The present invention relates to fuel for a fuel cell, a fuel cell and a generating method for that fuel and fuel cell made from a novel hydrogen-based/oxygen-based mixed gas obtained by vibrating and stirring and electrolyzing an electrolyte fluid.
To generate electricity from fuel cells of the related art, hydrogen is supplied to the fuel electrode (usually the negative electrode), and oxygen or air is supplied to the air electrode (usually the positive electrode). The reason for this method is that if only hydrogen is supplied to the fuel electrode, then the
2H2→4H++re−
chemical reaction does not develop. Also if a gas containing oxygen or air is not supplied to the air electrode then the chemical reaction
O2+rH++4e+→2H2O
does not occur.
A related technology disclosed in JP-A No. 348694/2002 utilized Brown's gas as a fuel for fuel cells. However in the case of this technology, a separator was required to separate the hydrogen and oxygen. This separator was a large factor in raising the unit price of the fuel. Separating the oxygen and hydrogen was of course assumed indispensable for the above chemical reactions.
Moreover forming an electrolytic layer within the fuel cell is indispensable in fuel cells up to now. The type of fuel cell also determined the type of electrolytic material for forming the electrolytic layer. For example, potassium hydroxide is the electrolytic material in alkali (soluble) fuel cells (AFC), phosphoric acid is the electrolytic material in phosphoric acid fuel cells (PAFC), lithium carbonate or potassium carbonate is the electrolytic material in molten carbonate fuel cells (MCFC), stabilized zirconium is the electrolytic material in solid oxygen fuel cells (SOFC), and ion exchange film is the electrolytic material in polymer electrolyte fuel cells (PEFC), so that the use of electrolytic materials is indispensable and these electrolytic layers prove an obstacle toward making the fuel cell more compact and inexpensive.
A first object of the present invention is to provide a fuel cell comprised of a novel hydrogen-based/oxygen-based mixed gas or hydrogen-based gas capable of being utilized in fuel cells.
A second object of the present invention is to provide a fuel for fuel cells comprised of a novel hydrogen-based/oxygen-based mixed gas or hydrogen-based gas.
A third object of the present invention is to provide a novel fuel cell not containing electrolytic layers.
A fourth object of the present invention is to-provide a fuel cell and method for generating electricity utilizing a novel hydrogen-based/oxygen-based mixed gas or hydrogen-based gas as the fuel.
In other words, in order to achieve the above objects, the present invention provides a hydrogen-based/oxygen-based mixed gas characterized in containing H and, H2 and, H3 and/or HD and, OH and, 16O, and O2. According to an aspect of the present invention, the hydrogen-based/oxygen-based mixed gas contains:
H2: 55 to 70 mole %
H: 0.12 to 0.45 mole %
H3 and HD totaling: 0.03 to 0.14 mole %
OH: 0.3 to 1.2 mole %
16O: 1.0 to 4.2 mole %
O2: 5 to 27 mole %.
In another aspect of the present invention, the hydrogen-based/oxygen-based mixed gas is obtained by utilizing a hydrogen-based/oxygen-based mixed gas generating means including:
(A) an electrolysis tank for storing the electrolyte fluid;
(B) an electrolyzing means including a pair of electrodes made from a negative electrode material and a positive electrode material installed so as to make contact with the electrolyte fluid stored inside the electrolysis tank:
(C) a vibro-stirring means for vibration-stirring of the electrolyte fluid stored inside the electrolysis tank: and
(D) a gas trapping means for trapping hydrogen-based gas and oxygen gas generated by the electrolyzing means for electrolyzing the electrolyte fluid stored inside the electrolysis tank.
To further achieve the above objects, the present invention provides a material for fuel cells made from hydrogen-based/oxygen-based mixed gas.
To still further achieve the above objects, the present invention provides a hydrogen-based gas characterized in containing H and, H2 and, H3 and/or HD and, OH. In this aspect of the present invention, the hydrogen-based gas is obtained by a hydrogen-based gas generating means including:
(A) an electrolysis tank for storing the electrolyte fluid;
(B) an electrolyzing means including a pair of electrodes made from a negative electrode material and a positive electrode material installed so as to make contact with the electrolyte fluid stored inside the electrolysis tank, and a power supply for applying a voltage across the negative electrode material and the positive electrode material;
(C) a vibro-stirring means for vibration-stirring of the electrolyte fluid stored inside the electrolysis tank: and
(D) a gas trapping means for trapping hydrogen-based gas generated by the electrolyzing means for electrolyzing the electrolyte fluid stored inside the electrolysis tank.
To further achieve the above objects, the present invention provides fuel for a fuel cell comprised of hydrogen-based gas.
To achieve the above objects, the present invention provides a fuel cell characterized in including a single cell or a stack of single cells containing a fuel electrode, an air electrode, and a hollow layer or electrolytic layer interposed between them, wherein, a supply port is formed on the fuel electrode side for supplying hydrogen-based gas obtained by a hydrogen-based gas generating means including:
(A) an electrolysis tank for storing the electrolyte fluid;
(B) an electrolyzing means including a pair of electrodes made from a negative electrode member and a positive electrode member installed so as to make contact with the electrolyte fluid stored inside the electrolysis tank, and a power supply for applying a voltage across the negative electrode member and the positive electrode member;
(C) a vibro-stirring means for vibration-stirring of the electrolyte fluid stored inside the electrolysis tank; and
(D) a gas trapping means for trapping hydrogen-based gas generated by the electrolyzing means for electrolyzing the electrolyte fluid stored inside the electrolysis tank; moreover
the fuel electrode to which the hydrogen-based gas is supplied is gas-permeable.
To further achieve the above objects, the present invention provides a fuel cell characterized in including a single cell or a stack of single cells containing a fuel electrode, an air electrode, and a hollow layer or electrolytic layer interposed between them,
wherein, a supply port is formed on the fuel electrode side or on both the fuel electrode side and the air electrode side for supplying hydrogen-based/oxygen-based mixed gas obtained by utilizing a hydrogen-based/oxygen-based mixed gas generating means including:
(A) an electrolysis tank for storing the electrolyte fluid;
(B) an electrolyzing means including a pair of electrodes made from a negative electrode member and a positive electrode member installed so as to make contact with the electrolyte fluid stored inside the electrolysis tank, and a power supply for applying a voltage across the negative electrode member and the positive electrode member;
(C) a vibro-stirring means for vibration-stirring of the electrolyte fluid stored inside the electrolysis tank; and
(D) a gas trapping means for trapping hydrogen-based gas and oxygen-based gas generated by the electrolyzing means for electrolyzing the electrolyte fluid stored inside the electrolysis tank,
and the electrode on the side supplied with the hydrogen-based/oxygen-based mixed gas is gas-permeable.
In another aspect of the present invention, the vibro-stirring means is comprised of at least one vibration generating means, and a vibration-stirring member made up of at least one vibrating rod linked to the vibration generating means and at least one vibrating blade installed on the vibrating rod.
To further achieve the above objects, the present invention provides an electrical generating method utilizing a fuel cell, and characterized by oscillating a vibrating motor at 10 to 500 Hz by utilizing an inverter, and transmitting that oscillation to a vibration adaptive absorbing means via a vibrating rod, and by oscillating the vibrating blades in one or multiple stages on the vibrating rod at an amplitude of 0.01 to 30.0 millimeters as well as a frequency of 500 to 30,000 revolutions per minute, supplies a hydrogen-based gas obtained by electrolysis during vibration-stirring of the electrolyte fluid, to the fuel cell.
To still further achieve the above objects, the present invention provides an electrical generating method utilizing a fuel cell, and characterized in that by oscillating a vibrating motor at 10 to 500 Hz by utilizing an inverter, and transmitting that oscillation to a vibration adaptive absorbing means via a vibrating rod, and by oscillating the vibrating blades in one or multiple stages on the vibrating rod at an amplitude of 0.01 to 30.0 millimeters as well as a frequency of 500 to 30,000 revolutions per minute, a hydrogen-based/oxygen-based mixed gas obtained by electrolysis during vibration-stirring of the electrolyte fluid is supplied to the fuel cell.
To yet further achieve the above objects, the present invention provides an electrical generating method for supplying electricity utilizing a fuel cell, and characterized in that by oscillating a vibrating motor at 10 to 500 Hz by utilizing an inverter, and transmitting that oscillation to a vibration adaptive absorbing means via a vibrating rod, and by oscillating the vibrating blades in one or multiple stages on the vibrating rod at an amplitude of 0.01 to 30.0 millimeters as well as a frequency of 500 to 30,000 revolutions per minute, supplies a hydrogen-based/oxygen-based mixed gas obtained by electrolysis during vibration-stirring of the electrolyte fluid, as a fuel to the gas permeable fuel electrode side or both the gas permeable fuel electrode side and the gas-permeable air electrode side of a single cell or a stack of laminated single cells containing a fuel electrode, and an air electrode, and a hollow layer interposed between the fuel electrode and the air electrode; for generating electricity.
The invention as described above, renders the following effects.
(1) The hydrogen-based/oxygen-based mixed gas or hydrogen-based gas of this invention exhibits amazingly high energy efficiency (capable of generating 2 to 3.5 times the electrical power) as a fuel for fuel cells compared to when conventional hydrogen gas is utilized. This effect is assumed to stem from the OH among the fuel elements, and further due to the H, H3 and/or HD.
(2) The hydrogen-based/oxygen-based mixed gas or hydrogen-based gas of this invention is extremely safe compared to Brown's gas and moreover is capable of being stored. The gas elements amazingly showed no changed after one to two months, and consequently maintained the electrical generating capacity as immediately after production.
(3) Conventional Brown's gas is very hazardous and cannot be compressed. However, the hydrogen-based/oxygen-based mixed gas or hydrogen-based gas of this invention is capable of being safely compressed up to approximately 100 to 300 kg/cm2 and maintains the same electrical generating capacity.
(4) The hydrogen-based/oxygen-based mixed gas or hydrogen-based gas of this invention is capable of generating 2 to 3.5 times the electrical power compared to conventional hydrogen gas when used as a fuel in conventional fuel cells.
(5) The hydrogen-based/oxygen-based mixed gas or hydrogen-based gas of this invention does not require forming an electrolytic layer which is a required condition conventional fuel cells. Instead, only a hollow layer need be installed to prevent the fuel electrode and the air electrode from shorting. The cost can therefore be reduced since no electrolytic layer is required.
(6) The fuel cell of this invention not requiring an electrolytic layer is simple to manufacture, with a low manufacturing cost, and along with lower repair costs, the probability of an equipment breakdown is also reduced.
(7) In the fuel cell utilizing conventional hydrogen gas, the gas being supplied must be heated to approximately 80° C. in order to accelerate the reaction between the hydrogen and oxygen. The temperature must also be maintained at 80° C. in order to prevent condensation. However, the hydrogen-based/oxygen-based mixed gas or hydrogen-based gas of this invention does not require heating.
The embodiments are hereafter described in detail while referring to the drawings. Members or sections in the drawings possessing identical functions are assigned the same reference numerals.
In these drawings, the reference numeral 10A denotes the electrolysis tank. An electrolyte fluid 14 is stored inside this electrolysis tank 10A. The reference numeral 16 is the vibro-stirring means. The vibro-stirring means 16 contains a base 16a installed via anti-vibration rubber on a support bed 100 installed separately from the electrolysis tank 10a; a coil spring 16b as a vibration absorbing material clamped to the bottom edge of the base, a vibration member 16c clamped to the top edge of that coil spring, a vibration motor 16d installed on that vibration member, a vibrating rod (vibration transmission rod) 16e installed on the top edge of the vibration member 16c, and a vibrating blade 16f unable to rotate and installed at multiple levels at a position immersed in the electrolyte fluid 14 on the lower half of the vibrating rod. The vibration generating means includes the vibration motor 16d, and a vibration member 16c and that vibration generating means is linked to the vibrating rod 16e. The vibration-stirring member is comprised of the vibrating rod 16e and the vibrating blade 16f, and the vibro-stirring means includes the vibration-stirring member and a vibration-generating member. The coil spring 16b may contain a rod-shaped guide member as shown later on in
Besides general-purpose mechanical vibration motors, the vibration generating means for the vibro-stirring means of the present invention may also utilize magnetic oscillating motors and air vibration motors, etc.
The vibration motors 16d vibrate at 10 to 500 Hertz controlled by the inverter 35 and more preferably vibrate at 20 to 200 Hertz and still more preferably vibrate at 20 to 60 Hertz. The vibration generated by the vibration motors 16d is transmitted to the vibrating blade 16f by way of the vibrating member 16c and the vibrating rods. The leading edge of the vibrating blade 16f vibrates at the required frequency in the electrolyte fluid 14. This vibration causes the vibrating blade 16f to generate a ripple or “flutter” from the attachment piece on the vibrating rod 16e towards the edges of the blade. The amplitude and frequency of this vibration will vary according to the motor 16d. However the amplitude and frequency are basically determined according to the interaction between the electrolyte fluid 14 and the force dynamics of the vibration transmission path. In this invention, the amplitude (vibration width) is 0.1 to 30 millimeters, and preferably 1 to 10 millimeters, and the frequency is 600 to 30,000 times per minute, and more preferably is 600 to 12,000 times per minute, and still more preferably is 600 to 7,200 times per minute, and a frequency of 1200 to 3600 times per minute is especially preferable.
The vibrating blade 16f may be made from resilient metal or plastic plate. The satisfactory thickness range for the vibrating blade 16f differs according to the vibration conditions and viscosity of the electrolyte fluid 14. However, during operation of the vibro-stirring means 16, the vibrating blades should be set to a vibration level where the tips of the vibrating blades 16f provide an oscillation (flutter phenomenon) for increasing the stirring (or agitating) efficiency without breaking the vibrating blade. If the vibrating blade 16f is made from metal plate such as stainless steel plate, then the thickness can be set from 0.2 to 2 millimeters. If the vibrating blade 16f is made from plastic plate then the thickness can be set from 0.5 to 10 millimeters. The vibrating blade 16f and clamping member 16j can be used in a state where integrated into one piece. Integrating them into one piece avoids the problem of having to wash away the electrolyte fluid 14 that penetrates into and hardens in the junction between the vibrating blade 16f and clamp member 16j.
The material for the metallic vibrating blade 16f may be titanium, aluminum, copper, steel, stainless steel, a ferromagnetic metal such as ferromagnetic steel, or an alloy of these metals. The material for the plastic vibrating blade 16f may be polycarbonate, vinyl chloride resin, or polyprophylene, etc. The plastic material on the vibrating blade may be surface-treated by electrical conduction process such as plating.
The extent of the “flutter phenomenon” generated by the vibrating blade that accompanies the vibration of vibrating blade 16f within the electrolyte fluid 14 will vary depending on the vibration frequency of the vibration motors 16d, the length of the vibrating blade 16f (dimension from the tip of clamping member 16j to the tip of vibrating blade 16f: D2 in
Preferably a length L1 shown as the first peak or a length L2 shown as the second peak is selected for the length of the vibrating blade. Here, L1 or L2 can be selected as needed, according to whether one wants to boost the path vibration or the flow.
The following results were obtained when finding L1 and L2 for vibrating blades of various thickness made of stainless steel (SUS304) and using a 75 kilowatt motor with a vibration frequency of 37 to 60 Hertz.
In this experiment, the distance from the center of the vibrating blade 16e to the tip of the clamping member is 27 millimeters. The tilt angle α on the vibrating blade 16f was made to face 15 degrees upward (+15°).
The vibro-stirring means 16 described above can be utilized in the following literature (relating to patent applications for inventions contrived by the present inventors) and vibration stirring apparatus (vibration stirring devices) as disclosed in patent documents JP-B No. 135528/2001, JP-B. No. 338422/2001 in patent applications for inventions by the present inventors
JP-A No. 275130/1991 (Patent No. 1941498)
JP-A No. 220697/1994 (Patent No. 2707530)
JP-A No. 312124/1994 (Patent No. 2762388)
JP-A No. 281272/1996 (Patent No. 2767771)
JP-A No. 173785/1996 (Patent No. 2852878)
JP-A No. 126896/1995 (Patent No. 2911350)
JP-A No. 40482/1997 (Patent No. 2911393)
JP-A No. 189880/1999 (Patent No. 2988624)
JP-A No. 54192/1995 (Patent No. 2989440)
JP-A No. 330395/1994 (Patent No. 2992177)
JP-A No. 287799/1994 (Patent No. 3035114)
JP-A No. 280035/1994 (Patent No. 3244334)
JP-A No. 304461/1994 (Patent No. 3142417)
JP-A No. 43569/1998 (Patent No. 3320984)
JP-A No. 309453/1998
JP-A No. 253782/1999 (Patent No. 3196890)
JP-A No. 282293/2000 (Patent No. 3046594)
JP-A No. 317295/2000
JP-A No. 053999/2002
JP-A No. 121699/2002
JP-A No. 146597/2002
WO01/090003A1
WO02/090621A1
WO 03/000395A1
WO 03/048424A1
In this invention, the vibro-stirring means 16 may be installed on both ends of the electrolysis tank as shown in
Using a vibro-stirring means with the vibrating blades in the bottom of the electrolysis tank as described in JP-A 304461/1994, allows a wider installation space for the electrode group within the electrolytic cell. Other advantages are that a larger quantity of gas is emitted from the electrolysis tank (volume) and if the electrodes are installed in the upward and downward directions, then there is no need to use many holes as described later on.
The description now returns to
The usual material utilized for hydroelectrolysis may be utilized as the electrode material. Materials such as lead dioxide (lead peroxide), magnetite, ferrite, graphite, platinum, Pt—Ir alloy, titanium alloy, titanium with rare-earth sheath (for example platinum-sheathed titanium) may be used as the anode positive electrode member. Rare earth metals such as rhodium, nickel, nickel alloy, (Ni—Mo2, Ni—Co, Ni—Fe, Ni—Mo—Cd, Ni—Sx, Raney nickel, etc.), titanium alloy may be used as the negative electrode member. The gap between the positive electrode and negative electrode may for example be 5 to 400 millimeters.
Since the negative electrode member 2y and the positive electrode member 2x are shaped as plates as shown in
The negative electrode member 2y and the positive electrode member 2x are respectively connected to an anode main bus-bar and a cathode main bus bar as shown in
In order to set the multiple blade negative electrode member 2y and the positive electrode member 2x within the electrolysis tank at fixed gaps, the electrode group is preferably assembled in the order of insulation frame/electrodes/insulation frame—electrode/insulation frame. The basic combination of insulation frame 70 and electrode 71 is shown in
The power supply 34 may supply direct current and preferably supplies normal low-ripple direct current. However, other power supplies with different waveforms may also be utilized. These types of electrolysis current waveforms are described for example, in “Electrochemistry” (Society of Japan) Vol. 24, P. 398-403, and pages 449-456 of same volume, the “Electroplating Guide” by the Federation of Electro Plating Industry Association, Japan” issued Apr. 15, 1996, P. 378-385, the “Surface Technology Compilation” issued by Koshinsha (Corp.) Jun. 15, 1983, P. 301-302, same volume P. 517-527, same volume P. 1050-1053, the Nikkan Kogyo Shinbun “Electroplating Technology Compilation” P 365-369 Jul. 25, 1971, same volume P. 618-622, etc.
In the present invention, among the various pulse waveforms, a rectangular waveform pulse is preferable, particularly in view of the improved energy efficiency. This type of power supply (power supply apparatus) can create voltages with rectangular waveforms from an AC (alternating current) voltage. This type of power supply further has a rectifier circuit utilizing for example transistors and is known as a pulse power supply. The rectifier for these type of power supplies may be a transistor regulated power supply, a dropper type power supply, a switching power supply, a silicon rectifier, an SCR type rectifier, a high-frequency (RF) rectifier, an inverter digital-controller rectifier, (for example, the Power Master [registered trademark] made by Chuo Seisakusho (Corp.)), the KTS Series made by Sansha Denki (Corp.), the RCV power supply made by Shikoku Denki Co., a means for supplying rectangular pulses by switching transistors on and off and comprised of a switching regulator power supply and transistor switch, a high frequency (RF) switching power supply (using diodes to change the alternating current into direct current, apply a 20 to 30 KHz high frequency waveform, and with power transistors add a transformer effect, once again rectify the voltage, and extract a smooth (low-ripple) output), a PR type rectifier, a high-frequency control type high-speed pulse PR power supply (for example, a HiPR Series (Chiyoda Corp.), etc.
The voltage applied across the positive electrode member and the negative electrode member is the same as during normal hydroelectrolysis.
The electrolyte fluid 14 is water containing electrolytic material. Here, a soluble alkali metal hydroxide (KOH, NaOH, etc.) or an alkali rare-earth metal hydroxide (for example, Ba (OH)2, Mg(OH)2, Ca(OH)2, etc.) or a ammonium alkyl 4 (tetra-alkylammonium), and materials of the known related art may be used as the electrolytic material. Among these KOH is preferable. The content of electrolytic material in the electrolyte fluid is preferably 5 to 30 percent. The pH of the electrolyte fluid is preferably 7 to 10 percent. Materials such as NaCl and HCl that generate halogen gas by electrolysis may make exhaust gas processing necessary to prevent environmental pollution when used in large quantities due to requirements such as chemically protecting the device, etc.
The lid member 10b is installed on the upper section of the electrolytic tank 10A as shown in
In this embodiment, the hydrogen gas and the oxygen gas are recovered as a hydrogen-based/oxygen-based mixed gas when the oxygen gas and hydrogen gas are present in equal proportions. Unlike the hydrogen-oxygen gas obtained by electrolysis not utilizing a vibration-flow stirring means, detonations do not occur in this hydrogen-based/oxygen-based mixed gas even if pressurized, and this hydrogen-based/oxygen-based mixed gas can be stored in a pressurized state, a depressurized state or a normal pressure state. Moreover, a separator wall can be formed as a partition to separate the upper space into a positive electrode member side space and a negative electrode member side space; and the oxygen-based gas and hydrogen-gas can each be separated out and recovered by installing a hydrogen gas extraction tube and an oxygen gas extraction tube.
The material for the electrolytic tank 10A and lid member 10B may for example be stainless steel, or plastic (synthetic resin) such as polycarbonate. A pipe 10A′ is connected to the electrolytic tank 10A for adjusting the level of the electrolyte fluid 14.
The vibrating rod 16e of the vibro-stirring means 16 extends upwards and downwards through the lid member 10B. As shown in
A means to attain even more complete sealing is the type shown in
The electrolysis is preferably performed at a fluid temperature of 20 to 100° C. and an electrical current density of 7 to 40 A/dm2. As shown by
The devices in
In this state, a laminated piece 3 comprised of a rubber plate 2 and the metal plates 1, 1′ is utilized as the vibration absorbing member instead of the coil spring 16b. In other words, the laminated piece 3 is clamped by way of an anti-vibration rubber 112 to a bracket member 118 affixed to an upper edge of electrolytic tank 10A by the metal plate 1′ and bolt 131. The rubber plate 2 is installed on that metal plate 1′, and the metal plate 1 installed on top of that rubber plate 2. This assembly is then assembled into one piece by using the bolts 116 and the nuts 117.
The vibration motor 16d is clamped by a bolt 132 and a vibration support member 115 to a metal plate 1. The upper edge of the vibrating rod 16e is installed by way of a rubber ring 119 to the laminated piece 3 with the metal plate 1 and rubber plate 2. In other words, the upper metal plate 1 renders the functions of the vibration member 16c described in
In the examples in
In
Stainless steel, titanium, steel, copper, aluminum and other suitable alloys may be used as the metal plates 1, 1′ and 1″. The thickness of the metal plate may for example be from 10 to 40 millimeters. However, metal plate (for example, the intermediate metal plate 1′) not directly clamped to members other than the laminated piece can be thin with a dimension from 0.3 to 10 millimeters.
Synthetic rubber or vulcanized natural rubber may be used as the material for the rubber plates 2 and 2′. The rubber plates 2 and 2′ are preferably anti-vibration rubber as specified in JIS K6386. The rubber plate in particular has a static shearing resilience of 4 to 22 kgf/cm2 and preferably of 5 to 10 kgf/cm2 and preferably has an elongation of 250 percent or more. Rubber specified for use as synthetic rubber may include: chlorophene rubber, nitrile rubber, nitrile-chlorophene rubber, styrene-chlorophene rubber, acrylonitrile butadiene rubber, isophrene rubber, ethylene propylene diene copolymer rubber, epichlorylhydrine rubber, alkylene oxide rubber, fluorine rubber, silicon rubber, urethane rubber, polysulfide rubber, phosphorbine rubber. The rubber thickness is for example 5 to 60 millimeters.
In the example in
In the above embodiments, the vibration stirring member for the vibro-stirring means is installed to face at least one of the surfaces of the positive electrode (anode) member and the negative electrode (cathode) member, so that a high gas generation efficiency can be obtained per each device (or apparatus) based on this high gas generation efficiency even if there is just one positive electrode (anode) member and the negative electrode (cathode) member.
The vibro-stirring means in this embodiment is the insulated type. In other words, the insulated type vibration stirring member is comprised of: a vibrating rod 16e including a vibrating rod upper section 16e′ installed on the upper edge of the vibrating member 16c and, a vibrating rod lower section 16e′″ installed on the vibrating blade and, an insulation region 16e″ interposed between the upper end of the vibrating rod lower section 16e′″ and the lower edge of the vibrating rod upper section 16e′.
A transistor inverter 35 for controlling the frequency of the vibration motor 16d is installed between the vibration motor 16d and the power supply (for example 200 volts) not shown in the drawing for driving that vibration motor 16d. The drive means for this vibration motor 16d can also be used in the other embodiments of the present invention. The vibration motors 16d vibrate at 10 to 500 Hertz under control of the inverter 35. The vibration generated by the vibration motors 16d is transmitted to the vibrating blade 16f by way of the vibrating member 16c and the vibrating rods 16e.
The electrical insulation area 16e″ can be formed for example from plastic or rubber. The electrical insulation area 16e″ is a structural part on the vibrating rod so preferably material should be selected that is able to sufficiently transmit the vibration of the vibrating motor without breaking due to the vibration and also have good insulating properties. In view of these conditions hard rubber is most preferable. One potential material is hard polyurethane rubber. If the member comprised only of insulation material has insufficient strength then a member made only of insulating material can for example be augmented with metal to obtain the required mechanical strength.
The electrical insulation area 16e″ more specifically may be made from a cylindrical insulating member (optional shape such as a polygon) manufactured from hard rubber as shown in the drawing. Insertion holes 124, 125 are formed in the center upper and lower sections to allow insertion respectively of the vibrating rod upper section 16e′ and a vibrating rod lower section 16e′″. These holes do not allow passage all the way through above and below so that the blocked section of the hole therefore functions as an insulating section.
If these upper and lower insertion holes are formed to allow passage all the way through, then insulation material can be filled into the hole spaces where the rod is not inserted or a space allowing sufficient insulation can be established so that the vibrating rod upper section 16e′ and a vibrating rod lower section 16e′″ do not make contact. The cylindrical insulation material for the insertion holes 124, 125 serves to couple the vibrating rod upper section 16e′ and vibrating rod lower section 16e′″. This coupling may be made with a setscrew (For example, cutting the male screws on the top edge of vibrating rod lower section 16e′″ and the bottom edge of vibrating rod upper section 16e′, cutting the female screws in insertion holes 124, 125, and joining both of them, and if necessary, applying a washer on the joint if further needed, and clamping with a machine screw.) or even joining them with adhesive is acceptable. Any other kind of structure may be used for this section as long as it achieves the desired object.
When the vibrating rod for example has a diameter of 13 millimeters, the insulation area 16e″ has a length (height) L for example of 100 millimeters, the outer diameter r2 for example is 40 millimeters, and the inner diameter r2 of the insertion holes 124, 125 is 13 millimeters.
As shown in
The vibrating rod lower section 16e′″, vibrating blade clamp member 16j and vibrating blade 16f are made from an electrically conductive member such as metal, then the vibrating rod lower section 16e′″, vibrating blade clamp member 16j and vibrating blade 16f of one of the insulation vibro-stirring means can also be utilized as the positive electrode (or anode) member; and the vibrating rod lower section 16e′″, vibrating blade clamp member 16j and vibrating blade 16f of the other insulation vibro-stirring means can be utilized as the negative electrode (cathode) member and electrolysis then performed.
When using the vibrating blade 16f as the positive electrode member or the negative electrode member, increasing the surface area of the vibrating blade is preferable, especially when the electrode surface area is inadequate such as when not using a positive and negative electrode member different from that described above. To accomplish this, a length L2 showing a second peak, or a length L3 showing a third peak as shown in
In this embodiment, utilizing the vibrating blade as the positive electrode member or the negative electrode member allows making the hydrogen-based/oxygen-based mixed gas compact. Moreover, the present embodiment vibrates and stirs the electrolyte fluid 14 with the insulated vibro-stirring means while electrolyzing so that electrolysis can be performed for example with a gap from 20 to 400 millimeters between the positive electrode member and the negative electrode member without electrical shorts occurring, the same as when utilizing the non-insulated vibro-stirring means.
In the present embodiment, the vibrating rod upper section 16e′ is electrically insulated from the vibrating rod lower section 16e′″ by the insulation area 16e″ so there is no effect on the vibrating motors 16d from electrical conduction by way of the vibrating rod lower section 16e′″. Also in this embodiment, the insulation area 16e″ has heat insulating properties so the vibrating rod lower section 16e′″ is also heat-insulated from the vibrating rod upper section 16e′, so there is little effect from the temperature of the electrolyte fluid 14 on the vibrating motors 16d.
Moreover, in the present embodiment, an insulation area 16e″ is present even when electrolyzing without utilizing the vibrating blade of the insulated vibro-stirring means as the positive electrode member or the negative electrode member and therefore renders the advantage that the effect of conducting electricity within the electrolyte fluid does not affect the vibrating motor 16d.
The electrode support blade 16f″ is preferably installed at a position midway between a vibrating blade and a vibrating blade on the vibrating rod. However the installation position is not limited to this position and may be installed at a position in proximity to a vibrating blade from above or below as long as there is not drastic reduction in the vibration-stirring effect. The electrode support blade 16f″ can be installed on the vibrating rod lower section 16e′″ in the same way as the vibrating blade 16f was installed.
The material of the electrode support blade 16f″ may be any material allowing use as an electrode. However since it must vibrate along the vibrating rod it must be sufficiently tough to withstand vibration. A conductive piece capable of usage as a vibrating blade made may for example of titanium (platinum plating can be deposited on its surface) or stainless steel (platinum plating can be deposited on its surface). The vibrating blade 16f need not always be an electrically conductive material when using the electrode support blade 16f″, and may be made of plastic (synthetic resin). To make the angle of the vibrating blade 16f uniform, the vibrating blade 16e can be assembled at a certain angle into one piece with the vibrating blade clamp member 16j.
Though not shown in the drawing, the present embodiment utilizes a power supply 34 as the electrolyzing means described in
Electrolysis can be performed with the insulated vibro-stirring means as shown in the figure by using an upward protruding blade as the positive electrode member, and using the downward protruding vibrating blade of the other insulated vibro-stirring means as the negative electrode member. In this case, the vibrating blades of both insulated vibro-stirring means can be set in a mutually inter-assembled state.
Moreover in theses embodiments, the vibrating blades need not always be installed facing upwards and downwards but may be used in an appropriate shape and installation according to the shape of the electrolysis tank, etc.
In this embodiment also, a power supply 34 is utilized for the electrolyzing means described in
A specific example of the hydrogen-based/oxygen-based mixed gas generating means is shown in
A specific example of the hydrogen-based/oxygen-based mixed gas generating means is shown in
In the present embodiment, two insulated vibro-stirring means are installed within the electrolysis tank 10A. The electrode support blades 16f′ of one insulated vibro-stirring means are positioned between the electrode support blades 16f′ of the other adjacent insulated vibro-stirring means. In this way, one of the two insulated vibro-stirring means can be used as the positive electrode member (anode) and the other used as the negative electrode member (cathode) so that a positive electrode member and negative electrode member with a large surface area can be installed in close mutual proximity to each other to make a drastic improvement in the electrical current density. Installing a positive electrode member and negative electrode member in a mutually inter-assembled state without making contact in this way, can be performed in the same way with mutual vibrating blades of the two insulated vibro-stirring means.
In the present embodiment, the distance between the positive electrode member (vibrating blade or electrode support blade) and negative electrode member (vibrating blade or electrode support blade) installed in close mutual proximity upwards and downwards may for example be 5 to 50 millimeters. In this embodiment, insulating tape 16fa is preferably affixed to the outer circumferential surfaces on both sides of the electrode support blades 16f′ as shown in
By utilizing the negative electrode member or the positive electrode member as a section (for example, the vibrating blade or electrode support blade) of the insulated vibration stirring member in the above examples, based on this highly efficient gas generation, each apparatus can deliver highly efficient gas generation even if there is no positive electrode member or negative electrode member other than the insulated vibration stirring member.
In other words, in
In this embodiment, the electrical insulation area 16e″ is installed between the vibration rod 16e and the vibration member 16c comprising the vibration generating means. In other words, the electrical insulation area 16e″ in this embodiment also functions as the attachment piece 111 for installing the vibrating rod 16e onto the vibration member 16c.
In this embodiment, the vibrating blade 16f forming the positive electrode member preferably has a surface of titanium coated with platinum. The negative electrode side is preferably coated with titanium.
In this embodiment, power is only supplied to the insulated vibro-stirring means for electrolysis so the apparatus can be made compact. Also the vibrating blades 16f can incorporate the functions of two types of electrodes and so from that viewpoint the device can also be made more compact.
In the above embodiments, both a positive electrode (anode) member and the negative electrode (cathode) member are attached to the insulated vibro-stirring means so electrolysis can be performed by supplying power via the electrolyte fluid 14 to these electrodes so that the apparatus can be made compact. Moreover, a high gas generation efficiency can be obtained per each device (or apparatus) based on this high gas generation efficiency.
The positive electrode (anode) member is for example made from lath-webbed titanium (preferably with platinum deposited on the surface).
In a state where the hydrogen-based/oxygen-based mixed gas is comprised of a uniform mixture of hydrogen gas and oxygen gas generated within the electrolysis tank; the trapping means for separately trapping the hydrogen gas and oxygen gas contains a lid member for covering the upper part of the tank, and a gas extraction outlet (or port) connected to that lid member, and a gas extraction tube connected to that gas extraction port. In the drawings for describing examples of the vibro-stirring means of this invention, the lid member for efficiently trapping the emitted gas is omitted from the drawings. However, in actual use, a lid member is always attached to the electrolysis tank of the gas generating means.
A variation of the lid member 10b is shown in
The vibrating rod 16e does not pass through the lid member of the vibro-stirring means when using this type of lid member. A sealed structure as described above is preferable in this case, in order to improve the recovery efficiency of the hydrogen-based/oxygen-based mixed gas and prevent the electrolyte fluid from scattering (into the air).
Sealing in the generated hydrogen-based/oxygen-based mixed gas by means of this lid member and enclosure member allows raising the gas pressure by a corresponding amount. A certain amount of gas pressure is convenient when handling the gas pressure later on. Adjusting the vertical position of the cover plates 64 allows adjusting the fluid level in the section above the electrode groups 2x, 2y and therefore adjusts the gas pressure.
Incorporating a means for adjusting the gas pressure is even more preferable. One example of a system as a gas pressure adjusting means is shown in
The positive electrode member and the negative electrode member installed in the electrolysis tank are preferably both usually electrode plates. In this case, a gap of about 50 millimeters at its shortest was required between the electrodes in the related art not utilizing a vibro-stirring means. Forming a gap any larger than this caused the possibility of accidents occurring due to excess current flow. However the distance (gap) between the electrodes can be shortened to between 1 to 20 millimeters by utilizing the vibro-stirring means of this invention. The electrical current efficiency can be vastly improved in this way. Making the electrodes and closer will cause excessive electrical current flow resulting in electrical shorts. The actual gap between electrodes in this invention is preferably 5 to 400 millimeters. Detailed information can be found in WO03/000395A1 application rendered by the present inventors.
In this invention, the vibrating blades and the electrode support blades function as electrodes utilizing the insulated vibro-stirring means. This example is shown in
The present invention is capable of generating hydrogen-based/oxygen-based mixed gas by electrolysis of electrolyte fluid consisting of 5 to 50 percent and preferably 50 to 30 percent weight by volume of electrolytic material at pH7 to 10 at a temperature of 20 to 100 degrees centigrade, and preferably 20 to 90 degrees centigrade to reach an electrical current density of 5 to 100 A/dm2 and preferably 5 to 50 A/dm2.
Soluble alkali metal hydroxide or alkali rare-earth metal hydroxide or ammonium alkyl 4 (tetra-alkylammonium), or inorganic acids such as sulfuric acid, phosphoric acid or organic acids may be utilized as the electrolytic material.
The water utilized as the electrolyte fluid is preferably distilled water however well water, industrial use water, tap water, river water or lake water may also be used.
The basic structure of the vibro-stirring means of this invention is: an insulated vibro-stirring means including at least one vibration generating means; and at least one vibrating rod for vibrating while linked to the vibration generating means; and an insulated vibration stirring member comprised of an electrical insulation area installed at a section linking at least one vibrating blade installed on the vibrating rod and the vibration rod and vibration generating means, or installed on a section nearer the linking section than where the vibrating blade is installed on the vibrating rod. In this embodiment, the stirring means is preferably an insulated vibro-stirring means.
On the insulated vibro-stirring means, the electrode support blades can be electrically connected with an electrical line to the vibrating blade on the vibrating rod of the insulated vibration stirring member. The electrode support blades are preferably installed on the vibrating rod so that the electrode support blade positions mutually alternate with the vibrating blade positions. The surface area of the electrode support blades is preferably larger than the surface area of the vibrating blades, moreover, the tips of the electrode support blades preferably protrude farther than the tips of the vibrating blades.
The generating means for the vibro-stirring means or the insulated vibro-stirring means includes a vibration motor. The vibration motor of the vibro-stirring means vibrates at 10 to 500 Hertz. The motor preferably vibrates at a frequency 10 to 200 Hertz and even more preferably is made to vibrate at 20 to 60 Hertz under the control of an inverter.
On the insulated vibro-stirring means, the electrode or in other words the positive electrode member or the negative electrode member can be utilized as the electrode for performing electrolysis by connecting an electrical wire to a position on the vibrating blade side from the electrical insulation area of the vibrating rod.
In this case, the vibrating blade can combine the function for vibration stirring the fluid, with the function of an electrode as shown for example in
The insulated vibro-stirring means can for example be used with the electrode pair in
In the present invention as described above, the vibrating blades of the vibro-stirring means cause a powerful vibrating flow movement in the electrolyte fluid so that the electrolyte fluid can make contact with the electrodes with ample, satisfactory uniformity and also an adequate supply quantity. Therefore even if the gap between the positive electrode member (anode) and the negative electrode member (cathode) is drastically reduced to a distance (gap) even smaller than in the related art, the ions that are required can still be supplied in an adequate quantity needed for electrolysis, and the electrolytic heat generated in the electrodes can be quickly dissipated. Electrolysis can therefore be performed at a high electrical current density so that hydrogen-based/oxygen-based mixed gas can be collected with high efficiency. Further, by reducing the distance between the positive and negative electrodes (cathode and anode) as described above, the effective surface area of the electrodes can be sufficiently increased per volumetric unit so that ample quantities of hydrogen-based/oxygen-based mixed gas can be generated even if the size is made more compact.
In particular, when performing electrolysis by vibrating and agitating the electrolyte fluid using the vibro-stirring means, the hydrogen and oxygen generated in the vicinity of the electrodes at an atomic level do not form bubbles between the electrodes and disperse within the fluid so there is no problem with the hydrogen and oxygen generated in the electrolyte fluid forming bubbles and adhering to the surface of the electrodes and increasing the electrical resistance. Therefore hydrogen-based/oxygen-based mixed gas can be generated in large quantities compared to the method of the related art.
In other words, in order to achieve the above objects, the present invention provides a hydrogen-based/oxygen-based mixed gas generated by a hydrogen-based/oxygen-based mixed gas generating means characterized in containing H and, H2 and, H3 and/or HD and, OH and, 16O, and O2. According to an aspect of the present invention, and the hydrogen-based/oxygen-based mixed gas in particular contains:
H2: 55 to 70 mole %
H: 0.12 to 0.45 mole %
H3 and HD totaling: 0.03 to 0.14 mole %
OH: 0.3 to 1.2 mole %
16O: 1.0 to 4.2 mole %
O2: 5 to 27 mole %.
This hydrogen-based/oxygen-based mixed gas differs from the so-called Brown's gas in the following points. Namely, satisfactory electrolysis can be achieved when utilized with the vibro-stirring means even if the gap between the negative electrode member and the positive electrode member is made smaller. Contact by the positive and negative electrode flow members with the electrolyte fluid is in particular made at a high uniform flow speed so that there is a satisfactory supply of ions required for electrolysis. Moreover, no bubbles are formed in the hydrogen-oxygen gas in the electrolyte fluid so that the electrical resistance will not become high. The hydrogen-based/oxygen-based mixed gas of this invention possesses a particularly high content of activized elements (activized hydrogen, activized oxygen) in a state near that of oxygen and hydrogen in the period prior to generation of H2 and O2.
In other words, when the hydrogen-based/oxygen-based mixed gas obtained by utilizing the vibro-stirring means was combusted and the spectrum measured on a spectrum analyzer, a peak indicating the presence of an OH radical as the activized element was observed in the vicinity of 620 nanometers as shown in
Moreover, when measurements checking for the presence of this OH or hydrogen in an atomic state made immediately after the hydrogen-based/oxygen-based mixed gas was generated by the vibro-stirring means of this invention were compared with measurements made 12 hours after the hydrogen-based/oxygen-based mixed gas had been stored in a gas accumulator, the results were found to be nearly the same. Therefore, this OH or hydrogen in an atomic state was present not just momentarily in the gas obtained by manufacturing. Also, when this hydrogen-based/oxygen-based mixed gas was combusted, it was observed to generate a high temperature.
No peak of this type was observed in the Brown's gas of the related art. The reason for this is still not clearly known however based on this type of difference, when the hydrogen-based gas or the hydrogen-based/oxygen-based mixed gas of this invention is utilized as fuel in fuel cells, a high level of electrical generating efficiency is probable that could not be obtained from other fuel cells up to now.
The present inventors analyzed the gas (In these specifications, this gas is named hydrogen-based/oxygen-based mixed gas.) obtained by the electrolysis of water utilizing this vibro-stirring means utilizing the mass spectrometer (dual-convergence) [product brand name EMD-O5SK] under the following conditions.
Ion acceleration speed: 1200 volts
Ion bombardment method: Voltage accelerated impact type
Resolution: 500
Ion flight distance: 26 cm
Vacuum intensity: 5×100−7 Torr
Full scale: 5 volts
The hydrogen-based/oxygen-based mixed gas supplied for this analysis that was generated from the electrolysis tank where the vibro-stirring means was installed, is stored in a gas accumulator of
A portion of the data (chart) obtained by mass spectrometry is shown in
However the heights shown in
Gas elements found from these figure are shown in Table 1 as follows.
(A), (a): Sampled in rubber container; measured vacuum intensity 8 × 10−7 Torr; measured 0.5 hours after gas sampling
(B), (b): Sampled in rubber container; measured vacuum intensity 8 × 10−7 Torr; measured 24 hours after gas sampling
(C), (c): Sampled in gas barrier container; measured vacuum intensity 5 × 10−7 Torr; measured 1 hour after gas sampling.
The hollow layer or the electrolytic layer may utilize the same electrolytic layer as used in the fuel cells of the related art. For example, potassium hydroxide is the electrolytic material in alkali (soluble) fuel cells (AFC). Phosphoric acid is used as the electrolytic material in phosphoric acid fuel cells (PAFC). Lithium carbonate or potassium carbonate is used as the electrolytic material in molten carbonate fuel cells (MCFC). Stabilized zirconium is used as the electrolytic material in solid oxygen fuel cells (SOFC). Ion exchange film (cation exchange film) is used as the electrolytic material in polymer electrolyte fuel cells (PEFC).
The hollow layer or the electrolytic layer may also utilize for example, air-gap layers comprised only of air or may also there utilize metal mesh, glass mesh, carbon mesh, filter paper, precision filter membrane, limit excess filter membrane, NF film, reverse penetration film, gas separator film, polymer gel, inorganic gel, polymer film, or multi-porous hollow film filled with graphite, (In other words, a layer containing a function for allowing gas flow through woven layers or gas permeable ceramic layers) etc.
The surface on the side bordering the fuel electrode and air electrode is preferably a surface with irregular shapes arrayed in numerous parallel grooves for enlarging the glass contact surface area.
Hydrogen-based gas or the hydrogen-based/oxygen-based mixed gas of this invention may be utilized as the first gas. Air, oxygen gas, the oxygen-based gas, or the hydrogen-based/oxygen-based mixed gas of this invention may be utilized as the second gas.
In fuel cells utilizing hydrogen gas of the related art as the fuel, an electrolytic layer is indispensable for forming protons in the fuel electrode and for making these protons react with the oxygen at the air electrode. In this invention, a hollow layer can be utilized in place of the electrolytic layer, by using hydrogen-based/oxygen-based mixed gas or hydrogen-based gas as the first gas. In this case, the fuel electrode must be gas-permeable. It is essential that the hollow layer not allow shorts to occur between the fuel electrode and the air electrode. In this invention, the hydrogen-based/oxygen-based mixed gas can be utilized as both the first gas and the second gas. In that case, the air electrode must also be gas-permeable. An important characteristic of these fuel cells of this invention is that an electrolytic layer is not required. Not requiring an electrolytic layer provides the benefit that the cell structure can be simplified and no maintenance of the electrolytic layer is required. In all other points, the structure and the material of the fuel cell of the related art can be utilized.
When supplying the hydrogen-based/oxygen-based mixed gas from the gas supply port formed on the fuel electrode side of the fuel cell, the hydrogen passes through the gas-permeable fuel electrode and enters the electrolytic layer or hollow layer while supplying electrons to the fuel electrode. The fuel electrode may for example possess a porous structure in order to be gas-permeable.
Since this invention does not require an electrolytic layer, that section may form a hollow state (May be a multi-porous plastic layer or a multi-porous ceramic layer.) to serve as the hollow layer. This section need only be capable of separating the fuel electrode and the air electrode. The thickness of the hollow layer is usually in a range from one micrometer to 10 centimeters.
For example, when using a solid polymer electrolytic material as the electrolytic material, and the cation exchange film serves as the electrolytic material, then the following battery reaction occurs.
Total reaction: ½ O2+H2→H2O (6)
Therefore, water which is a reactive substance must be drained from specified locations in the electrolytic layer or hollow layer. Since the gas must also flow smoothly in the case of non-reactive gas, a gas drainage port is preferably formed in the electrolytic layer or hollow layer. The non-reactive gas and the water from a reactive substance can both be simultaneously removed from one drainage port to outside the system.
Fuel cells are classified into various types according to the electrolytic material they utilize. These types for example include alkali fuel cells, solid oxygen fuel cells (SOFC), molten fuel cells, phosphoric acid fuel cells (PAFC), polymer electrolyte fuel cells (PEFC/PEM), and molten carbonate fuel cells, etc. The present invention can utilize any of these fuel cell types. However phosphoric acid fuel cells, solid polymer electrolyte fuel cells, solid oxygen fuel cells or methanol direct-type fuel cells (Of course, in this invention the hydrogen-based/oxygen-based mixed gas of the present invention is utilized rather than methanol as a fuel.) are preferably used, and solid polymer electrolyte fuel cells and solid oxygen fuel cells are particularly preferable.
In the present invention, a hollow layer may be utilized instead of the electrolytic layer. Needless to say, the hollow layer is more advantageous in terms of cost.
Solid polymer electrolyte fuel cells use solid polymer electrolytic material, and polymer ion exchange films of different types can be used as this solid polymer electrolytic material. Examples of these ion exchange films are described in page No. 100-103 and particularly on page No. 101 Table 1 of “Fuel Cell Generating Systems” published by Ohm Inc. on Mar. 15, 1993. These examples utilize “phenylsulfonate resin”, “polystyrene sulfonate”, “polytrifluorostyrenesulfonate”, and “(poly)perfluorocarbon sulfonate” in the following formulas.
(Here, x is the change due the degree of polymerization.). Items where M≦1, n=2 are marketed under the product name Nafion. Items where m=0, n=2 marketed under the product name DOW. These substances are described on Pages 116-128, and in particular on page 120 Table 6, 1 of “Fuel Cell Electrical Power Generation” published by Corona Inc. on Jan. 30, 2001.
The structures of solid state polymer electrolyte fuel cells are described on page 102,
The embodiments of this invention are described next. However the present invention is not limited in any way by these embodiments.
The hydrogen-based/oxygen-based mixed gas of
(a) Vibro-stirring Means
Japan Techno Co., Ltd. Product name: Ultravibration Alpha-Agitator Model Alpha-1 (An insulated vibro-stirring means designed so that electrical current flowing in the electrolyte fluid does not flow to the vibration motor.)
Vibration motor: 75 watt×200 volts×3-phase
Low-frequency vibration motor made by Murakami Seiki Seisakusho (Corp.)
Product name: Uras Vibrator
Vibrating rod: Two rods, 16 millimeters in diameter, SUS304
Vibrating blade: Four blades, 6 millimeters long, SUS304
Stationary member: SUS304
Resilient sheet: Product name: Teflon (Registered trademark) sheet
(b) Stationary Electrodes
(c) Inverter: Fuji Electric (Inc.) Product name FVR-E11S used after adjusted to 45 Hertz
(d) Rectifier (for vibration motor): Power Master made by Chuo Seisakusho (Corp.)) [Registered trademark], 200 volts
(e) Electrolytic tank: Manufactured from (SUS304) stainless steel (inner surface of heat-resistant polyvinyl plastic)
(f) Seal between lid member and vibrating rod (See
Gap is filled with silicon to form a complete seal so that no gas leaks occur even from vibration from the vibration motor shaft.
(h) To convey the hydrogen-based/oxygen-based mixed gas from the electrolysis tank to the fuel cell, the safety devices in
(i) Electrolyte fluid: Water required for electrolysis was added to a solution of distilled water added with KOH at 20 percent by weight at a temperature 55° C. and pH of 10.
In this embodiment, the hydrogen-based/oxygen-based mixed gas was manufactured at approximately 1,000 liters per minute at approximately three volts and 100 amperes.
(j) Fuel cell structure and usage method: Electrical power was generated utilizing a commercially available compact solid polymer electrolyte fuel cell and the hydrogen-based/oxygen-based mixed gas of this invention. The structure of this cell was the same as that shown in
The structure of the commercially available compact solid polymer electrolyte fuel cell of
When this battery as a single cell was used to generate electricity with the method essentially used for the commercially available compact solid polymer electrolyte fuel cell (example of the related art), the outputs were 0.6 to 0.7 volts, 0.15 to 0.2 watts. However the output was 2.5 times higher in the case of the first embodiment at 0.6 volts and 0.5 watts.
When electricity was generated with the method of the related art, heat of nearly 100° C. was generated during long term use that made long term operation impossible. However in the case of this embodiment not much heat was generated so long term operation is possible.
As shown in
The electrolytic layer of this cell is equivalent to the plate with outer circumferential rubber ring in
When the electrolytic layer was removed, and a hollow layer or in other words and air layer was formed in that section, and the hydrogen-based/oxygen-based mixed gas of this invention was supplied via a gas-permeable electrode, the moisture (H2O) contained within the mixed gas perhaps functioned as the electrolytic layer or in any case, the surprising fact was discovered that even without an electrolytic layer, electricity was generated absolutely the same as when an electrolytic layer was present. When a hollow layer was utilized, then platinum or palladium may also be used as well as nickel
When the hydrogen-based/oxygen-based mixed gas obtained in the first embodiment was subjected to analysis by the previously described analysis methods, the results were nearly identical to data for the processed gas in Table 1. A unique feature was the H, H3, HD and OH contained in the gas. The presence of these elements is assumed to be a factor in the high activation and high energy generation. Another unique feature was the rich hydrogen and that the ratio of hydrogen to oxygen was not 2-to-1,
The hydrogen-based/oxygen-based mixed gas or hydrogen-based gas possessing these type of elements was found only when utilizing the vibro-stirring means, and could not be found in hydrogen-based gas, oxygen gas, or hydrogen-based/oxygen-based mixed gas obtained by any other method.
The elements contained in the gas are considered extremely unstable. However, these elements in the hydrogen-based/oxygen-based mixed gas or hydrogen-based gas utilizing the vibro-stirring means of this invention were found to be present for a one to two month period in sealed containers or pressurized containers.
The gas generated in the second embodiment was not passed through a safety device and sent directly to a fuel cell as in the first embodiment, rather after storage in a gas accumulator for one day, the hydrogen-based/oxygen-based mixed (raw) gas was directly supplied to the hydrogen gas supply port of the fuel cell of the first embodiment without passing through the seal port of
In the present embodiment, the hydrogen-based/oxygen-based mixed gas generating means utilizing the vibro-stirring means of
(a) Vibro-stirring means
Japan Techno Co., Ltd. Product name: Ultravibration Alpha-Agitator Model Alpha-2
Vibration motor: 150 watt×200 volts×3-phase
Vibrating rod: Two rods, 16 millimeters in diameter, SUS304
Vibrating blade: Five blades, 6 millimeters long, SUS304
Electrode support blades:
Minus electrode: 3 sheets, SUS304
Plus electrode: Two sheets covered with platinum plating, (10 μm thick) SUS304
(b) Inverter: Fuji Electric (Inc.) Product name FVR-EL11S used after adjusted to 55 Hertz
(c) Rectifier: Hi-Mini made by Chuo Seisakusho (Corp.)), 200 volts
(d) Electrolytic tank: Manufactured from (SUS304) stainless steel (inner surface of heat-resistant polyvinyl plastic)
Inner diameter 220 mm×320 mm×400 mm (H)
Lid member is made of SUS304.
(e) Seal between lid member and vibrating rod (See
Gap is filled with silicon to form a complete seal so that no gas leaks occur even from vibration from the vibration motor shaft.
(f) To convey the hydrogen-based/oxygen-based mixed gas from the electrolysis tank to the fuel cell, the safety device in
(g) Electrolyte fluid: Water required for electrolysis was added to a solution of distilled water added with KOH at 20 percent by weight at a temperature 55° C. and pH of 10.
In this embodiment, the hydrogen-based/oxygen-based mixed gas was manufactured at approximately 1,000 liters per minute at approximately three volts and 100 amperes.
When the hydrogen-based/oxygen-based mixed gas obtained by the above described means was subjected to analysis by the previously described analysis methods, the results were nearly identical to data for the processed gas in Table 1, and another point in common (with the previous embodiment) is that the content of H, H3, HD, H2O, and, OH was confirmed as approximately the same. This hydrogen-based/oxygen-based mixed gas was supplied to the solid polymer electrolyte fuel cell shown in
Both the air electrode and the fuel electrode were gas-permeable platinum catalytic single electrodes. The solid polymer electrolytic film was air-conductive material of polyperfluorocarbon sulfonate under the product name Nafion made by the Dupont Corporation) and immersed in water.
Results from generating electricity were the same as obtained for the first embodiment.
Other than the fact that the polymer electrolytic layer was removed from the solid polymer electrolytic type fuel cell, and a hollow layer (air layer) was formed in that section, the electrical power generating results were the same when tests were performed.
This embodiment is the same as the first embodiment, with the exception that the fuel cell shown in
The solid electrolytic layer was a gas-permeable ion conducting thin film (less than 500 nm) interposed between a platinum gas-permeable minus electrode and a platinum plus electrode. The minus electrode was gas-permeable.
Polyperfluorocarbon sulfonate material with the product name Nafion was utilized as the gas-permeable ion conducting thin film. The gas-permeable minus electrode utilized powdered platinum shaken and attached to multi-porous, thin, conductive carbon paper.
In this embodiment, the surprising fact was revealed that approximately the same electrical power was obtained when compared to a fuel cell utilizing hydrogen gas in a commercially available hydrogen gas tank. This (electrical power) is characteristic of the hydrogen-based/oxygen-based mixed gas utilizing the vibro-stirring means.
Except for the utilization of the polymer electrolytic film as the hollow layer in the fuel cell shown in
The vibration motor in the first embodiment was changed to an RF vibration motor under the product name of Hi-FLURAS KHE2-2T, and except for the fact that the inverter was oscillated at 120 Hertz, nearly the same effects as in the first embodiment were obtained under the same conditions.
This embodiment utilized the hydrogen-based/oxygen-based mixed gas generating means of
Japan Techno Co., Ltd. Product name: Ultravibration Alpha-Agitator Model Alpha-2 Vibration motor: 150 watt×200 volts×3-phase
Low-frequency vibration motor made by Murakami Seiki Seisakusho (Corp.) Product name:
Uras Vibrator
Vibrating rod: Two rods, 16 millimeters in diameter, SUS304
Vibrating blade: Five blades, 6 millimeters long, SUS304
Electrode support blades:
Minus electrode: 3 sheets, SUS304
Plus electrode: Two sheets covered with platinum plating, (10 μm thick) SUS304
Stationary member: Made of SUS304
Resilient sheet: Product name: Teflon (Registered trademark) sheet
(b) Inverter: Fuji Electric (Inc.) Product name FVR-E11S used after adjusted to 55 Hertz
(c) Rectifier: Rectifier (for vibration motor): Power Master made by Chuo Seisakusho (Corp.)) [Registered trademark], 200 volts
(d) Electrolytic tank: Manufactured from SUS304stainless steel (inner surface of heat-resistant polyvinyl plastic)
Inner diameter 220 mm×320 mm×400 mm (H)
Lid member is made of SUS304.
A fuel cell structure shown in
The product with the commercial name Nafion was utilized as polymer solid electrolytic material film shown in
The hydrogen-based/oxygen-based mixed gas of this invention was supplied from the fuel electrode (negative electrode) side and the waste from the reaction drained from the drainage port. In this embodiment, the air vent on the air electrode side is sealed (In the basic usage method in the structure in
In this embodiment, electrical power can be generated continuously for a two day period while maintained below 80° C. even without water cooling. However, when used with the basic method in
As shown in the sixth embodiment, installing the support blade on the side opposite the vibrating blade renders the advantage that contact will not occur, even if the distance between the electrodes is shortened.
Utilizing this type of support blade and vibration blade allows eliminating the space for installing the stationary electrodes of the first and second embodiments so that vibration stirring electrodes can be set on both ends of the electrode tank of the sixth embodiment.
Electrical power generation was performed by utilizing the fuel cell of the sixth embodiment that makes use of the hydrogen-based/oxygen-based mixed gas generating means.
The hydrogen-based/oxygen-based mixed gas of this embodiment also possessed the same composition and characteristics as the processed gas shown in Table 1.
Hydrogen-based gas was supplied to the fuel cell of the sixth embodiment from a commercially available hydrogen gas tank, and air was supplied from the air port of the fuel cell and electricity was generated.
Electrical generation in the sixth and seventh embodiments as well as the first comparative example is shown below in Table 2.
The eighth embodiment utilized the fuel cell shown in
The structure of the fuel cell shown in
The solid state electrolytic film is a gas-permeable ion-conductive thin film (500 nanometers or less) interposed between a platinum gas-permeable fuel electrode and a platinum air electrode and the fuel electrode is gas-permeable.
An inorganic material (γ-A100H) of low density Bohmite was utilized as the gas-permeable ion-conductive thin film. The gas-permeable fuel electrode was powdered platinum affixed by sprinkling onto multi-porous, thin, conductive carbon paper. The surprising fact was revealed that the present embodiment yielded 3 to 3.5 times the electrical power compared to the fuel cell described in “Nature”. This results is characteristic of the hydrogen-based/oxygen-based mixed gas obtained utilizing a vibro-stirring means.
Also, an experiment was performed where the ceramic electrolytic material was replaced with a hollow layer (air layer) and approximately the same generated electrical power was obtained.
This embodiment utilized the “Micro Fuel Cell” of the Manhattan Scientific Corporation shown on pages 68 and 69 and in particular in
In this embodiment, the hydrogen-based/oxygen-based mixed gas (for both cases of raw gas and processed gas) of this invention was supplied instead of hydrocarbon and air mixed gas to the single-chamber solid electrolytic fuel cell disclosed in JP-A No. 280015/2002 and 0.5 watts per centimeter of electrical power was obtained.
The structure of this single-chamber solid electrolytic fuel cell is disclosed in JP-A No. 280015/2002 however a description is given next.
This single-chamber solid electrolytic fuel cell is made up of respectively of an air electrode and fuel electrode on the same surface of a disk-shaped oxygen ion conductive solid electrolytic material as shown in
Here, La1-zSrzGa1-WMgWO3-δ or Ce1-7LnyO2-δ is utilized as the oxygen ion-conductive solid electrolytic material. The air electrode utilizes Ln1-xSrxCoO3±δ (Here, Ln: rare earth elements, in particular La, Sm, Gd or Yb) and particularly Sm0.5Sr0.5CoO3∓δ doped with strontium. The fuel electrode is made from nickel, and a mixed compound (Ce1-ySmyO2-δ) of cerium oxide doped with samarium along with a 1 percent mass additive of palladium. The mixed compound of cerium oxide doped with samarium utilizes Ce0.8Sm0.2O1.9 (SDC). The mixture of Ni to SDC is a weight ratio of 7 to 3. The air electrode and the fuel electrode are formed with a gap so as to form a specified air gap as shown in
This single-chamber solid electrolytic fuel cell was fabricated as follows. A fuel electrode is first of all formed on the surface of the oxygen ion-conductive solid electrolytic material. Nickel oxide powder and SDC powder are weighed to specified amounts, and mix-pulverized using a suitable organic solution. Then a specified amount of palladium oxide powder is mix-pulverized to adjust the paste-shaped electrode material. This is then screen printed onto the oxygen ion-conductive solid electrolytic material and heat-treated at 1400° C.
An air electrode is next formed at a specified gap with the fuel electrode on the same side as the surface where the fuel electrode was formed on the oxygen ion-conductive solid electrolytic material. The Ln1-xSrxCoO3±δ (Here, Sm0.5Sr0.5CoO3±δ was used.) was liquefied, pulverized to adjust the paste-shaped electrode material. This was then screen printed onto the oxygen ion-conductive solid electrolytic material on the same surface as the fuel electrode and heat-treated at 900° C.
The gap between the electrodes was 3×10−3 m. Also, the Pd additive for the fuel electrode was set to 5 percent by weight, and the oxygen ion-conductive solid electrolytic material that was used was 7×10−3 m, 0.3×10−3 m thick, and possessed a surface roughness of Ra0.06×10−6 m.
In this embodiment, electricity was generated by utilizing the hydrogen-based/oxygen-based mixed gas generating means utilized in the first embodiment, the hydrogen-based/oxygen-based mixed gas that was generated was separated into hydrogen-based gas and oxygen-based gas by using an oxygen separator apparatus, and supplying hydrogen-based gas from the fuel electrode side, and supplying oxygen-based gas from the air electrode side of the fuel cell used in the sixth embodiment. A film divider was formed between the minus electrode and the plus electrode within the electrolysis tanks, and gas elements mainly comprised of hydrogen generated by the minus electrode or in other words hydrogen-based gas; and gas elements mainly constituted of oxygen generated by the plus electrode or in other words oxygen-based gas were separated at their generation step, trapped, and the hydrogen-based gas supplied to the fuel electrode of the fuel battery, and the oxygen-based gas supplied to the air electrode of the fuel cell, and electrical generation yielded exactly the same results. These results showed that the electrical generation rate was increased approximately five times compared to when generating electricity by utilizing the commercially available oxygen tank and the hydrogen tank. There is little room for doubt that the gas components comprising the main elements of the hydrogen-based gas, or in other words, the H and, H2 and, H3 and/or HD and, OH contributed to this result.
In the present embodiment, the hydrogen-based/oxygen-based mixed gas generating means of
Japan Techno Co., Ltd. Product name: Insulated Ultravibration Alpha-Agitator Model Alpha-3
Two units installed with the vibrating blades respectively facing each other in the electrolytic tank (shown in
Vibration motor: 250 watts×200 volts×3-phase
Low-frequency vibration motor made by Murakami Seiki Seisakusho (Corp.) Product name: Uras Vibrator
Vibrating rod: Two rods, 16 millimeters in diameter, made from SUS304
Vibrating blade: Seven blades, 6 millimeters long, made from SUS304
Stationary member: Made from SUS304
Resilient sheet: Product name: Teflon (Registered trademark) sheet
One of the Insulated Ultravibration Alpha-Agitators was used as the plus electrode, and the other was used as the minus electrode. A divider film was installed between these two units and gas elements comprised mainly of hydrogen gas or in other words, hydrogen-based gas, and gas elements comprised mainly of oxygen gas or in other words oxygen-based gas are separately sampled. The vibrating blades are made of SUS plate covered with platinum plating only in cases when the vibrating blades are used as the plus electrode.
(b) Inverter: Chuo Seisakusho (Corp.) used after adjusted to 50 Hertz.
(c) Rectifier (for vibration motor): Fuji Electric (Inc.) Product name FVR-C9S 200 volts
(d) Electrolytic tank: Manufactured from SUS304 stainless steel (inner surface of heat-resistant polyvinyl plastic)
Inner diameter 700 mm×500 mm×500 mm (H)
Lid member is made of SUS304.
(e) Seal between lid member and vibrating rod (See
Gap is filled with silicon to form a complete seal so that no gas leaks occur even from vibration from the vibration motor shaft.
(f) To convey the hydrogen-based/oxygen-based mixed gas from the electrolysis tank to the fuel cell, gas elements comprised mainly of hydrogen gas or in other words, hydrogen-based gas, and gas elements comprised mainly of oxygen gas or in other words oxygen-based gas were separated and both of the gases are passed through the safety device in
For purposes of comparison, electrical power was generated by supplying hydrogen gas from the commercially available hydrogen gas tank to the fuel electrode side of the fuel cell of the sixth embodiment, and supplying air to the air electrode side. This embodiment achieved a 50 percent increase in generated electrical power compared to the comparative example.
The reason for this improved electrical power generation is probably that elements comprised mainly of hydrogen gas or in other words, hydrogen-based gas of this embodiment included tiny amounts of H, H3 and HD and OH and is a characteristic feature (as viewed from analysis results) of the gas of this invention.
The respective electrolytic layers in the single cells were replaced with a hollow layer however approximately the same generated electrical power was obtained.
In the present embodiment, the hydrogen-based/oxygen-based mixed gas generating means of
Plus electrode: Eight pieces of stainless steel plate covered with platinum plating
Minus electrode: Nine pieces of stainless steel plate.
In the present embodiment, the hydrogen-based/oxygen-based mixed gas generating means of
Number | Date | Country | Kind |
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2003-114695 | Apr 2003 | JP | national |
2003-347649 | Oct 2003 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP04/05497 | 4/16/2004 | WO | 7/20/2006 |