CN100391827C - Field-assisted gas storage materials and fuel cells comprising same - Google Patents
Field-assisted gas storage materials and fuel cells comprising same Download PDFInfo
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- CN100391827C CN100391827C CNB2004800218129A CN200480021812A CN100391827C CN 100391827 C CN100391827 C CN 100391827C CN B2004800218129 A CNB2004800218129 A CN B2004800218129A CN 200480021812 A CN200480021812 A CN 200480021812A CN 100391827 C CN100391827 C CN 100391827C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
- H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
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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
- Y02E60/32—Hydrogen storage
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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
- Y02E60/50—Fuel cells
Abstract
Field-assisted gas storage materials having improved gas storage density/solubility and improved gas mobility are described. In some embodiments, the gas storage material comprises a material comprising gas storage space and enough ionic character to sustain an electric dipole during application of an applied field, wherein the applied field does not cause the material to become conductive, and wherein a gas is stored within the gas storage space in the material. In other emdodiments, the gas storage material comprises a meterial comprising gas storage space and enough magnetic character to allow magnetic dipoles therein to be enhanced during application of an applied field, and wherein a gas is stored within the gas storage space in the material. In embodiments, the gas is capable of diffusing through the material, and application of a field allows at least one of the following to be controlled: (a) gas solubility; (b) gas uptake; (c) gas discharge; and (d) gas mobility.
Description
Technical field
The present invention relates generally to auxiliary (field-assisted) gas storage material.More specifically, the present invention relates to field-assisted gas storage materials, the wherein storage density of gas or solvability and mobility, and the absorption of gas (uptake) and discharging can be controlled by applied field.Even more specifically, the present invention relates to an auxiliary hydrogen storage material and comprise its fuel cell, the wherein density of hydrogen or solvability and mobility, and the absorption of hydrogen (uptake) and discharge and to control by applied field.
Background technology
Fuel cell technology is the industry with fast development of potential far-reaching benefit.The current market of fuel cell is near 218,000, and 000 dollar, this quantity to 2004 year plans to rise to 2,400,000,000 dollars, and will reach 7,000,000,000 dollars by 2009.If implement successfully, in other interests, because the dependence of external mineral fuel is descended, the fuel cell technology expection can obtain the national energy security of raising, and because the airborne contaminants discharging significantly reduces the Air quality that the fuel cell technology expection can be improved.
Fuel cell can carry out extremely effectively, and energy transformation also can be used for transportation and static (stationary) purposes.For transport applications, fuel cell vehicle is hopeful to substitute conventional internal combustion engine vehicles.Fuel cell vehicle can and only discharge water and energy with hydrogen for combustion, and conventional internal combustion engine vehicles burn fossil fuels for example gasoline or diesel oil, and discharges deleterious particle and greenhouse gases to atmosphere.
Fuel cell vehicle also has many other advantages.The energy efficiency of fuel cell vehicle be conventional vehicles up to three times or more.Fuel cell vehicle can be converted into electric power with 40-45% in the fuel supplying or more energy, and conventional internal combustion engine vehicles can only be converted into electric power with about 16% in the fuel supplying.In addition, because fuel cell vehicle is provided by the electric engine work of moving-member considerably less (those pumps and the blower fan that promptly only provide fuel and refrigerant to need), therefore vibrations and the noise in the fuel cell vehicle will reduce greatly, and will save General Maintenance (that is, changing oil, change sparking plug etc.).
The work and the battery of fuel cell are closely similar, can recharge when power drain.Yet battery uses electric current to recharge, and fuel cell uses hydrogen to recharge.Usually, hydrogen fuel cell is by changing the chemical energy among hydrogen and the oxygen into water, obtain electricity and heat and work, then with in its input electric engine with the wheel of the driver fuel battery vehicles.
The ideal fuels that is considered to fuel cell vehicle at this area hydrogen.Hydrogen is element the abundantest in the universe, is the 3rd the abundantest element on the earth, can from multiple renewable energy source, obtain, and, when hydrogen acts as a fuel in fuel cell when consuming, only produce water and do not produce greenhouse gases such as carbonic acid gas.The usual manner that storage is used for the hydrogen that terminal uses and carry comprises: (1) liquid state or gaseous hydrogen, (2) hydrocarbon fuel (being mineral fuel) and (3) solid material (being metal hydride).
In fuel cell, use liquid state or gaseous hydrogen unsatisfactory as the energy.Hydrogen is highly combustible and burning needs low hydrogen-air concentration.In addition, hydrogen is than difficult transportation of other liquid fuel and storage.In addition, at present only there is the very limited Infrastructure can dispensing hydrogen for the public.
Unfavorable for what prevent to use pure hydrogen to act as a fuel and bring, the design of many fuel cells concentrates on uses hydrocarbon or pure fuel (for example methyl alcohol), Sweet natural gas and petroleum distillate.Yet these designs have their shortcomings own, for example, need apparatus for reforming of fuel, and this reformer is cracked into hydrogen, carbonic acid gas and water with hydrocarbon fuel.Hydrogen by such reformer production is impure, and it has reduced the efficient of fuel cell.In addition, adding reformer converts hydrocarbon fuel to total efficiency that hydrogen can make fuel cell and is reduced to about 30-40%.Use other shortcoming of hydrocarbon fuel to comprise: the reformer of (1) appendix has increased complicacy, cost and the maintenance of fuel cell system; (2) if reformer allows carbonic acid gas to arrive the anode of fuel cell, the performance of battery will descend gradually; And (3) reformer produces greenhouse gases and other air pollutant.
The hydrogen storage material that chemistry stores hydrogen fuel is considered to be in the favourable hydrogen source that is used for fuel cell in a large amount of potential application.But, in these materials, obtain enough hydrogen solubility, storage density and mobilities and proved very difficult.In addition, also there is not to obtain on power is exported on a large scale, to control the ability of hydrogen absorption and rate of release for the application of for example fuel cell.Therefore, need improved hydrogen storage material, comprise from other gas optionally separating hydrogen gas, catalysis and be used for the vehicles, special-purpose generating (personal power generation) and the static fuel cell that generates electricity to adapt to the requirement of extensive application.
The form that deep research has concentrated on solid metal hydride about 30 years stores hydrogen in the past.Common heat release produces metal hydride when metal contacts hydrogen with alloy.Most of hydrogen and these metals and/or alloy reaction also form new compound, and small portion hydrogen resolves into atomic hydrogen and enters subsequently in the gap of metal lattice in thermopositive reaction.By heating,, can use from the hydrogen of wherein regenerating by the electrolytic oxidation of hydride or by reacting with oxide compound or water.An advantage using metal hydride to store hydrogen is that the volume density that stores hydrogen in metal hydride is compared relatively large with other storage medium.Yet the hydrogen of regenerating from hydride is the same with secondary metal to be difficult.And metal has significantly increased the weight of fuel cell system.
The example of known hydrogen storage material comprises metal hydride, for example FeTiH
2And LaNi
5H
6, they contain the hydrogen of have an appointment 1.9% weight and about 1.5% weight respectively, release hydrogen when heating.Although FeTiH
2And LaNi
5H
6Have acceptable regeneration temperature, but too low based on the hydrogen richness of weight percentage to the fuel cells applications that is used for the vehicles.Other metal hydride is MgH for example
2And TiH
2Have higher hydrogen richness, be respectively about 7.6% weight and 4.0% weight, but must be heated to high temperature (promptly being higher than about 100 ℃) with regeneration hydrogen.The capacitance loss that uses metal hydride to comprise disproportionation, poison, follow as other shortcoming of gas storage material, and need some storage alloys of regeneration.
Carbon nanotube is the another kind of potential hydrogen storage material of having furtherd investigate.Carbon nanotube is the relevant structure of soccerballene, by constituting with the seamless graphite cylinder that contains pentacyclic top seal at arbitrary end.Carbon nanotube powders tends to have the volumetric efficiency of poor efficiency accumulation and difference.In addition, the carbon nanotube manufacturing is very expensive, can't obtain the amount that needs in the business-like hydrogen storage applications at present.
Other known hydrogen storage material is included as the zeolite of highly porous crystalline aluminosilicate.Yet according to the weight of per unit weight zeolite hydrogen, the ability of zeolite storage of hydrogen is not enough for the fuel cells applications of the vehicles.In addition, must heat zeolite to trigger therefrom release hydrogen, the time of response limited by thermal diffusion in the zeolite large section.
Hydrogen is stored and carried to following hydrogen economic needs effective means, is used for the application of the fuel cell of automobile and distributed power, and other a large amount of application.Proposed the method for several hydrogen gas storages, comprised those of above-mentioned discussion, but do not had material or method to demonstrate needed hydrogen solubility and storage density at present, hydrogen mobility, and/or the hydrogen absorption/releasability of commercial use requirement.
Therefore, the hydrogen storage material that need not have the whole shortcomings of present hydrogen storage material.
In addition, although hydrogen storage material has been described as above, various other gases also can be stored in the gas storage material, and these gas storage material can be used for a large amount of purposes, for example gas delivery, discharge chelating (emissions sequenstration) and drying air stream.Also need to store the improved gas storage material of the gas except that hydrogen.
Therefore, need light and handy, compact, relatively cheap, safe and wieldy gas storage material.Also need to provide the gas storage material that has higher gaseous solubility (promptly higher gas storage density) and higher gas transfer rate than present feasible material.These materials that need comprise the mechanism that makes the fine pilot-gas loading/absorption of energy and discharge equally.
Summary of the invention
These need and other need solve by embodiment of the present invention.The gas storage material of using in the embodiment that the present invention describes comprises wide variety of materials component and type, and light and handy, compact, relatively cheap, safely, be easy to use.In addition, embodiment of the present invention can be lower than under the desired temperature of traditional gas storage material, obtain more effective and controlled gas storage and recovery from gas storage material.
Embodiment of the present invention comprise the gas storage material with high atmosphere storage density and high gas transfer rate.These gas storage material can comprise the contained gas storage area and be enough to keep the material of the ion characteristic of eelctric dipole during applying impressed field, and wherein applying of impressed field can not make this material conduction that becomes; And gas storage is in the gas storage space of material, and wherein said gas can diffuse through material.Comprise electric field at this impressed field, might combine with stress field or strain field.
Other embodiment of the present invention comprises the gas storage material of heavy body.These gas storage material can comprise the material that comprises crystalline structure and be enough to keep the ion characteristic of eelctric dipole during applying impressed field, and wherein applying of impressed field can not make this material conduction that becomes; And gas storage is in material, and wherein said crystalline structure comprises the specially designed dipolar crystalline structure that comprises, and this dipole allows the crystalline structure of this design to keep the stored-gas of predetermined amount; Wherein stored-gas combines with the crystalline structure of design, has reduced the free energy of material, thereby has increased the available gas solvability of material.These gas storage material can further comprise being used for controlling to material to be taken in gas and discharge the mechanism of gas from material.Described mechanism can comprise impressed field (that is, electric field, stress field, strain field and their combination).
Utilize the gas storage material of extra electric field can comprise dielectric materials, piezoelectric, ferroelectric material, stupalith, non-metallic material, polymer materials, semiconductor material, and/or any other suitable material.
Other embodiment of the present invention comprises the gas storage material with high atmosphere storage density and high gas transfer rate.These gas storage material can comprise the contained gas storage area and be enough to make magnetic dipole wherein to arrange the material of the magnetic feature of (aligned) during applying impressed field; With the gas in the gas storage space that is stored in material, wherein said gas can diffuse through material.Impressed field in these embodiments can comprise independent magnetic field or with the combining of stress field and/or strain field.These gas storage material can comprise the magneticsubstance that comprises the ferro-magnetic composition, and wherein this magneticsubstance is added to solid-state material, metal, pottery, polymkeric substance, and/or in the mixture of magneticsubstance and nonmagnetic substance.
Other embodiment of the present invention comprises the gas storage material with high atmosphere storage density and high gas transfer rate.These gas storage material can comprise material, comprising: (a) gas storage space; (b) during applying extra electric field, be enough to keep the ion characteristic of eelctric dipole; (c) during applying externally-applied magnetic field, be enough to make wherein magnetic dipole enhanced magnetic feature; With the gas in the gas storage space that is stored in material, wherein said gas can diffuse through applying of material reconciling the exterior and interior of the body added electric field and externally-applied magnetic field to make following at least a controlled: (a) gaseous solubility of gas storage material; (b) the gas intake (gas uptake) of absorption gas storage material; (c) gas emissions (gas discharge) that discharges from gas storage material; (d) the gas transfer rate in the gas storage material.
In gas storage material of the present invention, the applying of impressed field makes following one or more controlled: (a) gaseous solubility of gas storage material; (b) the gas intake of absorption gas storage material; (c) gas emissions that discharges from gas storage material; (d) the gas transfer rate in the gas storage material.
The gas that stores in any of these gas storage material can comprise: hydrogen, gas (being carbonic acid gas) with permanent dipole, can be with molecule or atomic transport polarizable gas (being the hydrogen in the zeolite) by storage medium, and/or any other suitable gas.
In embodiments of the invention, per unit can utilize the average gas molecule in gas storage space (per available gasstorage space) to occupy rate (average occupancy rate) greater than about 25%.
The evolving path in gas storage material of the present invention (diffusion paths) can comprise that crystal boundary, hole (being space natural or design), defective (are the dislocation in the material lattice structure, planar disfigurement in the material lattice structure, surface impurity, step in the material lattice structure, Deng), the inherence structure of gas storage material, and/or the main body of gas storage material.
In embodiments, gas storage space or atmosphere storage density can for example be passed through in many ways to the small part generation: (a) crystalline network of chemically changed material by replacing aliovalent positively charged ion and negatively charged ion; (b) in the crystalline network of material, produce defective, thereby in the sublattice of material, have the gap; (c) in the crystalline network of material, produce defective, thereby in the sublattice of material, have the room; (d) change the crystalline network of material selectively,, make gas in material, flow so that gas diffusion path is provided; And/or (e) by impressed field dipole is introduced in the material, or the like.
Other embodiment of the present invention comprises the fuel cell that contains the above-mentioned gas stored material.
In following description process, further feature of the present invention, aspect and advantage will become more apparent for those skilled in the art, wherein reference illustrates the accompanying drawing of some preferred forms of the present invention, and wherein identical in the drawings parts are represented with identical Reference numeral.
Description of drawings
Below with reference to each figure system of the present invention and method are described, wherein:
Fig. 1 is as the disassociation of the molecular hydrogen that adopts in the embodiment of the present invention and the synoptic diagram that stores in hydrogen storage material as atomic hydrogen thereof;
Fig. 2 is as the disassociation of the molecular hydrogen that adopts in the embodiment of the present invention and the synoptic diagram that stores in hydrogen storage material as proton hydrogen thereof; With
Fig. 3 is the synoptic diagram that stores in hydrogen storage material as the molecular hydrogen that adopts in the embodiment of the present invention.
Embodiment
In order to help to understand the present invention, refer now to embodiments more of the present invention as Figure 1-3, and use language-specific described.Term used herein is used to describe rather than limit.Specific structural details of Pi Luing and function detail do not illustrate as restriction herein, and as just the basis of claims, and to be that instruction those skilled in the art are many-sided implement representative basis of the present invention to these claims.As those skilled in the art is often met, in described underwork with make any modifications and variations in its method, and as herein the further application principle of the present invention of explanation all think and be encompassed in the essence of the present invention.
According to an embodiment of the present invention, gas storage system 8 comprises at least a gas storage material 14 and at least a field 10, and field 10 is applied on the gas storage material 14, with the gaseous solubility of pilot-gas stored material 14, as Figure 1-3.Usually, although not necessarily, the gas that stores in gas storage system 8 comprises hydrogen.Hydrogen comprises ionic hydrogen, molecular hydrogen, atomic hydrogen, deuterium, tritium, its arbitrary combination, or the like.Other gas that can be stored in the gas storage system 8 comprises carbon monoxide, oxygen, carbonic acid gas, nitrogen, methane and nitrogen and sulfur oxide, and combination, or any polar gas or can polar gas.
In one embodiment, gas storage material 14 comprises dielectric medium.If gas storage material 14 is dielectric materialss, described at least a 10 generally includes electric field (describing as Fig. 1-3), stress field, strain field, or its combination.Gas storage 8 generally includes additional features, for example temperature-control device and pressure control device.In some embodiments, dielectric materials comprises at least a in piezoelectric, ferroelectric material, stupalith, non-metallic material, organic materials or the semiconductor material.In the situation of piezoelectric, an embodiment comprises barium titanate.In the situation of pottery, an embodiment comprises V
2O
5In the situation of organic materials, an embodiment comprises poly(vinylidene fluoride) (PVDF) or micropore organometallic skeletal (microporous metal-organic framework).
In another embodiment, gas storage material 14 comprises magneticsubstance, for example ferro-magnetic, paramagnetic material, diamagnetic body or ferrimagnetic material.If gas storage material 14 is magneticsubstances, then at least a 10 generally include magnetic field, might and other (for example stress field, strain field or electric field, and combination) combination.In one embodiment, ferromagnetic material comprises iron, cobalt, manganese, nickel and combination thereof, at least a in alloy and the compound thereof.
The present invention relates generally to the gas storage material that comprises high density of useable hydrogen and other gas storage sites, all based on the stored material of per unit mass and the stored material of per unit volume.Although many these gas storage sites can comprise naturally occurring low energy lattice or defect sites, perhaps those lattices or the defect sites that produces by chemically changed crystalline texture, these gas storage sites are that the field by material crystalline texture causes to change and produces.This variation has obtained having the gas transfer rate of raising and the gas storage material of solvability and door control mechanism (gating mechanism), and described door control mechanism is used for pilot-gas to the release from crystalline texture of the loading of crystalline texture and gas.In addition, these materials are durable, and are thermally-stabilised and chemically stable, and can make on relatively low cost ground.Term solvability used herein refers to " in body of material, on the surface of material, or storing the ability of a certain amount of gas in its combination ".
Gaseous solubility in gas storage material can increase by producing binding site, and described binding site gets the dipole that forms in the crystalline texture of comfortable gas storage material.Can in these materials, produce or strengthen dipole by the stoichiometry that changes basic compound.This change can obtain in many ways, for example, replaces aliovalent positively charged ion and negatively charged ion by chemistry.According to the present invention, dipole can also produce in material or enhancing by (that is, by stress field, strain field, and/or passing through electric field and/or magnetic field).Can make and in the sublattice of material, form the solvability that gas in the gas storage material is improved in gap and room by in material structure, forming crystal defect.The crystalline structure that changes material selectively can also obtain easier gas diffusion path.The change of some basic compound structures is produced as local eelctric dipole or the magnetic dipole that gas provides attachment site.A field enhanced dipole polarization gas atom of making peace, the relative dipole orientation of gas atom self wherein is so that reduce total free energy of system.
When at the loading days applied field, these dipoles attract and support gas atom, remove the field then and reduce effective solvability of gas in the material by the elimination dipole, thereby make gas release.Use counter field to drive away residual gas, this residual gas may be retained or needs extra activation to discharge because of permanent dipole.Applying as switch or door control mechanism of controlling field makes to take in gas and discharge gas in the cycle period of needs when loading and controlled.
Though metal and metal hydride materials of this invention may prove to be the stored material of preferred hydrogen or other gas for a long time as hydrogen storage material.When as gas storage material, material of the present invention provides gas transfer rate and the solvability improved.For example, most of potteries mainly are included in the ionic linkage that has positive charge and center of negative charge in its structure, but some potteries (that is Al,
2O
3, SiC) also having a large amount of covalent linkage, these covalent linkage are directive key.On the other hand, metal comprises metallic bond (that is, being mainly a large amount of electronics), and metal hydride mainly comprises covalent linkage and some metallic bonds and ionic linkage.Having with ionic linkage or covalent linkage (that is, pottery) is that main material works with electric field and other ion of putting into this material by the structure of resetting them, changes shape, physical structure or the electronic structure of material thus, and does not make the material conduction that becomes.Material with unpaired electron, particularly some d or f series elements (that is, and Fe, Co, Nd Sm) arranges (align) inherent magnetic dipole with response magnetic field.This response will be observed in the material with metallic bond, ionic linkage or covalent linkage.
In other words, the material (i.e. pottery) that mainly has an ion characteristic shows or has the potential of Van derWaals bonding (that is dipole-dipole interaction).When this material that mainly has ion characteristic applies external electrical field, the present invention has strengthened the eelctric dipole of material, and has promoted the class Van der Waals bonding with gas (for example hydrogen).Gas causes dipole with the antagonism field, thereby reduces the free energy of system by polarization (that is, the skew electronic orbit) response.On the contrary, the material with metalloid electroconductibility is by its nonbonding ionic motion extra electric field that dissipated, thereby got rid of the formation of eelctric dipole, and makes this material be not suitable for having the purposes of extra electric field.
In another embodiment of the present invention, applying magnetic field replacement electric field is better to improve gaseous solubility or mobility.For example, when when the material with a large amount of magnetic features applies magnetic field, permanent magnetic dipole is wherein arranged, thereby increases the solvability and the mobility that can store gas wherein.Hydrogen with single, unpaired electron and single proton is suitable for response magnetic field fully.
Make use, for example electric field, magnetic field, stress field and strain field faster time of response of time of response of controlling the absorption of gas in the gas storage material of the present invention and discharge to allow realizing to reach at present than conventional pressure activated or temperature-activated gas storage material.Conventional pressure activated or temperature-activated gas storage material are being exerted pressure or the time of response are being lagged behind during temperature.In addition, the needed high temperature of gas (＞100 ℃) that wherein stores of most of metal hydrides discharging is a problem.On the contrary, gas storage material of the present invention has the time of response instant substantially to the field in any temperature, and making them is ideal for widely applying (for example, the fuel cells applications of the vehicles).Herein the field is used for potentially: (1) increases the solvability of gas storage material gas, (2) utilize the dependence of the fast response time replacement of material to the material thermal diffusivity, (3) and field intensity is regulated the release of (throttle) gas pro rata and (4) allow low-temperature desorption gas.
Silicate material, for example mica, zeolite and vermiculite comprise open channels and laminate structure, allow hydrogen or other gas to enter their inside fast along those easy the evolving paths.In the material of for example zeolite, gas is trapped within by the storage site place in the cage shape crystalline texture that polyhedron limited that for example comprises Si-, Al-, Mg, Na, O-and F-.The absorption of majority of gas is subjected to for example strong control of above-mentioned internal electric field in the zeolite.These internal electric fields can change by chemical design crystalline texture with the structure of keeping them.In addition, crystal chemistry control can change the size of gas diffusion path, changes the size of storage cages, or changes the electronic state of storage cages, thereby even material also receives and keeps more gas and make it from wherein diffusion more quickly when not having impressed field.In addition, can applied field (for example electric field or magnetic field) to this structure to improve the storage volume and the release capacity of gas.
Ferroelectric material, ferromagnetic material, piezoelectric and dielectric materials are special desirable material for chemical modification or by applying storage volume/solvability and the gas transfer rate thereof that the electric field modification improves gas, and also are ideal for making use come the absorption of pilot-gas and discharge.Piezoelectrics are class stupaliths, and wherein impressed field (being stress field, strain field or electric field) can be induced big internal dipole.Stress on piezoelectric or strain cause separating of center of positive charge and center of negative charge, cause the field to cause dipole.This causes dipole and is used to attract for example hydrogen of gas, and this gas polarization and oneself arrange and form class Van der Waals key, thereby reduces the free energy and an opposing induced dipole of system.Its net effect is the increase of hydrogen solubility in the piezoelectric.Stress or strained are removed, are reversed or reduce and change dipolar intensity and change the hydrogen solubility of piezoelectric in the mode of needs, are used to control the door control mechanism that hydrogen is taken in and discharged thereby set up.
Also can use reverse piezoelectric effect to produce the field and cause dipole.At this moment, described can replace stress field or strain field with electric field, and this electric field can be applied to this piezoelectric more easily by the electrode attached to piezoelectric.Electric field also produces displacement along the dipole of following that causes in piezoelectric.The hydrogen of atom or proton form can have higher mobility than molecular hydrogen in some materials.Therefore, in order to utilize this phenomenon, during applying electric field, can use the known catalytic materials (as Pd and Pt) that molecular hydrogen is separated into atomic hydrogen.When applying electric field, by catalysis electrode molecular hydrogen is dissociated into atomic hydrogen, dissolving therein also therefrom is delivered to storage medium.Even when not having extra electric field, also can use these catalyzer,, molecular hydrogen is easier to the mobile form so that material is passed through in conveying so that being transformed into.
Most of potteries are known not to have high hydrogen diffusivity rates.Because making gas pass in and out these gas storage material as quickly as possible is favourable for the operation of gas storage system, therefore, the rate of diffusion that improves gas is useful, perhaps with some other mode to make gas input and output gas stored material and do not need long distance be useful by the main diffusion of material.A kind of mode that makes the quick input and output gas stored material of gas is the high gas diffusion path that utilizes in the gas storage material.These paths may natural being present in the material, and perhaps they can generate intentionally.For example, crystal boundary, defect structure and room are the high hydrogen diffusivity paths of natural formation.Hole or other defective of design also can produce in material wittingly, so that extra high gas diffusibility path is provided in material.The material that the field that utilization is included in wherein increases gaseous solubility causes dipole and increases the high flow expansion path of gas transfer rate therein will be an ideal.
Refer now to Fig. 1, it is the disassociation of molecular hydrogen and the synoptic diagram that stores in hydrogen storage material as atomic hydrogen thereof, as adopting in the exemplary of the present invention.In this embodiment, to two electrode 12a around gas storage material 14,12b applies electric field 10, and this moment, gas storage material 14 was described as hydrogen storage material.Preferably, electrode comprises H
2(molecular hydrogen) effectively is cracked into the material of H (atomic hydrogen), for example Pd and Pt.Shown in the amplifier section of this figure, when applying electric field and molecular hydrogen and be cracked into atomic hydrogen, atomic hydrogen 16 polarization are also arranged according to negatively charged ion in the stored material 18 and positively charged ion 20 oneselfs.The virtual dipole (virtual dipole) the 22nd that produces, the result of the composition of impressed field, material and the combined effect of structure thereof.Therefore, can see, electric field apply the hydrogen solubility that has improved this hydrogen storage material, play thus that control hydrogen is taken in and the effect of the door control mechanism that discharges.
Refer now to Fig. 2, it is the disassociation of molecular hydrogen and the synoptic diagram that stores in hydrogen storage material as proton hydrogen thereof, as adopting in the exemplary of the present invention.In this embodiment, to two electrode 12a around gas storage material 14,12b applies electric field 10, and this moment, gas storage material 14 was described as hydrogen storage material.Preferably, electrode comprises under the help of added electric field outside H
2(molecular hydrogen) effectively is cracked into H
+The material of (proton hydrogen), for example Pd or Pt.Shown in the amplifier section of this figure, when applying electric field and molecular hydrogen and be cracked into proton hydrogen, proton hydrogen 17 diffuses into material along the gradient of field, and arranges according to negatively charged ion in the stored material 18 and positively charged ion 20 oneselfs.The virtual dipole 22 that produces is results of the combined effect of the composition of extra electric field, material and structure thereof.Electronics can be stored in the external capacitor up to the needs release hydrogen.Therefore, can see, electric field apply the hydrogen solubility that has improved this hydrogen storage material, play thus that control hydrogen is taken in and the effect of the door control mechanism that discharges.
Refer now to Fig. 3, it is the synoptic diagram that molecular hydrogen stores in hydrogen storage material, as adopting in the exemplary of the present invention.In this embodiment, to two electrode 12a around gas storage material 14,12b applies electric field 10, and this moment, gas storage material 14 was described as hydrogen storage material.In this embodiment, the structure of hydrogen storage material 14 must enough be opened and accept H with former state
2Zeolite can perform well in this storage.Shown in the amplifier section of this figure, when applying electric field, molecular hydrogen diffuses through the uncovered zeolite channels that is formed by cage 16 collection dresses (assemblages), runs into dipole storage site up to it.This dipole storage site can be an inherent to base zeolite material, and it can produce or enhancing by chemical modification, and perhaps it can produce or enhancing by impressed field.Molecular hydrogen response dipole site polarizes and arranges according to negatively charged ion in the stored material and positively charged ion oneself then.The site of hydrogen storage is served as in known many positions in various specific cages.Therefore, can see, electric field apply the hydrogen solubility that has improved this hydrogen storage material, play thus that control hydrogen is taken in and the effect of the door control mechanism that discharges.
Although described several different modes of storage of hydrogen in hydrogen storage material, the present invention estimates any suitable gas of storage in any suitable material.Therefore, all these embodiments all mean and contain within the spirit and scope of the present invention.
As mentioned above, gas storage material of the present invention makes high performance gas storage materials be achieved for a large amount of application (for example fuel cell and the vehicles that comprise it).Advantageously, gas storage material of the present invention is used for commerce, industry and human consumer and is demonstrated huge application future.These materials can be used for gas phase storage, and are particularly suitable for the application of vehicle fuel battery.For many other advantages of those skilled in the relevant art is conspicuous equally.
Describe various embodiments of the present invention and fulfiled the various needs that the present invention satisfies.Should be realized that these embodiments only are the explanations to the principle of the various embodiments of the present invention.Do not departing under the spirit and scope of the invention, its many changes and improvements all are conspicuous for those skilled in the art.The present invention includes and be used for the gas storage material that great amount of terminals is used.For example, although described the hydrogen storage material that is used for the vehicle fuel battery applications, hydrogen storage material of the present invention can also be used for other a large amount of application examples such as special use generating.In addition, although described hydrogen in many embodiments, in gas storage material of the present invention, can store any suitable gas.In addition, although described pottery and electric field in detail, and metal and magnetic field, any suitable material and the suitable impressed field of any kind may be used to the present invention.Therefore, this means the present invention and is included in claim and all interior suitable modifications and variations of equivalent scope thereof.
Claims (11)
1. gas storage system comprises:
At least a gas storage material; With
At least aly be applied to field on the described gas storage material to control the gaseous solubility of described gas storage material, wherein said gas storage material comprises dielectric medium, and wherein said at least a field comprises electric field.
2. the gas storage system of claim 1, wherein said gas comprises hydrogen.
3. the gas storage system of claim 2, wherein hydrogen comprises and is selected from least a in ionic hydrogen, molecular hydrogen and the atomic hydrogen.
4. the gas storage system of claim 1, wherein said at least a field also comprise at least a in stress field, strain field and the combination thereof.
5. the gas storage system of claim 1, it further comprises the device that is used to control described gas storage system temperature.
6. the gas storage system of claim 1, it also comprises the device that is used to control described gas storage system pressure.
7. have the gas storage material of high gas storage density and high gas transfer rate, this gas storage material comprises:
The material of the ion characteristic of eelctric dipole is kept in contained gas storage area and being enough to during applying extra electric field, and wherein applying of extra electric field can not make the material conduction that becomes, and this material comprises dielectric materials; With
Be stored in the gas in the gas storage space of material,
Wherein said gas can diffuse through material, and middle impressed field apply make following at least a controlled:
The gaseous solubility of gas storage material;
Take in the gas intake of gas storage material;
Gas emissions from the gas storage material discharging; With
Gas transfer rate in the gas storage material.
8. the gas storage material of claim 7, wherein gas comprises at least a: hydrogen has the gas of permanent dipole and can carry polarizable gas by storage medium with molecule or atomic way.
9. the method for the gaseous solubility in the pilot-gas stored material, described method comprises:
At least a gas storage material is provided; With
Apply at least a to described at least a gas storage material,
Wherein said gas storage material comprises dielectric materials, and wherein said at least a field comprises electric field.
10. the method for claim 9, it further comprises to described gas storage material provides gas to be used to store this gas.
11. the method for claim 10, wherein said gas comprises hydrogen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US45884903A | 2003-06-10 | 2003-06-10 | |
| US10/458,849 | 2003-06-10 |
Publications (2)
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| CN1829655A CN1829655A (en) | 2006-09-06 |
| CN100391827C true CN100391827C (en) | 2008-06-04 |
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| CNB2004800218129A Expired - Fee Related CN100391827C (en) | 2003-06-10 | 2004-06-03 | Field-assisted gas storage materials and fuel cells comprising same |
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| Country | Link |
|---|---|
| EP (1) | EP1638885A2 (en) |
| JP (1) | JP2007513039A (en) |
| KR (1) | KR20060017640A (en) |
| CN (1) | CN100391827C (en) |
| AU (1) | AU2004247670A1 (en) |
| CA (1) | CA2528629A1 (en) |
| WO (1) | WO2004110922A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007058900A2 (en) | 2005-11-10 | 2007-05-24 | Alexander Eugene J | Calibrating an imaging device for generating three dimensional suface models of moving objects |
| DE102011012734B4 (en) * | 2011-02-24 | 2013-11-21 | Mainrad Martus | Method for the reversible storage of hydrogen and other gases as well as electrical energy in carbon, hetero or metal atom based capacitors and double layer capacitors under standard conditions (300 K, 1 atm) |
| CN102280631B (en) * | 2011-07-14 | 2013-03-27 | 辽宁石油化工大学 | Electrostrictive reversible hydrogen storage method |
| EP2657588B1 (en) | 2012-04-27 | 2015-01-28 | Belenos Clean Power Holding AG | Method for obtaining a piezoelectric liner for a high pressure storage vessel |
| AT513486B1 (en) * | 2013-07-04 | 2014-05-15 | Universität Linz | Method for charging and discharging a hydrogen storage |
| AU2018299410B2 (en) * | 2017-07-11 | 2023-09-07 | Rodolfo Antonio Gomez | Advanced electrolytic storage and recovery of hydrogen |
| CN113350983A (en) * | 2020-03-06 | 2021-09-07 | 顾士平 | Electric field polarized gas adsorption system |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1219567A1 (en) * | 1999-09-09 | 2002-07-03 | Sony Corporation | Carbonaceous material for hydrogen storage and method for preparing the same, and cell and fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4229196A (en) * | 1976-04-13 | 1980-10-21 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Atomic hydrogen storage method and apparatus |
| US4887556A (en) * | 1989-02-08 | 1989-12-19 | Ernest Gladstone | Arrangement for and method of supplying hydrogen gas |
| JPH03205301A (en) * | 1989-08-04 | 1991-09-06 | Canon Inc | Method for storing hydrogen, apparatus for nuclear fusion at ordinary temperature utilizing the same method and method for generating heat energy |
| GB9723140D0 (en) * | 1997-11-04 | 1998-01-07 | British Nuclear Fuels Plc | Improvements in and relating to material separations |
| JP2001039706A (en) * | 1999-07-26 | 2001-02-13 | Futaba Corp | Production of hydrogen absorbing material |
| EP1188477A1 (en) * | 2000-09-13 | 2002-03-20 | Thomas Maschmeyer | Method for absorbing compounds using zeolites |
-
2004
- 2004-06-03 WO PCT/US2004/017489 patent/WO2004110922A2/en active Application Filing
- 2004-06-03 JP JP2006533555A patent/JP2007513039A/en not_active Withdrawn
- 2004-06-03 KR KR1020057023707A patent/KR20060017640A/en not_active Application Discontinuation
- 2004-06-03 EP EP04754157A patent/EP1638885A2/en not_active Withdrawn
- 2004-06-03 AU AU2004247670A patent/AU2004247670A1/en not_active Abandoned
- 2004-06-03 CN CNB2004800218129A patent/CN100391827C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1219567A1 (en) * | 1999-09-09 | 2002-07-03 | Sony Corporation | Carbonaceous material for hydrogen storage and method for preparing the same, and cell and fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007513039A (en) | 2007-05-24 |
| EP1638885A2 (en) | 2006-03-29 |
| CN1829655A (en) | 2006-09-06 |
| KR20060017640A (en) | 2006-02-24 |
| AU2004247670A1 (en) | 2004-12-23 |
| WO2004110922A3 (en) | 2005-07-21 |
| WO2004110922A2 (en) | 2004-12-23 |
| CA2528629A1 (en) | 2004-12-23 |
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