saving inverters, etc. is steadily expanding at an average annual rate of about 3.7%, reaching a market of 1 trillion yen.

As such a capacitor, it is desirable to use one that does not use an inflammable element such as lithium or an environmental pollutant. That is, there is a demand for materials that are solid rather than liquid, harmless to health, and inexpensive.

Capacitors are broadly classified into high-voltage power circuits (heavy electric) and electronic/electrical equipment circuits (light electric). Among them, ceramic capacitors are mainly used as capacitors for electronic/electrical equipment circuits in the field of light current, and secondary batteries are also heavily used for storing electricity in mobile phones and the like. On the other hand, capacitors for the heavy electric field have not yet been put to practical use due to their insufficient voltage resistance and storage capacity.

Electricity storage bodies using capacitors are widely used as main components of electronic and electrical equipment, ranging from 1 pF to several tens of mF. The storage capacity C (F) is
C=Q/V=ε×(A/d)
(Here, Q: electric charge, V: voltage, ε: dielectric constant, A: electrode area, d: inter-electrode distance), so the larger the electrode area and the smaller the inter-electrode distance, the higher the charge capacity obtained. . However, from the viewpoint of lightness, thinness, shortness and miniaturization of electronic and electrical equipment and the required storage capacity, it is necessary to increase the electrode area A and reduce the distance d between the electrodes to achieve a maximum capacity, reduce the electrode area A, It is difficult to increase the inter-electrode distance d to make the capacitance extremely small. In addition, current lumped-constant circuit-based dielectric capacitors are already saturated in capacitance.

As a power storage method that surpasses conventional electric capacity, there is a method using a distributed constant circuit. For example, recently, an electric double layer capacitor made by moistening an electrolytic solution in activated carbon has been put to practical use. However, a solid-state electric double layer capacitor has not yet been used.

With regard to solid electricity storage materials, the present inventors have found that Si—(Al, Ti, V) alloys in which Al, Ti, and V have been extracted and removed from the surface, and Ti—Ni—Si-based amorphous alloys coated with TiO ₂ are capable of generating electric charges. can be accumulated regardless of direct current or alternating current (see, for example, Non-Patent Documents 1 to 7 and Patent Documents 1 to 3).

In addition, the present inventors have found that when the compound particles are 40 nm or less, preferably 10 nm or less, the electrons of the outermost layer atoms increase sharply with respect to the inner atoms, neutralization against electron shielding occurs, and lattice expansion has been reported (see, for example, Non-Patent Document 8). This is a quantum phenomenon explained by the theory of electron shielding that occurs on nano-sized solid surfaces, and is called the "quantum size effect." As an electricity storage material that utilizes this phenomenon, the present inventors have developed a material in which nano-sized unevenness is formed on the surface of amorphous titania or amorphous fluoropolymer (for example, Non-Patent Documents 4, 7, and 9). , see Patent Document 4). In these storage materials, due to the quantum nano-size effect, the smaller the diameter of the projections is, the more the Van der Waals electrostatic force acts on the diameter of the projections to the power of minus 6, and the more electrons can be attracted to the projections. increase (see, for example, Non-Patent Document 7). The work function, which is a measure of the magnitude of the electron adsorption capacity, is 5.5 eV for amorphous titania (see, for example, Non-Patent Document 7), and 10.3 eV to 13.35 eV for amorphous fluoropolymer (for example, Non-Patent Document 7). See Document 4 and Patent Document 4).

Furthermore, as a material that has a larger work function than these electricity storage materials and is capable of storing a large amount of electricity, the surface is composed of an amorphous material containing AlO ₆ as a main component, and has a diameter of 0.1 to 50 nm and a height difference of 0.1 to 50 nm. The present inventors have developed a power storage material having a plurality of unevenness of 1 to 50 nm (see, for example, Non-Patent Document 10).

Amorphous alumina includes not only octahedral AlO ₆ but also tetrahedral AlO ₄ and hexahedral AlO ₅ clusters. It consists of ₆ clusters (see, for example, Non-Patent Document 11).

Research has also been reported on perovskite Sr ₂ Nb ₃ O ₁₀ and Ca ₂ Nb ₃ O ₁₀ nanosheet thin film capacitor elements having a film thickness of 10 nm or less and a dielectric constant of 210 to 240 as electricity storage materials (for example, Non-Patent Document 12), the distance between the electrodes is large, and since it is ceramic, it is not easy to join with the electrode material, and the contact resistance is high. In addition, a high specific capacitance of 1,160 F/ ^cm has been reported in a MnO ₂ -coated nanoporous Au-based amorphous alloy separator in a chemical electrolyte (see, for example, Non-Patent Document 13), which is also conventional It is an application of electrochemical cells.

In addition, as a storage material, a physical secondary battery with a voltage of 1.5 V, power of 500 Wh/L, output density of 8 kW/L, cycle life of 100,000 times, and an operating temperature range of -25°C to +85°C has been developed ( For example, see Non-Patent Document 14), an electron trap level is formed in the bandgap of a semiconductor, and a Schottky junction is used in which charge and discharge are performed by filling or emptying this level with a potential. , the voltage is limited to 1.5V.

M. Fukuhara, T. Araki, K. Nagayama and H. Sakuraba, “Electric storage in de-alloyed Si-Al alloy ribbons”, EuroPhys. Lett., 2012, 99 ,47001 M. Fukuhara, “Electric Charging/Discharging Characteristics of Capacitor, Using De-alloyed Si-20Al Alloy Ribbons”, Elect. Electr. Eng., 2013, 3(2), p.72-76 M. Fukuhara and H. Yoshida, “AC charging/discharging of de-alloyed Si-Al-V alloy ribbons”, J. Alloys and Comp., 2014, 586, S130-S133 M. Fukuhara, H. Yoshida, M. Sato, K. Sugawara, T. Takeuchi, I. Seki, and T. Sueyoshi, “Superior electric storage in de-alloyed and anodic oxidized Ti-Ni-Si glassy alloy ribbons”, Phys. Stat. Sol. RRL, 2013, 7(7), p.477-480 M. Fukuhara and K. Sugawara, “Electric charging/discharging characteristics of super capacitor, using de-alloying and anodic oxidized Ti-Ni-Si amorphous alloy ribbons”, Nanoscale. Res. Lett., 2014, 9, p.253 M. Fukuhara and K. Sugawara, “Anodic oxidization of Ti-Ni-Si amorphous alloy ribbons and their capacitive and resistive properties”, Thin Solid Films, 2015, 595, p.1-4 M. Fukuhara, T. Kuroda and F. Hasegawa, “Amorphous titanium-oxide supercapacitors”, Sci. Rep., 2016, 6, 35870 M. Fukuhara, “Lattice expansion of nanoscale compound particles”, Physics Letters, 2003, A313, p.427-430 M. Fukuhara, T. Kuroda, F. Hasegawa and T. Sueyoshi, “Superior electric storage on an amorphous perfluorinated polymer surface,” Sci. Rep., 2016, 6, 22012 M. Fukuhara, T. Kuroda, F. Hasegawa, T. Hashida, E. Kwon and K. Konno, “Amorphous aluminum-oxide supercapacitors,” EuroPhys. Lett., 2018, 123, 58004 H. Zhang et. al., "Atomic structure of nanometer-sized amorphous TiO2", [online], April 16, 2009, eScholarship, Open Access Publications from the University of California, <https://escholoaship.org/ uc/item/64j177cw> M. Osada, K. Akatsuka, Y. Ebina, H. Funakubo, K. Ono, K. Takada and T. Sasaki, “Robust high-k response in molecularly thin perovskite nanosheets”, ACS NANO, 2010, 4, p. 5225-5232 X. Y. Lang, A. Hirata, T. Fujita and M. W. Chen, “Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors”, Nature Nanotechnology, 2011, 6, p.232-236 Micronics Japan Co., Ltd., secondary battery battenice, <http://www.mjc.co.jp/product/index3.html>

JP 2012-253321 A JP-A-2015-57808 JP 2016-134934 A JP 2017-41578 A

The electricity storage material described in Non-Patent Document 10 has an amorphous surface containing AlO ₆ as a main component, and does not use amorphous titania. In addition, the power storage material of Non-Patent Document 7 using amorphous titania has a problem that the power storage capacity is not as large as that of the power storage material of Non-Patent Document 10.

The present invention has been made in view of such problems, and an object of the present invention is to provide an ultracapacitor material and an ultracapacitor that use amorphous titania and are capable of storing a larger amount of electricity.

The inventors of the present invention focused on an amorphous material containing TiO ₆ as a main component as a solid ultracapacitor material, and arrived at the present invention. That is, amorphous titania is produced by a wet method such as an anodizing method, a sol-gel method, an alkoxide method, or a dry method such as a laser vapor deposition method or a plasma electrolytic oxidation method. , and no power storage effect is observed. However, the present inventors have found that the surface of amorphous titania (TiO ₂₋ x) consisting of octahedral oxygen-deficient TiO ₆ clusters is formed with nanometer-sized unevenness of, for example, about 0.1 to 30 nm. It was found that the quantum size effect on the surface causes high storage capacity. Furthermore, the present inventors have found that when some of the octahedral TiO ₆ clusters are oxygen-deficient, a positive charge is accumulated there, and even if the amount of adsorbed charge on the surface increases, the positive charge makes it electrically neutral. is maintained, insulation breakdown is avoided.

Further, the present inventors have disclosed in Patent Document 2 that a-Ti-Fe-Si, a-Ti-Ni-Ge, a-Ti-Ni-Cu, a-Zr-Al-Ni-Cu, a-Zr -(Fe, Ni)-Sn, a-Al-Y-Ni-Co, a-La-Al-Cu-Ni-Co-Ag system amorphous alloy is used as a starting material for anodization, but valve It has been found that if an alloy containing Fe, Ni, Co, Cu, and Sn, which is not a metal, is used, a dense oxide film cannot be formed during anodization, resulting in low electrical resistance and leakage of stored charges. . In the case of c-Ti-Al-Y, c-Si-Al-V-Ti, and c-Zr-(Fe, Ni)-Sn systems, the starting materials are crystalline, so oxygen We also found that it is difficult to fabricate TiO ₆ clusters with defect vacancies and nano-sized rough surfaces. In addition, a represents amorphous and c represents crystalline. The present inventors arrived at the present invention based on these findings.

That is, the ultracapacitor material according to the present invention is composed of Ti and a valve metal, and has a plurality of irregularities made of amorphous TiO ₆ clusters on the surface , and the valve metal is vanadium, silicon or tantalum. characterized by being In particular, the amorphous preferably has oxygen-deficient TiO ₆ clusters .

The ultracapacitor material according to the present invention can store and discharge electricity by utilizing the electron adsorption phenomenon due to the quantum size effect that occurs in the convex portions of a plurality of unevenness. In the ultracapacitor material according to the present invention, each of the plurality of uneven surfaces becomes a capacitor composed of a solid/gas electric double layer, and the plurality of capacitors form an electric distributed constant circuit in which the plurality of capacitors are finitely connected in parallel. As a result, the ultracapacitor material according to the present invention is capable of instantaneous or relatively short-time storage, and is capable of large-capacity storage.

The ultracapacitor material according to the present invention can be produced by an anodizing method or a sputtering method. In the ultracapacitor material according to the present invention, the valve metal includes Y of group IIIa, lanthanum metal, Zr, Hf of group IVa, V, Nb, Ta of group Va, Cr, Mo, W of group VIa, group IIb. Zn, IIIb group Al, IVb group Si, Vb group Sb, Bi, etc., may be any valve metal, but in particular, the ability to form dense oxides and non-stoichiometric oxides, high melting point, high work Vanadium (V), silicon (Si), or tantalum (Ta) is preferable from the viewpoint of function, low density, and cost reduction. In addition, the amorphous containing TiO ₆ clusters as a main component preferably consists of amorphous titania (TiO _2- x) containing 12% or less oxygen defects, and in this case, it plays an important role particularly in electricity storage. can.

In the ultracapacitor material according to the present invention, it is preferable that the amorphous has the plurality of irregularities with a diameter of 0.1 to 30 nm and a height difference of 0.1 to 30 nm. In this case, by reducing the size of the unevenness to nano-size, the electron adsorption ability can be enhanced by the quantum size effect, the work function can be increased, and the storage capacity can be further increased.

The ultracapacitor material according to the present invention is preferably in the form of a thin film with a thickness of 200 nm or less. In this case, since static electricity is attached and detached from the surface, the power density and energy density can be increased by forming a thin film.

The ultracapacitor material according to the present invention preferably has an electric resistance of 1 GΩ or more, more preferably 100 GΩ or more, and an electric capacitance of 10 mF/cm ² to 100 F/cm ² . In addition, it is preferable that a long-term discharge of one day or more is possible by instantaneous or short-time electric storage for 1 ms to 1 minute, and large-capacity electric storage. Also, it is preferable that rapid response charge/discharge of 1 mHz to 100 kHz, preferably 0.1 to 100 Hz is possible. It is believed that the ultracapacitor material according to the present invention can store current from a generator every 50/1000 to 60/1000 seconds by converting 50 Hz and 60 Hz alternating current to direct current using an AC/DC converter. . As a result, it becomes possible to transport the solid-state power storage unit by abolishing power transmission lines, and it can be freely transported domestically and internationally not only by automobile, but also by ship, airplane, and the like.

The ultracapacitor material according to the present invention preferably has a specific surface area of 1000 m ² /g or more. Further, it is preferable that the ultracapacitor material according to the present invention can increase the specific surface area by 10 to 100 times by dry etching of MEMS processing.

An ultracapacitor according to the invention is characterized in that it comprises an ultracapacitor material according to the invention.

The ultracapacitor according to the present invention is capable of instantaneous or relatively short-term power storage due to the ultracapacitor material, and is capable of large-capacity storage. In general, a capacitor that has a larger specific surface area than conventional capacitors and is formed by a power storage system consisting of an electric double layer is called a supercapacitor. It's called a capacitor.

In the ultracapacitor according to the present invention, the ultracapacitor material may be in the form of a thin film, and may comprise a power storage body having a pair of metal electrodes respectively provided on both sides of the ultracapacitor material so as to sandwich the ultracapacitor material. preferable. In this case, it is equivalent to a distributed constant type capacitor having a plurality of minute capacitors perpendicular to each metal electrode corresponding to the number of irregularities. That is, the fine unevenness itself becomes a high electrical resistance, which can be represented by a parallel equivalent circuit of C and R. Also, the ultracapacitor according to the present invention can be manufactured by forming upper and lower metal electrodes made of Al, Cu, etc. by a sputtering method or a casting method using a microelectromechanical system (MEMS). At that time, each metal electrode is preferably coated on the entire surface along the surface shape of the ultracapacitor material. Also, the ultracapacitor according to the present invention is preferably operable at -269°C to 500°C.

The ultracapacitor according to the present invention may comprise a laminate obtained by laminating a plurality of the power storage bodies. In this case, parallel lamination can be performed by, for example, a MEMS method such as spin coating or dip coating, and a solid electronic direct storage device in which each parallel equivalent circuit is coupled with an electric lumped constant can be obtained. Also, the ultracapacitor according to the present invention may comprise a parallel assembly in which a plurality of said ultracapacitor materials are arranged between each metal electrode along the inner surface of each metal electrode. In this case, a voltage resistance of 1 GV/m or more can be obtained.

The ultracapacitor according to the invention can be used, for example, as an AC capacitor in microelectronic circuits or as a battery on the backside of a solar panel. It can also be used for various backup power supply modules, coupling elements, noise filters, high-sensitivity acceleration sensors, high-output transformer cut-off prevention devices, and electronic and electric boards such as emergency power supply devices for automobiles and ships.

There are the following five conditions as physical power storage body conditions for using a solid as a power storage body.
(1) The surface must be a fine uneven surface to generate the quantum size effect. (2) The material must have a high work function. (3) The surface must have an amorphous structure with positive charges. is an electric distributed constant circuit (parallel connection) (stacking effect of charge amount)
(5) High electrical resistance in order not to cause leakage of stored charge. The ultracapacitor material and ultracapacitor according to the present invention can satisfy all of these five conditions, and the solid ultracapacitor storage material and ultracapacitor It has excellent performance as

According to the present invention, it is possible to provide an ultracapacitor material and an ultracapacitor that use amorphous titania and are capable of storing a larger amount of electricity.

1 is a perspective view showing the molecular structure of an ultracapacitor material according to an embodiment of the invention; FIG. 1 is an electrical distributed constant circuit showing an ultracapacitor material according to an embodiment of the invention; 1 is an atomic force microscope (AFM) image of the surface of Sample 1 of an ultracapacitor material according to an embodiment of the present invention; 1 is an X-ray diffraction (XRD) pattern at the surface of Sample 1 of an ultracapacitor material according to an embodiment of the invention; (a) Sample 2 of ultracapacitor material according to the embodiment of the present invention, (b) Capacitor material using Ti-15Ni-15Si amorphous alloy, storage capacity Cs at series junction and storage capacity Cp at parallel junction 4 is a graph showing frequency characteristics; FIG. 3 is a Nyquist diagram (Cole-Cole plot diagram) of AC impedance showing the frequency characteristics of Sample 3 of the ultracapacitor material according to the embodiment of the present invention. It is a side view which shows the manufacturing method of an ultracapacitor by the MEMS method using the ultracapacitor material of embodiment of this invention. 8 is an optical micrograph showing an ultracapacitor according to an embodiment of the invention fabricated by the method shown in FIG. 7; 1 is a side view showing an ultracapacitor according to an embodiment of the present invention, which is composed of a laminate obtained by laminating a plurality of power storage bodies using the ultracapacitor material according to the embodiment of the present invention. FIG.

Hereinafter, ultracapacitor materials and ultracapacitors according to embodiments of the present invention will be described based on the drawings and examples.
As shown in FIG. 1, the ultracapacitor material of the embodiment of the present invention contains Ti and a valve metal, and has a plurality of irregularities made of amorphous (amorphous titania) mainly composed of TiO ₆ clusters on the surface. ing. Also, the surface amorphous has TiO ₆ in the state of oxygen vacancy. In the example shown in FIG. 1, the oxygen defect rate is 11.7%.

The ultracapacitor material of the embodiment of the present invention can store and discharge electricity by utilizing the electron adsorption phenomenon due to the quantum size effect that occurs in the projections of a plurality of unevenness. In the ultracapacitor material of the embodiment of the present invention, a plurality of uneven surfaces are each a capacitor composed of a solid/gas electric double layer, and as shown in FIG. circuit. As a result, the ultracapacitor material of the embodiment of the present invention is capable of instant or relatively short-time high-voltage storage, and is capable of large-capacity storage.

Below are examples of ultracapacitor materials and ultracapacitors according to embodiments of the present invention. It should be noted that the following examples are provided merely to illustrate the present invention and for reference to specific embodiments thereof, and are not intended to limit or limit the scope of the invention disclosed herein. not a thing

Ultracapacitor materials according to embodiments of the present invention were produced. Table 1 shows the master alloy composition of the manufactured ultracapacitor materials of samples 1 to 3, the shape of the master alloy, the manufacturing method of the ultracapacitor material, the aqueous solution used during manufacturing, the manufacturing conditions such as current density, voltage, time, and temperature, and manufacturing. The electrical resistance (GΩ) and storage capacity (F/cm ² ) of the ultracapacitor materials are shown.

In the production of the ultracapacitor material, for both samples 1 to 3, first, in an Ar atmosphere, an ingot of each master alloy shown in Table 1 was arc-melted and cooled at a cooling rate of ¹⁰ m/s or less by a single-roll liquid quenching method. to prepare a ribbon-shaped sample. Next, under the conditions shown in Table 1, an ultracapacitor material having sub-nanometer-scale irregularities on its surface was produced by an anodizing method.

As shown in Table 1, each ultracapacitor material of Samples 1-3 was confirmed to have an electrical resistance of 60 GΩ to 185 GΩ and an electrical capacitance of 1 F/cm ² to 10 F/cm ² . It was also confirmed that the specific gravity was as low as 4 or less. It was also confirmed that each of the ultracapacitor materials of Samples 1-3 could operate from -269° to 300°C and 500V. In addition, voltage resistance up to 1,100°C was also confirmed. Moreover, the specific surface area of each ultracapacitor material was 1000 m ² /g or more as a result of measurement by the BET adsorption method. From these facts, each ultracapacitor material is considered to be the most suitable material for heavy electric field and atmospheric current (lightning) storage.

An atomic force microscope (AFM) image of the surface of sample 1 is shown in FIG. As shown in FIG. 3, it was confirmed that the surface of the ultracapacitor material had a plurality of irregularities with a diameter of 30 nm or less and a height difference of 30 nm or less (average of about 20 nm). Note that white portions in FIG. 3 indicate convex portions. Also, the X-ray diffraction (XRD) pattern on the surface of the ultracapacitor material of Sample 1 is shown in FIG. As shown in FIG. 4, in the X-ray diffraction (XRD) pattern, only a broad halo peak without a Bragg peak of a crystalline phase was observed, confirming an amorphous phase.

The ultracapacitor materials of Samples 1 to 3 are manufactured by the anodizing method, which is well known as a method for manufacturing uniform micropores, but the amorphous titania is manufactured by the sputtering method using Ar partial pressure gas. It can also be manufactured by When this sputtering method is used, a sintered body having the same composition as the target amorphous titania may be used as the sputtering material.

Using the ultracapacitor material of sample 2, the storage capacity was measured in series junction and parallel junction with alternating current. Copper electrodes were mechanically fixed above and below the thin film of sample 2 with a surface area of 1 mm×10 mm, and the storage capacity was measured in the frequency range of 1 mHz to 1 MHz using a potentiostat/galvanostat. The measurement results are shown in FIG. 5(a). For comparison, the same measurement was performed on a capacitor material using the Ti-15Ni-15Si amorphous alloy disclosed in Patent Document 3, and the results are shown in FIG. 5(b).

As shown in FIG. 5( a ), the ultracapacitor material of Sample 2 has a logarithmic storage capacity increase with a decrease in frequency, and at 1 mHz, the capacitance Cs at the series junction is 9.8 F/cm ² It was confirmed that the capacitance Cp at the junction reached about 0.1 mF/cm ² . This is because, in the ultracapacitor material of the embodiment of the present invention, charging and discharging occur at the electrode interface existing in the nano-sized pores in the low frequency range, but in the high frequency range, it occurs deep in the pores with a large difference in height. It is considered that this is because charging and discharging do not occur.

Also, the value of Cs=9.8 F/cm ² of the ultracapacitor material of sample 2 is about 2,000 times the limit value of Cs=5 mF/cm ² of the Al electrolytic capacitor. The Ti—Ni—Si-based capacitor material shown in FIG. 5(b) has a series junction capacitance Cs and a parallel junction capacitance Cp of about 0.05 to 0.1 μF/cm ² at 1 mHz. . From this, it was confirmed that the ultracapacitor material of sample 2 has a larger storage capacity than the Ti--Ni--Si based capacitor material by about 8 digits for Cs and about 3 digits for Cp. Thus, it can be said that the ultracapacitor material of the embodiment of the present invention can be charged and discharged by the quantum nanosize effect, and can store a large amount of electricity.

Using the ultracapacitor material of sample 3, the frequency characteristics were measured. The measurement was performed by mechanically fixing copper electrodes to the top and bottom of the thin film of Sample 3 having a surface area of 1 mm×10 mm. The Nyquist diagram of AC impedance was measured in the frequency range of 1 mHz to 1 GHz, and the results are shown in FIG.

A semicircular Nyquist plot was obtained, as shown in FIG. Such an AC impedance characteristic shows the same characteristics as a simple parallel equivalent circuit in which countless capacitances are connected in parallel to the resistor R, and it is one huge ultracapacitor by the electric distributed constant circuit shown in FIG. is shown.

Table 2 compares the properties of the ultracapacitor materials of the embodiments of the present invention with the properties of commercially available Li-ion batteries and electric double layer capacitors, as well as physical secondary batteries (battenite) being developed. In Table 2, "◯" indicates relatively good characteristics, "x" indicates relatively poor characteristics, and "Δ" indicates average characteristics. As shown in Table 2, the ultracapacitor material of the embodiment of the present invention has superior characteristics, particularly in charging voltage, operating temperature, charging time, AC storage, fire resistance, and environmental pollution, for Li-ion batteries. It has superior characteristics to electric double layer capacitors, especially in terms of charging voltage, operating temperature, fire resistance, and environmental pollution. It has superior properties.

As shown in FIG. 7, using the ultracapacitor material of sample 2, an ultracapacitor 10 was fabricated by the MEMS method. First, a Cr (thickness: 20 nm)/Cu layer (thickness: 500 nm) 12 is formed by sputtering on the surface of a glass substrate (20×20×0.5 mm) 11 (see FIG. 7.1), and a photoresist 13 is formed thereon. was applied and patterned (see FIG. 7.2), and after etching, the photoresist 13 was removed (see FIG. 7.3). A polyimide layer (5 μm thick) 14 was coated thereon and dried at 150° C. (see FIG. 7.4).

Next, a ribbon-shaped ultracapacitor material (sample 2) 15 is placed on the polyimide layer 14 (see FIG. 7.5), and a photoresist 16 is applied thereon and patterned (see FIG. 7.6). ), and a polyimide layer (thickness 5 μm) 17 was coated on the portion other than the photoresist 16 and dried at 150° C. (see FIG. 7.7). Next, the photoresist 16 was removed (see FIG. 7.8), and an Al layer 18 was formed on the surface by ultrasonic bonding (see FIG. 7.9). The glass substrate 11 was removed, and it was used as a basic body of one electric storage layer for electronic circuits. The Cr/Cu layer 12 and the Al layer 18 form a pair of metal electrodes.

An example of an ultracapacitor 10 manufactured in this way is shown in FIG. The ultracapacitor 10 shown in FIG. 8 uses gold layers as the pair of metal electrodes. Also, the arrows in FIG. 8 indicate the connection relationship of the wiring. As shown in FIG. 9, the ultracapacitor 10 may be formed by laminating a plurality of electric storage layers for electronic circuits with an insulator 19 interposed therebetween. In this case, the ultracapacitor 10 made of the manufactured laminate consists of the Al layer 18 of the uppermost electronic circuit storage layer and the Cu layer of the Cr/Cu layer 12 of the lowermost electronic circuit storage layer. As a terminal, the ultracapacitor material 15 of each electric storage layer for electronic circuits is connected in parallel. Therefore, for example, a laminate in which 100 electric storage layers for electronic circuits are laminated has a capacity 100 times that of one electric storage layer for electronic circuits.

The ultracapacitor 10 of the embodiment of the present invention can be used, for example, as an AC capacitor in a microelectronic circuit or as a battery on the backside of a solar panel. In addition, for example, various backup power supply modules for lightning arresters, welding, overdischarge prevention, etc., coupling elements, noise filters, high-sensitivity acceleration sensors, high-output transformer cutoff prevention devices, and emergency power supply devices for automobiles and ships. It can also be used for electronic and electric boards such as.

REFERENCE SIGNS LIST 10 ultracapacitor 11 glass substrate 12 Cr/Cu layer 13 photoresist 14 polyimide layer 15 ultracapacitor material 16 photoresist 17 polyimide layer 18 Al layer 19 insulator

Claims (8)

Consists of Ti and a valve metal, and has a plurality of amorphous irregularities on the surface composed of TiO ₆ clusters ,
An ultracapacitor material , wherein the valve metal is vanadium, silicon or tantalum . 2. The ultracapacitor material of claim 1, wherein the amorphous has TiO ₆ clusters in an oxygen-deficient state. 3. The ultracapacitor material according to claim 1, wherein the amorphous has a plurality of unevennesses with a diameter of 0.1 to 30 nm and a height difference of 0.1 to 30 nm. 4. The ultracapacitor material according to any one of claims 1 to 3 , which has an electrical resistance of 1 GΩ or more and an electrical capacitance of 10 mF/cm ² to 100 F/cm ² . 5. An ultracapacitor material according to any one of claims 1 to 4 , characterized in that the surface has a specific surface area of 1000 m ^<2> /g or more. An ultracapacitor comprising an ultracapacitor material according to any one of claims 1-5 . 7. The ultracapacitor material according to claim 6 , wherein said ultracapacitor material is in the form of a thin film and comprises a power storage body having a pair of metal electrodes respectively provided on both sides of said ultracapacitor material so as to sandwich said ultracapacitor material. ultracapacitor. 8. The ultracapacitor according to claim 7 , wherein the ultracapacitor comprises a laminate in which a plurality of the electric storage bodies are laminated.

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