CN101600647A - Power generation assembly - Google Patents
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- CN101600647A CN101600647A CNA2007800367165A CN200780036716A CN101600647A CN 101600647 A CN101600647 A CN 101600647A CN A2007800367165 A CNA2007800367165 A CN A2007800367165A CN 200780036716 A CN200780036716 A CN 200780036716A CN 101600647 A CN101600647 A CN 101600647A
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- 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
- Y02E60/10—Energy storage using batteries
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The present invention relates to comprise the power generation assembly of two systems.In a system, generate hydrogen and produce electric power by the hydrogen susceptor by hydrolysis.In another system, produce electric power by electrode and the reaction of ionic redox chemistry.This power generation assembly comprises: use the hydrogen that is mounted with functional materials to generate the hydrogen release unit of container.Perhaps, also can adopt following method: at negative pole and anodal arrangement functional materials, and setting comprises positive pole, negative pole and electrolytical cell device in container.This power generation assembly also comprises: comprise the hydrogen generation unit that generates the fluid container of hydrogen by following dual mode, promptly by with functional materials and water or the aqueous solution (electrolytic solution) reaction and hydrolysis generates hydrogen, and change to make by the functional materials character that causes by hydrolysis and be fixed on the combination of knot intergranular hydrogen atom and generate hydrogen; First generator unit, wherein hydrogen generates the cell device generating in the container; Second generator unit, wherein the hydrogen susceptor utilizes hydrogen to generate the hydrogen gas generation that container generates; And control unit, this device is used for putting on the magnitude of current that is produced behind the load device according to the electric power that first generator unit is produced and controls the amounts of hydrogen that hydrogen producing apparatus generates.
Description
Technical field
The present invention relates to comprise the power generation assembly of two systems, one of them system generates hydrogen and produces electric power by the need hydrogen storage equipment by hydrolysis, and another system produces electric power by relating to the reaction of electrode and many ionic redox chemistries.
Background technology
Proposed power generation assembly, wherein, water has been hydrolyzed generating hydrogen or by making the reaction of drying solid hydride and water vapour generating hydrogen, provide hydrogen to fuel cell etc., and hydrogen and oxygen are reacted with the generation electric current by heating of metal material at high temperature etc.
This device is disclosed in following document.
Patent documentation 1: the open 2004-149394 of Japanese Patent
Patent documentation 2: the open 2002-069558 of Japanese Patent
Patent documentation 3: the open WO2003/020635 of international monopoly
This shortcoming that has the huge device of needs and can produce thermal damage with the method that generates hydrogen by the heat metallic substance.By there being the problem that makes equipment deteriorations such as polymer electrolyte fuel cell because of acid, alkali in the hydrogen generation method that makes the reaction of the drying solid hydride that contains acidity or basic material and water vapour, even and also can under low humidity, generate the serious problems of hydrogen during the existence shut-down operation.
In addition, adopt the method for forming hydrogen of heat metallic substance also to have following defective.In this method, under the environment more than 600 ℃ or 600 ℃, finish reaction.Therefore, violent to water itself evaporation that the hydrolysis purpose provides, and a large amount of water need be provided, thus cause the hydrogen formation efficiency low.On the other hand, adopt to make drying solid hydride that contains acidity or property base material and the water vapour generation method that water vapour reacts also have another shortcoming, i.e. the regeneration of hydride bothers and can generate objectionable impurities very much.
In addition, in known technology, be difficult to control the hydrogen of generation, and also be not provided for the means of excess of storage hydrogen.Therefore may cause because the pressure of the excess gas that is generated sets off an explosion.In addition, with known technology dangerous and be not suitable as be used for industry or commercial such as polymer electrolyte fuel cell, hydrogen fuel engine, hydrogen brazing connect/diced system and semiconductor-fabricating device etc. need the hydrogen supply source of hydrogen storage equipment.
When device (particularly small-sized mobile telephone or automobile) be reversed uses, maybe when needs provide hydrogen at random, the problem of controlling the hydrogen generation is especially remarkable.Device contains the water or the aqueous solution that is injected into.Because the water or the aqueous solution rest on a side of action of gravity usually, therefore be difficult to discharge the hydrogen of generation and guarantee its stream, and be difficult to the change of hydrogen consumption is controlled.
Following document illustration be mounted with hydrogen storage alloy at negative pole, and utilize this alloy and anodal nickel compound to carry out ionic oxide formation reduction chemical reaction and nickel (the Ni)-hydrogen rechargeable cell of charge/discharge.
Patent documentation 4: the open 2002-105564 of Japanese Patent
Summary of the invention
Invent problem to be solved
In this airtight Ni-hydrogen rechargeable cell, when wanting to increase output rating, then increase the content of the magnesium that hydrogen-storage amount is the highest in the hydrogen storage alloy (Mg).But the content that increases magnesium produces following problem: along with the increase of Mg content, the also increase inversely of hydrolysis reaction with electrolytic solution causes weather resistance to reduce and cause because of the pressure that generates hydrogen the problem of battery explosion.
Therefore, the object of the present invention is to provide the technology that can solve the problems referred to above in the prior art, this technology is by using the power supply of power generation assembly as small-sized mobile telephone or automobile etc., even when described device was reversed use or need provides hydrogen at random, the function of also bringing into normal play satisfied the supply of electric power.Increase the hydrogen growing amount and improve miniaturization that battery performance also can implement device and the technology of cost degradation even another object of the present invention is to provide.Another purpose of the present invention is to provide and can converts material (functional materials) by the electric energy that uses easy acquisition material will derive from nature or renewable energy source to, and help the technology of safe and a large amount of storage and transportation, described material can not cause resource exhaustion and environmentally friendly.
Solve the method for problem
According to the present invention, a kind of power generation assembly is provided, it comprises: hydrogen generates the hydrogen release unit of vessel form, and this hydrogen generates container and comprises to be placed in the functional materials in the container or to comprise and be placed in negative pole and anodal functional materials and be arranged on the cell device that is formed by ionogen in the container; The hydrogen generation unit that comprises fluid container, this fluid container generates hydrogen by following dual mode, promptly generate hydrogen, and change to make by the functional materials character that causes by hydrolysis and be fixed on knot intergranular hydrogen atom in conjunction with generation hydrogen by hydrolysis with functional materials and water or the aqueous solution (electrolytic solution) reaction; Make hydrogen generate first generator unit of the cell device generating in the container; Utilize hydrogen to generate second generator unit that the hydrogen that generates in the container makes needs the hydrogen storage equipment generating; And control device, thereby being used for that the electric power that first generator unit produces is put on load device, this device controls the amounts of hydrogen that hydrogen producing apparatus generates according to the magnitude of current of regulating by the load of load device.
When pulverizing functional materials for micro mist, the surface-area of the per unit mass of functional materials increases, and the particle diameter of described micro mist is for reducing the available ultimate size of particle diameter naturally to 1nm.This has significantly promoted the surface reaction of per unit mass, and produces the functional of the unknown.Optimum grain-diameter at 3 μ m with in the scope of 1nm.In order to utilize this micro mist, need to solve variety of issue.The example of these problems comprise micro mist easy placement, disperse and the perviousness of the predetermined substance of preventing of poisoning, heat and electric conductivity and coating material.Form the film of plastic macromolecule resin etc. by micro mist surface, can solve variety of issue at the functional materials of preparation.For example, when functional materials is hydrogen storage alloy, can avoids the surface of hydrogen storage alloy directly to contact main oxygen in the atmosphere, and avoid directly contacting carbon dioxide, nitrogen, moisture etc.Therefore, for example, can prevent to poison and surface reaction.Perhaps, conductive solids or the coarse particle that the powder particle of functional materials is mutually combined to improve heat and electricity to form.In addition, when using the water-soluble polymer resin to film as coating material, even because the pucker ﹠ bloat of functional materials causes film breaks, film also can by by automatic heat release (from own development Hot self-heat generation) thus produce low warm and selfreparing prevents coming off of micro mist and keep tight contact fixes, described water-soluble polymer resin is at the fluidised low-temperature thermoplastic macromolecule resin of molecule below 70 ℃, for example aliphatic polyester resinoid.
In addition, adopt conventional electrochemical plating, filming of vacuum deposition method to have the high problem of manufacturing cost.On the other hand, water-soluble or organic solvent soluble high-molecular resin can be easy to realize that film forms step by making water or organic solvent.In the device of in lower temperature range, operating, can use for example emulsion-type material, described material for example will adopt water soluble organic polymer resin dispersion that chemical synthesis process obtains by lactic acid polymerizes in water and form, and described resin for example is aliphatic polyester resinoid or polyolefin resin etc.In addition, also can use other conventional organic polymer resins.Particularly, when functional materials being placed in the device and cracking along with the passing film surface of working time, the low-temperature thermoplastic of macromolecule resin can be repaired the crackle of film voluntarily, the heat release during for example by operation.
These functions can have following application.When functional materials is hydrogen storage alloy, can and solidifies various functional particulate materials of filming and tackiness agent mixing, and can settle cured article by the inboard or the outside that cured article are seated in the pipe in the device.In the case, preferably adopt following method, that is, the functional particulate material of filming is activated in advance and mix with tackiness agent subsequently, solidify with the organic solvent gelatinization and with thickener again, then it is placed in the inboard or the outside of the pipe in the device.Perhaps, can with thickener as solids adhering in the groove of waved plate.In the case, need be postactivated.Therefore, large-scale plant needn't be firm measuring body container.The application also can obtain identical effect in the array apparatus down: be hydrogen purification devices purpose, that have tubulose or plate-like shape, that be used for reformed gas and low-purity hydrogen with the purified hydrogen; With the heat pump is the heat exchanger of purpose; Or be the hydrogen compressed device of purpose with the pressure that increases hydrogen.
In addition, to have functional materials as the plastic macromolecule resin of coating material when being placed on the battery electrode paper tinsel of nickel metal hydride battery or lithium metal battery etc., and can prevent to make coming off of active material that the particle diameter of active material reduces to cause owing to containing and discharge convergent-divergent that hydrogen or lithium cause.Comprise the generating element of positive pole, negative pole and separatory membrane and to cover insulating film thereon integrated to carry out by connection, can strengthen the function of generating element.Therefore, also can realize the prolongation of battery life.
With regard to the hydrogenation process of functional materials, in the pressurized vessel that imports High Pressure Hydrogen, place the coarse particle of functional materials such as metal or alloy, in temperature-control device, select and be provided with nichrome wire, glow plug, Laser emission plug (レ one サ one radiation プ ラ グ laser emission plug) etc. then, and to carry out calcination, can realize utilizing the automatic heat release of hydrogenation to synthesize an end heat of functional materials.Therefore, can easily obtain to contain nano level metal crystalline hydride micro mist with low cost.
In laser radiation, the refrigerative method reducing metal then of can gasifying by the material of heat such as metallic compound.For example, during magnesium oxide after process object is to use as functional materials, can adopt following method: apply the laser that produces by renewable energy sources such as natural energy resources from the Laser emission plug, thereby the magnesium oxide heat is gasified, wave afterwards and loose oxygen and cool off magnesium gas, can make metal particle by the reductive mode thus.
Use nature or renewable energy source to reduce and hydrogenation and the functional materials for preparing can seal and preserve in water-proof container or waterproof bag.In other words, by using the electric energy that produces by nature or renewable energy source, convert electric energy to the high-density safe material that to preserve and to transport.
For example, when the hydrogenant functional materials is magnesium hydride, can fills it into hydrogen and generate in the container, and in hydrogen generates container, inject the water or the aqueous solution.The result shows, can obtain a large amount of hydrogen from the hydrogen that following two kinds of approach produce: by the hydrogen of magnesium hydrolysis generation; Generate the hydrogen that hydrogen molecule generates by two hydrogen atoms are mutually combined, wherein said hydrogen atom discharges for being fixed between the magnesium crystallization and changing into magnesium hydroxide by reactive magnesium.
When this container was devoted in bath water, cleaning water, the breed water etc., a large amount of hydrogen that generated by hydrolysis can directly be dissolved in the water, therefore, and can be used as the function water manufactured materials of giving function water reduction potential and weakly alkaline pH value.
In addition, provide the hydrogen of generation to the need hydrogen storage equipment, when the need hydrogen storage equipment is fuel cell or hydrogen fuel engine, oxygen and hydrogenation symphysis Cheng Shui.Because this generation water do not contain any acid or alkali, therefore can directly circulate once more enters hydrogen and generates in the container, and does not need to provide water from the external world and can obtain to be used for the raw water of hydrolysis.
Though usually known by using acid or base material the aqueous solution or in the heating of carrying out under the hyperbaric environment more than 140 ℃, described hydrolysis reaction can spontaneously carry out, though and can't continue with the reaction of normal-temperature water, if but use natural existence and (aqueous solution (electrolytic solution) of magnesium chloride/MgCl), then the spontaneous reaction of hydrolysis can be carried out at normal temperatures and pressures to human body beneficial's common bittern.
When this reaction was used for forming cell device in container, the self-discharge phenomenon that this reaction can cause by the short circuit by local element generated electricity.The structure of cell device is as follows.For example, on the active material of negative pole, settle functional materials magnesium (Mg) or magnesium hydride (MgH
2).Use magnesium chloride (MgCl) aqueous solution (electrolytic solution) and polymer solid electrolyte as ionogen.In the anodal diffusion layer, settle metal (Ni, Ti etc.), alloy, metal compound powders, active carbon powder or graphite and catalyzer are mixed formed functional materials with fluoro-resin.Therefore can make the battery that has such as the various active material of oxygen, nickel hydroxide.In this battery, also can be had the unit surface of expansion and can promote the diffusion layer of surface reaction to accept even contain the different kinds of ions of polyvalent ion.Therefore, this battery can be used as polarization resistance and reduces and can realize the magnesium cell of hydrolysis and functionating.
In addition, if not airtight battery, the necessity consideration of covering the hydrogen downstream from ionogen is had, except that polymer solid electrolyte, can also be used in combination and make it to comprise electrolytic solution nonwoven fabric and gelinite (ゲ Le body) with capillary function, therefore hydrogen can be transported to the need hydrogen storage equipment and not make the hydrogen that generates in the hydrogen generation container be lost to the outside, and also can prevent container explosion from the anodal open base area.So just can be applied to the miniaturization battery field of handheld devices such as flat plate cell (tabular Electricity pond tabular battery) and button cell.
Simultaneously, when forming enclosed-type battery, cell device can be constituted so that mix and contain each the ionic active material that to accept hydrogen and magnesium at positive pole, for example metal such as Ni and Ti, alloy, metal compound powders and catalyzer etc., therefore, by enlarging unit surface and can promote the battery element of surface reaction to accept to contain the different kinds of ions of polyvalent ion, reduce and can realize the battery of hydrolysis and functionating but can be used as polarization resistance.
In addition, for example, the electric power that produces by the cell device with container puts on load device to change the magnitude of current by load device, can make the ionization of the magnesium (Mg) of negative pole increase or reduce, begin from the surface of magnesium (Mg) metallic crystal change the amount of magnesium hydroxide into can be correspondingly proportional with it.At this moment, hydrogen atom has lost the fixed position between the Mg metallic crystal, and per two atoms formation hydrogen molecule that mutually combines, thereby generates hydrogen.Its growing amount depends on the reaction that is caused by the electric current by load, so the generation of hydrogen also can be controlled by electric current.
In addition, the cell box (セ Le cell) by stack container or cell device to be constituting battery, also can easily control the hydrogen generation even have the field that high-voltage and hydrogen consumption change need hydrogen storage equipment greatly in use such as fuel cell motive force automobiles.
In addition, utilize this battery structure, magnesium (Mg) particle or powder can be placed in negative pole with the manufacturing container, thereby it can be used as magnesium (Mg) the hydrogenant large vol galvanic cell use that makes negative pole by at first charging.
In addition, when container is constituted as oxygen (O) is used as the store battery (charge/discharge) of active material, with metal or plastic macromolecule coating magnesium (Mg) powder and with the solid-state negative pole that is attached to, use alkaline aqueous solution or non-aqueous solution as electrolytic solution, and for each ion of accepting hydrogen and magnesium and eliminate polarization resistance and at anodal diffusion layer combined function material, thereby can carry out charge/discharge, described functional materials forms by mix metal, alloy, metal compound powders and catalyzer etc. such as Ni and Ti in fluoro-resin.
Under the situation of this battery structure owing to anodal use oxygen in the atmosphere,, and electric capacity is increased sharply so the electric weight that an anodal side can be discharged is unrestricted as active material, in addition can by provide electric and hydrogen these two charge.
In addition, when except oxygen, thionyl chloride and nickel hydroxide, also use metal oxide or cobalt-lithium oxide (LiCoO
2), nickel oxide lithium (LiNiO
2) and manganese oxide lithium (LiMn
2O
4) wait the functional materials of transition metal oxide as the anodal active material, use ionogen and various material as the negative pole functional materials, and when in container, constituting cell device, can form and eliminate) because the composite battery (Complex of the polarization resistance that different kinds of ions (for example hydrogen ion, metal ion and lithium ion etc.) forms closes Electricity pond composite battery.
In addition, when internal tank is not provided with cell device, can reaction chamber be set in its underpart.For example, as the magnesium (Mg) or the magnesium hydride (MgH that adhere to various ways such as tabular, fragment, powder or solidified powder in inside
2) functional materials, on top liquid chamber is set, and add the aqueous solution (electrolytic solution) when constituting battery, the pressure that utilizes siphonage to pass through the hydrogen that generates will push away (outflow) on the aqueous solution (electrolytic solution), and make the pressure reduction and liquid is descended (inflow) by the hydrogen that generates at need hydrogen storage equipment internal consumption, therefore can control the hydrolysis reaction between the aqueous solution (electrolytic solution) and functional materials automatically.
The accompanying drawing summary
Fig. 1 is the overall schematic of an embodiment of the invention;
Fig. 2 has settled small-sized hydrogen to generate the integral body and the partial sectional view of the device of container in an embodiment of the invention;
Fig. 3 has settled medium-and-large-sized hydrogen to generate the integral body and the partial sectional view of container in an embodiment of the invention;
Fig. 4 is the global sections figure that the hydrogen generation container of cell device is not provided in an embodiment of the invention.
The best mode that carries out an invention
With reference to related accompanying drawing, the present invention will be described in more detail.
Below description is reduced the step of functional materials particle diameter, the step that makes functional materials hydrogenant step, the film forming step of shape and settle functional materials.
When functional materials is hydrogen storage alloy, for example have: calcium (Ca), lanthanum (La), magnesium (Mg), nickel (Ni), titanium (Ti) and such as the element of vanadium (V) as the material of hydrogen storage alloy is known usually.Cast hydrogen storage alloys to make La-Ni class alloy and Mg-Ti class alloy etc. with these material mixing together, and with the mixture fusion.Make hydrogen contain (Xi KURA occlude) in these alloys, then make the micro mist of hydrogen storage material by elementary pulverizing (initial stage Fen crushed initial pulverization) or mechanical disintegration.The method of the micro mist of another manufacturing function material is as described below.In pressure vessel, put into particle or Mg particle as the metal or alloy of functional materials.In pressure vessel, import High Pressure Hydrogen, by a end with functional materials heat calcination functional materials, utilize the automatic heat release of hydrogenation generation and burn synthetic, and then make the nano-scale micro mist of Mg-Ni-Fe class alloy, Ti-Cr-V class alloy, Mg-Ca-Ni class alloy etc., perhaps contain the metal hydride crystalline nano-scale micro mist of metals such as Al and Mg.In another approach, by with laser radiation heat material so that material gasification and cooling through the material of gasification, thereby make the micro mist of non-equilibrium (amorphous).
Functional materials also can be formed by hydrogen adsorption material and hydrogen storage alloy, for example, for example mix with one or more hydrogen storage alloys, carbide or oxide powder by carbon material powder with graphite-structure or amorphous structure, and use rare gas element etc. to carry out mechanical disintegration, thereby the nano-scale micro mist of manufacturing function material.Generally well-known catalystic material also can be adopted the manufacturing that uses the same method.
When the median size of the functional materials micro mist of above-mentioned manufacturing was 20nm, specific surface area was about 45m
2/ g.Because being the specific surface area of the powder of 0.5 μ m, particle diameter is about 1m
2/ g, in the micro mist of nano-scale, the surface-area of per unit mass significantly increases.Therefore in the micro mist of nano-scale, except the adsorption function that contains function, hydrogen and methane of hydrogen, catalyst functions such as deodorizing and decomposition also are improved, and in hydrolysis etc. the reaction times of per unit weight also be shortened.
The material of functional materials comprises: halogen or its compounds such as iodine; Oxygen family element such as sulphur and selenium, or its alloy or compound; Nitrogen group elements such as arsenic, antimony, bismuth, or its alloy or compound; Carbon group elements such as carbon, silicon, tin, or its alloy or compound; Alkali metals such as lithium, sodium, potassium, or its alloy or compound; Alkali earth metals such as beryllium, magnesium, calcium, or its alloy or compound; Neat or the mercury element of zinc, cadmium, zinc amalgam, cadmium mercury, or its alloy or compound; Boron group elements such as boron, aluminium, gallium, or its alloy or compound; Transition element, transition element such as the titanium of periodic table of elements period 4, chromium, manganese, iron, nickel for example, transition element such as the lanthanum of transition element such as the zirconium of periodic table of elements period 5, ruthenium, palladium, periodic table of elements period 6, tantalum, platinum, the transition element such as thorium in the 7th cycle of the periodic table of elements, and the alloy of these transition element or compound.Select in these metals one or more to use as required as functional materials.
The functional materials of the nano-scale micro mist form of above-mentioned manufacturing will be through filming step.
Use is dispersed in emulsion-type water-soluble polymer resin in the water as film forming material.Described resin comprises low-temperature thermoplastic aliphatic polyester (Unitika for example, the Terramac that Ltd. makes) or polyolefine (for example Unitika, the Arrowbase that Ltd. makes) and tetrafluoroethylene.The dilute with water film forming material is also kneaded with the functional materials micro mist.Under 110 ℃-150 ℃ that the film forming material heating is also dry then, cause glass transition, and form the film that thickness is 1-5 μ m thus.
When in the film forming step, causing damage, also can adopt following method with the reaction pair functional materials of water.When resin is the agent of plasticity-organic solvent soluble high-molecular, can be in organic solvent with resin dissolves.Solution and functional materials powder are kneaded, and will be mediated the product crushed after being dried and make particle.On the other hand, when resin is the water-soluble polymer agent,, then the exsiccant polymeric agent is pulverized the solution drying of this polymeric agent.Powder is mixed with the functional materials micro mist, and the amount of described powder is for forming the needed amount of film that thickness is 1-5 μ m after the crystallization around the functional material particles.At 110 ℃ of-150 ℃ of following heat treated mixtures, for example the electricity consumption hot extrude is coated with the glass transition that roller (Electricity Hot is pressing ロ one ラ one electrothermal pressure bondingroller) causes film forming material then, and forms film by crystallization.
With the functional materials of above-mentioned manufacturing and the tackiness agent formation thickener of kneading.With thickener be applied in the destination device pipe in this device maybe the inboard or the outside, be applied in the groove of waved plate or be applied on the electrode.Then the coating drying is also heated so that paint solidification and adhesion.As required, can be at the water-soluble of solidified used for surface applying solvent cut or organic solvent solubility plastic macromolecule resin, to carry out film forming.
Spendable herein tackiness agent comprises macromolecule resin commonly used, for example tetrafluoroethylene class (PTFEs), polychlorotrifluoroethylene class (PCTFEs) and polyvinylidene difluoride (PVDF) class fluorine type resin, styrene-butadiene rubber(SBR) class and carboxy celluloses such as (PVDFs).
Stowage arrangement for functional materials, can adopt following method, wherein heat the mixture of the dried powder of the powder of magnesium for example or magnesium hydride or this powder and aliphatic polyester resinoid etc., be ground into particle after causing glass transition, fill and seal with rare gas element and preserve in water-proof container or waterproof bag with any required particle diameter.
To using magnesium (Mg) or magnesium hydride (MgH
2) describe as the hydrolysis and the generator experimental of functional materials.
Trial is carried out the fastest spontaneous hydrolysis reaction experiment with the aqueous solution of the solute that exists naturally.In experiment, use two kinds of samples.Sample 1:1g particle diameter is the above magnesium (Mg) of 200 μ m.Sample 2:1g particle diameter is the following magnesium hydride (MgH of 50 μ m
2).
Use three kinds of aqueous solution as the aqueous solution in the experiment.The aqueous solution 1: water (H
2O).Aqueous solution 2:8% citric acid (C
6H
8O
7) aqueous solution.Aqueous solution 3:5% bittern (Magnesium dichloride hexahydrate MgCl
26H
2O) aqueous solution.
Get three kinds of each 5cc of the aqueous solution under the room temperature (20 ℃), in each sample, begin experiment in the injecting tube.When the spontaneous reaction rate is low, Yi Bian on one side add hydrothermal solution gradually and observe and measure.
For sample 1, at the aqueous solution 1: water (H
2O) in, do not react, observing particle surface when being heated to 90 ℃ has a small amount of bubble.On the other hand, at aqueous solution 2:8% citric acid (C
6H
8O
7) in the aqueous solution, reaction is violent, causes temperature to raise, and at 2 minutes with interior end reaction.At aqueous solution 3:5% bittern (Magnesium dichloride hexahydrate MgCl
26H
2O) in the aqueous solution, reaction is carried out slowly, is accompanied by reacting by heating and quickens, and observes floating of bubble under 90 ℃.
For sample 2, at the aqueous solution 1: water (H
2O) in, observe bubble, when being heated to 90 ℃, observe floating of bubble.At aqueous solution 2:8% citric acid (C
6H
8O
7) in the aqueous solution, reaction is violent, causes temperature to raise, and at 1.5 minutes with interior end reaction.At aqueous solution 3:5% bittern (Magnesium dichloride hexahydrate MgCl
26H
2O) in the aqueous solution, reaction is carried out fast, and the increase that is accompanied by the time is risen by automatic Heating temperature.When being heated to 90 ℃, observe significantly floating of bubble.
The final collecting amount of the hydrogen of each aqueous solution is identical: sample 1:800cc (the magnesium weight ratio is 8% (weight)), sample 2:1400cc (magnesium weight ratio: 14% (weight)).
Then, adopt air (oxygen) as the anodal active material, with magnesium hydride (MgH
2) as the cell device of negative pole, attempt carrying out generator experimental.Commercially available magnesium cell is decomposed, and remove the magnesium that is placed in negative pole.With organic solvent mixing magnesium hydride powder and water-soluble plastic macromolecule agent.Joint has the shell of electrode size, and heats so that the gained mixture is bonded on the electrode foil as solid in compression.
Use is as the single battery box (Unit セ Le single cell of commodity parts) assembling barrier film, positive collector electrode and miscellaneous part, use 5% bittern (Magnesium dichloride hexahydrate MgCl
26H
2O) aqueous solution is as electrolytic solution.Burn till (baked becomes firing) then by active carbon powder or graphite, catalyzer etc. are mixed and are applied on the Copper Foil with fluoro-resin, thereby form the positive collector electrode of netted commodity.
The measured value of the reaction formula of experiment and electric voltage (play Electricity and press electromotive voltage) is as follows: anodal reaction formula: 2Mg → 2Mg
2++ 4e
-Negative reaction formula: O
2+ 2H
2O+4e
-→ 4OH
-Net reaction: 2Mg+O
2+ 2H
2O → 2Mg (OH)
2↓; Initial electric voltage is 2.7V.
Known to use magnesium can obtain the battery that can compare favourably with lithium cell at negative pole.The theoretical electromotive force of air and magnesium is 2.7V, but simultaneously because by hydrolysis reaction (reaction formula: MgH
2+ 2H
2O → Mg
2++ 2OH
-+ 2H
2↑) the resulting polarization resistance of plural ion that produces, electromotive force is reduced gradually.
In this experiment, because galvanic cell is used as electrolytic solution with the muriatic aqueous solution, thereby hydrolysis reaction is promoted.But when using other functional materialss and this battery to be used as rechargeable cell, the preferred use comprises the alkaline electrolyte of potassium hydroxide (KOH) and organic solvent as electrolytic solution.
The observed value of hydrogen growing amount is about 650cc/g (the magnesium weight ratio is 6% (weight)).The proportional relation of the reduction of electric weight and magnesium.The reduction that shows magnesium in the table 1 is with respect to the chart of electric weight and the electric current chart with respect to the negative pole area.The measuring result of using faraday's rule basis to obtain calculates the numerical value in the chart.
[table 1]
According to faraday's rule, theoretical electric weight Q (unit: C or As) can calculate by Q=Fmn/M.Wherein, F is a Faraday's number; M is the quality of active material; M is the formula weight of active material; N is the electronic number of participation reaction, and the quality of electric weight and active material is proportional.
Describe with reference to Fig. 1,2 and 3 pairs of embodiments of the present invention.Among Fig. 1, anodal 6, barrier film 4 and negative pole 3 laminations that are mounted with functional materials 2 are constituted cell device and be arranged on hydrogen generate in the container 1.Lead by electric wire self-electrode in future is connected with conduction current with load device 10, by hydrogen conduit 12 container 1 is connected and is communicated with needing hydrogen storage equipment 30 simultaneously, thereby constitute whole device 101 of the present invention.
The embodiment 102 of Fig. 2 display power supply device has this device in use usually.In this embodiment 102, hydrogen is generated container 1 be assembled in the portable phone 40.Fig. 3 shows that stack hydrogen generates the embodiment 103 of the medium-and-large-sized device of container 1.
When hydrogen generates container 1 is open galvanic cell or with oxygen during as the rechargeable cell of active material, the positive pole 6 that following formation is netted: with the mixture of metal or alloy such as Ni and MgTi, metal oxide powder, active carbon powder or graphite and fluoro-resin functional materials as diffusion layer 5, it is inboard and coating burnt till this mixture to be applied to Copper Foil again, and connects the line on the electrode foil.On the other hand, when hydrogen generates container 1 is when oxygen is used as the airtight rechargeable cell of active material, followingly form anodal 6: with metal or alloy such as Ni and MgTi, metal oxide powder blending dispersion functional materials in the precursor solution (precursor solution precursor solution) as diffusion layer 5, it is inboard and coating burnt till to disperse thing to be applied to Copper Foil again, and connects the line on the electrode foil.
With solid macromolecule electrolyte film, glass fibre or nonwoven fabric and acrylic resin or with radiation exposure as the polyglutamic acid of natto silk composition and synthetic natto (through the soybean of fermentation) resin isogel material mixing, thereby form barrier film 4.From improving electricity generate function and energy siphon water or the aqueous solution (electrolytic solution) 21 to replenish the viewpoint of enough water, barrier film 4 partly extends in the fluid container 20 from cell device.
When hydrogen generation container 1 has closed structure, not to need to use gelatinous material especially in barrier film 4.Can't as the barrier film 4 of Fig. 2, be provided with but work as fluid container, or when positive pole one side of container is open, nonwoven fabric that employing is flooded through electrolytic solution etc. and gelatinous material.
When hydrogen generation container 1 had hydrolysis function or galvanic cell function, the functional materials 2 that is placed in negative pole 3 inboards was the cured product of tabular of magnesium (Mg), fragment, perhaps is magnesium hydride (MgH
2) the cured product of coarse particle.On the other hand, when hydrogen generates container 1 and has the function of rechargeable cell, by will mixing, and make mixture forming with magnesium (Mg) powder particle and the tackiness agent of plastic macromolecule or metal coated, thus formation functional materials 2.Functional materials 2 is connected with the electrode foil that is provided with lead.
Material and form to cell device are not particularly limited, and can use material known and form.When using the plastic macromolecule agent powder of functional materials to be filmed or when bonding, the breakage and prevent that powder from dispersing of can selfreparing filming.Therefore, can improve weather resistance.Equally, for example adopting this technology to help to improve weather resistance and other performances in alkali button battery, nickel-cadmium cell, nickel metal hydride battery, lithium ion battery and the lead storage battery.
In fluid container 20, make water or bittern (Magnesium dichloride hexahydrate MgCl
26H
2O) aqueous solution is as the aqueous solution (electrolytic solution) 21.But,, according to the structure and the purpose of battery, select conventional electrolysis liquid such as potassium hydroxide (KOH), sodium hydroxide (NaOH) and non-aqueous solution, and inject in the fluid container 20 according to the functional materials of cell device.
Though do not express connector element in the drawings, but generate the outside of container 1 at hydrogen, be provided with by the distribution pipe box (joining Line ソ ケ Star ト wiring socket) of load device 10 and control device, need the hydrogen pipe box (the plain ソ ケ of water Star ト pipe socket) of hydrogen storage equipment 30 and be used for water or the aqueous solution (electrolytic solution) are transported to the connector element that the sealing liquor charging mouth institute combination of barrier film 4 forms from fluid container 20.Therefore, constitute hydrogen with dismountable form and generate container 1.
Need hydrogen storage equipment 30 for using the device of hydrogen, for example, the hydrogen burner in hydrogen fuel engine in the fuel cell in the battery, the hydrogen engine and the jet-propelled engine of hydrogen, the welding/cutting, the hydrogen pump in the hydrogen station.Connection by the hydrogen pipe and connection make hydrogen generate container needs hydrogen storage equipment to interosculate with purpose, and hydrogen is provided to and needs in the hydrogen storage equipment 30 and do not generate stop in the container 1 at hydrogen.
In addition, when single battery box that cell device is formed or hydrogen generate container 1 stack constituent apparatus, can more easily this device need be applied to high-voltage and hydrogen consumption Application Areass such as fuel cell car at random.
In medium-and-large-sized device, with the air blast pump air 22 is sent in the container, with reaction of promotion anodal and increase external pressure, thereby can prevent that hydrogen is from the container internal leakage.
Below the hydrogen with said structure is generated container 1 sequence of operations be described.In galvanic cell, when the switch opens of load device 10, electronics leaves hydrogen and generates active material in the container 1, arrives anodal 6 by lead via load device 10 as electric current.Simultaneously, the active material of negative pole 3 is oxidized, ionization, stripping in electrolytic solution, and the ion of gained arrives anodal 6 via barrier film 4.In anodal 6 diffusion layer 5, nickel hydroxide isoreactivity material and the electron reaction that has arrived.With this reaction while, when negative pole 3 was the hydrogenant functional materials, functional materials began oxidized and ionization from a surperficial side, thereby caused the character of functional materials to change and consumption, and made the hydrogen atom that is fixed between the crystallization lose the fixed position.The result causes two hydrogen atoms formation hydrogen molecule that mutually combines, thereby generates hydrogen.Be dissolved in that hydrogen partial in the electrolytic solution is ionized and arrive anodal 6 via barrier film 4.In anodal 6 diffusion layer 5, as the oxygen (O) in the air 22 of active material or other active materials and the electron reaction that arrives anodal 6.Remaining hydrogen offers need hydrogen storage equipment 30 via hydrogen conduit 12 and is consumed.
In addition, in load device 10, when load resistance reduced, the magnitude of current increased, and the growing amount of hydrogen also increases.When switch cut out, the generation of hydrogen also was reduced to minimum.
If formed the hermetic type rechargeable cell of anodal 6 functional materials by metal or alloy such as Ni, MgTi and metal oxide powder, then discharge process is as follows.When load device 10 switch opens the time, for example, flowed out in the electrolytic solution from hydrogen generates the functional materials of the negative pole 3 the container 1 by the hydrogen atom that contained, and be ionized, arrive anodal 6 diffusion layer 5 by barrier film 4.Simultaneously, electronics arrives anodal 6 via load device 10 as electric current, thus the oxygen in hydrogen ion and the oxide compound (O), nickel hydroxide and the electron reaction that arrived positive pole 6.
On the other hand, during charging, make hydrogen be dissolved in the electrolytic solution and contain in the active material of negative pole by hydrogen-permeable membrane (water Su Tou Over film hydrogen permeablemembrane).In another method, external voltage is connected on two electrodes, make electrifying electrodes to be hydrolyzed to generate hydrogen, hydrogen is wrapped up in the active material of negative pole 3 afterwards.
Because polarization resistance reduces, so it is easy to use to have the structure of hydrogen generation container of this cell device.Except above-mentioned advantage, the structure that hydrogen generates container also has the advantage that can use external power source to start or control, also can utilize various ionogen and ionization reaction to carry out the generation and the reduction of material in addition.
With reference to Fig. 4 embodiment 104 is described.Hydrogen generates container 1 and comprises reaction chamber 29 in container 1 bottom.Various forms of functional materialss 2 such as tabular, fragment, powder or solidified powder or hydrogenant functional materials 2 are placed in reaction chamber 29.On the top of container 1 liquid chamber 28 is set, and the aqueous solution (electrolytic solution) 21 is put into liquid chamber 28.
In hydrogen generates container 1, on the connecting tube in the interlayer that is arranged between liquid chamber 28 and the reaction chamber 29 check valve 37 is set.On the connecting tube between the top of the bottom of reaction chamber 29 and liquid chamber 28, check valve 38 is set.Be provided with and the hydrogen conduit 12 that needs hydrogen storage equipment 30 to be connected and to be communicated with on the top of reaction chamber 29.A plurality of identical hydrogen that are connected in parallel generate container 1.
When functional materials 2 is magnesium (Mg) or magnesium hydride (MgH
2) time, in the aqueous solution (electrolytic solution) 21, use magnesium chloride (MgCl) can not generate any objectionable impurities.Therefore, also can select to use the aqueous solution commonly used (electrolytic solution).
These two generates a large amount of hydrogen to the hydrogenant functional materials from hydrolysis and hydride.Therefore, even consider the water yield that reduces in the atmosphere because of being diffused into, in the need hydrogen storage equipment, generate, condense into the also needed water yield of sufficient to guarantee hydrolysis of the water yield revealing and collect.So the circulation that makes the water of generation enter fluid container once more can be eliminated the needs from extraneous make up water.
When adopting this mode to constitute hydrogen generation container, carry out following sequence of operations.The pressure that utilizes siphonage to pass through the hydrogen that generates will push away (outflow) with stopped reaction on the aqueous solution (electrolytic solution) 21.When need hydrogen storage equipment 30 consumes the hydrogen that generates, thereby the pressure reduction makes the aqueous solution (electrolytic solution) 21 descend (inflow) to cause hydrolysis reaction of the aqueous solution (electrolytic solution) 21 and functional materials 2.Therefore, need not just can realize control automatically by any electronic controls.
Describe the present invention, but the present invention is not limited only to above-mentioned embodiment, and can in the scope of the present invention's design, improves or change.
Utilizability on the industry
According to the above description, the present invention can realize improving function, weight reduction, saving cost Deng. And, use harmless, natural existence and inexhaustible material, can Realize the natural energy resources of storage and transportation safety. The present invention can provide resource can be inexhausted, help In preventing global warming and can realizing the energy of future generation that complete zero-emission circulates.
Claims (20)
1. power generation assembly, it comprises:
Hydrogen generates the hydrogen release unit of vessel form, and described container comprises to be placed in the functional materials in the container or to comprise and is placed in negative pole and anodal functional materials and is arranged on the cell device that is formed by ionogen in the container;
The hydrogen generation unit that comprises fluid container, described unit generates hydrogen by following dual mode, promptly generate hydrogen, and change to make by the functional materials character that causes by hydrolysis and be fixed on knot intergranular hydrogen atom in conjunction with generating hydrogen by functional materials and water or as the reactant aqueous solution hydrolysis of electrolytic solution;
Make described hydrogen generate first generator unit of the cell device generating in the container;
Utilize described hydrogen to generate second generator unit that the hydrogen that generates in the container makes needs the hydrogen storage equipment generating; And
Control unit, this unit are used for the electric power that described first generator unit produces is put on load device, to control the amounts of hydrogen that described hydrogen producing apparatus generates according to the magnitude of current of being regulated by the load of described load device.
2. the hydrogen of claim 1 generates container, and wherein, described functional materials is piece, fragment or the powder of any one or multiple material of following (1)-(4):
(1) such as the alloy of the carbon group element of silicon (Si), carbon group element or contain the compound of the hydride of carbon group element;
(2) such as the alloy of the alkali metal of lithium (Li), alkali metal or contain the compound of the hydride of alkali metal;
(3) such as the alloy of the alkali earth metal of magnesium (Mg) and calcium (Ca), alkali earth metal or contain the compound of the hydride of alkali earth metal;
(4) such as the alloy of the boron group element of aluminium (Al) and boron (B), boron group element or contain the compound of the hydride of boron group element.
3. claim 1 or 2 functional materials, wherein, described functional materials is powder, coats and through the solidified powder or from the surface or after the solidified surface is with the plastic macromolecule coating coating is converted into film through plastic macromolecule film or metallic membrane, and is used for following any application:
(1) is used for the catalyzer of moulded products, coating material or soaker etc.;
(2) be mixed into medicine, food etc. or be used for the material of container etc., this material is dissolved in liquid with hydrogen;
(3) preserve the energy storage material of container in waterproof and sealing, bag etc.;
(4) be used for the gas detection material of detection part etc.;
(5) the device etc. in be used for the purifying or the storage (adsorbing/contain) of predetermined substance or be used for heat pump or the material of hydrogen supercharging;
(6) be used to comprise the electrode of chemical devices of battery or the material of diffusion layer.
4. each hydrogen generates container among the claim 1-3, wherein, it is the composite battery that comprises the cell device that is made of anodal, ionogen and negative pole in container that described hydrogen generates container, also uses any one or multiple active material such as thionyl chloride, nickel hydroxide, metal oxide, transition metal oxide outside the described anodal deoxygenation.
5. each hydrogen generates container among the claim 1-4, wherein, it is open container that described hydrogen generates container, in the described container, at the netted diffusion layer of the following formation of an anodal side: for example functional materials is applied on the Copper Foil and subsequently coating is burnt till, described functional materials is formed by the mixture of powder such as metal, alloy, metallic compound and active carbon powder or graphite and fluoro-resin.
6. each hydrogen generates container among the claim 1-5, and wherein, it is encloses container that described hydrogen generates container, in the described container, settles the functional materials that is formed by the mixture of powder such as metal, alloy, metallic compound etc. to form diffusion layer in an anodal side.
7. each hydrogen generates container among the claim 1-6, and wherein, described electrolytic solution comprises any one or multiple material of following (1)-(5):
(1) water,
(2) organic solvent,
(3) bittern (MgCl),
(4) muriate, and
(5) aqueous solution of acid or alkali or organic solution.
8. each hydrogen generates container among the claim 1-7, it is characterized in that, comprises the barrier film that constitutes by solid macromolecule electrolyte etc., fiber with capillary function are made up with colloid.
9. each hydrogen generates container among the claim 1-8, and wherein, the magnesium cell of described container for being made of negative pole, described negative pole are mounted with the magnesium (Mg) of the cured form of tabular, fragment or particle, or are mounted with magnesium hydride (MgH
2) active material that forms of the cured form of powder.
10. each hydrogen generates container among the claim 1-9, wherein, with the air blast pump air is sent into an anodal side.
11. each hydrogen generates container among the claim 1-10, wherein, uses external power or hydrogen to charge.
12. each hydrogen generates container among the claim 1-11, wherein, described hydrogen generates container and comprises and be used for water or as the detachable fluid container of the aqueous solution of electrolytic solution.
13. each hydrogen generates container among the claim 1-12, wherein, the cell box that described hydrogen generates container or cell device can use separately or use with stacking pattern.
14. each hydrogen generates container among the claim 1-13, wherein, external power source starting or control electrode in the described cell device perhaps causes the generation or the reduction of material in electrode.
15. the power generation assembly of claim 1, wherein, the described hydrogen storage equipment that needs is for using the device of hydrogen, the for example hydrogen burner in hydrogen fuel engine in the fuel cell in the battery, the hydrogen engine and the jet-propelled engine of hydrogen, the welding/cutting, the hydrogen pump in the hydrogen station, and the connection by the hydrogen conduit and connection make hydrogen generate container to interosculate with purpose need hydrogen storage equipment.
16. each power generation assembly in claim 1 and 15, wherein, described hydrogen generates the hydrogen that container generates and is provided for the described hydrogen storage equipment that needs, and closes to generate with oxidation and to enter fluid container by circulation subsequently and reuse water.
17. each power generation assembly in the claim 1,15 and 16, wherein, the electric power that first power generation assembly in the described cell device is produced puts on described load device, and control the growing amount of hydrogen according to the magnitude of current, the following generation of described hydrogen: the character that causes the functional materials of negative pole by ionization changes, and makes the knot intergranular hydrogen atom that is fixed on functional materials become hydrogen molecule.
18. each power generation assembly among claim 1, the 15-17, it is characterized in that, form liquid chamber and reaction chamber with position difference, to utilize the water in the siphonage control reaction chamber or as the aqueous solution of electrolytic solution and the hydrolysis reaction of functional materials, described siphonage is produced by the pressure change of the hydrogen of hydrogen that generates and the consumption of described need hydrogen storage equipment.
19. one kind is used for each the method for functional materials of hydrogenation claim 1-18, wherein, in pressure vessel, import High Pressure Hydrogen, and the end by calcination functional materialss such as laser radiations, with the automatic heat release that utilizes hydrogenation hydrogenation is carried out automatically, thereby obtain the powder of hydrogenant functional materials.
20. one kind is used for reducing each the method for functional materials of claim 1-19, it is characterized in that, comprise following steps with the restoring function material: in pressure vessel, put into alloy or metallic compound material, in described pressure vessel, import hydrogen or rare gas element etc., heat described material by high temperature such as laser radiations, then with the material cooled that gasifies.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP209157/2006 | 2006-07-31 | ||
| JP2006209157 | 2006-07-31 | ||
| JP142528/2007 | 2007-04-27 |
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| Publication Number | Publication Date |
|---|---|
| CN101600647A true CN101600647A (en) | 2009-12-09 |
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ID=41421529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800367165A Pending CN101600647A (en) | 2006-07-31 | 2007-06-05 | Power generation assembly |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111003688A (en) * | 2019-12-31 | 2020-04-14 | 世能氢电科技有限公司 | Magnesium-based hydride MgH2Method for preparing hydrogen by hydrolysis |
| CN114554834A (en) * | 2019-10-14 | 2022-05-27 | 海尔智家股份有限公司 | Atmosphere control system for indoor gardening equipment |
-
2007
- 2007-06-05 CN CNA2007800367165A patent/CN101600647A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114554834A (en) * | 2019-10-14 | 2022-05-27 | 海尔智家股份有限公司 | Atmosphere control system for indoor gardening equipment |
| CN114554834B (en) * | 2019-10-14 | 2024-02-20 | 海尔智家股份有限公司 | Atmosphere control system for indoor gardening equipment |
| CN111003688A (en) * | 2019-12-31 | 2020-04-14 | 世能氢电科技有限公司 | Magnesium-based hydride MgH2Method for preparing hydrogen by hydrolysis |
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Open date: 20091209 |