CN101189201A - Storage-stable fuel concentrate - Google Patents

Storage-stable fuel concentrate Download PDF

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Publication number
CN101189201A
CN101189201A CNA2005800486466A CN200580048646A CN101189201A CN 101189201 A CN101189201 A CN 101189201A CN A2005800486466 A CNA2005800486466 A CN A2005800486466A CN 200580048646 A CN200580048646 A CN 200580048646A CN 101189201 A CN101189201 A CN 101189201A
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CN
China
Prior art keywords
enriched material
metal hydride
hydride compound
container
hydroxide ion
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CNA2005800486466A
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Chinese (zh)
Inventor
盖纳蒂·芬克尔斯坦
亚历山大·西尔伯曼
尤利·卡茨曼
马克·埃斯特林
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More Energy Ltd
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More Energy Ltd
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Publication of CN101189201A publication Critical patent/CN101189201A/en
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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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
    • 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
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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

A storage-stable liquid concentrate for use with a fuel cell. The concentrate comprises at least one metal hydride compound, a solvent comprising one or more polar solvent components, and at least one hydroxide ion providing compound. Following a storage of the concentrate for 4 weeks at about 25 DEG C not more than about 2% of the at least one metal hydride compound have decomposed. This abstract is neither intended to define the invention disclosed in this specification nor intended to limit the scope of the invention in any way.

Description

The fuel enriched material of shelf-stable
Technical field
The present invention relates to be used for fuel cell shelf-stable enriched material and prevent or reduce the method that the fuel that is used for fuel liquid battery decomposes at its lay up period.
Background technology
Fuel cell is wherein at anodic fuel (for example molecular hydrogen or methyl alcohol) catalytic oxidation with at the oxygenant of negative electrode (often being molecular oxygen) the simultaneous electrochemical power source of electrical catalyze reduction.Traditional fuel such as hydrogen and methyl alcohol cause various storages and transportation problem, particularly for portable fuel battery (for example being used for portable electricity or electronics such as portable computer, mobile phone etc.).
Fuel based on hydroborate (with other hydride) is especially meaningful for portable fuel battery, this be because their very high specific energy capacity (referring to for example J.ofElectrochem.Soc., 150, (3), A398-402,2003).Such fuel can directly act as a fuel or indirectly as the producer of hydrogen (it is oxidized at anode), for example as portable proton exchange film (PEM) fuel cell component (referring to for example US20010045364 A1, US 20030207160 A1, US 20030207157 A1, US 20030099876 A1 and U.S.Patent Nos.6,554,877 B2 and 6,562,497B2).The open of all above-mentioned documents is incorporated herein with for referencial use especially with its integral body.
The main oxidizing reaction of the hydroborate at anode of fuel cell place can be expressed as follows:
BH 4 -+8OH -＝BO 2-+6H 2O+8e -
Yet, also there is the side reaction cause liberation of hydrogen (hydro gen evolution) during the catalytic oxidation:
BH 4 -+4OH -＝BO 2 -+2H 2O+2H 2+4e -
And, at the borohydride fuel lay up period, spontaneous decomposition reaction takes place usually:
BH 4 -+2H 2O＝BO 2 -+4H 2
Above-mentioned decomposition reaction not only causes the specific energy capacity of borohydride fuel to reduce undesirably, and causes owing to particularly also causing the dangerous hydrogen that increases of fuel tank internal pressure to produce the problem that causes storage and transportation.
One of factor that the rate of decomposition of borohydride fuel and other metal hydride fuel is had strong influence is a temperature.Along with the rising of temperature, rate of decomposition is pressed index and is increased.Equally, the rate of decomposition that the existing of catalytic impurities (salt of Ni, Fe, Co, Mg, Ca etc.) can remarkably influenced (increase) fuel.
Improving the alkalescence be used for the borohydride fuel of fuel cell and contain hydride liquid usually is to improve the cheap and efficient manner of its stability.Yet, for the purpose of storing and transporting the basicity of fuel is increased to the level that the ideal fuel stability is provided need usually fuel viscosity increase unrealisticly (that is, make the suction of fuel become difficult or not even may), the solubleness of reaction product in fuel reduces and/or the specific energy electric capacity of fuel descends.Especially, for practical purpose, hydroxide concentration best in the fuel is usually in about scope of 3 to about 6mol/L.On the other hand, observe to store and the rule request of transportation obtainable fuel stability under about 8mol/L or higher hydroxide ion concentration only.
Summary of the invention
The invention provides the liquid concentrate of the shelf-stable that is used for fuel cell.Solvent and at least a hydroxide ion that this enriched material comprises at least a metal hydride compound, contain one or more polar solvent components provide compound.This enriched material about 25 ℃ down stored for 4 weeks after, being not more than about 2% at least a metal hydride compound will decompose.
Aspect of this enriched material, metal hydride compound can carry out the anodic oxidation in the liquid fuel within battery and/or decompose under the condition that promotes its hydrolysis producing hydrogen.Preferably, at least a metal hydride compound comprises hydride, hydroborate and/or the alanate of basic metal and/or alkaline-earth metal.As non-limiting example, at least a metal hydride compound can comprise NaBH 4, KBH 4, LiBH 4, Be (BH 4) 2, Ca (BH 4) 2, Mg (BH 4) 2, (CH 3) 3NHBH 3, NaCNBH 3, LiH, NaH, KH, CaH 2, BeH 2, MgH 2, NaAlH 4, LiAlH 4And KAlH 4At least a, preferred NaBH 4, KBH 4, LiBH 4, LiH, NaH and KH at least a, NaBH for example 4And/or KBH 4
On the other hand, this enriched material can have hydroxide ion concentration at least about 7.5mol/L, and for example at least about 8mol/L, and/or this enriched material can contain at least a metal hydride compound with the concentration at least about 3mol/L.
Aspect another, this at least a hydroxide ion provides compound can comprise at least a basic metal or alkaline earth metal hydroxides and/or aluminium hydroxide.As non-limiting example, this at least a hydroxide ion provides compound can comprise LiOH, NaOH, KOH, RbOH, CsOH, Ca (OH) 2, Mg (OH) 2, Ba (OH) 2And NH 4OH's is at least a, preferred NaOH and/or KOH.
More on the one hand, solvent can comprise water, have up to about 6 carbon atoms with up to about fatty alcohol, the C of 4 hydroxyls 2-4Aklylene glycol, two (C 2-4Alkylidene group) glycol, C 2-4Aklylene glycol or two (C 2-4Alkylidene group) list-C of glycol 1-4-alkyl oxide, C 2-4Aklylene glycol or two (C 2-4Alkylidene group) two-C of glycol 1-4-alkyl oxide, have aliphatic ether, have aliphatic ketone and/or C up to about 6 carbon atoms up to about 6 carbon atoms 1-3The C of paraffinic acid 1-3Alkyl oxide.As non-limiting example, this solvent can comprise one or more of water, methyl alcohol, ethanol, ethylene glycol, glycol ether, glycerine, acetone, methylethylketone, diethyl ketone, methyl acetate, ethyl acetate, diox, tetrahydrofuran (THF), diglyme and triglyme.This solvent can often comprise water at least.
On the other hand, this enriched material can comprise the NaBH of total concn at least about 4mol/L 4And KBH 4At least a, water and NaOH and/or KOH.
Aspect further, this enriched material can be mainly by NaBH 4, KBH 4, LiBH 4, (CH 3) 3NHBH 3And/or NaCNBH 3, bag aqueous solvent and NaOH and/or KOH form, and can have the hydroxide ion concentration at least about 8mol/L.
On the other hand, this enriched material can contain the metal hydride compound that can be used as of capacity is used for the liquid fuel and/or the hydrogen generator of fuel cell when it is diluted to hydroxide ion concentration and is not higher than about 6mol/L.As non-limiting example, when being diluted to the about 6mol/L of hydroxide ion concentration, this enriched material can be with at least about 2mol/L, and for example the concentration at least about 3mol/L contains metal hydride compound.
On the other hand, this enriched material can not contain any fuel dope that influences metal hydride compound stability unfriendly substantially.For example it can essentially no softening agent, washing composition (detergents) and frostproofer, and/or it can essentially noly be used for the stablizer of metal hydride compound.
On the other hand, this enriched material is not more than approximately 5% after about 25 ℃ down keep 1 year, preferably is not more than approximately 3%, even will be decomposed more preferably no more than about 2% metal hydride compound.
The present invention also provides the method that is used for the metal hydrogenation thing liquid of fuel cell by the enriched material preparation of shelf-stable.This method comprises with enriched material with the solvent combination at least about the amount of 15 volume % of this enriched material.This enriched material comprises at least a metal hydride compound and polar solvent, and has the hydroxide ion concentration at least about 7mol/L.Equally.When this enriched material kept for 4 weeks under about 25 ℃, be not more than 2% metal hydride compound decomposes.
In the one side of this method, the combination of enriched material and solvent preferably provides the hydroxide ion concentration of gained mixture not to be higher than about 6mol/L.
In this method on the other hand, when this enriched material kept for 4 weeks under about 25 ℃, preferably be not more than 0.5% metal hydride compound decomposes.
On the other hand, the hydroxide ion concentration in this enriched material can be at least about 7.5mol/L, and for example at least about 8mol/L, and/or the concentration of this at least a metal hydride compound is at least about 3mol/L.
Aspect this method another, this metal hydride compound can comprise NaBH 4, KBH 4, LiBH 4, Be (BH 4) 2, Ca (BH 4) 2, Mg (BH 4) 2, (CH 3) 3NHBH 3, NaCNBH 3, LiH, NaH, KH, CaH 2, BeH 2, MgH 2, NaAlH 4, LiAlH 4And KAlH 4At least a, preferred NaBH 4And/or KBH 4
More on the one hand, this enriched material can further comprise LiOH, NaOH, KOH, RbOH, CsOH, Ca (OH) 2, Mg (OH) 2, Ba (OH) 2And/or NH 4OH.
Aspect this method another, this solvent can comprise at least a of water, methyl alcohol, ethanol, ethylene glycol, glycol ether, glycerine, acetone, methylethylketone, diethyl ketone, methyl acetate, ethyl acetate, diox (dioxin), tetrahydrofuran (THF), diglyme and triglyme.
On the other hand, this enriched material preferably comprises NaBH 4And/or KBH 4, water and NaOH and/or KOH.
On the other hand, this enriched material is diluted to the concentration at least about 2mol/L that the about 6mol/L of hydroxide ion concentration will preferably cause this at least a metal hydride compound.
The present invention also is provided for the method for metal hydrogenation thing liquid of packing of the shelf-stable of fuel cell.This liquid comprises at least a metal hydride compound and comprise the polar solvent of first part and at least one second section, and has hydroxide ion concentration and be not higher than about 7mol/L.This method comprises provides the container with first Room and at least one second Room, with enriched material part or all of filling first Room with this at least one second Room of the part or all of filling of at least one second section of this polar solvent, this enriched material is that it only comprises the first part of polar solvent and is that it has hydroxide ion concentration and is at least about 8mol/L with different (at least) of liquid.
In the one side of this method, will preferably cause the hydroxide ion concentration of this combination not to be higher than about 6mol/L the content of first Room and the content combination of this at least one second Room.
On the other hand, when this enriched material when keeping for 4 weeks for about 25 ℃, preferably being not more than this at least a metal hydride compound of about 1% will decompose.
Aspect another, this enriched material contains this at least a metal hydride compound with the concentration at least about 3mol/L.
This method further aspect, this metal hydride compound can comprise NaBH 4, KBH 4, LiBH 4, Be (BH 4) 2, Ca (BH 4) 2, Mg (BH 4) 2, (CH 3) 3NHBH 3, NaCNBH 3, LiH, NaH, KH, CaH 2, BeH 2, MgH 2, NaAlH 4, LiAlH 4And KAlH 4At least a.
On the other hand, this enriched material can further comprise LiOH, NaOH, KOH, RbOH, CsOH, Ca (OH) 2, Mg (OH) 2, Ba (OH) 2And NH 4OH's is at least a.
Aspect another, this enriched material comprises NaBH 4And/or KBH 4, water and NaOH and/or KOH.
More on the one hand, when this enriched material is diluted to the about 6mol/L of hydroxide ion concentration when it, preferably contain this at least a metal hydride compound at least about 2mol/L.
On the other hand, can design this container so that at least one second component of this enriched material and this polar solvent (being at least some) in this container is mixed.
The present invention also provides the metal hydrogenation thing liquid by the packing of the obtainable shelf-stable of aforesaid method, comprises its all respects.
The present invention also provides the container that is filled with metal hydrogenation thing liquid.This container comprises first Room and at least one second Room.Enriched material is contained in this first Room, and this enriched material comprises at least a metal hydride compound and polar solvent and has hydroxide ion concentration at least about 8mol/L.Solvent is contained with the amount that is enough to cause hydroxide ion concentration not to be higher than about 7mol/L in this at least one second Room, with respect to the mixture of solvent in this at least one second Room and the enriched material in this first Room.
On the one hand, this container can be sealed and at least one second component of this enriched material and this polar solvent is mixed, and then it is discharged from container.This container in addition with explanation so that at least one second component of this enriched material and this polar solvent is mixed, then it is discharged from this container.
On the other hand, this container can comprise internal partition, and this internal partition limits this first Room and this at least one second Room.As non-limiting example, this first Room can to small part by this at least one second Room around, perhaps this at least one second Room can to small part by this first Room around.
Aspect this container another, the quantity of solvent at least one second Room can be enough to cause not being higher than the hydroxide ion concentration of about 6mol/L, with respect to the mixture of the enriched material in the solvent in this at least one second Room and this first Room.
More on the one hand, this enriched material can contain this at least a metal hydride compound with the concentration at least about 3mol/L.
Aspect another, this metal hydride compound can contain NaBH 4, KBH 4, LiBH 4, Be (BH 4) 2, Ca (BH 4) 2, Mg (BH 4) 2, (CH 3) 3NHBH 3, NaCNBH 3, LiH, NaH, KH, CaH 2, BeH 2, MgH 2, NaAlH 4, LiAlH 4And KAlH 4At least a, and/or this enriched material can further comprise LiOH, NaOH, KOH, RbOH, CsOH, Ca (OH) 2, Mg (OH) 2, Ba (OH) 2And NH 4OH's is at least a.As non-limiting example, this enriched material can comprise NaBH 4And/or KBH 4, water and NaOH and/or KOH.
At container of the present invention on the other hand, this enriched material when with its dilution so that the hydroxide ion concentration of about 6mol/L to be provided, can contain at least about 2mol/L, for example at least about the metal hydride compound of 3mol/L concentration.
The present invention also is provided for the equipment that refills of fuel liquid battery.This equipment comprises container of the present invention, comprises its all respects.
On the one hand, design this equipment can hold waste liquid from fuel liquid battery.
The present invention also is provided for the packaged combination of the metal hydrogenation thing liquid of fuel cell.This combination comprises first container and at least one second container.This first container contains enriched material, and this enriched material comprises at least a metal hydride compound, polar solvent and at least a hydroxide ion to be provided compound and have hydroxide ion concentration at least about 8mol/L.This at least one second container contains solvent with the amount that is enough to cause hydroxide ion concentration not to be higher than about 7mol/L, with respect to the mixture of solvent at least one second container and the enriched material in first container.
On the one hand, this combination can with explanation with this enriched material in first container with from the combination of at least a portion solvent of second container.In this combination on the other hand, this enriched material can comprise NaBH 4And/or KBH 4, water and NaOH and/or KOH.
Aspect this combination another, solvent in this at least one second container can contain the additive that is useful on fuel, it is preferably selected from softening agent, washing composition, be used for the stablizer of this at least a metal hydride compound (for example, aliphatic series or aromatic amine) and/or frostproofer.
The method that the fuel that the present invention also provides reduction to be used for fuel liquid battery decomposes during bunkering.This method comprises with enriched material form discussed above and keeps this fuel, comprises its all respects, and only the use of the fuel in fuel cell was not long ago diluted this enriched material with preparation fuel.
The liquid concentrate of shelf-stable of the present invention comprises several components.In this respect, notice that the narration reach these components in the appended claims herein needn't think that meaning these components must former state be present in the enriched material.But, those skilled in the art understand these components can be preparation during enriched material parent material and can be by with other parent material and/or the component reaction of this enriched material and/or interact to react and form new type.
The preferred such compound of metal hydride compound that is used for enriched material of the present invention, this compound can be oxidized electronics to be provided and/or can (at least) to be used as the molecular hydrogen producer that for example passes through the metal hydride compound hydrolysis in the anode former state of fuel cell, and this molecular hydrogen can be used as the fuel of fuel cell conversely again.Should understand the term " metal hydride compound " that is used for this specification and the appended claims and broadly use, and comprise that especially it is compound such as NaH, KH etc. of " simply " hydride and the compound such as hydroborate, the alanate etc. that comprise the hydride complex ion.The non-limiting example that is used for metal hydride compound of the present invention comprise basic metal such as Li, Na, K, Rb and Cs and alkaline-earth metal such as Be, Mg, Ca, Sr and Ba and organic cation as single-, two-, three-and hydride, hydroborate (comprising the cyanogen hydroborate) and the alanate of tetraalkyl ammonium ion.Corresponding particular compound includes but not limited to LiBH 4, NaBH 4, KBH 4, Be (BH 4) 2, Ca (BH 4) 2, Mg (BH 4) 2, (CH 3) 3NHBH 3, NaCNBH 3, LiH, NaH, KH, CaH 2, BeH 2, MgH 2, NaAlH 4, LiAlH 4And KAlH 4For the purposes of the present invention, hydroborate, particularly NaBH 4And KBH 4Be preferred.
The solvent that constitutes another component of enriched material of the present invention comprises one or more polarity (proton and/or non-proton) solvent composition.If this solvent is a neat solvent, promptly only there is a kind of solvent composition, it must be a polar.If this solvent is a solvent mixture, that is, comprise one or more (for example, two kinds, three kinds, four kinds or even more kinds of) independent solvents, at least a of the component of mixture must be polar.Preferably, all or all basically solvent compositions are polar.Be used under the preferred room temperature of solvent of the present invention and solvent mixture for liquid and preferably to be enough to being dissolved to small part (and all preferred) metal hydride compound and hydroxide ion provides the amount of compound to exist.The non-limiting example of appropriate solvent comprises that water, monobasic-and many-unit's alcohol (for example, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and glycerine) and single-and poly--aklylene glycol is (for example, ethylene glycol, glycol ether, propylene glycol and dipropylene glycol), single-and the aliphatic ester of many-first carboxylic acid (for example, ethyl acetate, methyl acetate, ethyl formate and oxalic acid diethyl ester), aliphatic ketone (for example, acetone, methylethylketone and diethyl ketone) and (ring) aliphatic ether (as tetrahydrofuran (THF), diox and single-and polyvalent alcohol with singly-and the part or all of alkyl ester of polyalkylene glycol).Preferred solvent composition is a water, as long as metal hydride compound and protonic solvent do not react to any substantial extent.Other preferred solvent components comprises monobasic and polynary aliphatic series and alicyclic alcohol such as methyl alcohol and ethanol.
The hydroxide ion that is used for enriched material of the present invention provide compound can be this enriched material can be for example by disassociation, decompose or by with any other compound (original position) reaction that may reside in this enriched material or interact any compound of hydroxide ion is provided.Should understand these compounds and not be taken in the operation of disturbing fuel cell on any significant degree, particularly the electrochemical reaction that wherein takes place.Usually, hydroxide ion provides compound to comprise at least a basic metal or alkaline earth metal hydroxides and/or ammonium hydroxide.Suitably the indefiniteness specific examples of compound is LiOH, NaOH, KOH, RbOH, CsOH, Ca (OH) 2, Mg (OH) 2, Ba (OH) 2And NH 4OH.Corresponding oxide compound, carbonate and supercarbonate are to can be used as the non-limiting example that hydroxide ion provides the other compound of compound.Often use NaOH and/or KOH.Hydroxide ion provides the amount of compound to depend on hydroxide ion concentration required in this enriched material significantly.
Enriched material shelf-stable of the present invention, that is, with this enriched material about 25 ℃ down stored for 4 weeks after, be not more than about 2mol%,, for example be not more than about 0.5% more preferably no more than about 1%, be not more than approximately 0.25%, or be not more than about 0.1% metal hydride compound and will decompose.In addition, this enriched material preferably is being not more than about 5% in storage under 25 ℃ after 1 year, for example be not more than about 3%, for example be not more than approximately 2%, be not more than approximately 1%, perhaps even will not decompose (calculating) based on mole number greater than about 0.5% metal hydride compound.
Provide the hydroxide ion concentration of the enriched material of required stability especially to depend on concrete metal hydride compound, solvent and amount thereof and may have the stability of metal hydride compound disadvantageous effect fuel dope etc. existence or do not exist.In general, the hydroxide ion concentration in the enriched material is usually above about 6mol/L, but is not higher than about 14mol/L usually, preferably is not higher than about 12mol/L.Usually, the hydroxide ion concentration in the enriched material is at least about 7mol/L, preferably at least about 7.5mol/L, even more preferably at least about 8mol/L, for example at least about 8.5mol/L, at least about 9mol/L, perhaps even at least about 10mol/L.
Some is relevant for hydroxide ion concentration in the desired concn of the metal hydride compound in the enriched material of the present invention and the enriched material.Especially, because this enriched material is intended to use as the fuel/hydrogen generator that is used for fuel cell with the form of dilution, hydroxide ion concentration in the enriched material high more and the dilution enriched material (promptly, fuel/hydrogen generator) hydroxide ion concentration required in is low more, and the preferred concentration of the metal hydride in the enriched material is high more.In other words, after enriched material was diluted to required hydroxide ion concentration, gained liquid also should contain the metal hydride compound of enough concentration to use the fuel/hydrogen generator that acts on fuel cell.Although the usable concentration of metal hydride compound especially depends on fuel cell and capacity thereof and depends on a lot of other factorses, but enriched material of the present invention contains metal hydride compound with such concentration usually, after this concentration is diluted to the hydroxide ion concentration of about 6mol/L at enriched material, the concentration that metal hydride compound is provided is at least about 0.5mol/L, preferably at least about 1mol/L, or at least about 2mol/L, for example at least about 3mol/L, at least about 4mol/L, perhaps even at least about 5mol/L.Usually, (always) concentration of the metal hydride compound in the enriched material is through being everlasting about 4mol/L to the scope of about 12mol/L.
In order further to improve the stability of enriched material of the present invention, preferably this enriched material is substantially free of any material that influences the stability of the metal hydride compound that wherein contains unfriendly.For example, may expect to have additive one or more of softening agent, washing composition and frostproofer for example that are present in the fuel/hydrogen generator that is used for fuel cell.Enriched material of the present invention does not preferably have such additive or only contains its minute quantity (for example, total amount is less than about 0.1 weight %, even is more preferably less than about 0.01 weight %).Same preferred enriched material provides and does not contain any material the compound except that metal hydride compound, separately solvent or solvent composition and hydroxide ion.If other material exists, their total concn preferably is no more than about 5 weight %, and preferably is no more than 1 weight %.Unless otherwise noted, the weight percent that herein provides is based on the gross weight of enriched material.If the expectation final fuel/hydrogen generator contain any material that preferably is not present in this enriched material (or at least not with required concentration), can with they its dilution not long ago or during join in this enriched material.For example, these desired substances of all or part can be joined in the liquid (solvent) (that is thinner) that is used to dilute enriched material.Especially advantageously the stablizer that one or more is used for metal hydride compound joins thinner, because the enriched material of dilution can no longer have sufficiently high hydroxide ion concentration and metal hydride compound steady in a long-term satisfactorily.The non-limiting example of suitable stablizer comprises aromatics and aliphatic amine.The indefiniteness embodiment of other additive such as softening agent, washing composition and frostproofer comprise polyvalent alcohol, for example glycerine and ethylene glycol (frostproofer).Certainly, under many circumstances, latter's compound can be used as thinner (polar solvent) equally or its component exists.
The thinner that is used for enriched material of the present invention comprises the solvent composition that one or more are present in enriched material with the ratio identical or different with enriched material (preferred same ratio) usually.This thinner also can contain at least a different solvent composition, or can be fully be present in solvent composition in the enriched material by one or more.Certainly, in the situation of back, must especially take care one or more solvents of thinner and one or more solvent compositions, the hydroxide ion of enriched material provides compound and particularly metal hydride compound compatible.Especially, when thinner and enriched material combination, thinner should preferably not cause any tangible precipitation.Thinner does not contain any metal hydride compound usually.Equally, it does not contain hydroxide ion usually provides compound, if perhaps it contains, also the concentration of hydroxide ion concentration contains in the enriched material significantly to be lower than.Yet, to describe as top, it is additive and other material that ideal but its may influence (for a long time) stability of the metal hydride compound in the enriched material that this thinner can contain that it is present in the fuel.Depend on various factors for appropriate amount, especially the required hydroxide ion concentration of the enriched material of hydroxide ion concentration in the enriched material and dilution (that is fuel/hydrogen generator) with the thinner of enriched material combination.Usually, the amount of thinner be enriched material at least about 15 volume %, often at least about 20 volume %, for example at least about 30 volume %, at least about 40 volume % or at least about 50 volume %.
Therefore, for commercial purpose, there are the various possible methods that enriched material and thinner combination are provided.For example, this combination can be arranged in the single container or at least two isolating containers, one contains enriched material and another contains at least the dilution dosage that (with preferably exactly) brings necessity of the required ultimate density of enriched material.Under one situation of back, the content of these at least two containers can be randomly by the outside and/or inner combination of mixing equipment at fuel cell.
If enriched material and thinner are arranged in the single container, this container can have different designs.This container should be able to prevent directly liquid-liquid contact between enriched material and the thinner basically.As non-limiting example, this container can comprise two compartments or the chamber of shared spacer, perhaps compartment or chamber can be separated from each other fully (that is no shared structural element).The outlet of these chambers can be connected and/or incorporates into the public exit opening of container in container.As selection, can design this container so that the content in the chamber mixes basically fully, enriched material and thinner are still at internal tank simultaneously.For example, containing the chamber of enriched material and contain spacer between the chamber of thinner can be movably and/or removable (preferred, container still seals simultaneously).In addition, between these chambers, valve can be set.As selection, spacer (for example, barrier film) can tear (for example) by bending or squeeze receptacle otherwise make its be unsuitable for stoping between enriched material and the thinner and in container, directly contact (for example,, use slide fastener by piercing through, for example, Ziploc
Figure A20058004864600221
Ridge-the groove of kind (ridge-and-charmel) " zipper " etc.)。Certainly, in case with enriched material dilution (that is, with the thinner combination), it should preferably excessively lingeringly not discharged from container, this is because the enriched material, the particularly stability of wherein contained metal hydride compound of dilution may no longer be suitable for long-term or intermediate time scale storage.
Being used for the enriched material of the present invention especially preferred container of (with thinner for this reason) (for example, be used for fuel cell refill box (refill cartridge)) is described in the name of submitting on January 16th, 2004 that has and is called Refilling System for a Fuel Celland Method of Refilling a Fuel Cell (contriver: GennadiFinkelshtain, Mark Estrin, Moti Meron, Rami Hashimshoni and Erik Torgeman; Application number 10/758,080) (copending) of pending trial application the time.The open of this application introduced with for referencial use especially herein with its integral body.
Embodiment
Details shown here is as embodiment and only for the illustrative discussion of embodiment of the present invention, and it is for the description of thinking the most useful and easy to understand principle of the present invention and notion aspect is provided and represent.In this respect, do not attempt to show this description makes those skilled in the art how can in practice several forms of the present invention be specialized apparently than the more detailed structural details of the present invention of basic comprehension content essential to the invention.
Embodiment 1
Be dissolved in 22.4g KOH (Frutarom Ltd.) in the 80ml deionized water and be cooled to room temperature.Stirring under the 30min 15.12gNaBH 4Be dissolved in the gained solution.Then water is added to final volume 100ml.This solution contains 4M KOH and 4MNaBH 4This solution (100ml) placed flask and 70 ℃ of following balances 10 minutes to reach temperature constant state.After this, separating out by the amount of measuring replacing water of hydrogen measured.Hydrogen evolution rate is determined as 1.42ml/min.
Embodiment 2
Except using 44.8g KOH and 30.24g NaBH 4, cause containing 8M KOH and 8MNaBH 4Solution outside, repeat embodiment 1.Hydrogen evolution rate is determined as 0.053ml/min.
Abreast, with 50ml 8M KOH and 8M NaBH 4Solution mix with the 50ml deionized water.Hydrogen evolution rate measure with embodiment 1 in identical.Thereby KOH concentration increases twice and causes NaBH 4Stability increase about 25 times.
Embodiment 3
18g KOH (Frutarom Ltd.) is dissolved in the 65ml deionized water and is cooled to room temperature.Stirring under the 30min 19.5g KBH 4Be dissolved in the gained solution.Then water is added to final volume 100ml.This solution contains 3.2M KOH and 3.6M KBH 4This solution (100ml) placed flask and 70 ℃ of following balances 10 minutes to reach temperature constant state.After this, separating out by the amount of measuring replacing water of hydrogen measured.Hydrogen evolution rate is determined as 0.23ml/min.
Embodiment 4
36gKOH (Frutarom Ltd.) is dissolved in the 30ml deionized water and is cooled to room temperature.Stirring under the 30min 39gKBH 4Be dissolved in the gained solution.Then water is added to final volume 100ml.This solution contains 6.4M KOH and 7.2M KBH 4This solution (100ml) placed flask and 70 ℃ of following balances 10 minutes to reach temperature constant state.After this, separating out by the amount of measuring replacing water of hydrogen measured.Hydrogen evolution rate is determined as 0.01ml/min.
Abreast, 50ml 6.4M KOH and 7.2M KBH 4Solution mix with the 50ml deionized water.Hydrogen evolution rate measure with embodiment 3 in identical.Thereby KOH concentration increases twice and causes KBH 4Stability increase about 23 times.
Embodiment 5
14.11g KOH and 6.72g NaOH (Frutarom Ltd.) are dissolved in the 60ml deionization and are cooled to room temperature.Stirring under the 30min 12.7g NaBH 4Be dissolved in gained solution.Then water is added to final volume 100ml.This solution contains 2.5M KOH, 1.7M NaOH and 3.4M NaBH 4This solution (100ml) placed flask and 70 ℃ of following balances 10 minutes to reach temperature constant state.After this, separating out by the amount of measuring replacing water of hydrogen measured.Hydrogen evolution rate is determined as 0.45ml/min.
Embodiment 6
28.22g KOH and 13.44g NaOH (Frutarom Ltd.) are dissolved in the 30ml deionization and are cooled to room temperature.Stirring under the 30min 25.4g NaBH 4Be dissolved in gained solution.Then water is added to final volume 100ml.This solution contains 5M KOH, 3.4M NaOH and 6.8M NaBH 4This solution (100ml) placed flask and 70 ℃ of following balances 10 minutes to reach temperature constant state.After this, separating out by the amount of measuring replacing water of hydrogen measured.Hydrogen evolution rate is determined as 0.024ml/min.
Abreast, 50ml 5M KOH, 3.4M NaOH and 6.8M NaBH 4Solution mix with the 50ml deionized water.Hydrogen evolution rate measure with embodiment 5 in identical.Thereby KOH and NaOH concentration increase twice and cause NaBH 4Stability increase about 19 times.
Embodiment 7
18.5g KOH (Frutarom Ltd.) is dissolved in the 60ml deionization and is cooled to room temperature.Stirring under the 30min 15gNaBH 4Be dissolved in gained solution.Then water is added to final volume 100ml.This solution contains 3.3M KOH and 4M NaBH 4This solution (100ml) placed flask and 70 ℃ of following balances 10 minutes to reach temperature constant state.After this, separating out by the amount of measuring replacing water of hydrogen measured.Hydrogen evolution rate is determined as 1.07ml/min.
Embodiment 8
Be dissolved in 18.5g KOH (Frutarom Ltd.) in the 60ml deionized water and be cooled to room temperature.Stirring under the 30min 15g NaBH 4Be dissolved in gained solution.Then the 10ml G ﹠ W is added to final volume 100ml.This solution contains 3.3M KOH and 4M NaBH 4This solution (100ml) placed flask and 70 ℃ of following balances 10 minutes to reach temperature constant state.After this, separating out by the amount of measuring replacing water of hydrogen measured.Hydrogen evolution rate is determined as 3.2ml/min.
Thereby the adding of glycerine causes NaBH 4Thermostability reduced about 3 times.Yet glycerine reduces the zero pour of mixture, therefore it is desirable to use its act as a fuel additive and it is sneaked in the thinner.
Notice that previous embodiment only provides for illustrative purposes, never be construed as limiting the invention.Although the present invention's embodiment of reference example describes, should understand the vocabulary that has used herein is the vocabulary of describing and illustrating, is not the vocabulary of restriction.As record at present and the scope appended claims of revising in, can make and change and do not break away from the scope and spirit of the present invention in its each side.Although the present invention describes at this with reference to specific method, material and embodiment, the present invention also is not intended to be limited to details disclosed herein; On the contrary, the present invention extends to all functions equivalent configurations, method and purposes, as in the scope of appending claims.

Claims (69)

1. liquid concentrate that is used for the shelf-stable of fuel cell, wherein, solvent and at least a hydroxide ion that this enriched material comprises at least a metal hydride compound, contain one or more polar solvent components provide compound, and wherein this enriched material about 25 ℃ down stored for 4 weeks after, be not more than this at least a metal hydride compound of about 2% and decompose.
2. enriched material according to claim 1, wherein, this at least a metal hydride compound can carry out the anodic oxidation in the liquid fuel within battery and carry out promote to decompose under the condition of its hydrolysis produce hydrogen one of at least.
3. enriched material according to claim 1, wherein, this at least a metal hydride compound comprises at least a of basic metal and alkaline earth metal hydride, hydroborate and alanate.
4. enriched material according to claim 1, wherein, this at least a metal hydride compound comprises NaBH 4, KBH 4, LiBH 4, Be (BH 4) 2, Ca (BH 4) 2, Mg (BH 4) 2, (CH 3) 3NHBH 3, NaCNBH 3, LiH, NaH, KH, CaH 2, BeH 2, MgH 2, NaAlH 4, LiAlH 4And KAlH 4At least a.
5. enriched material according to claim 1, wherein, this at least a metal hydride compound comprises NaBH 4, KBH 4, LiBH 4, LiH, NaH and KH at least a.
6. enriched material according to claim 1, wherein, this at least a metal hydride compound comprises NaBH 4And KBH 4At least a.
7. enriched material according to claim 2, wherein, this enriched material has hydroxide ion concentration at least about 7.5mol/L.
8. enriched material according to claim 6, wherein, this enriched material has hydroxide ion concentration at least about 8mol/L.
9. enriched material according to claim 8, wherein, this enriched material contains this at least a metal hydride compound with the concentration at least about 3mol/L.
10. enriched material according to claim 4, wherein, this at least a hydroxide ion provides compound to comprise one or more basic metal and alkaline earth metal hydroxides and aluminium hydroxide.
11. enriched material according to claim 7, wherein, this at least a hydroxide ion provides compound to comprise LiOH, NaOH, KOH, RbOH, CsOH, Ca (OH) 2, Mg (OH) 2, Ba (OH) 2And NH 4OH's is at least a.
12. enriched material according to claim 1, wherein, this at least a hydroxide ion provides compound to comprise at least a of NaOH and KOH.
13. enriched material according to claim 11, wherein, this solvent comprises water, have up to about 6 carbon atoms with up to about fatty alcohol, the C of 4 hydroxyls 2-4Aklylene glycol, two (C 2-4Alkylidene group) glycol, C 2-4Aklylene glycol or two (C 2-4Alkylidene group) list-C of glycol 1-4-alkyl oxide, C 2-4Aklylene glycol or two (C 2-4Alkylidene group) two-C of glycol 1-4-alkyl oxide, have aliphatic ether, have aliphatic ketone and C up to about 6 carbon atoms up to about 6 carbon atoms 1-3The C of paraffinic acid 1-3Alkyl oxide at least a.
14. enriched material according to claim 5, wherein, this solvent comprises at least a of water, methyl alcohol, ethanol, ethylene glycol, glycol ether, glycerine, acetone, methylethylketone, diethyl ketone, methyl acetate, ethyl acetate, diox, tetrahydrofuran (THF), diglyme and triglyme.
15. enriched material according to claim 6, wherein, this solvent comprises water.
16. enriched material according to claim 1, wherein, this enriched material comprises the NaBH of total concn at least about 4mol/L 4And KBH 4At least a, water and NaOH and KOH at least a.
17. enriched material according to claim 16, wherein, this enriched material comprises the hydroxide ion of concentration at least about 8mol/L.
18. enriched material according to claim 1, wherein, this enriched material is mainly by being selected from NaBH 4, KBH 4, LiBH 4, (CH 3) 3NHBH 3And NaCNBH 3At least a composition of at least a metal hydride compound, aqueous solvent and NaOH and KOH, and have hydroxide ion concentration at least about 8mol/L.
19. enriched material according to claim 18, wherein, this enriched material is when being diluted to it hydroxide ion concentration and not being higher than about 6mol/L, and it contains this at least a at least a metal hydride compound that can be used as liquid fuel and be used for the hydrogen generator of fuel cell of capacity.
20. enriched material according to claim 13, wherein, this enriched material is when being diluted to the about 6mol/L of hydroxide ion concentration with it, and it contains concentration this at least a metal hydride compound at least about 2mol/L.
21. enriched material according to claim 6, wherein, this enriched material is when being diluted to the about 6mol/L of hydroxide ion concentration with it, and it contains concentration this at least a metal hydride compound at least about 3mol/L.
22. enriched material according to claim 20, wherein, this enriched material is substantially free of any fuel dope that influences this at least a metal hydride compound stability unfriendly.
23. enriched material according to claim 21, wherein, the essentially no softening agent of this enriched material, washing composition and frostproofer.
24. enriched material according to claim 1, wherein, the essentially no stablizer that is used for this at least a metal hydride compound of this enriched material.
25. enriched material according to claim 24, wherein, this enriched material is not more than this at least a metal hydride compound of about 5% and decomposes after about 25 ℃ are down stored 1 year.
26. enriched material according to claim 19, wherein, this enriched material is not more than this at least a metal hydride compound of about 3% and decomposes after about 25 ℃ are down stored 1 year.
27. enriched material according to claim 22, wherein, this enriched material is not more than this at least a metal hydride compound of about 2% and decomposes after about 25 ℃ are down stored 1 year.
28. method that is used for being used for the metal hydrogenation thing liquid of fuel cell by the enriched material preparation of shelf-stable, wherein, this method comprises (a) enriched material and (b) the solvent combination at least about the amount of 15 volume % of this enriched material, this enriched material comprises at least a metal hydride compound and polar solvent and has hydroxide ion concentration at least about 7mol/L, when this enriched material kept for 4 weeks under about 25 ℃, be not more than this at least a metal hydride compound decomposes of 2%.
29. method according to claim 28, wherein, combination (a) and (b) cause hydroxide ion concentration not to be higher than about 6mol/L.
30. method according to claim 29 wherein, when this enriched material stored for 4 weeks under about 25 ℃, is not more than this at least a metal hydride compound decomposes of 0.5%.
31. method according to claim 29, wherein, this enriched material comprises this at least a metal hydride compound with the concentration at least about 3mol/L.
32. method according to claim 30, wherein, this hydroxide ion concentration in this enriched material is at least about 8mol/L.
33. method according to claim 29, wherein, this at least a metal hydride compound comprises NaBH 4, KBH 4, LiBH 4, Be (BH 4) 2, Ca (BH 4) 2, Mg (BH 4) 2, (CH 3) 3NHBH 3, NaCNBH 3, LiH, NaH, KH, CaH 2, BeH 2, MgH 2, NaAlH 4, LiAlH 4And KAlH 4At least a.
34. method according to claim 28, wherein, this at least a metal hydride compound comprises NaBH 4And KBH 4At least a.
35. method according to claim 28, wherein, this enriched material further comprises LiOH, NaOH, KOH, RbOH, CsOH, Ca (OH) 2, Mg (OH) 2, Ba (OH) 2And NH 4OH's is at least a.
36. method according to claim 35, wherein, this solvent comprises at least a of water, methyl alcohol, ethanol, ethylene glycol, glycol ether, glycerine, acetone, methylethylketone, diethyl ketone, methyl acetate, ethyl acetate, diox, tetrahydrofuran (THF), diglyme and triglyme.
37. method according to claim 32, wherein, this enriched material comprises NaBH 4And KBH 4At least a, water and NaOH and KOH at least a.
38. method according to claim 36, wherein, this enriched material is when being diluted to the about 6mol/L of hydroxide ion concentration with it, and it contains this at least a metal hydride compound at least about 2mol/L.
39. the method for the metal hydrogenation thing liquid of the packing of a shelf-stable that is provided for fuel cell, wherein, this liquid comprises at least a metal hydride compound and comprises the polar solvent of first part and at least one second section, this liquid has hydroxide ion concentration and is not higher than about 7mol/L, and wherein this method comprises provides the container with first Room and at least one second Room, with this first Room of the part or all of filling of enriched material with this at least one second Room of the part or all of filling of at least one second section of this polar solvent, this enriched material is that it only comprises the first part of polar solvent and is that it has hydroxide ion concentration and is at least about 8mol/L with the different of liquid.
40., wherein, at least one second section of this polar solvent in the enriched material in first Room and this at least one second Room made up cause hydroxide ion concentration not to be higher than about 6mol/L according to the described method of claim 39.
41., wherein, when this enriched material stored for 4 weeks under about 25 ℃, be not more than this at least a metal hydride compound decomposes of about 1% according to the described method of claim 40.
42. according to the described method of claim 40, wherein, this enriched material contains this at least a metal hydride compound with the concentration at least about 3mol/L.
43. according to the described method of claim 41, wherein, this at least a metal hydride compound comprises NaBH 4, KBH 4, LiBH 4, Be (BH 4) 2, Ca (BH 4) 2, Mg (BH 4) 2, (CH 3) 3NHBH 3, NaCNBH 3, LiH, NaH, KH, CaH 2, BeH 2, MgH 2, NaAlH 4, LiAlH 4And KAlH 4At least a.
44. according to the described method of claim 42, wherein, this enriched material further comprises LiOH, NaOH, KOH, RbOH, CsOH, Ca (OH) 2, Mg (OH) 2, Ba (OH) 2And NH 4OH's is at least a.
45. according to the described method of claim 40, wherein, this enriched material comprises NaBH 4And KBH 4At least a, water and NaOH and KOH at least a.
46. according to the described method of claim 41, wherein, this enriched material contains this at least a metal hydride compound at least about 2mol/L when it is diluted to the about 6mol/L of hydroxide ion concentration.
47., wherein, design this container in this container so that at least one second component of this enriched material and this polar solvent is mixed according to the described method of claim 46.
48. the packing metal hydride that contains liquid of a shelf-stable, it can be obtained by the described method of claim 39.
49. container, it is filled with metal hydrogenation thing liquid, wherein, this container comprises first Room and at least one second Room, enriched material is contained in this first Room, this enriched material comprises at least a metal hydride compound and polar solvent and has hydroxide ion concentration at least about 8mol/L, and solvent is contained with the amount that is enough to cause hydroxide ion concentration not to be higher than about 7mol/L in this at least one second Room, with respect to the combination of solvent in this at least one second Room and the enriched material in this first Room.
50. according to the described container of claim 49, wherein, this container is sealed and at least one second component of this enriched material and this polar solvent is mixed, and then it is discharged from this container.
51. according to the described container of claim 50, wherein, this container, is discharged it so that at least one second component of this enriched material and this polar solvent is mixed then with explanation from this container.
52. according to the described container of claim 49, wherein, this container comprises internal partition, this internal partition limits this first Room and this at least one second Room.
53. according to the described container of claim 49, wherein, this first Room to small part by this at least one second Room around.
54. according to the described container of claim 49, wherein, this at least one second Room to small part by this first Room around.
55. according to the described container of claim 52, wherein, the quantity of solvent in this at least one second Room is enough to cause not being higher than the hydroxide ion concentration of about 6mol/L, with respect to the mixture of the enriched material in the solvent in this at least one second Room and this first Room.
56. according to the described container of claim 55, wherein, this enriched material contains this at least a metal hydride compound with the concentration at least about 3mol/L.
57. according to the described container of claim 49, wherein, this at least a metal hydride compound comprises NaBH 4, KBH 4, LiBH 4, Be (BH 4) 2, Ca (BH 4) 2, Mg (BH 4) 2, (CH 3) 3NHBH 3, NaCNBH 3, LiH, NaH, KH, CaH 2, BeH 2, MgH 2, NaAlH 4, LiAlH 4And KAlH 4At least a, and this enriched material can further comprise LiOH, NaOH, KOH, RbOH, CsOH, Ca (OH) 2, Mg (OH) 2, Ba (OH) 2And NH 4OH's is at least a.
58. according to the described container of claim 55, wherein, this enriched material comprises NaBH 4And KBH 4At least a, water and NaOH and KOH at least a.
59. according to the described container of claim 57, wherein, this enriched material when with its dilution so that the hydroxide ion concentration of about 6mol/L to be provided, it will contain concentration this at least a metal hydride compound at least about 2mol/L.
60. according to the described container of claim 58, wherein, this enriched material when with its dilution so that the hydroxide ion concentration of about 6mol/L to be provided, it will contain concentration this at least a metal hydride compound at least about 3mol/L.
61. the equipment that refills that is used for fuel liquid battery, wherein this equipment comprises the described container of claim 49.
62. according to the described equipment of claim 61, it designed to be able to the waste liquid that holds from fuel liquid battery.
63. packaged combination that is used to be provided for the metal hydrogenation thing liquid of fuel cell, wherein, this combination comprises first container and at least one second container, this first container contains enriched material, this enriched material comprises at least a metal hydride compound, polar solvent and at least a hydroxide ion provide compound and have hydroxide ion concentration at least about 8mol/L, this at least one second container contains solvent with the amount that is enough to cause hydroxide ion concentration not to be higher than about 7mol/L, with respect to the mixture of the enriched material in the solvent in this at least one second container and this first container.
64. according to the described packaged combination of claim 63, wherein, this combination with the explanation with this enriched material in this first container with make up from least a portion solvent in this second container.
65. according to the described packaged combination of claim 64, wherein, this enriched material comprises NaBH 4And KBH 4At least a, water and NaOH and KOH at least a.
66. according to the described packaged combination of claim 63, wherein, the solvent in this at least one second container comprises at least a additive that is used for fuel.
67. according to the described packaged combination of claim 66, wherein, this additive is selected from softening agent, washing composition, is used for the stablizer and the frostproofer of this at least a metal hydride compound.
68. according to the described packaged combination of claim 63, wherein, this solvent in this at least one second container comprises at least a of the aliphatic series that is used for this at least a metal hydride compound and aromatic amine stablizer.
69. the method that the fuel that a reduction is used for fuel liquid battery decomposes during this bunkering, wherein, this method comprises stores this fuel with the enriched material in the claim 1, and only dilutes this enriched material to prepare this fuel before this fuel is used for this fuel cell.
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