EP2032732A1 - Hydrogen activating material and consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells - Google Patents

Hydrogen activating material and consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells

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Publication number
EP2032732A1
EP2032732A1 EP06780811A EP06780811A EP2032732A1 EP 2032732 A1 EP2032732 A1 EP 2032732A1 EP 06780811 A EP06780811 A EP 06780811A EP 06780811 A EP06780811 A EP 06780811A EP 2032732 A1 EP2032732 A1 EP 2032732A1
Authority
EP
European Patent Office
Prior art keywords
consumption controlling
water
cell
iron
soluble electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06780811A
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German (de)
French (fr)
Other versions
EP2032732A4 (en
Inventor
Yasuo Sakakura
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Individual
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Individual
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Publication date
Application filed by Individual filed Critical Individual
Publication of EP2032732A1 publication Critical patent/EP2032732A1/en
Publication of EP2032732A4 publication Critical patent/EP2032732A4/en
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a hydrogen activating material capable of activatinghydrogen to improve thereactivity of hydrogen. It also relates to a consumption controlling material for water-soluble electrolyte chemical cells capable of improving the consumption controlling performance of the water-soluble electrolyte chemical cells. It further relates to a consumption controlling material for fuel cells capable of improving the consumption controlling performance of the fuel cells.
  • Patent Document 1 JP-A 8-275413 and Patent Document 2: JP-A 6-37479
  • germanium and selenium which may be alloyed with iron.
  • Alloys containing iron and semiconductor components such as silicon, have properties that have not yet been elucidated and may be utilized in various uses possibly.
  • the present invention therefore has an object to find out new uses of the iron-semiconductor alloy such as silicon-iron.
  • the present invention provides a hydrogen activating material, a hydrogen activating agent , or ahydrogen activating composition , including as a major constituent an iron-semiconductor alloy containing iron and semiconductor components .
  • the iron-semiconductor alloy containing iron and silicon ' is capable of improving the consumption controlling performance of water-soluble electrolyte chemical cells such as manganese dry cells , alkaline drycells, oxiride drycells, rechargeable nickel-hydrogen cells and nickel dry cells.
  • the present invention provides a consumption controlling material, consumption controlling agent or consumption controlling composition for water-soluble electrolyte chemical cells, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor to improve the consumption controlling performance of the water-soluble electrolyte chemical cells.
  • the iron-semiconductor alloy containing iron and silicon is capable of improving the consumption controlling performance of fuel cells.
  • the present invention provides a consumption controlling material, consumption controlling agent or consumption controlling composition for fuel cells, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor to improve the consumption controlling performance of the fuel cells.
  • iron-semiconductor alloy such as silicon-iron can be found for hydrogen activating and for consumption controlling of the water-soluble electrolyte chemical cells and the fuel cells, or the like.
  • Fig. 1 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in an alkaline dry cell
  • Fig. 2 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in an oxiride dry cell;
  • Fig. 3 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in a nickel-hydrogen cell;
  • Fig. 4 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in a manganese dry cell;
  • Fig. 5 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in a nickel dry cell
  • Fig. 6 is a graph illustrating variations with time in voltage with and without a consumption controlling material for fuel cells according to the present invention located in a fuel cell ;
  • Fig. 7 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in a lithium-manganese dioxide cell.
  • the semiconductor may include: element semiconductors such as silicon (Si), germanium (Ge), tin (Sn), selenium ( Se) , and tellurium (Te) . It may also include a compound semiconductor such as GaAs, GaP, GaSb, AlN, AlP, AlAs, AlSb, InP, InAs, InSb, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlGaAs, GaInAs, AlInAs, and AlGaInAs.
  • silicon is preferable.
  • the hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells , or the like , maycontain other components such as nickel (Ni) , aluminum (Al) , manganese (Mn), carbon (C) , chromium (Cr) , molybdenum (Mo) , tungsten (W) , vanadium (V) , cobalt (Co) , titanium (Ti) , titaniumnitride (TiN) , zirconium (Zr), niobium (Nb), tantalum (Ta), beryllium (Be), group 11 elements (IB) (gold, silver, copper, unununium) , graphite, fluorine compounds , and far infrared radiant material such as ceramics, than iron and semiconductor.
  • other components such as nickel (Ni) , aluminum (Al) , manganese (Mn), carbon (C) , chromium (Cr) , mo
  • the consumption controlling performance refers to the performance of suppressing cell consumption and efficient discharge suppresses the cell consumption and extends the cell life.
  • the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells according to the present invention are characterized in that efficient discharge retains a high voltage and suppresses the cell consumption at the same time.
  • the content of the semiconductor is preferably 1-20 wt. %, and more preferably 1-10 wt . %.
  • the content of iron is preferably 78-98 wt . %, and more preferably 86-96 wt. %.
  • That thehydrogen activatingmaterial or the like according to the present invention activates nearby hydrogen can be understood from the fact that the rechargeable nickel-hydrogen cell having an improved consumption controlling performance discharges through a solid phase reaction of hydrogen as shown in Formula 1.
  • the hydrogen activating material In the hydrogen activating material according to the present invention, different types of atoms cause an electrochemical potential across iron and semiconductor crystals.
  • the electrochemical potential exerts a reverse piezoelectric effect on the semiconductor to cause a mechanical strain. Repeated occurrences of such the strain vibrate the semiconductor, which radiates vibrating-electromagnetic waves to external.
  • the semiconductors contained in the iron- semiconductor alloys have various shapes and sizes and cause various electrochemical potentials , radiating vibrating-electromagnetic waves of various frequencies accordingly.
  • Such the electromagnetic waves attack hydrogen atoms having a magnetic moment , exciting hydrogen atoms and activating them.
  • the electromagnetic waves generatedfromthehydrogenactivatingmaterial canbe considered to especially attack hydrogen atoms in the vicinity of the material, which performs chemical reactions and contributes to chemical reactions or the like.
  • the present invention provides an hydrogen activating method, which comprises irradiation of electromagnetic waves to the iron-semiconductor alloy containing iron and semiconductor components to activate hydrogen in the vicinity of the alloy.
  • the present invention also provides a method, which comprises irradiation of electromagnetic waves to the iron-semiconductor alloy containing iron and semiconductor components to improve the consumption controlling performance of water-soluble electrolyte chemical cells and fuel cells .
  • the present invention further provides a hydrogen activating material, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor components , which enhances activation of nearbyhydrogen on irradiation of electromagnetic waves thereto .
  • the present invention provides a consumption controlling material, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor components, which improves the consumption controlling performance ofwater-soluble electrolyte chemical cells and fuel cells of nearby hydrogen on irradiation of electromagnetic waves thereto .
  • the irradiatedelectromagneticwaves mayinclude alight (electromagnetic wave) emitted from an incandescent lamp.
  • the light propagates in the vicinity and is transmitted and propagated to clamps such as a bulb socket, bulb reflectors (mirror, plate), and cords.
  • clamps such as a bulb socket, bulb reflectors (mirror, plate), and cords.
  • it receives electromagnetic waves from various lights such as headlights, lamps and meters, engines, motors, and batteries, even if the hydrogen activating material or the like is not directly subjected to irradiation. Even where the consumption controlling material is shielded from light, it may receive the influence of electromagnetic waves radiated from bulbs and so forth.
  • the electromagnetic waves irradiated to the alloy include electromagnetic waves with wavelengths of from 1 nm to 1 mm, preferably electromagnetic waves ranging from visible beams to far infrareds with wavelengths of from 380 nm to 1 mm.
  • the electromagnetic waves irradiated include sunlight and white light.
  • the range of activation of hydrogen influenced from the hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells according to the present invention depends on the amount of the iron-semiconductor alloy, the temperature condition, the humidity, and the wavelengths, amplitude, waveforms and intensity of the electromagnetic waves irradiated.
  • the hydrogen influenced from the hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells and so forth according to the present invention may have shapes that are not specially limited but may be formed preferably in the shape of a plate (plates or thin pieces) or a foil.
  • the iron-semiconductor alloy employed in the present invention can be produced through steel making with addition of a semiconductor such as silicon to the melt of iron. After completion of the steel making, the melt of iron is injected into a mold to form an ingot. The ingot is heated at about 1250 0 C , and then theproperties of the alloyare established toproduce a slab. The slab is next heated up to 1000 0 C or higher, then gradually thinned to a thickness of severalmmthroughhot rolling under load of about 2 ton/mm in the roll width to produce the iron-semiconductor alloy.
  • a semiconductor such as silicon
  • the hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells according to the present invention are located in the vicinity of respective aimed objects to exert respective functions.
  • the consumption controlling material for water-soluble electrolyte chemical cells it may be installed in a cell case.
  • the present invention provides a method for improvement of the consumption controlling performance of water-soluble electrolyte chemical cells and fuel cells, comprising locating an iron-semiconductor alloy containing iron and semiconductor components in the vicinity of the cells.
  • examples of the water-soluble electrolyte include ionic aqueous solutions such as an aqueous solution of potassium hydroxide, an aqueous solution of zinc chloride, an aqueous solution of sodium hydroxide and an aqueous solution of lithium hydroxide, and do not contain any organic solvent or the like.
  • the consumption controlling material according to the present invention can not improve the consumption controlling performance of cells that use an organic solvent system, such as a lithium-manganese dioxide cell.
  • Examples of the hydrogen activating material according to thepresent invention are describednext .
  • ahydrogen activating material water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material
  • a thin plate of silicon-iron containing 90.5 wt. % or more iron, 3.0 wt. % or less silicon, and others such as 0.5 wt. % or less carbon, 1.5 wt. % or less manganese, 2.0 wt. % or less aluminum, 2.5 wt. % or less nickel and so on
  • silicon-iron containing 90.5 wt. % or more iron, 3.0 wt. % or less silicon, and others such as 0.5 wt. % or less carbon, 1.5 wt. % or less manganese, 2.0 wt. % or less aluminum, 2.5 wt. % or less nickel and so on
  • the hydrogen activating material (water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material) according to this example was cut out for preparation of 50 mm long x 13 mm wide x 0.05 mm thick samples. A transparent polyester film with a thickness of 0.1 mm was laminated on this piece.
  • a hydrogen activating material water-soluble electrolyte consumption controlling material, fuel cellconsumptioncontrollingmaterial
  • a thin plate of silicon-iron containing 87 wt. % or more iron, 6.5 wt. % or less silicon, and others such as 0.5 wt. % or less carbon, 1.5 wt. % or less manganese, 2.0 wt. % or less aluminum, 2.5 wt . % or less nickel and so on
  • the hydrogen activating material water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material
  • the hydrogen activating materials (water-soluble electrolyte consumption controlling materials, fuel cell consumption controlling materials) according to the first and second examples were installed on the bottoms of cell cases, on which respective dry cells were located one by one.
  • the cell case (for one dry cell, item number: UM3X1, available from Morikawa Kogyo Inc . ) contains the dry cell ( size : 6 ( IEC) ) therein .
  • the cell case was connected via a lead with a length of 480 mm (item number: 10/0.14A, 1.5 ⁇ , available from Sanko Denki Inc. ) and a bulb socket (item number: ES-T238-C (ElO) , available from Tozai Denki Sangyo Inc. ) to a bulb (FLASHLIGHT BULB, available fromTozai Denki Sangyo Inc . ) .
  • Avoltmeter DigitalMultimeter, R6441A, available from Advantest Inc. was used to measure variations in voltage.
  • an alkaline dry cell (LR6/primary cell, available from MatsushitaKandenchiKogyo Inc. ) was preparedforthe experiment .
  • this alkaline dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the first example was installed.
  • a comparative example 1 the alkaline dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed.
  • the temperature in the room during measurement was kept at 18-20 °C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix).
  • the cell cases of the embodiment 1 and the comparative example 1 were located on an office table at an interval of 1 m to measure voltages every 10 minutes. The results are shown in Table 1 and Fig. 1.
  • oxiride dry cell (ZR6(Y) /primary cell, available from MatsushitaKandenchiKogyoInc. ) was preparedforthe experiment .
  • this oxiride dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the second example was installed.
  • the oxiride dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed.
  • the temperature in the room during measurement was kept at 18-20 0 C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix).
  • the cell cases of the embodiment 2 and the comparative example 2 were located on an office table at an interval of 1 m to measure voltages every 10 minutes. The results are shown in Table 2 and Fig. 2.
  • a nickel-hydrogen cell (Ni-MH AA/1.2V, secondary cell, available from Sony Inc. ) was prepared for the experiment.
  • this nickel-hydrogen cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the first example was installed.
  • a comparative example 3 the nickel-hydrogen cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed.
  • the temperature in the room during measurement was kept at 18-20 0 C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix).
  • the cell cases of the embodiment 3 and the comparative example 3 were located on an office table at an interval of 1 m tomeasure voltages every 10 minutes. The results are shown in Table 3 and Fig. 3. Table 3
  • a manganese dry cell (R6/primary cell, available from Toshiba Denchi Inc.) was prepared for the experiment.
  • this manganese dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the second example was installed.
  • the manganese dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed.
  • a transparent tape 40 mm long x 15 mm wide
  • a sample was prepared as an embodiment 5 by irradiating the sample according to the embodiment 4 with incandescence for a spot light (item number: OE855450, available from ODELIC Co. , Ltd) of 15,000 luxes (Ix) from 500 mm distant position.
  • a spot light (item number: OE855450, available from ODELIC Co. , Ltd) of 15,000 luxes (Ix) from 500 mm distant position.
  • These embodiments 4 and 5 and the comparative example 4 were experimented.
  • the temperature in the room during measurement was kept at 18-20 0 C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix).
  • the cell cases of the embodiments 4 and 5 were located on an office table at intervals of 3 m, and the cell cases of the comparative example 4 was located at intervals of 3 m from the embodiment 5 to measure voltages every 10 minutes. The results are shown in Table 4 and Fig. 4.
  • a nickel dry cell (ZR6H 4BP/primary cell, available from Toshiba Denchi Inc . ) was prepared for the experiment .
  • this nickel dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the first example was installed.
  • the nickel dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed.
  • the temperature in the room during measurement was kept at 18-20 0 C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix) .
  • a hydrogen activating material water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material
  • a thin plate of silicon-iron containing 90.5 wt. % or more iron, 3.0 wt. % or less silicon, and others such as 0.5 wt. % or less carbon, 1.5 wt. % or less manganese, 2.0 wt. % or less aluminum, 2.5 wt. % or less nickel and so on
  • the hydrogen activating material (water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material) according to this example was cut out for preparation of 25 mm long x 20 mm wide x 0.05 mm thick samples .
  • a transparent polyester film with a thickness of 0.1 mm was laminated on the pieces to prepare two laminated pieces .
  • the consumption controlling was experimentedwith respect to a fuel cell.
  • a fuel cell small fuel cell PFC-ED3, available fromDaidoMetal Kogyo Inc .
  • two pieces of the consumption controlling material for fuel cells according to the third example were arranged on positions 10 mm distant from both sides of the cell.
  • An output cord (100 mm long) from the fuel cell was connected to a motor (DC 0.5V/0.05W, available from Daido Metal Kogyo Inc. ) .
  • variations in voltage were measured every 60 seconds while any load such as a propeller was not imposed on the shaft of the motor and only the shaft was rotated. In this case, as there was the sharp variation during 180-240 seconds, the measurement was performed at finer time intervals .
  • Electric energy was generated by the hydrogen fuel subjected to reaction with oxygen extracted from the air after a hydrogen gas was supplied from a hydrogen gas can (MAX 0.3 MPa, available from Iwatani Gas Inc.) with the fuel cell.
  • a hydrogen gas was supplied from a hydrogen gas can (MAX 0.3 MPa, available from Iwatani Gas Inc.) with the fuel cell.
  • a hydrogen gas can MAX 0.3 MPa, available from Iwatani Gas Inc.
  • a lithium-manganese dioxide cell (CR2/primary cell, available from Toshiba Denchi Inc . ) was prepared for the experiment .
  • this lithium-manganese dioxide cell was mounted in a cell case (item number: UM5X2, available from IshikawaSeisakusho Inc. ) inwhichthe consumption controlling material for water-soluble electrolyte chemical cells according to the first example, processed in 25 mm long x 10 mm wide x 0.05 mm thick, was installed.
  • the lithium-manganese dioxide cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed.
  • the temperature in the room during measurement was kept at 18-20 0C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix).
  • the cell cases of the comparative examples 7 and 8 were located on an office table at an interval of 1 m to measure voltages every 10 minutes. The results are shown in Table 7 and Fig. 7.
  • the electrolyte in the lithium-manganese dioxide cell is not water-soluble and uses an organic solvent. Accordingly, the effect of the consumption controlling material according to the first example can not be exerted, as obvious from Table 7 and Fig. 7.

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Abstract

The invention provides a hydrogen activating material, which includes as a major constituent an iron-semiconductor alloy containing iron and semiconductor components. It also provides a consumption controlling material for water-soluble electrolyte chemical cells and fuel cells. In addition a hydrogen activating method is also provided.

Description

HYDROGEN ACTIVATING MATERIAL AND CONSUMPTION CONTROLLING MATERIALS FOR WATER-SOLUBLE ELECTROLYTE CHEMICAL CELLS AND FUEL CELLS
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a hydrogen activating material capable of activatinghydrogen to improve thereactivity of hydrogen. It also relates to a consumption controlling material for water-soluble electrolyte chemical cells capable of improving the consumption controlling performance of the water-soluble electrolyte chemical cells. It further relates to a consumption controlling material for fuel cells capable of improving the consumption controlling performance of the fuel cells.
Description of the Related Art
An alloy consisting of iron and silicon, that is, silicon-iron has beenwidelyutilized as ametallic soft magnetic material in various uses such as motor cores andmagnetic shields (Patent Document 1: JP-A 8-275413 and Patent Document 2: JP-A 6-37479), and as a deoxidizer in the steel industry. In addition to silicon, there are other various semiconductors such as germanium and selenium, which may be alloyed with iron.
SUMMARY OF THE INVENTION
Alloys containing iron and semiconductor components , such as silicon, have properties that have not yet been elucidated and may be utilized in various uses possibly. The present invention therefore has an object to find out new uses of the iron-semiconductor alloy such as silicon-iron.
To achieve the above object, the inventor found after repetition of eager studies that the iron-semiconductor alloy containing iron and silicon has a property capable of activating hydrogen and improving the reactivity thereof. Thus, the present invention provides a hydrogen activating material, a hydrogen activating agent , or ahydrogen activating composition , including as a major constituent an iron-semiconductor alloy containing iron and semiconductor components .
The inventor also found that the iron-semiconductor alloy containing iron and silicon ' is capable of improving the consumption controlling performance of water-soluble electrolyte chemical cells such as manganese dry cells , alkaline drycells, oxiride drycells, rechargeable nickel-hydrogen cells and nickel dry cells. Thus, the present invention provides a consumption controlling material, consumption controlling agent or consumption controlling composition for water-soluble electrolyte chemical cells, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor to improve the consumption controlling performance of the water-soluble electrolyte chemical cells. The inventor also found that the iron-semiconductor alloy containing iron and silicon is capable of improving the consumption controlling performance of fuel cells. Thus, the present invention provides a consumption controlling material, consumption controlling agent or consumption controlling composition for fuel cells, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor to improve the consumption controlling performance of the fuel cells.
As described above, in accordance with the present invention, new uses of the iron-semiconductor alloy such as silicon-iron can be found for hydrogen activating and for consumption controlling of the water-soluble electrolyte chemical cells and the fuel cells, or the like.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in an alkaline dry cell; Fig. 2 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in an oxiride dry cell;
Fig. 3 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in a nickel-hydrogen cell;
Fig. 4 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in a manganese dry cell;
Fig. 5 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in a nickel dry cell; Fig. 6 is a graph illustrating variations with time in voltage with and without a consumption controlling material for fuel cells according to the present invention located in a fuel cell ;
Fig. 7 is a graph illustrating variations with time in voltage with and without a consumption controlling material for water-soluble electrolyte chemical cells according to the present invention located in a lithium-manganese dioxide cell.
DETAILED DESCRIPTION OF THE INVENTION In the hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells, or the like, according to the present invention, the semiconductor may include: element semiconductors such as silicon (Si), germanium (Ge), tin (Sn), selenium ( Se) , and tellurium (Te) . It may also include a compound semiconductor such as GaAs, GaP, GaSb, AlN, AlP, AlAs, AlSb, InP, InAs, InSb, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlGaAs, GaInAs, AlInAs, and AlGaInAs. It may further include an oxide semiconductor such as SnO2, ZnO, Fe2O3, V2O5, TiO2, NiO, Cr2O3, Cu2O, MnO2 , and MnO . In particular, silicon is preferable. The hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells , or the like , according to the present inventionmaycontain other components such as nickel (Ni) , aluminum (Al) , manganese (Mn), carbon (C) , chromium (Cr) , molybdenum (Mo) , tungsten (W) , vanadium (V) , cobalt (Co) , titanium (Ti) , titaniumnitride (TiN) , zirconium (Zr), niobium (Nb), tantalum (Ta), beryllium (Be), group 11 elements (IB) (gold, silver, copper, unununium) , graphite, fluorine compounds , and far infrared radiant material such as ceramics, than iron and semiconductor. In the present invention, the consumption controlling performance refers to the performance of suppressing cell consumption and efficient discharge suppresses the cell consumption and extends the cell life. In particular, the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells according to the present invention are characterized in that efficient discharge retains a high voltage and suppresses the cell consumption at the same time.
In the hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells or the like, according to the present invention, the content of the semiconductor is preferably 1-20 wt. %, and more preferably 1-10 wt . %. In this case, the content of iron is preferably 78-98 wt . %, and more preferably 86-96 wt. %.
That thehydrogen activatingmaterial or the like according to the present invention activates nearby hydrogen can be understood from the fact that the rechargeable nickel-hydrogen cell having an improved consumption controlling performance discharges through a solid phase reaction of hydrogen as shown in Formula 1.
[Formula 1]
MH + NiOOH <~ M + Ni(OH)2
In the hydrogen activating material according to the present invention, different types of atoms cause an electrochemical potential across iron and semiconductor crystals. The electrochemical potential exerts a reverse piezoelectric effect on the semiconductor to cause a mechanical strain. Repeated occurrences of such the strain vibrate the semiconductor, which radiates vibrating-electromagnetic waves to external. The semiconductors contained in the iron- semiconductor alloys have various shapes and sizes and cause various electrochemical potentials , radiating vibrating-electromagnetic waves of various frequencies accordingly. Such the electromagnetic waves attack hydrogen atoms having a magnetic moment , exciting hydrogen atoms and activating them. In particular, the electromagnetic waves generatedfromthehydrogenactivatingmaterialcanbe considered to especially attack hydrogen atoms in the vicinity of the material, which performs chemical reactions and contributes to chemical reactions or the like.
Irradiation of electromagnetic waves to the hydrogen activating material according to the present invention causes severe vibrations of the semiconductor, enhancing vibrating-electromagnetic waves , and further activating nearby hydrogen atoms. Thus, the present invention provides an hydrogen activating method, which comprises irradiation of electromagnetic waves to the iron-semiconductor alloy containing iron and semiconductor components to activate hydrogen in the vicinity of the alloy. The present invention also provides a method, which comprises irradiation of electromagnetic waves to the iron-semiconductor alloy containing iron and semiconductor components to improve the consumption controlling performance of water-soluble electrolyte chemical cells and fuel cells . The present invention further provides a hydrogen activating material, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor components , which enhances activation of nearbyhydrogen on irradiation of electromagnetic waves thereto . In addition, the present invention provides a consumption controlling material, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor components, which improves the consumption controlling performance ofwater-soluble electrolyte chemical cells and fuel cells of nearby hydrogen on irradiation of electromagnetic waves thereto . The irradiatedelectromagneticwaves mayinclude alight (electromagnetic wave) emitted from an incandescent lamp. The light propagates in the vicinity and is transmitted and propagated to clamps such as a bulb socket, bulb reflectors (mirror, plate), and cords. Where mounted on vehicles and so forth, it receives electromagnetic waves from various lights such as headlights, lamps and meters, engines, motors, and batteries, even if the hydrogen activating material or the like is not directly subjected to irradiation. Even where the consumption controlling material is shielded from light, it may receive the influence of electromagnetic waves radiated from bulbs and so forth.
In the hydrogen activating method or the like according to the present invention, the electromagnetic waves irradiated to the alloy include electromagnetic waves with wavelengths of from 1 nm to 1 mm, preferably electromagnetic waves ranging from visible beams to far infrareds with wavelengths of from 380 nm to 1 mm. The electromagnetic waves irradiated include sunlight and white light. The range of activation of hydrogen influenced from the hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells according to the present invention depends on the amount of the iron-semiconductor alloy, the temperature condition, the humidity, and the wavelengths, amplitude, waveforms and intensity of the electromagnetic waves irradiated. The hydrogen influenced from the hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells and so forth according to the present invention may have shapes that are not specially limited but may be formed preferably in the shape of a plate (plates or thin pieces) or a foil.
The iron-semiconductor alloy employed in the present invention can be produced through steel making with addition of a semiconductor such as silicon to the melt of iron. After completion of the steel making, the melt of iron is injected into a mold to form an ingot. The ingot is heated at about 1250 0C , and then theproperties of the alloyare established toproduce a slab. The slab is next heated up to 10000C or higher, then gradually thinned to a thickness of severalmmthroughhot rolling under load of about 2 ton/mm in the roll width to produce the iron-semiconductor alloy.
The hydrogen activating material and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells according to the present invention are located in the vicinity of respective aimed objects to exert respective functions. Thus, where it is used as the consumption controlling material for water-soluble electrolyte chemical cells, it may be installed in a cell case. Thus, the present invention provides a method for improvement of the consumption controlling performance of water-soluble electrolyte chemical cells and fuel cells, comprising locating an iron-semiconductor alloy containing iron and semiconductor components in the vicinity of the cells.
In the water-soluble electrolyte chemical cells and the consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells according to the present invention, examples of the water-soluble electrolyte include ionic aqueous solutions such as an aqueous solution of potassium hydroxide, an aqueous solution of zinc chloride, an aqueous solution of sodium hydroxide and an aqueous solution of lithium hydroxide, and do not contain any organic solvent or the like. For example, the consumption controlling material according to the present invention can not improve the consumption controlling performance of cells that use an organic solvent system, such as a lithium-manganese dioxide cell.
First Example
Examples of the hydrogen activating material according to thepresent inventionare describednext . First , as ahydrogen activating material (water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material) according to a first example, a thin plate of silicon-iron (containing 90.5 wt. % or more iron, 3.0 wt. % or less silicon, and others such as 0.5 wt. % or less carbon, 1.5 wt. % or less manganese, 2.0 wt. % or less aluminum, 2.5 wt. % or less nickel and so on) was prepared. The hydrogen activating material (water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material) according to this example was cut out for preparation of 50 mm long x 13 mm wide x 0.05 mm thick samples. A transparent polyester film with a thickness of 0.1 mm was laminated on this piece.
Second Example Similarly, as a hydrogen activating material (water-soluble electrolyte consumption controlling material, fuel cellconsumptioncontrollingmaterial ) according to asecond example, a thin plate of silicon-iron (containing 87 wt. % or more iron, 6.5 wt. % or less silicon, and others such as 0.5 wt. % or less carbon, 1.5 wt. % or less manganese, 2.0 wt. % or less aluminum, 2.5 wt . % or less nickel and so on) was prepared. The hydrogen activating material (water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material) according to this example was cut out for preparation of 50 mm long x 13 mm wide x 0.05 mm thick samples.
The hydrogen activating materials (water-soluble electrolyte consumption controlling materials, fuel cell consumption controlling materials) according to the first and second examples were installed on the bottoms of cell cases, on which respective dry cells were located one by one. In an experiment of the consumption controlling performance, the cell case (for one dry cell, item number: UM3X1, available from Morikawa Kogyo Inc . ) contains the dry cell ( size : 6 ( IEC) ) therein . The cell case was connected via a lead with a length of 480 mm (item number: 10/0.14A, 1.5φ, available from Sanko Denki Inc. ) and a bulb socket (item number: ES-T238-C (ElO) , available from Tozai Denki Sangyo Inc. ) to a bulb (FLASHLIGHT BULB, available fromTozai Denki Sangyo Inc . ) . Avoltmeter (DigitalMultimeter, R6441A, available from Advantest Inc.) was used to measure variations in voltage.
Experiment 1 (Alkaline Dry Cell)
An alkaline dry cell (LR6/primary cell, available from MatsushitaKandenchiKogyo Inc. ) was preparedforthe experiment . In an embodiment 1 , this alkaline dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the first example was installed. In a comparative example 1 , the alkaline dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed. The temperature in the room during measurement was kept at 18-20 °C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix). The cell cases of the embodiment 1 and the comparative example 1 were located on an office table at an interval of 1 m to measure voltages every 10 minutes. The results are shown in Table 1 and Fig. 1.
Table 1
(V)
As obvious from Table 1 and Fig. 1, it is more effective at suppressing discharge from the cell in the embodiment 1 provided with the consumption controlling material according to the first example than in the comparative example 1.
Experiment 2 (Oxiride Dry Cell)
An oxiride dry cell (ZR6(Y) /primary cell, available from MatsushitaKandenchiKogyoInc. ) was preparedforthe experiment . In an embodiment 2 , this oxiride dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the second example was installed. In a comparative example 2, the oxiride dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed. The temperature in the room during measurement was kept at 18-200C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix). The cell cases of the embodiment 2 and the comparative example 2 were located on an office table at an interval of 1 m to measure voltages every 10 minutes. The results are shown in Table 2 and Fig. 2.
Table 2
(V)
As obvious from Table 2 and Fig. 2, it is more effective at suppressing discharge from the cell in the embodiment 2 provided with the consumption controlling material according to the second example than in the comparative example 2.
Experiment 3 (Rechargeable Nickel-Hydrogen Cell)
A nickel-hydrogen cell (Ni-MH AA/1.2V, secondary cell, available from Sony Inc. ) was prepared for the experiment. In an embodiment 3, this nickel-hydrogen cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the first example was installed. In a comparative example 3, the nickel-hydrogen cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed. The temperature in the room during measurement was kept at 18-200C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix). The cell cases of the embodiment 3 and the comparative example 3 were located on an office table at an interval of 1 m tomeasure voltages every 10 minutes. The results are shown in Table 3 and Fig. 3. Table 3
(V)
As obvious from Table 3 and Fig. 3, it is more effective at suppressing discharge from the cell in the embodiment 3 provided with the consumption controlling material according to the first example than in the comparative example 3.
Experiment 4 (Manganese Dry Cell)
A manganese dry cell (R6/primary cell, available from Toshiba Denchi Inc.) was prepared for the experiment. In an embodiment 4 , this manganese dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the second example was installed. In a comparative example 4, the manganese dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed. In the embodiment 4, a transparent tape (40 mm long x 15 mm wide) was used to additionally attach the consumption controlling material for water-soluble electrolyte chemical cells according to the second example onto the dry cell. In the experiment 4, a sample was prepared as an embodiment 5 by irradiating the sample according to the embodiment 4 with incandescence for a spot light (item number: OE855450, available from ODELIC Co. , Ltd) of 15,000 luxes (Ix) from 500 mm distant position. These embodiments 4 and 5 and the comparative example 4 were experimented. The temperature in the room during measurement was kept at 18-200C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix). The cell cases of the embodiments 4 and 5 were located on an office table at intervals of 3 m, and the cell cases of the comparative example 4 was located at intervals of 3 m from the embodiment 5 to measure voltages every 10 minutes. The results are shown in Table 4 and Fig. 4.
Table 4
Comparative 0.065 0.054 0.048 0.048 0.041 0.039 Example 4
(V)
As obvious from Table 4 and Fig. 4, it is more effective at suppressing discharge from the cell in the embodiments 4 and
5 provided with the consumption controlling material according to the second example than in the comparative example 4. As can been seen, it is more effective at suppressing discharge from the cell in the incandescence-applied embodiment 5 than in the embodiment 4.
Experiment 5 (Nickel Dry Cell)
A nickel dry cell (ZR6H 4BP/primary cell, available from Toshiba Denchi Inc . ) was prepared for the experiment . In an embodiment 6 , this nickel dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells according to the first example was installed. In a comparative example 5, the nickel dry cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed. The temperature in the room during measurement was kept at 18-20 0C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix) . The cell cases of the embodiment
6 and the comparative example 5 were located on an office table at an interval of 1 m to measure voltages every 10 minutes. The results are shown in Table 5 and Fig. 5.
Table 5
(V)
As obvious from Table 5 and Fig. 5, it is more effective at suppressing discharge from the cell in the embodiment 6 provided with the consumption controlling material according to the first example than in the comparative example 5.
Third Example
Next, as a hydrogen activating material (water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material) according to a third example, a thin plate of silicon-iron (containing 90.5 wt. % or more iron, 3.0 wt. % or less silicon, and others such as 0.5 wt. % or less carbon, 1.5 wt. % or less manganese, 2.0 wt. % or less aluminum, 2.5 wt. % or less nickel and so on) was prepared. The hydrogen activating material (water-soluble electrolyte consumption controlling material, fuel cell consumption controlling material) according to this example was cut out for preparation of 25 mm long x 20 mm wide x 0.05 mm thick samples . A transparent polyester film with a thickness of 0.1 mm was laminated on the pieces to prepare two laminated pieces .
Experiment 6 (Fuel Cell)
The consumption controlling was experimentedwith respect to a fuel cell. First, a fuel cell (small fuel cell PFC-ED3, available fromDaidoMetal Kogyo Inc . ) was prepared and two pieces of the consumption controlling material for fuel cells according to the third example were arranged on positions 10 mm distant from both sides of the cell. An output cord (100 mm long) from the fuel cell was connected to a motor (DC 0.5V/0.05W, available from Daido Metal Kogyo Inc. ) . Then, variations in voltage were measured every 60 seconds while any load such as a propeller was not imposed on the shaft of the motor and only the shaft was rotated. In this case, as there was the sharp variation during 180-240 seconds, the measurement was performed at finer time intervals .
Electric energy was generated by the hydrogen fuel subjected to reaction with oxygen extracted from the air after a hydrogen gas was supplied from a hydrogen gas can (MAX 0.3 MPa, available from Iwatani Gas Inc.) with the fuel cell. In an embodiment 7 , two pieces of the consumption controlling material for fuel cells according to the third example were arranged. In an embodiment 8, the entire of the embodiment 7 was covered with a black vinyl sheet and shielded from light. In a comparative example 6 , the consumption controllingmaterial for fuel cells according to the third example was not arranged. The temperature in the room during measurement was kept at 18-20
0C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix) . These measurement results are shown in Table 6 and Fig. 6.
(V)
As obvious from Table 6 and Fig. 6, it is more effective at suppressing discharge from the cell in the embodiments 7 and 8 provided with the consumption controlling material according to the third example than in the comparative example 6. As can been seen, it is more effective at suppressing discharge from the cell in the embodiment 7 not shield from light and irradiated with light than in the embodiment 8 shield from light and not irradiated with light.
Comparative Experiment (Lithium-Manganese Dioxide Cell)
A lithium-manganese dioxide cell (CR2/primary cell, available from Toshiba Denchi Inc . ) was prepared for the experiment . In a comparative example 7 , this lithium-manganese dioxide cell was mounted in a cell case (item number: UM5X2, available from IshikawaSeisakusho Inc. ) inwhichthe consumption controlling material for water-soluble electrolyte chemical cells according to the first example, processed in 25 mm long x 10 mm wide x 0.05 mm thick, was installed. In a comparative example 8, the lithium-manganese dioxide cell was mounted in a cell case in which the consumption controlling material for water-soluble electrolyte chemical cells was not installed. The temperature in the room during measurement was kept at 18-20 0C, the relative humidity at 45-49 %, and the illumination at 600 luxes (Ix). The cell cases of the comparative examples 7 and 8 were located on an office table at an interval of 1 m to measure voltages every 10 minutes. The results are shown in Table 7 and Fig. 7.
(V)
The electrolyte in the lithium-manganese dioxide cell is not water-soluble and uses an organic solvent. Accordingly, the effect of the consumption controlling material according to the first example can not be exerted, as obvious from Table 7 and Fig. 7.

Claims

1. Ahydrogen activatingmaterial, including as amajor constituent an iron-semiconductor alloy containing iron and semiconductor components .
2. The hydrogen activating material according to claim 1 , wherein saidhydrogen activatingmaterial enhances activation of nearby hydrogen on irradiation of electromagnetic waves thereto .
3. The hydrogen activating material according to claim 1 or 2 , wherein said semiconductor is silicon.
4. A consumption controlling material for water-soluble electrolyte chemical cells, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor components to improve the consumption controlling performance of the water-soluble electrolyte chemical cells.
5. The consumption controlling material for water-soluble electrolyte chemical cells according to claim 4, wherein the consumption controlling performance is further improved on irradiation of electromagnetic waves thereto.
6. The consumption controlling material for water-soluble electrolyte chemical cells according to claim 4 or 5, wherein said semiconductor is silicon.
7. A consumption controlling material for fuel cells, including as a major constituent an iron-semiconductor alloy containing iron and semiconductor components to improve the consumption controlling performance of the fuel cells .
8. The consumption controllingmaterial for fuel cells according to claim 7 , wherein the consumption controlling performance is further improved on irradiation of electromagnetic waves thereto.
9. The consumption controlling material for fuel cells according to claim 7 or 8 , wherein said semiconductor is silicon .
10. A hydrogen activating method, comprising irradiating electromagnetic waves to an iron-semiconductor alloy containing iron and semiconductor components to activate hydrogen in the vicinity of the alloy.
EP06780811A 2006-06-28 2006-06-28 Hydrogen activating material and consumption controlling materials for water-soluble electrolyte chemical cells and fuel cells Withdrawn EP2032732A4 (en)

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