JPH07503578A - electrolytic double layer capacitor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] electrolytic double layer capacitor This application was filed on October 29, 1991, and is currently abandoned. Continuation of patent application bundle 07/783.850, dated October 13, 1992. This application is a continuation-in-part of co-pending U.S. patent application Ser. No. 07/960.251.

Background of the invention The present invention relates to double layer capacitors, and more particularly, to high energy, high power and tolerant capacitors. Concerning solution capacitors.

Normal electrolytic capacitors have an interface between the electrode surface of each capacitor and the electrolytic solution between the electrodes. It stores energy by accommodating so-called double layers of charge on its surfaces. follow Therefore, the electrode surface area limits the energy storage capacity of such capacitors. The larger the area, the larger the double layer of charge that is generated and therefore the co The energy storage capacity of the capacitor increases. However, typical applications are limits the actual range of the physical size of the capacitor, thereby limiting the physical size of the capacitor limits the achievable energy storage capacity provided by the surface.

A type of double layer capacitor design that overcomes the limitations of macroscopic capacitor surface area. Capacitors using powdered electrode materials (e.g., large area activated carbon particles) Macroscopically increases the surface area of the electrode. In such a capacitor, less than one carbon particle to form a porous electrode structure in which the exposed surfaces of the particles force (contributes to the total electrode surface area; internal resistance of the porous structure and capacitance (sitance and 1 It is a complex function of carbon particle structure and shape.

Summary of the invention Generally, the present invention provides two electrodes, each in contact with a common electrolyte solution, in embodiment (1). double layer electrolytic capacitors. at least one of the electrodes (or Contains crystalline materials characterized by the presence of Nderwaals channels. these fans A der Waals channel is a van der Waals channel when a voltage is applied between two electrodes. suitable for containing electrolytes. van der Waer as an extension of the macroscopic surface of the electrode. Apparently increases luspasitance. Having a van der Waals channel A more detailed description of compounds and devices using these compounds can be found in “Electrolytic Double Layer The following applications, all filed on the same day as "Capacitors", are related here as references: : Provided in “capacitive thermoelectric devices” and “energy storage devices”.

In a preferred embodiment, one of the electrodes includes a crystalline material and the other electrode is coupled with an electrolyte. a conductive container in which a crystal electrode is arranged; more preferably a capacitor; Both electrodes are made of crystalline material. Preferably, each electrode is made of crystalline material. Composed of single crystal. In another preferred embodiment, the two electrodes each have a crystalline material. The particles are composed of single crystal powder particles of approximately 70 microns in longest size.

Preferably, the crystalline material is Bi, ch. l: In the formula, ch is a group consisting of Te and Se. y is 1 or 2, and 2 is within the range of 1 to 3] It is bismuth lucogenide.

In one preferred embodiment, the electrolyte is 1.0 MLic in propylene carbonate. 104 solution: In other embodiments, the electrolyte is dissolved in dimethoxyethane. 1.2M solution of perchlorate organic cation in a mixture of propylene carbonate Or an aqueous solution of potassium hydroxide.

Preferably, the van der Waals channels of the electrodes transport ions from the electrolyte. training, including insertion into the Nderwaals channel. ng) method to accommodate the electrolyte, and the voltage allows the channel to pass through the electrolyte. High enough. Preferably, the polarity is reversed periodically between the electrodes during the insertion process. let Most preferably, the voltage is applied to the electrodes for about 600 minutes and the polarity of the voltage is about 30 minutes. Reverse every minute. This training method uses an electrolyte to connect van der Waal to the electrodes. permeate the channel to form a double layer of charge on the channel surface, thereby This clearly increases the total surface area of the electrode. The features and advantages of the pond of the present invention are explained below. This will be described in the description and claims.

Brief description of the drawing Figure IA is a schematic diagram of one embodiment of a capacitor of the present invention; Figure IB is a schematic diagram of one embodiment of a capacitor of the present invention; FIG. 2A is a schematic diagram of a second embodiment of the condenser; FIG. 2A is an initial stage of training; Figure 2B is a schematic diagram of the capacitor in Figure IB at a later stage of training. 2A is a schematic diagram of the condenser of FIG. 2A in a floor; Figure 20 is a schematic diagram of the capacitor of Figure 2A at the final stage of training; : FIG. 2D is a schematic diagram of the capacitor of FIG. 2A, including the formation of a double layer of charge; 3 is a diagram of a similar circuit representing the capacitors of FIGS. I8 and IB.

Description of preferred embodiments As an example of a range of capacitors, the capacitance of a typical parallel plate capacitor is the following formula: %formula% [In the formula, ε. is the dielectric constant (constant) in vacuum; ε is the medium between the capacitor electrodes. S is the surface area of the capacitor electrodes and d is the dielectric constant of the capacitor electrodes separating the electrodes. width of the medium]. Therefore, the capacitance of a constant capacitor The amount of energy stored and the corresponding amount of energy stored are determined by the external geometry, i.e. surface area, electrode spacing, material properties ial properties).

The capacitance of a double layer capacitor is defined by the structure of the charged double layer and its external form. further specified by. This double layer causes charge accumulation on the electrode surface and and ion accumulation at the interface between the electrolyte and the electrolyte. Therefore, double layer electrolytic capacitor Then, the width d in the capacitance equation is determined by the distance between the centers of the two regions that make up the double layer. is given.

The capacitor of the present invention has a corresponding increase in the surface area of the capacitor electrodes and The capacitance and energy storage can be clarified by appropriate selection of the electrolyte and Increase to white. The most notable of the benefits of the present invention is that the increased surface area It does not depend on the increase in the macroscopic size of the poles and also increases the grain size as in typical carbon electrodes. It does not depend on the child surface area. Rather, the increase in electrode surface area leads to a layered crystal structure. It is obtained using a specific type of characterized substance, namely an insertion compound. insertion compound The crystalline layers of an object are weakly coupled together and separated from each other by van der Waals regions includes the face of molecules or atoms that are These van der Waals regions are molecules or primitives. forming anisotropic channels in the crystal lattice between the child planes, effectively creating a “two-dimensional” crystal structure. give rise to a body. Insertion material typically has a thickness of the order of 106 to 107 per mm of material thickness. - indicates the layer of Due to the weak van der Waals forces between the crystal layers, the lattice channels may contain the physical introduction or so-called insertion of parasite inserts into them. can.

In the capacitor electrode of the present invention, the surface of the crystal lattice channel (however, (inner side) contributes to the total electrode surface area, thereby reducing the effective electrode surface area to its macroscopic surface. Treat the van der Waals area of the electrode material so as to increase it. below As detailed in , the van der Waals channel surface of the electrode material It forms a double layer with the electrolyte, just as the macroscopic surface actually forms a double layer. can be done. The recognition and utilization of this physical process is made it possible to obtain a remarkable energy storage capacity of the capacitor.

The inventors of the present invention have identified a particular type of insertion compound, namely bismuth chalcogenide ( (including Bi, Te3 and 13i2Se) as an extension of the electrode surface area. It has been found that it is particularly well suited for the formation of Lewars channels. these materials When used in combination with a suitable electrolyte, an electrode composed of Forms a highly homogeneous bilayer. As is well known to those skilled in the art, chalcogenated bis The mass has a layered crystal lattice that is layered at the molecular level, with each layer containing on the order of 3 to 4 people. separated by van der Waals channels with widths. chalcogenated vinyl Other material properties of Sumas, filed on the same date as this application, are incorporated herein by reference. Co-pending U.S. patent application titled “Layered Crystal Material Capable of High Parasitic Loading” Are listed. Regarding the material studied, the inventors found that in bismuth chalcogenide Bi2Te3 has the best conductivity and is therefore most preferred as an electrode material, but B i2Se3 has low conductivity and is therefore less preferred as an electrode material discovered.

Bismuth chalcogenides are actually layered intercalated substances, their van der Waals The possibility of processing the channels to increase the electrode surface area is The purity of the quality and the density of defects are significantly given. Impurities and crystal lattice defects are Distorts the external morphology of the Vanderwaals channel and brings this channel closer to the inserted species. damage the channel surface structure and thus damage the electrical and mechanical properties of the channel. Deteriorates mechanical properties. Therefore, the materials chosen for the capacitor electrodes are Developed by Ming inventors to produce single crystal materials with high purity and as few defects as possible , ideally preferred to be produced using a unique method. For this, Calco The following single crystal growth method for bismuth genide materials is preferred. Despite that , alternative methods of forming less than ideally pure but defect-free materials are available for certain Can be used for capacitor applications. Those skilled in the art will understand the important material parameters and performance results.

A preferred method of making insertion compounds involves producing stoichiometric amounts of high purity (99,9999% pure) bismuth and tellurium (or other specific chalcogenides) of Charge during pull. If necessary, the material is zone purified before use. Non-stoichiometric ( off-stoichiometry) results in poor lattice structure and associated performance. This results in a p-type or p-doped material. ampoule to 10-’mmHg Evacuate to ) to a pressure of 10-3 mmHg (3 to 10 cycles) and then sealed. Ru. Hydrogen reacts with oxygen during processing to prevent chalcogenide oxidation and reduce segregation. Therefore, hydrogen is particularly preferred.

A highly homogeneous polycrystalline material is produced in the first process step. sealed ampoule is placed in a furnace at room temperature and heated to a temperature 5-10°C above its melting point. run The ramp rate, temperature and reaction time depend on the final compound. There are many reaction conditions. Table 1 describes the production of crystals Bi253, B1□Se, and Bi2Te3. . The temperature of the furnace over the entire length of the ampoule is controlled within ±0.5°C. chalcogen Due to the high volatility of the compounds, careful and precise control of temperature is important. Amplifier Temperature changes along the length of the tube cause chalcogenide segregation, resulting in out-of-stoichiometry. . Long furnaces can be used to optimize temperature control along the ampoule length. Wear. Use additional heating coils at the end of the furnace to reduce temperature gradients at the exit of the furnace. can do.

Table 1. Processing conditions for polycrystalline materials Heating rate up to Tl16 (°C/hour) 30 20 15T+: at a+10°C Exposure time (hours 10 15 20 Cooling rate ('C/hr) 50 40 35 During the last hour of reaction time, the amplifier Stir or vibrate the ampoule to ensure thorough mixing of the ampoule components. Shaking the ampoule The vibration is preferably within the range of 25 to 100 Hz, and one end of the ampoule is used as the vibration source. This is done by fixing. Any conventional vibration means may be considered by the present invention. available. After the reaction is complete, the ampoule is cooled at a slow, controlled rate.

Once a homogeneous polycrystalline material is obtained, this material can be further processed to obtain a highly A defect-free bismuth chalcogenide single crystal can be obtained. For example, bridge Single crystal methods such as Mann method, Czochralski method and zone purification method (recrystallization method) Any known means of growing can be used. In particular, band purification produces high-purity single crystals. It has been proven to be highly effective in obtaining

Zone refining consists of a quartz port containing a seed crystal of the desired lattice structure (e.g. hexagonal lattice structure). This will be carried out during the training session. It is desirable to maintain a clean room level of 100 class. stomach. Orient the seed crystal in the boat so that the crystal layer is horizontal. The entire device is a ring. should be shock mounted to protect against environmental vibrations. bowl of polycrystalline material ( boule) 44 is placed in surface contact with the seed crystal.

The furnace consists of two parts, an outer furnace and a polycrystalline material to maintain high temperatures along the entire length of the bowl. and a unidirectionally movable narrow zone for heating a small portion. Polycrystalline outer furnace The temperature is maintained at 35 °C below the melting point of the polycrystalline material, and a zone 2-3 cm long is The temperature is maintained at 10°C above the melting point of the material. Polycrystalline material in the above first treatment step Unlike quality manufacturing, the bowl can be quickly heated to working temperature. The obi region is first placed at the seed crystal/bowl interface and this region is heated to the melting point of the material. . The band is then gradually moved along the length of the bowl. Band movement speed depends on the composition The specific speeds are shown in Table 2 along with other process parameters. band Travel speed is an important processing parameter. If this speed is too high, crystallization It becomes incomplete and defects are formed. If this rate is too slow, the layer will become distorted. A problem arises. Remove the lower part of the heat-treated bowl that contacts the quartz port before use. It is preferable.

Table 2. Processing conditions for growth of hexagonal single crystal Processing conditions Bi2Te3 Bi2T e3 BI2S3I2S3 Pomo 5℃ M, -35°CM, -35°CM, -35 °C band temperature 10°C M, +10°C Mp +10°C M, +10°C band movement speed 8mm/hour 6mm/hour 3mm/hour Cooling rate 50℃/hour 40℃/hour 3 5°C/hour By slightly modifying the above method, it is possible to produce crystals with a rhombohedral crystal structure, In this case, rhombohedral variety crystals are used in the zone purification process. In addition, rhombohedral crystals In order to obtain The area is maintained at the melting point of the polycrystalline material.

Preferably, a single crystal insertion compound, most preferably bismuth chalcogenide, is used as described above. A method is used to grow a single crystal electrode structure. For example, one embodiment of the present invention As an embodiment, it has a rectangular shape with sides of 4 mm length and 5 mm length, and has a length of 0.5 to 1 m. A single crystal bismuth chalcogenide having a thickness of m is produced. fan inside this crystal Metallize one of the planes of the single crystal material that is perpendicular to the plane of the Del Waals channel It is preferable to do so. This metallization may consist, for example, of nickel paste, which coated on top of the crystal to form a 10-20 micron thick metal layer. This metallization In addition to providing electrical contact to the crystal piece, it also strengthens the rigidity of the crystal piece. Ru.

Alternatively, this single-crystal bismuth chalcogenide material can be finely pulverized and used to form electrodes. such powdered materials are easier to process than single-crystalline materials; be managed. The crystal pulverization method is carried out using, for example, a ball mill device or other pulverization device. to obtain single crystal particles preferably each having a diameter of about 70 microns. be able to. Other particle sizes may be more preferred depending on the particular case. crystal The particles are then mixed with a suitable compound to bind the crystal particles together. In reality The mixture acts to “glue” the particles together, but it also separates the particles from each other completely. Do not provide complete electrical insulation. The binder material is selected depending on the electrolyte. Non When using protic electrolyte solvents, the binder is preferably carboxymethyl It consists of a 3% aqueous solution of cellulose into which the particles are mixed: Alternatively, alternative binders such as a 5% polyethylene dispersion in n-hexane may be used. I can be there. The resulting powder-binder mixture is placed in an electrode at room temperature. dry. Determined by the type, the external form of the electrode is e.g. It is a commonly used disk shape with an electrode thickness of 0.3-1 mm. alternative Other electrode surface configurations can also be used.

The above milling methods result in some crystal damage and corresponding crystal defects. However, the insertion Due to the weak van der Waals attraction between the crystal layers of these compounds, can be easily accessed along the length of the channel without the risk of significant lattice damage or distortion. I'm concerned.

Electrodes formed using the above method can be used in any of a variety of capacitor configurations. be able to. With respect to Figure IA (not drawn to scale), in one form, chalcogenide The capacitor 10 including the bismuth oxide electrode 20 is manufactured as follows. condensation The sir electrode 20 may be composed of either a single crystal piece or a crystal powder compact. placed in contact with a specific electrolyte 30 supported by a conductive container 35. be placed. Ideally, this conductive container would be ideally non-polar. larizable) substance. For example, consider a power source 40 such as a battery. electrically coupled to the electrode 20 via a conductor 45, such as a wire; It is coupled to the conductive container 45 via a similar conductor 50.

The electrolyte 30 is suitably an aqueous alkaline solution, or preferably a propylene carcinogen. Consisting of 1.0M LiClO4 in carbonate. Each layer is 100 μm thick and A separator consisting of two layers of non-woven polypropylene saturated with solution solution. ator) mechanically supports the electrolyte. Alternatively, for various electrode materials, The solution is of perchlorate in a mixture of propylene carbonate in dimethoxyethane. 1.2M solution of organic cation, aqueous potassium hydroxide solution, aqueous solution of -valent metal sulfate , or other aqueous solutions.

Referring also to Figure IB, in the second capacitor configuration 20, two identical Calco The bismuth hydrogenide electrodes 20 are separated by an electrolyte 30. LiClO4 mentioned above Apply a suitable voltage to the polypropylene separator using a propylene carbonate electrolyte. It is impregnated with a solute solution and placed between the electrodes 20. separated by a separator The electrodes held in place are then inserted into a support frame (not shown) and placed in a press mold (p Seal with ressing form). The power source 40 is connected to a similar conductor 45 (e.g. electrically coupled to each electrode 20 by a good conductive wire).

Electrolytic capacitors with electrodes of an insertion compound, preferably bismuth chalcogenide can provide a large surface area when used as a capacitor. van der Waals of bismuth chalcogenide to give an increased surface area. Channels must be processed or “trained” . As explained above, the van der Waals channel surface is After the electrolysis, the macroscopic surface of the electrode forms a double layer. The liquid forms a double layer. Therefore, “training is electrolyte (and ion) is driven in the van der Waals channel to cause electrolyte to flow into the channel and It is the process described below that facilitates outflow from the channel.

Regarding Figure 2A, the two chalcogenated bisma at the beginning of the training process 2 shows a capacitor 60 having space electrodes 20a, 20b. electrode van der waer The sizes of the channels 70a, 70b are greatly exaggerated for clarity; Recall that the electrode consists of on the order of 10' to 107 such channels. There must be. An electrolytic solution 30 based on LiC1 (L) is placed between the two electrodes. be done. During the training process, the power supply 40 is powered by Farad for cation insertion. – The voltage is set to give a voltage greater than the capacitor voltage. It depends directly on the particular combination of electrode material and electrolyte used. Specific electrode-electrolyte combinations If one assumes that the corresponding Faradaic potential is You may recognize that it is determined from the standard table.

At the beginning of electrode training, a voltage exceeding the Faraday voltage is applied to the capacitor. If the electrode 20b is coupled to the positive terminal of the power supply, it will accumulate a positive surface charge. . The surface of the van der Waals channel 70b of the electrode similarly has this positive surface charge. Accumulate. Correspondingly, the macroscopic surface of electrode 20a coupled to the negative terminal of the power supply A negative surface charge is accumulated with respect to the surface of the Nderwaals channel 70a.

Depending on the form of this surface charge, free Li+ ions 72 have favorable charge and energy. - due to the morphology and their ionic radius is the width of the van der Waals channel. Since it is relatively smaller than the above, it easily enters the negatively charged electrode 20a. moreover, The solvated Li complex 74 migrates towards the negatively charged electrode surface and forms a solvated ClO4 -”The complex 76 moves in the direction of the positively charged electrode surface. It has a width of 3-4λ (to van der Waals of the positively charged electrode (during its formation before the training process) Channels 70b are too small and ClO4- complexes penetrate inside them. However, the solvated L-pi complex is It slightly penetrates into the four-width channel 70a and is released along with the free i4 ions onto the electrode surface and the electrode surface. effectively carried within the polar channels. As a result, the solvated L14 complexes show that they are negatively Slightly enlarge the channel that partially enters the charged electrode.

To infiltrate the solvated L-bicomplex into the opposite electrode: 20 bl, reverse the polarity of the power supply. Ru. The accumulated surface charge distribution then reverses: the previously positively charged electrode now accumulates a negative surface charge and attracts free Li+ ions 72 and solvated complexes 74. Ru. , free L14 ions 72 readily enter the channel and the solvated complex 74 re-pairs. partially into the van der Waals channel, thereby slightly extending the channel. Enlarge the crab.

With respect to FIG. 2B, repeating this process of switching voltage polarity on electrode 20a1 20b, each van der Waals channel is gradually enlarged. this process Throughout, the voltage increases depending on the initial applied voltage, thereby van del Enhances the attraction of ions and electrolytes to the Waals channel. As shown in the figure , at the midpoint of the training process, the solvated L-bicomplex 74 and the free Li' ion completely penetrates the enlarged channel 70b of the now negatively charged electrode 70b. .

However, the solvated ClO4− complex, which is larger in size than the solvated Li+ complex, is now However, it is still not possible to completely penetrate the channel of the positively charged electrode 70a.

At the end of the training process period, referring to FIG. 20, the solvated CIO, -R body 76 and solvated Li complex 74 are van der Waer of both electrodes 20a and 20b. It is possible to completely penetrate the rus channels 70a, 70b. As shown in Figure 2D. Therefore, at this time, an electrically neutral electrolyte (CIO, -complex and L i1 complex) completely penetrates the van der Waals channel and charges van der Waals of each electrode in a manner similar to that which occurs at the macroscopic surface of the poles. Electric charges 80.82 and 84.86 are applied to the electrode-electrolyte interface through the gas channel. A double layer can be formed. Penetration of electrolyte through crystal channels is achieved by the present invention. to achieve significant capacitance and energy storage increases provided by form the basis for

Permeating the electrolyte and its solvated ionic species within the van der Waals channels of the electrode The degree of training required to achieve this depends on the specific combination of electrode material and electrolyte used. depends decisively on Van der Waals before undergoing the training process The width of the channel and the radius of the solvated complex in the electrolyte determine the training required. : If the radius of the complex is large (and the width of the van der Waals channel is small, The required training time will be longer. Electrode materials Bf2Te3 and LiCl04 Based on (with respect to electrolytes, training is preferably done by each cycle) Approximately 20 training cycles of approximately 30 minutes each, reversing the polarity of the power supply. Consisting of icules. However, for specific capacitance requirements, this trace can be adjusted. With less training, within the mild channel Electrolyte penetration is obtained, resulting in a correspondingly low double layer capacitance. follow Therefore, training should be optimized to obtain the maximum possible capacitance of a constant electrode. It should be made larger. Those skilled in the art will appreciate that certain electrode-electrolyte combinations and capacitance It will be understood that training operations are determined empirically with respect to targets. .

Alternative training processes are also within the contemplation of the present invention. For example, the above process voltage polarity can be kept constant or a charging/discharging process can be used. can be used to widen the van der Waals channel. like this The process involves applying a voltage above the Faradaic potential between the electrodes in the manner described above. for a period of time and then discharge the capacitor through a suitable load. this pro If the voltage polarity is kept constant during the training process, or if the If the voltage polarity is not switched during the process, it depends on the electrode material and electrolyte composition. Therefore, one of the electrodes may not reach channel expansion. For example, if the voltage polarity is constant Based on Bi = Tes electrode and L i CI O <- for the training operation that is When using an electrolyte with a negative polarity, free and solvated Li+ ions are A positive electrode is inserted (thereby containing the electrolyte), but the positive electrode remains free and The solvated i''' ion has the benefit of starting to open its lattice channels. , whereby the solvated ClO4- ions enter such channels for electrolyte accommodation. as a result, the positive polarity electrode does not enlarge the van der Waals surface. It will be bad.

A capacitor designed with a single-insertion compound-electrode (Figure IA) can also be used using the above method. It is important to note that the training will be carried out in the following manner. Voltage application and voltage polarity reversal The process combines free and solvated Li-ion solvated clo4- ions into an electrode. to accommodate the electrolyte within the electrode to achieve the desired electrode surface enlargement. bring about the possibility of achieving

This training process deforms the crystal planes of the layered crystal electrode material to a significant degree. Of particular importance is the fact that it does not cause any damage or distortion. The degree of deformation of the crystal plane depends on the appearance of the electrode material. related to purity and defect density and other properties resulting from the growth process: The fact that there are almost no phase defects means that there are almost no crystal plane deformations caused by training. become. At the end of the training, the crystal planes should have little or no strain (if not, Van der Waals channels in the electrode are easily penetrated by electrolyte ions Reserving the possibility, a bilayer can accordingly be generated within a short time.

The training process pushes van der Waals channels beyond their elastic limits. It is said that the channel will not shrink to a smaller size later. The fact that this is true is also important.

Referring now to FIG. 3, the first and second capacitors are separated by a resistor 96. As a circuit 90 having an applied voltage 40, the circuit 90 includes a capacitor. electrically model the Resistance 96 is the resistance of the electrolyte and is typically about 0°. 003Ω. In a single-insertion compound-electrode capacitor (Figure IA), the first A capacitor 92 corresponds to the double layer capacitance of the electrode 20 and a second capacitor 9 4 corresponds to the capacitance of the conductive container 35. In fact, the container material As a result of the material, this capacitance is several orders of magnitude smaller than the capacitance of the electrode 20. Sai. As a result, the series capacitance of the two capacitors is the smaller capacitor. -94. Therefore, the double insertion compound capacitor (Fig. IB) is a more preferred system; in this case two capacitors 9 2.94 represents the double layer capacitance of the two electrodes 20. Each electrode is configured the same , exhibiting the same capacitance, the total series capacitance of the capacitors is become maximum.

A dual electrode capacitor of the design and material described above was manufactured, which farad/cm" and has an internal resistance of about 0.02 Ω/cm2. This extreme The low internal resistance gives the capacitor discharge the possibility of achieving high power. theoretical A pure, defect-free bismuth chalcogenide single crystal capacitor structure is 1000 farad/cm3 is shown. Double layer capacitor with Bi2Te3 electrodes - was charged to 2.6 volts and observed, but the specific energy did not change until 1000 cycles. showed no decrease in energy. Table 3 below shows the specific energy of this capacitor based on the corresponding voltage. Shown for solution solution.

0.5M LiCIO470 in PC IMI in PC, i CI O4105 1.5M LiCIO498 in PC In addition to capacitor materials and training schemes embodiments are also intended to be included within the spirit and scope of the invention.

International search report T7.38°, 7. ,. 4□,,,,,,,-,,-,,,, ,,j/US 92109244Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, SE), 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD, TG), AT, AU, BB, BG, BR, CA, CH, C3゜DE, DK, ES, FI, GB, HU, JP, KP, KR, LK, LU, MG, MN, MW, NL, No, PL, RO, RU, SD , SE, U.A. (71) Applicant Kovalyuk, Zakhar Bui - Republic of Laflina 2740018 7 (71) Enzzyastov Street, Chernivtsi, applicant Cosmi Ivan Bui - Chernovtsi, Bakinskaya Street, Rakhlin Republic REIT 9/37 (71) Applicant Barmachuk, Bogdan Pilafryna Republic Ivanovhra Nkovsk Region, Sunyatin District, Zavoltov, Zavodos Kaya 6 (72) Inventor: Grigorchak, Ivano, Republic of Ivan Aira Flaina Frankovsk Region, Sunyatin District, Zavoltov, Podo Barnaya Street Ga (72) Inventor: Tovstoyuk, Korney Bui - Republic of Laflina 2900 18 Livoff, Staring Zassskaya 60/3 (72) Inventor: Kovalyuk, Zakhar Bui - Republic of Laflina 2740018 　Chernovtsi, Enzzyastov Street 7A47゛ (72) Inventor: Cosmic, Yvan Bouy - Chernovts, Republic of Laflina Bakinskaya Street 9/37 (72) Inventor: Barmachuk, Bogdan Pilav Ivanovra Republic of Phryna Nkovsk Region, Sunyatin District, Zavoltov, Zavodos Power 6

Claims (1)

[Claims] 1. Double layer electrolytic capacitor containing two electrodes, each in contact with a common liquid electrolyte - wherein at least one of the electrodes has a van der Waals channel. the Van der Waals channel comprises a crystalline material characterized by is adapted to contain an electrolyte within, thereby applying a voltage to the two electrodes. A double layer of charge is formed at the interface between the van der Waals channel and the electrolyte. said capacitor. 2. The capacitor of claim 1, wherein both electrodes include said crystalline material. 3. 3. A capacitor according to claim 2, wherein said two electrodes each include a single crystal of said crystalline material. . 4. 3. A computer according to claim 2, wherein said two electrodes each include single crystal powder particles of said crystalline material. Denser. 5. 6. A capacitor according to claim 2, wherein said crystalline material is bismuth chalcogenide. The crystalline substance is Bix(Te3-ySey) [where x is 1 or 2 and y is 3. The capacitor according to claim 2, comprising a solid solution of 0 to 3. 7. The electrolyte comprises a 1.0 M LiCIO4 solution in propylene carbonate. 6. The capacitor according to claim 2 or 5. 8. The electrolyte is a supersalt in a mixture of propylene carbonate in dimethoxyethane. 6. A method according to claim 2 or 5, comprising a 1.2M solution of an organic cation of a mate salt. condenser. 9. 3. The capacitor 10 of claim 2, wherein the electrolyte includes an aqueous solution of potassium hydroxide. ．． 3. The capacitor of claim 2, wherein the electrolyte comprises an aqueous solution of a sulfate of a monovalent metal. 11. One of the electrodes includes a conductive container in which the electrolyte is placed. 2. A capacitor according to claim 1, wherein a liquid and the other of said electrodes are disposed. 12. The single crystal powder may include single crystal grains having a maximum size of about 70 microns. The capacitor according to claim 4. 13. Claim further comprising a binder for binding the single crystal powder particles to each other. 12. The capacitor according to 12. 14. 14. The binder of claim 13, wherein said binder comprises 5% polyethylene dispersed in acetone. mounted capacitor. 15. 13. The binder comprises a 3% carboxymethylcellulose solution in water. Capacitors listed. 16. the van der Waals channel is in the van der Waals channel; A training process involving the insertion of electrolyte into the The capacitor according to claim 2 or 5. 17. the insertion is caused by applying a voltage between the electrodes, and the voltage is applied to the channel. 17. The condenser of claim 16 which is sufficiently high to achieve solvated ion complex penetration of the solvent. Sir. 18. 18. The capacitor of claim 17, wherein the polarity of the voltage is periodically reversed between the electrodes. Sir. 19. The voltage is set to a first voltage sufficient to cause a Faraday process in the electrolyte. voltage to a second voltage sufficient to achieve electrolyte penetration of said channels. 20. The capacitor of claim 18, wherein the capacitor is increased by 100%. 20. 20. The capacitor of claim 19, wherein the voltage is applied to the electrode for about 600 minutes. -. 21. 21. The capacitor of claim 20, wherein the polarity of the voltage is reversed about every 30 minutes. -. 22. 19. The capacitor of claim 18, wherein the capacitor is periodically discharged across a resistive load. .