US20040011444A1 - Method of absorption-desorption of hydrogen storage alloy and hydrogen storage alloy and fuel cell using said method - Google Patents

Method of absorption-desorption of hydrogen storage alloy and hydrogen storage alloy and fuel cell using said method Download PDF

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US20040011444A1
US20040011444A1 US10/381,647 US38164703A US2004011444A1 US 20040011444 A1 US20040011444 A1 US 20040011444A1 US 38164703 A US38164703 A US 38164703A US 2004011444 A1 US2004011444 A1 US 2004011444A1
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hydrogen
storage alloy
hydrogen storage
temperature
desorption
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Masuo Okada
Takahiro Kuriiwa
Shinichi Yamashita
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Tohoku Techno Arch Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C13/00—Details of vessels or of the filling or discharging of vessels
    • F17C13/02—Special adaptations of indicating, measuring, or monitoring equipment
    • F17C13/026—Special adaptations of indicating, measuring, or monitoring equipment having the temperature as the parameter
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • 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
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/1642—Controlling the product
    • C01B2203/1671—Controlling the composition of the product
    • C01B2203/1676—Measuring the composition of the product
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • 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

Definitions

  • the present invention concerns a hydrogen absorption and desorption method of repeating pressurization and depressurization of hydrogen to a hydrogen storage alloy. More specifically, the present invention relates to a body-centered cubic hydrogen storage alloy having two-stage plateau characteristics or inclined plateau characteristics. Particularly, the present invention relates to a hydrogen absorption and desorption method of increasing the amount of desorbed hydrogen within a practical pressure range and temperature range, a hydrogen storage alloy suitable to the absorption and desorption method, as well as a fuel cell using the hydrogen absorption and desorption method described above.
  • the hydrogen storage alloys are metals and alloys capable of absorbing and desorbing hydrogen under appropriate conditions.
  • hydrogen can be stored at a lower pressure and at a higher density compared with existent hydrogen reservoirs and the volumic density thereof is substantially equal with or higher than liquid hydrogen or solid hydrogen.
  • V reacts with hydrogen at an ambient temperature and forms two kinds of hydrides depending on the pressure of hydrogen.
  • an extremely stable hydride is formed as V ⁇ VH 0.8 ( ⁇ phase ⁇ phase) (hereinafter referred to as “low pressure plateau area”), and the reverse reaction is scarcely taken plate near the room temperature.
  • VH 0.8 ⁇ VH 2.01 ( ⁇ phase ⁇ phase: referred to as high pressure plateau area). Since the equilibrium pressure of hydrogen in this reaction is at an appropriate pressure of about several atm near the room temperature, the V-containing BCC alloys have been studied vigorously as hydrogen storage alloys of high capacity.
  • the low pressure plateau observed at a hydrogen pressure of 0.1 Pa to 10 Pa in FIG. 1 tends to appear on the side of higher pressure as the addition amount of V is smaller.
  • FIG. 2 shows high pressure PCT curves for the same specimen. A flat area near 10 6 Pa in FIG. 2 is a high pressure plateau area and the high pressure plateau area shifts to lower pressure side as the addition amount of V is smaller. Further, from FIG. 1 and FIG. 2, it is also confirmed that Ti—Cr—V system alloys show two-stage plateaus.
  • FIG. 1 and FIG. 2 it is also confirmed that Ti—Cr—V system alloys show two-stage plateaus.
  • FIG. 3 is a PCT curve for a Ti 40 Cr 58 Mo 2 alloy which is plotted for the pressure range from 1 Pa to 10 MPa, and an inclined plateau is observed in a low pressure region.
  • FIG. 4 is an XRD chart for the alloy and it has been confirmed that a BCC mono-phase is formed by quenching from 1420° C. in iced water.
  • the inclined area between the inclined plateau area of the low pressure region and the high pressure plateau areas is a region in accordance with the Sievert's law.
  • Nb is also a metal having two-stage plateaus (low pressure phase NbH and high pressure phase NbH2). Further, Ti shows two-stage plateaus transforming as ⁇ , this being a high temperature operation.
  • FeTi is an intermetallic compound having two-stage plateaus that operates near 40° C.
  • alloys such as (Zr, Ti)V2 alloys show inclined plateaus and such alloys are also used as hydrogen storage alloys.
  • the hydrogen storage alloys showing the two-stage plateau or the inclined plateau have a feature that the PCT characteristic curve is in contact with three or more parallel lines, or a feature of having three or more knick points in the PCT curve within the pressure range from a low pressure of 1 Pa or less to 10 MPa.
  • the PCT characteristic curves of existent AB5 type alloys such as an LaNi 5 alloy are in contact with two parallel lines and have two knick points.
  • the prior art which is considered to be based on the idea for attaining a hydrogen storage alloy of high capacity by the two-stage plateau and inclined plateau characteristics described above includes the followings; (a) a spinodal curve decomposition structure is developed in a Ti alloy of a body-centered cubic structure (JP-A No. 10-110225), (b) Cu and/or rare earth element is added to Ti—Cr—V system alloys (JP-B No. 4-77061), (c) a molten Ti alloy is quenched to form a BCC mono-phase at a room temperature (JP-A No. 10-158755), and (d) a lattice constant of a BCC alloy comprising Ti—Cr as a main element is controlled (JP-A No. 7-252560).
  • JP-A No. 10-110225 and JP-A No. 7-252560 include descriptions regarding hydrogen absorbing and desorbing temperature. Each of the methods conducts hydrogen absorption and desorption at a constant temperature. In the latter JP-A No. 7-252560, the activating pre-treatment is conducted in two steps, that is, a pre-stage at low temperature and post stage but the absorbing and desorbing temperature is constant (20° C.).
  • a method of absorbing hydrogen to a hexagonal system Ti—Cr—V system alloy which is not a BCC alloy and heating at 100° C. (column 4, lines 32-39) in JP-B No. 59-38293 is also an absorption and desorption method at a constant temperature.
  • the equilibrium pressure with hydrogen can be controlled by controlling the alloy ingredients. Further, while the equilibrium pressure of hydrogen storage alloy with hydrogen can be controlled by the operation temperature, the existent development for alloys lacks in the technical idea of effectively utilizing the hydrogen absorbing characteristics in the low pressure area of the PCT characteristic curve.
  • the present invention intends to provide a hydrogen absorption and desorption method capable of absorbing and desorbing more hydrogen by effectively utilizing not only the reaction between ⁇ phase ⁇ phase but also hydrogen therebetween, that is, in the low pressure region of the PCT curve, for pure V and pure Nb or solid solubilized materials shown hydrogen absorbing/desorbing reactivities similar to those of the pure V and Nb materials, as well as solid solubilized BCC alloys such as Ti—Cr based alloys exhibiting the two-stage plateau characteristics or inclined plateau characteristics, alloys suitable to the method described above, as well as a fuel cell using the method and the method of using the same.
  • the hydrogen absorption and desorption method according to the present invention for solving the subject described above is a method of absorbing and desorbing hydrogen by repeating pressurization and depressurization of hydrogen properly for a body-centered cubic hydrogen storage alloy exhibiting two-stage plateau characteristics or inclined plateau characteristics in which a hydrogen storage alloy temperature in the final stage of a hydrogen desorption process (T2) is controlled to a temperature higher than a hydrogen storage alloy temperature in the hydrogen absorption process (T0) and a hydrogen storage alloy temperature in the initial stage of the hydrogen desorption process (T1) (T2>T1 ⁇ T0).
  • the two-stage plateau characteristic or the inclined plateau characteristics specifically mean that a PCT curve showing equilibrium characteristics of reaction between the hydrogen storage alloy and hydrogen is in contact with three or more parallel lines, or the PCT curve has three or more knick points.
  • the measuring range for the PCT curve referred to herein is a range from a low pressure of 0.1 Pa or less to a high pressure of about 10 MPa.
  • the hydrogen storage alloy of the invention has two-stage plateau characteristics or inclined plateau characteristics in the PCT curve wherein hydrogen utilizable effectively can be increased by making the low pressure region of the PCT curve instable.
  • the plateau stability in the low pressure region varies depending on the addition amount of V. That is, in an alloy having a low pressure plateau or an inclined plateau in a low pressure region of a PCT curve, hydrogen present in the low pressure region of the PCT curve can be made into an effectively utilizable form by changing the composition. A portion of hydrogen in the low pressure region of the PCT curve which is rendered instable can be utilized effectively by making the temperature in the desorption process (T2) higher than the temperature in the hydrogen absorption process (T0) in this state.
  • FIG. 5 shows vacuum PCT curves of specimens obtained by keeping a Ti 24 Cr 36 V 40 alloy at 1673K for one hour and then rapidly quenching the same in iced water.
  • increment of hydrogen by temperature elevation is at most about 0.05 wt % at 0.01 MPa and, at a further lower hydrogen pressure, the amount of effectively utilizable hydrogen is decreased further (FIG. 6).
  • the hydrogen storage alloy temperature in the initial stage of the desorption process (T1) is made lower than the hydrogen storage alloy temperature in the final stage of the desorption process (T2) (T2>T1), in order to suppress the cycle deterioration on the effective hydrogen absorbing capacity of the alloy.
  • T1 is sometimes controlled to higher than the hydrogen storage alloy temperature in the absorption process (T0) in order to control the hydrogen desorption rate of the alloy, and the amount of utilizable hydrogen can also be increased in this case by setting as: T2>T1 in the final desorption process.
  • Temperature elevation conducted only in the initial stage of hydrogen desorption or only temporarily has an effect of increasing the hydrogen desorbing rate but the amount of effectively utilizable hydrogen is not increased.
  • the final stage of the hydrogen desorption process is at or after any instance where the residual amount of hydrogen in the hydrogen storage alloy is reduced to 50% or less, more preferably, 25% or less, and temperature elevation in the final stage of the process is effective for the suppression of the cycle deterioration.
  • the hydrogen storage alloys suitable to applications of the hydrogen absorption and desorption method of the invention and capable of obtaining a large amount of effective hydrogen absorption capacity are body-centered cubic alloys represented by the general formula: Ti X Cr Y M Z in which M is one or more members selected from elements belonging to the groups IIa, IIIa, IVa, Va, VIa, VIIa, VIII, IIIb, IVb of the periodical table, in 20 ⁇ X+Y ⁇ 100 atomic %, 0.5 ⁇ Y/X ⁇ 2 and 0 ⁇ 80 atomic %, and including inevitably intruded oxygen or nitrogen and inevitably forming minimum spinodal decomposition phase.
  • Ti—Cr binary alloy Addition of one or more members selected from the elements belonging to the groups IIa, IIIa, IVa, Va, VIa, VIIa, VIII, IIIb, IVb of the periodical table to a Ti—Cr binary alloy gives an effect of not only stabilizing the body-centered cubic structure but also of instabilizing the PCT curve low pressure area.
  • the Cr/Ti ratio is defined as 0.5 ⁇ Y/X ⁇ 2, because the plateau pressure is greatly deviated from a normal pressure if the rate is out of the range described above, which is not practical.
  • oxygen deteriorates the effective absorption amount of hydrogen, it is preferably as less as possible.
  • the effective absorption amount of hydrogen is decreased when the spinodal decomposition phase is formed, lowering of the absorption amount can be suppressed by not applying a heat treatment that tends to cause spinodal decomposition or shortening the treating time.
  • the alloy is set as a body-centered cubic hydrogen storage alloy comprising V at 60 atomic % or less, and/or Mo, Al, Mn and/or rare earth elements at 10 atomic % or less for the constituent M, 2.5% by weight or more effective absorption amounts of hydrogen can be obtained in method determined original point on evaccuation, and the hydrogen absorption and desorption method of the invention can be utilized more efficiently.
  • the effective absorption amount of hydrogen in the prior art alloys remains at about 2% by weight. While BCC mono-phase can be formed within a compositional V range from 5 to 100 atomic %, since the stability of VH 0.8 formed as a hydride product of pure V is remarkably lowered by lowering the amount of admixed V to 60% or less, effective utilization of hydrogen in the PCT curve low pressure region is facilitated. Further, since V is an expensive element as well, an excess amount of admixed V over 60 atomic % will lead to difficulty in practical use.
  • the effective hydrogen absorption amount shows a satisfactory value as 2.6% by weight but as the Mn addition amount is increased to 15% and 20%, the effective absorption amount of hydrogen lowers remarkably to a value less than 2% by weight.
  • the effective absorption amount of hydrogen of the alloy in which the addition amount of V is changed to 20 atomic % and controlled to show a plateau near the normal pressure is substantially equal with a case where the addition amount of V is 30 atomic % and it is considered that the effective absorption amount of hydrogen depends on the addition amount of Mn.
  • the trend is identical also for Mo, Al and rare earth elements.
  • the rare earth elements act as a getter for oxygen or the like intruded as impurities, addition of the rare earth elements by a small amount is also effective for suppressing deterioration by oxygen and maintaining high characteristics.
  • the fuel cell according to the present invention has a feature comprising a hydrogen storage tank incorporating a hydrogen storage alloy having two-stage plateau characteristics or inclined plateau characteristics, a temperature control device for elevating or cooling the temperature of the hydrogen storage alloy directly or the atmospheric temperature of the absorption alloy, a fuel cell capable of outputting electric power via chemical change of hydrogen supplied from the hydrogen storage tank and a control section for controlling such that a hydrogen absorption alloy temperature in the final stage of hydrogen desorption process (T2) is made to a temperature higher than a hydrogen storage alloy temperature in a hydrogen absorption process (T0) and a hydrogen storage alloy temperature in the initial stage of the hydrogen desorption process (T1) (T2>T1 ⁇ T0).
  • the temperature of the hydrogen storage alloy in the final stage of the hydrogen desorption process (T2) is made higher than the temperature in the hydrogen absorption process (T0), hydrogen absorbed in the PCT curve low pressure region which was neither desorbed from the hydrogen storage alloy nor utilized in the prior art can be taken out as a utilizable hydrogen and the electric power obtained from the fuel cell can be increased. Further, since the temperature T2 is made higher than the hydrogen storage alloy temperature in the initial stage of the hydrogen desorption process (T1) the life of the fuel cell can be increased.
  • control section can properly control the pressure, temperature and flow rate of the hydrogen gas supplied to the hydrogen storage tank and the fuel cell.
  • the control section can properly control the pressure, temperature and flow rate of the hydrogen gas supplied to the hydrogen storage tank and the fuel cell.
  • the temperature control device described above can utilize the heat dissipated from the fuel cell or the heat of exhaust gases exhausted from the fuel cell for the temperature elevation.
  • the dissipated heat or discharged heat from the fuel cell can be utilized for the temperature elevation of the hydrogen storage alloy, electric power, etc. are no more required for the temperature elevation of the hydrogen storage alloy, which can improve the efficiency in the overall hydrogen fuel cell.
  • FIG. 3 is a PCT curve of a Ti 40 Cr 58 Mo 2 alloy and four parallel lines and knick points.
  • FIG. 4 is an XRD chart for a Ti 40 Cr 58 Mo 2 alloy.
  • FIG. 5 is vacuum PCT curves for a specimen of a Ti 24 Cr 36 V 40 alloy after keeping at 1673K for 1 hour and quenching in iced water.
  • FIG. 6 is PCT curves for an LaNi 5 alloy.
  • FIG. 8 is an XRD charts for a Ti 39 Cr 57.5 Mo 2.5 La 1 alloy, a Ti 39.5 Cr 56 Mo 2.5 Al 1 La 1 alloy and a Ti 35.5 Cr 50.5 Mo 2 Mn 5 V 7 alloy.
  • FIG. 9 is vacuum PCT graphs for a Ti 39 Cr 57.5 Mo 2.5 La 1 alloy.
  • FIG. 10 is high pressure PCT graphs for a Ti 39.5 Cr 57.5 Mo 2.5 La 1 alloy, a Ti 39.5 Cr 56 Mo 2.5 Al 1 La 1 alloy and a Ti 35.5 Cr 50.5 Mo 2 Mn 5 V 7 alloy.
  • FIG. 11 shows dependence of the hydrogen absorption amount of a Ti 39 Cr 57.5 Mo 2.5 La 1 alloy, a Ti 39.5 Cr 56 Mo 2.5 Al 1 La 1 alloy and a Ti 35.5 Cr 50.5 Mo 2 Mn 5 V 7 alloy on the number of cycle tests.
  • FIG. 12 is a system flow chart showing an embodiment of a fuel cell according to the invention.
  • FIG. 13 is a model view showing a mechanism of forming electric power in a fuel cell used for the fuel cell according to the invention.
  • This example shows possibility for excellent absorption amount and effective suppression of cycle deterioration, by using a body-centered cubic hydrogen storage alloy having an inclined plateau in a PCT curve low pressure region and controlling a hydrogen storage alloy temperature in the final stage of a hydrogen desorption process (T2) to a temperature higher than a hydrogen storage alloy temperature in the hydrogen absorption process (T0) and a hydrogen storage alloy temperature in the initial stage of the hydrogen desorption process (T1) (T2>T1 ⁇ T0).
  • FIG. 8 shows XRD charts for specimens after quenched in iced water. All the prepared specimens had BCC mono-phase.
  • FIG. 9 shows vacuum PCT characteristics of a Ti 39 Cr 57.5 Mo 2.5 La 1 alloy. When the temperature was elevated from 40° C. to 100° C., instabilization of the inclined plateau in the low pressure region was confirmed.
  • FIG. 10 shows high pressure PCT characteristics before the cycle test of the Ti 39.5 Cr 57.5 Mo 2.5 La 1 alloy, a Ti 39.5 Cr 56 Mo 2.5 Al 1 La 1 alloy and a Ti 35.5 Cr 50.5 Mo 2 Mn 5 V 7 alloy. Presence of the phase stabilized at low pressure is confirmed by FIG. 9.
  • BCC type hydrogen storage alloys show large effective absorption amount of hydrogen and the absorption amount can be increased further by desorption at higher temperature.
  • comparative example LaNi 5 it can be seen that the effect of utilizing the temperature difference of the alloy according to the invention is remarkably large.
  • FIG. 11 is a graph showing relation between the number of the cycle test and the absorption amount of hydrogen for a Ti 39 Cr 57.5 Mo 2.5 La 1 alloy, a Ti 39.5 Cr 56 Mo 2.5 Al 1 La 1 alloy and a Ti 35.5 Cr 50.5 Mo 2 Mn 5 V 7 alloy. It can be seen that the result shown by solid lines in which the temperature was elevated to 100° C.
  • cycle deterioration can be suppressed by controlling the temperature in the final stage of the desorption process is higher than that in the initial stage of the desorption process. Accordingly, it can be seen that large effective absorption amount of hydrogen can be attained and cycle deterioration can be suppressed by effectively utilizing hydrogen in the PCT curve low pressure region using the invention.
  • This example shows a constitutional view of a fuel cell having a feature comprising hydrogen storage tank incorporating a hydrogen storage alloy, a temperature control device for elevating or cooling the temperature of the hydrogen storage alloy directly or the atmospheric temperature of the absorption alloy, a fuel cell capable of outputting electric power by chemical change of hydrogen supplied from the hydrogen storage tank and a control section for controlling such that a hydrogen absorption alloy temperature in the final stage of hydrogen desorption process (T2) is made to a temperature higher than a hydrogen storage alloy temperature in a hydrogen absorption process (T0) and a hydrogen storage alloy temperature in the initial stage of the hydrogen desorption process (T1) (T2>T1 ⁇ T0), and a method of increasing the amount of electric power obtained by the fuel cell and suppressing cycle deterioration.
  • a hydrogen absorption alloy temperature in the final stage of hydrogen desorption process T2 is made to a temperature higher than a hydrogen storage alloy temperature in a hydrogen absorption process (T0) and a hydrogen storage alloy temperature in the initial stage of the hydrogen desorption process (T1) (T2
  • FIG. 12 shows a system flow chart showing an embodiment of a fuel cell according to the present invention.
  • a hydrogen fuel tank 4 is a tank for supplying hydrogen to a fuel cell to be described later and the tank is incorporated with a body-centered cubic hydrogen storage alloy having two-stage plateau characteristics or inclined plateau characteristics.
  • the tank is provided with a solenoid valve V 11 for introducing starting hydrogen, as well as a solenoid valve V 1 for supplying hydrogen to the fuel cell and a solenoid valve V 2 for recovering the hydrogen returned from the fuel cell to the tank disposed between the tank and the fuel cell 1, and they are adapted to supply hydrogen by a pump P 2 .
  • pressure valves B 1 and B 2 and flow meters FM are provided in the course of the pipeline for controlling the pressure and the flow rate of hydrogen, and the entire system is controlled, including temperature by the control device 3 .
  • a heat exchanger 5 controlled by the control device is utilized for temperature elevation and temperature lowering of a hydrogen storage alloy. In the heat exchanger 5 , heat exchange is conducted between exhausted heat possessed in steams at a relatively high temperature exhausted from the fuel cell 1 and cold water as a cold temperature medium and temperature sensors TS 1 -TS 3 or the flow meters FM and the pumps are controlled to control the temperature to an aimed level. From the fuel cell 1 , a DC power can be obtained by reaction between oxygen and hydrogen and an inverter 2 for converting the DC power into a predetermined AC power is connected with the fuel cell.
  • a DC/DC converter may be connected instead of the inverter 2 .
  • LS in the drawing is a water level sensor in an accumulation tank for accumulating water formed when steams exhausted from the fuel cell are cooled by the heat exchanger 5 .
  • control device 3 When the fuel cell is operated, signals from various kinds of sensors are received by the control device 3 , opening/closure of the solenoid valves V 1 and V 2 and the pressure valves B 1 and B 2 are controlled to supply hydrogen to the fuel cell 1 . In this step, control for supplying heat from the heat exchanger 5 is also conducted for controlling the rate of supplying hydrogen.
  • the alloy temperature in the final stage of hydrogen desorption process (T2) is controlled to higher than the alloy temperature in the initial stage of the hydrogen desorption process (T1), to effectively utilize hydrogen absorbed in the hydrogen storage alloy, particularly, hydrogen in the PCT curve low pressure region.
  • Hydrogen is thus supplied to the fuel cell 1 and, at the same time, oxygen is supplied from the oxygen electrode in which oxygen and hydrogen are reacted to obtain electric power in the fuel cell.
  • the reaction provide electric power by using a reaction opposite to that formed by hydrogen and oxygen through electrolysis of water when a DC current is applied to a water incorporated with an electrolyte.
  • Hydrogen molecules supplied from the hydrogen fuel tank 4 release electrons at the hydrogen electrode to form hydrogen ions and the electrons are transferred toward the anode to obtain electric power.
  • the hydrogen ions transfer through the electrolyte toward the anode, accept electrons at the anode and return to hydrogen atoms, which react with oxygen to form water (steams), and exhaust gases containing steams at a relatively high temperature (about 70 to 90° C.) are formed by the heat of reaction.
  • exhaust gases By controlling the exhaust gases to flow into the heat exchange by way of the valve, they can utilized as a heat source for heating.
  • Electric power obtained could be increased by about 14% compared with the case of desorption at a temperature constant at 20° C. by using the Ti 39 Cr 57 Mo 3 La 1 alloy for the hydrogen absorption tank, absorbing hydrogen at 20° C. and desorbing the same at 85° C. in the final stage of desorption process. Further, the life of the tank at which the absorption amount of hydrogen was reduced to 90% of the initial value was extended by about 30% compared with a case of keeping the hydrogen storage alloy temperature in the desorption process (T2) constant at 85° C. from the initial stage.
  • the upper limit for T2 was defined at 90° C. since water was used as cold temperature medium but the invention is not limited only thereto and heating by a heater can also be utilized.
  • a coolant other than water for cooling or utilize the method of enabling both cooling and heating, for example, by a Peltier device.

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WO2005017218A2 (en) * 2003-08-08 2005-02-24 Texaco Ovonic Hydrogen Systems Llc Hydrogen storage alloys providing for the reversible storage of hydrogen at low temperatures
US20050135961A1 (en) * 2003-12-19 2005-06-23 Kwo Young Hydrogen storage materials having excellent kinetics, capacity, and cycle stability
KR100731146B1 (ko) * 2005-12-21 2007-06-22 주식회사 하이젠 수소 저장체의 수소 저장 성능 평가 장치
US20070261552A1 (en) * 2006-05-15 2007-11-15 Gerd Arnold Direct gas recirculation heater for optimal desorption of gases in cryogenic gas storage containers
US20100089070A1 (en) * 2006-11-06 2010-04-15 Thorsten Allgeier Fluid Reservoir with Thermal Management
US20190051907A1 (en) * 2017-08-11 2019-02-14 The Board Of Trustees Of The Leland Stanford Junior University Metal-hydrogen batteries for large-scale energy storage

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ATE413694T1 (de) 2005-03-07 2008-11-15 Fiat Ricerche Wasserstoffversorgungsystem für brennstoffzelle
CN105911244B (zh) * 2016-06-22 2018-11-13 珠海格力节能环保制冷技术研究中心有限公司 一种储氢合金的性能曲线的测试方法、装置及系统
KR20220041202A (ko) * 2019-08-05 2022-03-31 뉴사우스 이노베이션스 피티와이 리미티드 수소 저장 합금의 제조 방법

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US20050067060A1 (en) * 2003-08-08 2005-03-31 Baoquan Huang Hydrogen storage alloys providing for the reversible storage of hydrogen at low temperatures
WO2005017218A3 (en) * 2003-08-08 2006-02-16 Texaco Ovonic Hydrogen Systems Hydrogen storage alloys providing for the reversible storage of hydrogen at low temperatures
US7108757B2 (en) * 2003-08-08 2006-09-19 Ovonic Hydrogen Systems Llc Hydrogen storage alloys providing for the reversible storage of hydrogen at low temperatures
WO2005017218A2 (en) * 2003-08-08 2005-02-24 Texaco Ovonic Hydrogen Systems Llc Hydrogen storage alloys providing for the reversible storage of hydrogen at low temperatures
US7344676B2 (en) * 2003-12-19 2008-03-18 Ovonic Hydrogen Systems Llc Hydrogen storage materials having excellent kinetics, capacity, and cycle stability
US20050135961A1 (en) * 2003-12-19 2005-06-23 Kwo Young Hydrogen storage materials having excellent kinetics, capacity, and cycle stability
KR100731146B1 (ko) * 2005-12-21 2007-06-22 주식회사 하이젠 수소 저장체의 수소 저장 성능 평가 장치
US20070261552A1 (en) * 2006-05-15 2007-11-15 Gerd Arnold Direct gas recirculation heater for optimal desorption of gases in cryogenic gas storage containers
US7611566B2 (en) * 2006-05-15 2009-11-03 Gm Global Technology Operations, Inc. Direct gas recirculation heater for optimal desorption of gases in cryogenic gas storage containers
US20100089070A1 (en) * 2006-11-06 2010-04-15 Thorsten Allgeier Fluid Reservoir with Thermal Management
US20190051907A1 (en) * 2017-08-11 2019-02-14 The Board Of Trustees Of The Leland Stanford Junior University Metal-hydrogen batteries for large-scale energy storage
CN111033883A (zh) * 2017-08-11 2020-04-17 里兰斯坦福初级大学理事会 大规模储能的金属氢电池
US11855294B2 (en) * 2017-08-11 2023-12-26 The Board Of Trustees Of The Leland Stanford Junior University Metal-hydrogen batteries for large-scale energy storage

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