JP2009283425A - Oxidation reduction-type electricity storage device using circulatory regenerated pure water as electrolyte solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolyte solution oxidation reduction-type electricity storage device with a high electric density by dissolving a high concentration vanadium salt into pure water. <P>SOLUTION: The electrolyte solution regeneration circulatory device, in which hydrogen bonding of pure water is separated by resonance electromagnetic wave in an infrared ray region and the water is enabled to have a large dissolving capacity of vanadium salt, is provided in an electrolyte solution circulatory system and the electrolyte solution undergoes circulatory regeneration to dissolve the vanadium salt stably and in high concentration. Further, an electrode auxiliary plate made of carbon fine powder and a small amount of resin, kneaded and pressure-densified, is intervened between an electrode plate and the electrolyte solution to improve a current collection efficiency, and the electrode plate is made unnecessary to contact directly with the electrolyte solution to dispense with a use of an expensive corrosion resistant metal, and the device can be provided at a low cost. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a power storage device using an oxidation-reduction action of an electrolytic solution in which an electrolytic substance whose ionic valence changes in pure water.

  Conventional batteries are charged and discharged by the chemical change of the electrodes, and have low durability and electrical density. Therefore, there are problems in realizing large capacity devices and practical use of inexpensive and high conductivity electrodes.

  Also, a redox power storage device similar to the device of the present invention using an electrolytic solution in which vanadium salt is dissolved in dilute sulfuric acid has been put into practical use. Since charging and discharging are performed by changing the ionic valence of vanadium dissolved in the electrolyte, it is possible to realize a power storage device that has no long-lived, long-capacity, large-capacity, and large installation space freedom through no electrode chemical reaction. However, due to the risk of electrolyte solution, corrosiveness, and generation of hydrogen sulfide gas, miniaturization and general dissemination are difficult.

  In addition, in order to solve the above-mentioned drawbacks, a redox type power storage device similar to the device of the present invention using an electrolytic solution obtained by diluting a stock solution obtained by dissolving vanadium having different ionic valence with dilute sulfuric acid with pure water has been developed. However, there is a problem with the solubility of vanadium salt in pure water, and it has not been put into practical use.

  As described above, the power storage device using the redox action of the vanadium electrolytes having different ionic valences has many advantages, but there are some problems to be solved for its practical use. First, there is a need for a highly concentrated, stable, easy to maintain and safe vanadium electrolyte to increase device efficiency and miniaturization.

  In addition, expensive electrode plates such as platinum and titanium alloys having high corrosion resistance and excellent conductivity are used because they are in contact with the electrolytic solution in the battery cell and collect electricity, but their general use is difficult due to their high price. There is a need for an inexpensive electrode plate or electrode device that has high corrosion resistance and excellent conductivity.

  In addition, since hydrogen gas is generated on the cathode side when the operation of the battery starts and stops and smooth operation is hindered, it is necessary to prevent hydrogen gasification and accumulation.

  In addition, when the electrolytic solution storage tank is installed outdoors, freezing of the electrolytic solution and a rise in temperature become a problem depending on the season.

  In order to solve such problems, the present inventor separated hydrogen bonds of water by resonance electromagnetic waves in the far-infrared region of 5 to 10 terahertz emitted from natural plutonic rocks, tuffs, metals, and sintered bodies thereof. The present inventors have found that the fine powder of vanadium salt can be stably dissolved by refining a cluster in which water molecules are bonded to each other and making pure water with small gaps between water molecules, thereby achieving the present invention. .

  That is, in order to solve the above-mentioned problems, the pure water electrolyte circulation regeneration device of the present invention is a resonance electromagnetic wave in the far-infrared region of 5 to 10 terahertz radiated from natural plutonic rock, tuff, metal, or a sintered body thereof. Thus, the hydrogen bond in the energy region of the far infrared region is excited and separated.

  The fact that the electrolyte circulation regenerator cuts off the hydrogen bonds of pure water and made the clusters smaller is that the air bubbled into the water that passes through this electrolysis circulation regenerator allows oxygen that has been nanobubbled into the gap It is proved by the fact that it is dissolved stably and the dissolved oxygen amount increases 1.5 to 2.5 times, and the pH of water rises 1.5 to 3 times that of ordinary pure water.

  Further, in the second oxidation-reduction type power storage device of the present invention, an electrode having increased bulk specific gravity and increased conductivity by kneading carbon fine powder with a resin binder at a weight ratio of about 90 to 95% and repeating compaction. By using the auxiliary plate on the side in direct contact with the electrode and in direct contact with the electrolyte, the electromotive force generated by the oxidation / reduction of the electrolyte or the power for charging / discharging is collected through the electrolyte with high efficiency. By supplying, the battery cell can be reduced in size and the corrosion of the electrode can be prevented.

  In the third oxidation-reduction type power storage device of the present invention, the coarse density of the sponge-like carbon charged in the electrolytic solution chamber of the battery cell for efficiently collecting the electric charge in the electrolytic solution on the cathode electrolytic solution chamber side, By making it finer than the cathode electrolyte chamber side, hydrogen gas that hinders smooth operation during battery operation is prevented from accumulating at the cathode.

  Further, in the fourth oxidation-reduction type power storage device of the present invention, by attaching a film that shields radiant heat on the outer surface of the electrolyte storage tank, the electrolyte storage tank is caused by radiant heat such as ultraviolet rays when the electrolyte storage tank is installed outdoors. It prevents the electrolyte from freezing due to temperature rise and radiation cooling of the electrolyte, and also prevents harmful electromagnetic noise from affecting the electrolyte.

  According to the present invention, the vanadium salt can be stably dissolved at a high concentration, and the electrode chamber is filled with high efficiency by the electrode auxiliary plate having a high carbon content so as to prevent hydrogen gas accumulation on the cathode side. By increasing the density of the sponge carbon, a small and highly efficient electrolytic redox power storage device can be produced at low cost.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a flowchart showing the concept of the present invention. In this power storage device, the cathode electrolyte chamber 9 and the cathode electrolyte chamber 10 having different ion valences are in contact with each other across the ion exchange membrane 11 in the battery cell, and hydrogen ions pass through the ion exchange membrane 11 during charging. The cathode electrolyte chamber moves from the cathode electrolyte chamber to the anode electrolyte chamber, and at the time of discharge, the hydrogen ions move from the anode electrolyte chamber 9 to the cathode electrolyte chamber 10, and the power is supplied to the anode electrode plate 7 and the cathode electrode plate. 8 to be taken out.

  The positive and negative electrode electrolytes are respectively stored in the positive electrode electrolyte storage tank 1 and the cathode electrolyte storage tank 2, and are circulated through the battery cells by the positive electrode electrolyte circulation pump 3 and the cathode electrolyte circulation pump 4, so that the battery Charging / discharging is performed by moving hydrogen ions between the positive electrode and the cathode electrolyte chambers 9 and 10 through the ion exchange membrane 11 in the cell. Therefore, the charge / discharge capacity is determined by the battery cell capacity, but the charged amount is determined by the capacity of the electrolyte storage tanks 1 and 2.

  In order to make the entire device small and highly efficient, it is necessary to increase the electric density. Therefore, as a method for stably and uniformly dissolving the vanadium salt, in the present invention, natural plutonic rock, tuff, metal, and the like are used. Electrolyte circulation regenerators 5 and 6 filled with resonant electromagnetic wave generators 51 and 61 in the far-infrared region of 5 to 10 terahertz made of the sintered body are provided on the outlet side of the electrolyte circulation pumps 3 and 4 of the electrode solution circulation system. Thus, hydrogen bonds between water molecules in the electrolyte are separated, and the vanadium salt is stably dissolved at a high concentration.

  FIG. 2 is a schematic diagram of a battery cell according to the present invention, which has a positive electrode electrolyte chamber 9 and a cathode electrolyte chamber 10 with an ion exchange membrane 11 interposed therebetween. Vanadium aqueous solutions having different ion valences are circulated by circulation pumps 3 and 4. In the anodic electrolyte chamber 9 transferred from the electrolyte storage tanks 1 and 2, the tetravalent vanadium becomes a pentavalent vanadium during charging, and becomes a pentavalent vanadium during discharging. In the cathode electrolyte chamber 10, trivalent vanadium becomes divalent vanadium during charging, and divalent vanadium becomes trivalent during discharging. Ions are moved by hydrogen ions.

  The positive electrode and cathode electrolyte chambers 9 and 10 are filled with carbon sponge carbonized with pure cotton in order to efficiently collect current by the movement of electric charges in the positive electrode and cathode electrode auxiliary plates 71 and 81 of the electrolyte solution. The liquid chamber 10 is made of a material that is finer than the positive electrode electrolyte chamber 9 and has a small gap size, so that hydrogen gas is accumulated in the cathode electrolyte chamber 10 when the battery operation is stopped. Prevent obstructive driving.

  In the charge / discharge operation, 90 to 95 carbon fine powder is used to efficiently collect the charges moving through the ion exchange membrane 11 through the positive and negative electrode electrolyte chambers 9 and 10 and prevent corrosion of the metal electrode. The positive and negative electrode auxiliary plates 71 and 81 having increased bulk specific gravity and increased conductivity are mixed with the positive electrode plate 7 and the negative electrode plate 8 by pressing and kneading with a resin binder at a weight ratio of about%. Configured.

  When the electrolytic solution storage tanks 1 and 2 are separated from the battery cell and installed outdoors, the electrolytic solution temperature rise due to radiant heat such as ultraviolet rays and the electrolytic solution freezing due to radiation cooling can be prevented, or the electrolyte solution can generate harmful electromagnetic noise. In order to prevent the influence of the above, a film for shielding radiant heat is stuck on the outer surfaces of the electrolyte storage tanks 1 and 2.

Industrial applicability

  According to the present invention, it is possible to provide an electrolyte redox power storage device that is easy to perform maintenance and has a long life and a relatively large capacity at a low price. Accumulation of natural energy from electric power is possible, which can contribute to reducing greenhouse gas emissions. In addition, low-cost electricity at night can be stored and used as daytime power, which is in high demand, so that power leveling and power saving can be achieved.

FIG. 3 is a flowchart showing the concept of the present invention. These are the cross-sectional schematic diagrams of the battery cell of this invention.

Explanation of symbols

1. 1. Positive electrode electrolyte storage tank 2. Catholyte storage tank 3. Positive electrode electrolyte circulation pump 4. Catholyte circulation pump 5. Cathode electrolyte circulation regeneration device 6. Cathode electrolyte circulation regeneration device Positive electrode plate 8. 8. Cathode electrode plate Positive electrode electrolyte chamber 10. Cathode electrolyte chamber 11. Ion exchange membrane 20. Positive electrode electrolyte inlet pipe 21. Positive electrode outlet piping 30. Cathode electrolyte inlet piping 31. Cathode electrolyte outlet pipe 51. Resonant electromagnetic wave generator 61. Resonant electromagnetic wave generator 71. Positive electrode auxiliary electrode plate 81. Cathode auxiliary electrode plate

Claims (4)

  An oxidation-reduction type power storage device in which vanadium salt of an electrolyte is dissolved in pure water to form an electrolyte solution, and a device that generates electromagnetic waves in the far infrared region is provided in a circulation piping system of the electrolyte solution, .   In the oxidation-reduction type power storage device according to claim 1, the bulk specific gravity is increased and the electrical conductivity is increased by repeating compaction by kneading the carbon fine powder with a resin binder at a weight ratio of 90% to 95%. An oxidation-reduction power storage device, wherein the electrode auxiliary plate is used in contact with the electrode plate and is in contact with the electrolyte.   3. The oxidation-reduction type power storage device according to claim 1 or 2, wherein the cathode chamber is narrower than the cathode chamber, in a sponge shape, in the electrolyte chamber divided between the cathode and cathode across the ion exchange membrane. An oxidation-reduction type power storage device characterized by being filled with carbon fibers woven in layers with a high fiber density.   4. The oxidation-reduction power storage device according to claim 1, wherein a film that shields radiant heat is attached to an outer surface of the electrolyte storage tank.

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