CN101679023A - Hydrogen storing method and unit - Google Patents
Hydrogen storing method and unit Download PDFInfo
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- CN101679023A CN101679023A CN200880007177A CN200880007177A CN101679023A CN 101679023 A CN101679023 A CN 101679023A CN 200880007177 A CN200880007177 A CN 200880007177A CN 200880007177 A CN200880007177 A CN 200880007177A CN 101679023 A CN101679023 A CN 101679023A
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- negative electrode
- hydrogen
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- wall
- ionic
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to a method for storing hydrogen and for producing hydrogen in which, for storing hydrogen, a unit (2) having: a cation donor, particularly of H- ions, an anode (20), a cathode capable of storing atomic and/or molecular (22) hydrogen, a wall (21) permeable to ions, having an electrical non conducting but ionic conducting material, between the cathode and the cation donor, issubjected to an electric field allowing the formation, at least at the cathode and electrical non conducting material interface, of atomic and/or molecular hydrogen and storing said hydrogen at leastin the cathode, and in which, to restitute hydrogen gas, the cathode is heated and/or depressed.
Description
Technical field
The present invention relates to the storage of hydrogen, more specifically, relate to the storage of the hydrogen that produces by electrochemical means, and the recovery of stored hydrogen.
Background technology
A kind of method that is used for hydrogen manufacturing and Chu Qing is disclosed in the International Application No. WO 2006/003328.
Need a kind of storage element, this storage element can store considerable hydrogen and can it be recovered to outside the unit with the form of molecular hydrogen.
Summary of the invention
According to an aspect of the present invention, theme of the present invention thereby be the method for a kind of hydrogen manufacturing and Chu Qing, wherein, in order to store hydrogen, a kind of unit comprises:
-positively charged ion donor, particularly H
+The ionic donor;
-anode;
-can store the negative electrode of atomic hydrogen and/or molecular hydrogen; With
-can see through the ionic wall, it is between described negative electrode and positively charged ion donor, comprise material non-conductive but conducting ion, described wall is in the electric field, described electric field makes it possible at least to be stored at the atomic hydrogen of formation at the interface of negative electrode and electrically nonconducting material and/or molecular hydrogen and with it at least in the negative electrode, and wherein in order to reclaim gaseous hydrogen, negative electrode is heated and/or places under the vacuum.
Chemistry or physical absorption or absorption in that term " storage " is interpreted as representing atomic level and/or the material hole.
Negative electrode can comprise hydrogenatable material.
" interface " this term between negative electrode and the electrically nonconducting material is interpreted as being illustrated in and has the molecule contact phenomena between negative electrode and the electrically nonconducting material.Between electrically nonconducting material and negative electrode, the interface is formed and guarantees that hydrogen ion is transformed into hydrogen atom on cathode surface, and wherein, negative electrode is constructed to it is absorbed immediately." electrically nonconducting material " this statement is interpreted as representing that its specific conductivity is enough low but do not damage the material of cation conductive.
The method according to this invention can be stored up hydrogen in the preparation process of hydrogen, and voluntary recovery hydrogen as required.
Described storage can be carried out under the situation that does not cause the negative electrode degraded.
The present invention need can be applicable in the energy-producing numerous areas of gaseous hydrogen, for example the vehicles, electrical equipment or generator.The present invention is applicable to that also the intermittence of any type of renewable energy source stores, and the intermittence that for example comes from the renewable energy source of wind turbine, tidal power generation or the sun stores.
The water-permeable that can see through the ionic wall can be lower than the hydrogen that is produced quality 5%.
Negative electrode can contain the water that is lower than 5% weight percent.
For can seeing through the ionic wall, under normal temperature and pressure conditions, measure with liquid water, perhaps be no more than under the condition of 4 crust (bar) with the water gaging of vapor form at the pressure reduction that is lower than 900 ℃ temperature and film both sides, this can see through the ionic wall can have zero water-permeable.
Make it possible to achieve formed atomic hydrogen and/or molecular hydrogen is stored in the negative electrode at total impermeability of wall described in described preparation and the storage process.The absorption of required for this reason hydrogen can be depending on the character of negative electrode.Particularly, in negative electrode, there is water and has following risk: stop and in negative electrode, to set up the molecule contact, set up gratifying conductivity, and stop then in negative electrode or form hydrogen at the interface thereby stop.On the other hand, may be unimportant at the water that has at the interface of negative electrode and proton exchange membrane to system.Particularly, water is equivalent to see through the continuity of ionic wall owing to having ionic conductivity.In addition, near the scope negative electrode,,, for storage hydrogen, or not problem and there is water so medium is reduced owing to there is hydrogen.
Anode can be with any and H
+The compatible electro-conductive material of ion donor is made, for example platinum, graphite, be lined with the RuO of porous (for example 30% to 50%) titanium plate or conductive polymers plate or the like
2, IrO
2Mixture film or RuO
2, IrO
2And TiO
2Mixture film or RuO
2, IrO
2And SnO
2Mixture film is made.The thickness of described film can be between 5 μ m between the 20 μ m, for example about 10 μ m.
Anode can contact with electrically nonconducting material.
Negative electrode can be solid, liquid or powder-form; Powder-form helps making the unit with different shape.
Negative electrode can comprise intermetallic compound, and described intermetallic compound particularly is selected from brilliant crack of complexing or metal hydride, for example is selected from as follows: AB
5Type (A and B are metal), for example LaNi
5, lava (lava) (Zr, Ti), (Mn, V, Cr, Ni)
2Various phases, ZrMn for example
2Or TiMn
2, Mg, TiFe, Mg
2Ni is based on the heart cube sosoloid of vanadium, BaReH
9(this formula is corresponding to hydrogenation state), Mg
2FeH
6(this formula is corresponding to hydrogenation state), NaAlH
4(this formula is corresponding to hydrogenation state), LiBH
4(this formula is corresponding to hydrogenation state), and all compounds and derivative or its alloy.
Negative electrode can be embedded in the boron nitride agglomerate, and the periphery of this boron nitride agglomerate forms described electrically nonconducting material.This electrode can for example comprise the metal foam that is embedded in the boron nitride agglomerate or the foam of any conduction and hydrogenatable material.
Electrically nonconducting material can comprise pottery, for example comprises hexagonal boron nitride (preferably under electric field through peracid solutions activation), lithium nitride, boric acid, ionic conduction polymer and more generally comprises the pottery of any ion-exchange material.The ion-exchange pottery of electrically nonconducting material optional do for oneself PEMFC or the exploitation of PCFC battery.
Electrically nonconducting material can for example comprise random layer boron nitride, that is to say, for random layer boron nitride, crystal plane can cause described combination so not good, because of the latter separates far away with respect to theoretical crystallization position (for example brilliant position of six reef knots of boron nitride) slight shift.
Electrically nonconducting material can comprise hexagonal boron nitride crystal grain disposed adjacent one another, for example is of a size of the crystal grain of about 100 μ m or has the crystal grain of nano-grade size.
Boron nitride crystal grain preferably can be oriented to complete parallel with described wall, but for example vertical orientated, to guarantee better mechanical strength, perhaps is orientated unevenly, to guarantee better proton conduction.
Boron nitride can be the crystal grain form of about 7 μ m to the 11 μ m of for example mean sizes.The part by weight of boron nitride can be between 5% to 100% in the material, and is for example high to 70%.Described wall can be made by the high-pressure sinter boron nitride powder fully.As modification, described wall can comprise boron nitride and tackiness agent, by HIP (hot isostatic pressing) prepared.
Electrically nonconducting material can comprise infiltration (percolated) boron nitride crystal grain, described crystal grain for example is immobilizated in together each other by compound, and described compound is for for example being selected from following compound: nickel, boron oxide, lime borate, ethyl cellulose, boric acid, polyvinyl alcohol, caprolactam, PTFE
Sulfonated polyether sulfone.
Electrically nonconducting material can be formed by the boron nitride that is inserted in the tackiness agent (for example boric acid or polymeric film), and it can be electrically nonconducting material extraordinary proton conduction is provided.
Described polymkeric substance can be for example PVA (polyvinyl alcohol), caprolactam, PTFE
Sulfonated polyether sulfone.
Can use polymkeric substance such as PVA to stop up the hole that exists in the boron nitride.Adding polymkeric substance can for example carry out under vacuum, makes polymkeric substance be sucked in the hole of boron nitride.
Electrically nonconducting material can obtain by following technology.
Boron nitride crystal grain mixes with the polymer binder of liquid form, and this mixture is poured on the base material, heats under the temperature of enough temperature such as about 600 ℃ or 700 ℃ then, to cause the calcining of tackiness agent, makes the infiltration each other on base material of boron nitride crystal grain.
In replenish step, gains in heating down in inert atmosphere (as nitrogen or argon gas) between 800 ℃ to 1700 ℃ or under the temperature between 1000 ℃ to 1500 ℃, are caused crystal grain sintering each other.
At last, in replenish step, base material is removed, obtain the rigidity boron nitride film of forming by agglomerating crystal grain.
Described base material can for example comprise by for example
The zephyr that polyether-ether-ketone, ethylene-tetrafluoroethylene copolymer, polyethylene terephthalate or polyester generate.
In aforementioned content, boron nitride can activate in advance, activation in the time of perhaps can or finishing in the technological process of preparation electrically nonconducting material.
" activation " this term of boron nitride is interpreted as representing to promote the technology of the proton conduction in the boron nitride.
Boron nitride can be for example in acid solution by placing electric field to activate.
Boron nitride also can activate under the situation that applies or do not apply electric field in sodium hydroxide solution.
In another technology, boron nitride can be by activating having iron (as the iron net) and apply to be immersed in the solution (for example water) under the situation of electric field.
The boron nitride of use powder-form can promote the activation of boron nitride.
Boron nitride can perhaps for example activate according to used tackiness agent afterwards in inserting this tackiness agent before with its powder-form activation in inserting tackiness agent (for example polymkeric substance).
In above-mentioned technology, boron nitride crystal grain can be in being inserted into polymer binder before or activation after the sintering of crystal grain.
Under the sintering situation, activation can be carried out when this technology finishes, to avoid it because sintering and ruined risk.
Can see through the layer that the ionic wall can comprise one or more differing materials, the cation conductive function of layer may travelling of at least one in these layers.Between layer with this function and ionogen, described wall can comprise the porous layer that for example has supporting role.
Can see through the ionic wall at least in part (preferably entirely) hide negative electrode, hide especially at least negative electrode on the anodic face.
In one exemplary embodiment, the electrically nonconducting material that can see through the ionic wall can stop any contact the between negative electrode and positively charged ion donor.
In addition, electrically nonconducting material preferably can not see through gaseous hydrogen, to be easier to make gaseous hydrogen to gaseous hydrogen outlet rather than ion donor evacuation on the sunny side in the recovery process of gaseous hydrogen.
The positively charged ion donor can be ionogen, for example, comprises at least a acidic aqueous solution that is selected from following compound: sulfuric acid, hydrochloric acid, weak acid or faintly acid salt.
As mentioned above, the positively charged ion donor can be liquid, and perhaps, as modification, the positively charged ion donor can be solid, gas or is the slurry form.
For example use pump or rotating shaft, the positively charged ion donor is circulated in the unit.This circulation can remain in the unit, or part carries out outside the unit, for example carries out being used for the described unitary equipment of supply.Consider that the unit may consume water form hydrogen with assurance, such circulation can for example be avoided forming H in described unit
+Ion gradient.In addition, make the circulation of positively charged ion donor can make the feature of anode and negative electrode exchange surface on every side keep substantially constant.
Can for example between 1V and 3000V, be more preferably between 1.24V and 200V at the voltage that applies between anode and the negative electrode in the hydrogen production process, preferably between 1.24V and 4V.
Negative electrode can be more preferably in the temperature more than 50 ℃ (for example between 70-350 ℃) heating in for example heating of the temperature more than 30 ℃, and to collect gaseous hydrogen, described temperature may be selected according to the difference of material.
Heating can be carried out after discharging ionogen, and described ionogen can be discharged in the replenishment device.As a kind of modification, not for being that the heating of purpose drains the positively charged ion donor to discharge hydrogen.
During hydrogen manufacturing and storage hydroformylation stage, described unit also can cause heating below the temperature of described release to improve storage hydrogen.
The heating of negative electrode can advantageously be carried out in a controlled manner, accurately operates with for example amount to the gaseous hydrogen that discharges.As a kind of modification, perhaps additionally, described unit, especially negative electrode can be placed in the vacuum, are beneficial to the extraction of gaseous hydrogen.
Heating can be caused by the joule effect in the middle electric current flow process of for example conductor in being integrated into described unit (for example extending in negative electrode).Heating also can be undertaken by the circulation of hot-fluid.
In case of necessity, atomic hydrogen and/or molecular hydrogen also can be stored in and can see through in the electrically nonconducting material of ionic wall.
The atomic hydrogen or the molecular hydrogen that produce in the described unit can only be stored in the negative electrode, perhaps, as a kind of modification, not only be stored in the negative electrode but also be stored in the electrically nonconducting material.
In addition, hydrogen can atom and/or molecular form be stored in the negative electrode, this depends on choosing the material that particularly forms negative electrode.
Can collect the gaseous hydrogen that leaves negative electrode to be used for fuel cell and/or as fuel or reactant.
Another theme of the present invention (be independent of aforementioned content or combine with aforementioned content) is a kind of unit that is used to store and recover hydrogen, and described unit comprises:
-anode;
-can store the negative electrode of atomic hydrogen and/or molecular hydrogen;
-positively charged ion donor, especially H
+The ionic donor;
-can see through the ionic wall, it comprises material non-conductive but conducting ion between described negative electrode and positively charged ion donor;
-randomly, be used for the member of heated cathode; With
-electric connector, but the power supply of described electric connector anode and negative electrode between anode and negative electrode, to produce electric field, described electric field makes it possible to form at least atomic hydrogen and/or molecular hydrogen in negative electrode, and it is stored at least in the negative electrode;
Described unit is arranged to be convenient to collect the gaseous hydrogen that is discharged by negative electrode at least in the process of heated cathode;
Described unit also comprises:
-fluid connector, described fluid connector can be directed to the gaseous hydrogen that so discharges outside the unit.
The described unit that is used to store and recovers hydrogen can comprise outside envelope, and this outside envelope is used for covering at least anode, negative electrode, positively charged ion donor, the non-conductive but material of conducting ion, optional heater, and randomly also covers electric connector.This outside envelope can be made by synthetic materials or metallic alloy to small part.
The described unitary anode that is used to store and recovers hydrogen can be porous and/or be installed with the hole, for example, forms or forms with metal or metallization foamy form with the mesh form.
Heater can comprise resistance element, and can be positioned within the outside envelope or outside.
Heater can for example be heated to described unit the temperature more than or equal to 30 ℃, the temperature that more excellent is more than or equal to 50 ℃, for example temperature between 70 ℃ and 350 ℃.
Heater can comprise resistance element, described resistance element to small part is arranged in negative electrode or is arranged in the element that contacts with negative electrode, for example be arranged in the member of elastically deformable, the member of this elastically deformable can make negative electrode lean against on the material of non-conductive but conducting ion and the variation of compensated cathode volume.
When heater when small part is arranged in negative electrode, heater can for example comprise run through negative electrode and with cathodic electricity insulating resistance wire.
Described unit also can comprise temperature sensor, and more excellent is the equipment that is used to regulate cathode temperature, with the heating of for example control cathode, so that the required hydrogen flow rate of thermal adaptation.
Described unit can be configured to allow negative electrode to expand in its operating process, especially provides permanent at negative electrode with storeroom non-conductive but conducting ion and contacts.
Described unit can comprise the member of elastically deformable in the relative side of the electrically nonconducting material with seeing through the ionic wall of negative electrode, and described member is arranged to make negative electrode to lean against on this electrically nonconducting material.The member elastically deformable of such elastically deformable is with for example variation of this cathode volume when negative electrode expands because of hydrogen gathers of compensation.
The member of described elastically deformable is for example made by the metallic alloy such as the spring steel of elastically deformable to small part, perhaps makes by having enough stable on heating elastomerics, and this elastomerics is for example based on the polysiloxane that can bear at least 250 ℃ of temperature.
In one exemplary embodiment, negative electrode is a piped, and for example around an internal space, this internal space allows cathode expansion.When comprising one or more, negative electrode can when hydrogen gathers in the process for example about 25% to 30% the intermetallic compound of volumetric expansion, need such structure.
Described internal space can hold the member of elastically deformable, and this member for example is the form of elastomeric sleeve.
Described internal space also can hold for example heater and/or temperature sensor.
Described unit can comprise the junctor that is used for filling and/or removing the positively charged ion donor, and randomly, described connector device is furnished with valve, with described valve open during the outer filled or scavenge system in described unit links to each other.
Described unit can comprise hydrogen outlet coupling part, and described hydrogen outlet coupling part can be sent to the gaseous hydrogen that discharges outside the unit.
These fill and/or remove junctor and hydrogen and go out opening connector and can be equipped with suitable tightness system, encircle as O shape.
Another theme of the present invention is a kind of unitary equipment that supply is defined as above that is used for, this equipment comprises and is used to hold at least one chamber of described storage element and treats link to each other to produce at least one electric connector of electric field between negative electrode and anode, heated cathode under suitable situation with described unitary electric connector.
Described replenishment device can comprise several chambers, and these chambers can be simultaneously or some unit of supply successively.
On the other hand, described replenishment device can comprise that can be held a deposit water or lay in electrolytical chamber, described deposit water or lay in electrolytical chamber and can supply with one or more unit by home loop, and choose wantonly in emptying these unitary processes and reclaim ionogen.
Described replenishment device can be arranged to monitor supply, and interrupts supply when reaching some condition.
Described replenishment device can comprise one or more supply telltales, for example one or more photodiodes and/or pressure detection device.Detecting pressure increases and can indicate negative electrode to be full of hydrogen and storage volume uses up.
Described replenishment device can be arranged to begin to cut off the electricity supply from certain force value.
Described replenishment device can for example comprise in the bottom of each chamber that is used for accomodating unit that at least one is treated and hydrogen exports and/or fill and/or remove junctor or above-mentioned junctor coupled junctor.In the process of supply material of in replenishment device, packing into, can open one or more valves.
Another theme of the present invention is a kind of method, and described method comprises that the hydrogen that will extract from the storage element that is defined as above offers the step of fuel cell.
Under situation in the electric installation was waited to be introduced in described unit, storage element can empty the positively charged ion donor before it is introduced into, be under the situation of liquid at the positively charged ion donor especially.The positively charged ion donor that goes out clearly can enter in for example above-mentioned replenishment device.
Another theme of the present invention is a kind of electric installation, particularly mobile telephone or laptop computer, and described electric installation comprises at least one chamber, and described chamber can hold at least one storage element that is defined as above.
Described unit can be configured at room temperature or be higher than under 60 ℃ the temperature (for example under the temperature more than 100 ℃) and for example operating under 0.1 internal pressure of clinging between 100 crust.Under pressure, the storage in negative electrode can be improved.
Under suitable situation, described unit can be coupled with fuel cell, for example, is coupled in integrated component.
Under suitable situation, fuel cell can with the units shared big envelope that is used for hydrogen manufacturing and Chu Qing.
Under these circumstances, hydrogen discharges to fuel cell under the situation of not leaving the big envelope that comprises described storage element and fuel cell.
Description of drawings
By following detailed description to the nonrestrictive exemplary embodiment of the present invention, and in conjunction with the accompanying drawings, the present invention may be better understood, in the accompanying drawings:
Fig. 1 with schematically and the mode of simplifying the unit that is used for Chu Qing and hydrogen manufacturing and relevant replenishment device are shown;
Fig. 2 is the view similar to Fig. 1, and here, the unit that is used for hydrogen manufacturing and Chu Qing takes out from replenishment device;
Fig. 3 is an exploded view, shows the assembly that comprises Chu Qing and hydrogen manufacturing unit and fuel cell;
Fig. 4 shows and is in the assembly of Fig. 3 of assembled state;
Fig. 5 shows described unitary embodiment variant;
Fig. 6 is the unitary schematic partial longitudinal section of Fig. 5;
Fig. 7 is the schematic partial cross section of described unitary embodiment variant; With
Fig. 8 shows according to the some voltages that apply between anode and negative electrode, the time dependent hydrogen speed of filling.
Embodiment
Be system 1 shown in Fig. 1, this system 1 comprises that two are used for the detachable unit 2 of hydrogen manufacturing and Chu Qing and can be the replenishment device 3 of these unit 2 supply hydrogen between twice use of successive.
Especially, as shown in Figure 2, replenishment device 3 can comprise the chamber 4 that respectively holds a unit 2, and replenishment device 3 can comprise reservoir 5, and reservoir 5 can be filled the liquid that uses for unit 2, as ionogen.
In a modification, replenishment device 3 comprises single chamber 4.
As shown in Fig. 3 and Fig. 4, each unit 2 can be arranged in use and fuel cell 6 couplings in assembly 10 for example, described assembly 10 comprises: at least one fluid connector, and it can reclaim the hydrogen that produced by unit 2 to be injected in the fuel cell 6; And electric connector, it can be for unit 2 power supplies, for example to discharge stored hydrogen by heating.
As shown in Figure 4, assembly 10 can comprise electric connector 11, and this electric connector 11 makes that fuel cell can be for having introduced the electric installation power supply of assembly 10.
Figure 3 shows that another example of unit 2, it typically is round shape.
This unit 2 comprises outside envelope 15, and this outside envelope 15 at one end has and covers 16.Certainly, the invention is not restricted to a kind of big envelope 15 of particular form, under suitable situation, big envelope 15 can be the integral type form.
In this example, big envelope 15 covers anode 20, wall 21, negative electrode 22 and returns elastically member 24, wherein, anode 20 preferably is perforated to increase the swap table area, wall 21 is to see through ionic, and comprises material non-conductive but conducting ion, and negative electrode 22 is made by the material that can store hydrogen.
Be arranged to non-conductive but conducting ion, so that H with negative electrode 22 materials that contact, that can see through ionic wall 21
+Ion can pass through.When the contact area between negative electrode 22 and this electrically nonconducting material 21 is big, help the storage of hydrogen.
The electrically nonconducting material of wall 21 can comprise hexagonal boron nitride, and it is by being activated by ionogen with ionogen contact number hour under electric field.
Return for example sleeve pipe for being made by elastomer material (as polysiloxane) of member 24, this material can bear the negative electrode heating to discharge the temperature of hydrogen.
When negative electrode 22 is liquid or powdery, wall 21 and return member 24 and negative electrode 22 can be trapped between them.
Returning member 24 can be pressed in negative electrode 22 on the wall 21, although also to guarantee contacting between negative electrode 22 and the wall 21 when negative electrode 22 expands.
Hydrogen can leave described unit via aperture 27, and aperture 27 forms or is equipped with male connector or female connector, and randomly, aperture 27 has valve.
Ionogen can cycle through described unit by aperture 14.The round-robin ionogen contacts with wall 21 with anode 20.
Press one aspect of the present invention, negative electrode 22 is made by the material that can store up hydrogen (as hydrogenatable material).Under the effect of electric field of anode 20 and 22 generations of negative electrode (described anode links to each other with the plus end of generator in for example being integrated in replenishment device 3, and described negative electrode links to each other with the negative terminal of this generator), contained H in the ionogen
+Positively charged ion passes wall 21 to negative electrode 22 migration, and is reduced to atomic hydrogen at the interface at negative electrode 22 and wall 21.
Atomic hydrogen of Chan Shenging and/or molecular hydrogen directly are stored in negative electrode 22 like this, and randomly, are to be stored in the wall 21 under the situation about generating according to application WO 2006/003328 at wall 21.
Described hydrogen preferably is stored in the negative electrode with the form of atomic hydrogen, directly is fixed in the negative electrode by absorption.Comprise at negative electrode under the situation of intermetallic compound, the hydrogenation of negative electrode (hydrideation) can be reacted via chemisorption and be carried out, and wherein, molecular hydrogen splits into atomic hydrogen when contacting with intermetallic compound.For facilitating this chemisorption reaction, hydrogenatable negative electrode can randomly be heated and/or place under the pressure.
When the diameter in the hole of wall 21 less than H
+Contained H in the ion donor
3O
+During the ionic size, the intensity of the electric field that applies between anode and negative electrode must be enough to make H
3O
+Ion ruptures by following reaction:
H
3O
+→H
2O+H
+
Preferably there is water in this reaction consumes water in ionogen.
The reaction that produces hydrogen causes that also the gaseous state of oxygen discharges.This gaseous state discharges and can cause formation bubble in anode 20 places in the ionogen.
The corresponding exit that the gaseous oxygen that forms in the hydrogen production process can be arranged in the unit is reclaimed and is stored or directly uses, or discharges into the atmosphere.
Can be by heated cathode and/or by negative electrode being placed vacuum get off to extract the hydrogen that so stores, for example to supply with fuel cell and/or to use described hydrogen to act as a fuel or reactant.
Preferably before heated cathode, described unitary ionogen is emptied.The ionogen that empties can for example enter in the replenishment device.
Can control the flow rate of the hydrogen of extraction by the Heating temperature of for example operating negative electrode.
In a unshowned modification, heater is outside big envelope 15.
In the modification shown in Fig. 7, heater 25 is positioned at negative electrode 22.
Also show anode 20 in the figure and support this option by seeing through ionic wall 21.
Ionogen 40 passes anode 20, and under suitable situation, the reserve of the side that ionogen 40 can be relative with being arranged in anode 20 and negative electrode 22 is communicated with.
Can see through ionic wall 21 and can have multilayered structure, the layer 21b that for example has supporting layer 21a and make by material non-conductive but conducting ion, as shown in Figure 7.
Supporting layer 21a can be made of for example porous ceramics.
Exist supporting layer 21a can reduce the thickness of support function that is used to provide layer 21b of layer 21b.
By supporting anodes 20, layer 21a also makes and can use the lower anode of physical strength 20.
Fig. 8 shows and utilizes similar with the unit of the example shown in Figure 6 but different heaters that are to place the result's of the outer unit acquisition of big envelope example.
Used anode is made by graphite.Wall 21 is by making by contact the hexagonal boron nitride that was activated in three hours with ionogen under 50V voltage.Wall 21 is for example by being that the bar of 1mm carries out mechanical workout and produces to thickness.Ionogen is the sulfuric acid of 5M.Negative electrode 22 is based on the powdery LaNi that uses in the NiMH battery
5
Certainly, the invention is not restricted to previously described example.
Described unit may be made in different shape and size, and can be made by other materials.Under suitable situation, anode and negative electrode can intersect mutually.Described unit can comprise some preparations and storage batteries, and each comprises negative electrode and anode.Ionogen can be positioned at inside, by anode, can see through the ionic wall and negative electrode be surrounded, negative electrode thus with respect to anode externally, and himself can be surrounded by the member of elastically deformable.
Except as otherwise noted, otherwise the statement " comprising " be interpreted as with " comprising at least one " synonym.
Claims (29)
1, a kind of method that is used for Chu Qing and hydrogen manufacturing, wherein, for storing hydrogen, unit (2) comprising:
-positively charged ion donor, particularly H
+The ionic donor;
-anode (20);
-can store the negative electrode (22) of atomic hydrogen and/or molecular hydrogen; With
-can see through ionic wall (21), described wall is between described negative electrode and described positively charged ion donor, include material non-conductive but conducting ion, described wall places electric field, described electric field makes it possible at least to be stored in the described at least negative electrode at the atomic hydrogen of formation at the interface of described negative electrode and described electrically nonconducting material and/or molecular hydrogen and with it, and
Wherein, for collecting gaseous hydrogen, described negative electrode is heated and/or places under the vacuum.
2, as the described method of last claim, wherein, the described water-permeable that sees through ionic wall (21) be lower than the hydrogen that is produced quality 5%.
3, as the described method of last claim, wherein, described negative electrode contains the water that is lower than 5% weight percent.
4, each described method in the claim as described above, wherein, the described ionic wall (21) that sees through has zero water-permeable.
5, each described method in the claim as described above, wherein, described negative electrode comprises intermetallic compound, and described intermetallic compound especially is selected from as follows: AB
5Type (A and B are metal), for example LaNi
5, lava (Zr, Ti), (Mn, V, Cr, Ni)
2Various phases, ZrMn for example
2Or TiMn
2, Mg, TiFe, Mg
2Ni is based on the heart cube sosoloid of vanadium, BaReH
9(this formula is corresponding to hydrogenation state), Mg
2FeH
6(this formula is corresponding to hydrogenation state), NaAlH
4(this formula is corresponding to hydrogenation state), LiBH
4(this formula is corresponding to hydrogenation state), and all compounds and derivative or its alloy.
6, each described method in the claim as described above, wherein, described electrically nonconducting material comprises pottery, particularly comprise hexagonal boron nitride, more excellent be by acid solution activatory boron nitride, lithium nitride, ionic conduction polymer, boric acid under electric field.
7, each described method in the claim as described above describedly sees through the layer that ionic wall (21) comprises one or more differing materials, and at least one in these layers layer has the function of cation conductive.
8, as the described method of last claim, described wall (21) comprises the porous layer with supporting role between layer with described cation conductive function and described ionogen.
9, each described method in the claim as described above, described positively charged ion donor is an acidic aqueous solution.
10, each described method in the claim as described above, wherein, described positively charged ion donor circulates in described unit.
11, each described method in the claim as described above, wherein, the voltage that applies between described anode and described negative electrode in the hydrogen production process is between 1V and 300V, and more excellent is between 1.24V and 200V, preferably between 1.24V and 4V.
12, each described method in the claim as described above, wherein, described negative electrode is being higher than 30 ℃, particularly is being heated to produce gaseous hydrogen under the temperature between 70-350 ℃.
13, method as claimed in claim 12, described heating is produced by the joule effect in the current cycle process.
14, method as claimed in claim 12, described heating is carried out after discharging described ionogen.
15, method as claimed in claim 12, in hydrogen manufacturing and storage hydroformylation stage process, described unit is heated below the temperature of hydrogen release to improve storage hydrogen causing.
16, each described method in the claim as described above, wherein, described atomic hydrogen and/or molecular hydrogen also are stored in the material of described non-conductive but conducting ion.
17, a kind of unit (2) that is used to store and recover hydrogen comprising:
-anode (20);
-can store the negative electrode (22) of atomic hydrogen and/or molecular hydrogen;
-positively charged ion donor, especially H
+The ionic donor;
-can see through ionic wall (21), described wall comprises material non-conductive but conducting ion between described negative electrode and described positively charged ion donor;
The member (25) of-optional heated cathode; With
-electric connector, described electric connector can be powered to produce electric field between described anode and described negative electrode to described anode and described negative electrode, and described electric field makes it possible to form atomic hydrogen and/or molecular hydrogen at least and it is stored in the described at least negative electrode in described negative electrode;
Described unit is arranged to collect the gaseous hydrogen that is discharged by described negative electrode in the process of the described negative electrode of heating,
Described unit also comprises:
-fluid connector, described fluid connector can be directed to the gaseous hydrogen that so discharges outside the described unit.
18, as the described unit of last claim, described heating unit comprises resistance element.
19, as a described unit in preceding two claims, described unit also comprises the device (26) of the temperature that is used to regulate described negative electrode.
20, as each the described unit in the first three items claim, wherein, described negative electrode (22) comprises intermetallic compound.
21, as each the described unit among the claim 17-20, wherein, described electrically nonconducting material comprises pottery, especially amorphous ceramic.
22, as each the described unit among the claim 17-21, described positively charged ion donor is an aqueous acid solution.
23, as each the described unit among the claim 17-22, comprise returning elastically member (24), make described negative electrode lean against on the material of described non-conductive but conducting ion.
24,, comprise the junctor that is used for filling and/or removing described positively charged ion donor as each the described unit among the claim 17-23.
25, as each the described unit among the claim 17-24, comprise the coupling part that to realize extracting stored gaseous hydrogen.
26, as each the described unit among the claim 17-25, described anode (20) is supported by the described ionic wall (21) that sees through.
27, a kind of method that produces electricity comprises to fuel cell providing from the step of the hydrogen that extracts according to the storage element that limits in the claim 17-26 each.
28, a kind of unitary equipment of limiting in each of supply such as claim 17-26 of being used for comprises being used to hold at least one chamber (4) of described unit (2) and treating link to each other to produce at least one electric connector of electric field between described negative electrode and described anode with described unitary electric connector.
29, a kind of electric installation, particularly mobile telephone or laptop computer, described electric installation comprises at least one chamber, described chamber can hold at least one as each the described storage element among the claim 17-26.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0701614A FR2913417B1 (en) | 2007-03-06 | 2007-03-06 | METHOD AND UNIT FOR STORING HYDROGEN |
| FR0701614 | 2007-03-06 | ||
| PCT/FR2008/050379 WO2008129182A2 (en) | 2007-03-06 | 2008-03-06 | Hydrogen storing method and unit |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101679023A true CN101679023A (en) | 2010-03-24 |
Family
ID=38521174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880007177A Pending CN101679023A (en) | 2007-03-06 | 2008-03-06 | Hydrogen storing method and unit |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20100089767A1 (en) |
| EP (1) | EP2129621A2 (en) |
| JP (1) | JP2010520145A (en) |
| CN (1) | CN101679023A (en) |
| AU (1) | AU2008240532B2 (en) |
| CA (1) | CA2679788A1 (en) |
| FR (1) | FR2913417B1 (en) |
| WO (1) | WO2008129182A2 (en) |
| ZA (1) | ZA200906056B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627019A (en) * | 2019-09-26 | 2019-12-31 | 电子科技大学 | Hydrogen isotope extraction assembly for hydrogen-containing mixed gas under high-temperature condition |
| CN110870119A (en) * | 2017-07-11 | 2020-03-06 | 鲁道夫·安东尼奥·戈麦斯 | Advanced electrolytic storage and recovery of hydrogen |
| WO2021174795A1 (en) * | 2020-03-06 | 2021-09-10 | 顾士平 | Gas adsorption system using electric field polarization |
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| FR2916906B1 (en) | 2007-05-28 | 2009-10-02 | Ceram Hyd Soc Par Actions Simp | PROTONIC EXCHANGE MEMBRANE AND CELL COMPRISING SUCH A MEMBRANE |
| FR2928492B1 (en) | 2008-03-06 | 2011-10-21 | Ceram Hyd | MATERIAL FOR AN ELECTROCHEMICAL DEVICE. |
| JP6024588B2 (en) * | 2013-05-13 | 2016-11-16 | トヨタ自動車株式会社 | Hydrogen storage device |
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-
2007
- 2007-03-06 FR FR0701614A patent/FR2913417B1/en not_active Expired - Fee Related
-
2008
- 2008-03-06 CA CA002679788A patent/CA2679788A1/en not_active Abandoned
- 2008-03-06 AU AU2008240532A patent/AU2008240532B2/en not_active Ceased
- 2008-03-06 CN CN200880007177A patent/CN101679023A/en active Pending
- 2008-03-06 US US12/529,292 patent/US20100089767A1/en not_active Abandoned
- 2008-03-06 EP EP08775682A patent/EP2129621A2/en not_active Withdrawn
- 2008-03-06 WO PCT/FR2008/050379 patent/WO2008129182A2/en active Application Filing
- 2008-03-06 JP JP2009552257A patent/JP2010520145A/en active Pending
-
2009
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110870119A (en) * | 2017-07-11 | 2020-03-06 | 鲁道夫·安东尼奥·戈麦斯 | Advanced electrolytic storage and recovery of hydrogen |
| CN110627019A (en) * | 2019-09-26 | 2019-12-31 | 电子科技大学 | Hydrogen isotope extraction assembly for hydrogen-containing mixed gas under high-temperature condition |
| CN110627019B (en) * | 2019-09-26 | 2022-12-13 | 电子科技大学 | Hydrogen isotope extraction assembly for hydrogen-containing mixed gas under high-temperature condition |
| WO2021174795A1 (en) * | 2020-03-06 | 2021-09-10 | 顾士平 | Gas adsorption system using electric field polarization |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2008240532A1 (en) | 2008-10-30 |
| WO2008129182A3 (en) | 2009-03-12 |
| CA2679788A1 (en) | 2008-10-30 |
| AU2008240532B2 (en) | 2013-01-10 |
| ZA200906056B (en) | 2010-11-24 |
| WO2008129182A2 (en) | 2008-10-30 |
| FR2913417B1 (en) | 2009-11-20 |
| US20100089767A1 (en) | 2010-04-15 |
| FR2913417A1 (en) | 2008-09-12 |
| EP2129621A2 (en) | 2009-12-09 |
| JP2010520145A (en) | 2010-06-10 |
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