EP1395517A1 - Procede de stockage reversible d'hydrogene et reservoir d'hydrogene - Google Patents

Procede de stockage reversible d'hydrogene et reservoir d'hydrogene

Info

Publication number
EP1395517A1
EP1395517A1 EP02735315A EP02735315A EP1395517A1 EP 1395517 A1 EP1395517 A1 EP 1395517A1 EP 02735315 A EP02735315 A EP 02735315A EP 02735315 A EP02735315 A EP 02735315A EP 1395517 A1 EP1395517 A1 EP 1395517A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
storage
voltage
electrode
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02735315A
Other languages
German (de)
English (en)
Inventor
Dominik Kramer
Jörg WEISSMÜLLER
Herbert Gleiter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Karlsruher Institut fuer Technologie KIT
Original Assignee
Forschungszentrum Karlsruhe GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Forschungszentrum Karlsruhe GmbH filed Critical Forschungszentrum Karlsruhe GmbH
Publication of EP1395517A1 publication Critical patent/EP1395517A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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

Definitions

  • the invention relates to a method for the reversible storage of hydrogen and a hydrogen storage.
  • the technical problem of storing hydrogen arises especially in the context of the hydrogen economy, which provides for the use of hydrogen as an energy source, i. H. wants to use as an energy storage and transport medium.
  • Hydrogen can easily be produced from water by electrolysis, e.g. B. from solar power.
  • the stored energy can be easily recovered thermally by combustion, but it can also be converted directly into electrical energy in fuel cells.
  • the question of the storage of hydrogen, especially smaller quantities and especially for mobile applications (fuel cell cars) has not yet been satisfactorily solved technically.
  • the object of the invention is to provide a method and an apparatus of the e. G. Way to be designed so that the hydrogen release at low temperatures is possible.
  • Gaseous hydrogen is supplied to the storage device in order to load the storage device with hydrogen.
  • This is the What ⁇ serstoff arrivedelektrode placed in the device by an appropriate system of pipes, channels, pores or the like.
  • the gas space B. extends either up to the H-memory electrode (eg, by being executed even tube-shaped, or porous electric ⁇ LYTEN), or the hydrogen is brought very close to the electrode (eg. Up to a thin electrolyte layer on the Electrode).
  • the hydrogen is then taken up by the storage electrode, which is made of a hydrogen storage material such.
  • a hydrogen storage system should not only absorb the hydrogen, but should also be able to dispense it in doses if desired. In the fuel cell car, this happens when accelerating: When the accelerator pedal is pressed, the accumulator releases the necessary amount of hydrogen to the engine as soon as possible.
  • the hydrogen storage When refueling the hydrogen tank, the hydrogen storage should provide the H2 gas presented quickly and readily, i.e. e.g. without the need for high pressures to resume.
  • An electrically conductive hydrogen storage material is used for storage.
  • the usable hydrogen is mainly stored on the surface or below the surface of the material, which is why the material with a very large surface, e.g. sponge-like or as a thin film on a conductive carrier, is brought into the device.
  • the uptake and release is regulated via a charge layer on the surface of the hydrogen storage material. For this purpose, it is completely or largely covered with electrolyte. Using a counter electrode and a fine sett ⁇ bare voltage or current source, the charge can at the Oberflä ⁇ che and the hydrogen storage capacity can be changed.
  • the hydrogen storage device according to the invention can also absorb or release hydrogen at a constant temperature and pressure.
  • Devices in electrolysis e.g. B. for the electrolysis of water also for hydrogen production. This is broken down by the electric current.
  • the memory described here does not carry out electrolysis: a charge passage at the electrode / electrolyte interface is not desired. Only a surface charge is to be generated.
  • the pressure and temperature range in which the hydrogen is taken up or released is generally predetermined by the composition of the material. It is desirable to adapt the pressure and temperature to the technical requirements. So far, this has mostly required either the additional modules mentioned or a change in the composition of the material, but this also changes the storage properties. Modification of the storage properties without changing the composition of the storage material is therefore desirable.
  • Electrodes immersed in an electrolyte and a voltage source connected to them is reminiscent of a device for electrolysis. New, however, is that hydrogen is not produced electrolytically (there is no charge transfer takes), but that he is released because chermaterials be changed by the elekt ⁇ roche mix double layer the properties of Wasserstoffspei ⁇ .
  • a passage reaction at the counter electrode may be useful, but in principle the device can also be designed in such a way that only a double-layer charge is built up at the counter electrode. Then typical features such as diaphragms / separating membranes for the separation of cathode and anode space can also be omitted. The separate removal of oxygen required for water electrolysis is also not necessary.
  • a typical feature of our invention is also the dependence of the storage capacity on the electrolyte-wetted surface. Even with conventional adsorption storage, the capacity depends on the surface, but what is new is that the surface wetted by the electrolyte is decisive for our device.
  • the storage unit described here can also absorb hydrogen at a constant temperature and pressure or submit.
  • the regulation takes place via a fine setting ⁇ bare voltage or current source which produces a charge layer on the surface of the hydrogen storage material. Therefore, heating or cooling devices and pumps or compressors can at least be constructed more simply and therefore more cheaply, or may even be omitted entirely. Since there is no need to heat up or reform a chemical substance, there are no latencies.
  • the invention offers the possibility of improving the properties of already tried or future materials by making it possible to change their properties: since in our arrangement the charge on the surface of the materials can be varied, the electronic density of states and thus the hydrogen storage capacity can be changed , Given the urgent need for better storage, it offers a valuable option.
  • the invention is based on the effect that the hydrogen storage in adjacent material is influenced by the charge in an electrochemical double layer.
  • palladium foil 25 x 25 x 0.025 mm was used as the hydrogen storage material.
  • a solution of lithium perchlorate in methyl acetate served as the electrolyte.
  • the surfaces examined so far were relatively small, and therefore, with the previous test arrangements, only a very small adjustable storage capacity (especially in the Compared to the conventional storage capacity of the palladium). Therefore, gaseous hydrogen was not detected, but the change in the hydrogen storage capacity was detected indirectly via a current flow, in that the palladium foil was wetted on one side by phosphoric acid and glycerol in a double cell arrangement. The palladium foil could be loaded with hydrogen from this side.
  • FIGS. 4 to 6 show current-time diagrams of hydrogen loads.
  • Hydrogen uptake and release is regulated by a charge layer on the actual storage material set with the aid of an external voltage source
  • the new type of hydrogen storage device consists of the following essential parts:
  • the hydrogen storage electrode consists of an electron-conducting hydrogen storage material, e.g. As palladium, magnesium or magnesium alloys such as. B. Mg2Ni, Mg2Cu, Mg-Ln, or intermetallic compounds such as LaNi5, CaNi5 or LaNi4.7A10.3.
  • the hydrogen storage material is carried out with a very large surface, e.g. B. sponge-like or as a thin film on a support. New is that a particularly large surface is used for the device presented here, with the usable storage area of our device with increasing ⁇ top of the hydrogen reservoir increases (in previous storing: Capacity depends mostly on the amount of the storage material).
  • the storage material can also be applied to an electron-conducting carrier material.
  • Both solid-state electrolytes and electrolyte solutions are suitable as the electrolyte, ie ion-conducting material.
  • the electrolyte completely or largely covers the storage electrode, since the covered surface is important for usable capacity. Incomplete coverage may be necessary for technical reasons, e.g. B. to keep clear paths for gas transportation.
  • the electrolyte must not be decomposed by the applied voltages, as no electrolysis should take place (work in the double layer area, capacitive charging instead of the Faraday process). Therefore, aprotic electrolytes such as salt solutions in methyl acetate or dimethylformamide may be more suitable than water, for example.
  • the counter electrode consists of a material that conducts electrons well, eg metals such as gold or platinum. Base metals or conductive polymers that do not corrode in the electrolyte can also be used.
  • the counterelectrode has a large area (to avoid high current or charge densities), which is why porous or rough material is
  • the voltage and current source must be finely adjustable.
  • the gas supply or discharge is, for example, a linear, branched or network-like system of fine capillaries, pores or tubes, which enable rapid gas transport.
  • the hydrogen storage material 1 is applied as a thin layer on a conductive carrier material 2.
  • the counter electrode 4 consists of tubes with pores for the hydrogen passage. The tubes are not wetting on the inside and conductive on the outside.
  • the two electrodes are in contact with one another via the electrolyte.
  • the hydrogen storage material 1 consists of branched nanotubes on a conductive carrier material 2.
  • the hydrogen is fed in and out via the porous electrolyte 3.
  • Fig. 3 shows an embodiment with a bipolar Elect ⁇ clearing arrangement.
  • the conductive carrier material 5 serves as a counter electrode. The individual electrodes are separated from one another by insulators.
  • Gaseous hydrogen is supplied to the storage device in order to load the storage device with hydrogen. This is achieved in the device using a suitable system of pipes, channels, pores or the like. brought to the hydrogen storage electrode.
  • the gas space either extends to the H-storage electrode (e.g. by making it itself tubular or with porous electrolytes), or the hydrogen is brought very close to the electrode (e.g. up to a thin electrolyte layer on the electrode) ,
  • the hydrogen is then taken up by the storage electrode, which is made of a hydrogen storage material such.
  • the voltage source must be able to supply a constant current (galvanostatic operation) in order to enable an even release of hydrogen.
  • the voltage used must not exceed the decomposition voltage of the respective electrolyte.
  • the device presented here does not perform electrolysis: a charge passage at the electrode / electrolyte interface is not desired. Only a surface charge is to be generated. If the maximum voltage of the voltage source used exceeds the decomposition voltage, a voltage limit must be used.
  • FIG. 5 shows a diagram in which the voltage was reversed every hour on the charge side (lithium perchlorate in methyl acetate).
  • the curves contain a large proportion of electricity, which corresponds to the loading of the entire film with hydrogen.
  • FIG. 6 the curves from FIG. 5 were adapted to a double exponential curve and this was subtracted.
  • a current signal can now be clearly recognized due to the polarity reversal.
  • the function of the potential on the loading corresponds to the expectation that the hydrogen charging of the palladium be ⁇ Sonders sensitive to a change in the electronic density of states in Pd, when the hydrogen loading is close to the phase transition ⁇ - ⁇ '.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention se rapporte à un procédé de stockage réversible d'hydrogène ainsi qu'à un réservoir d'hydrogène. L'objectif de l'invention est de concevoir un procédé et un dispositif permettant une distribution d'hydrogène à des températures basses. A cet effet, une tension est appliquée à une contre-électrode et à la matière stockée afin de récupérer l'hydrogène, la vitesse de distribution de l'hydrogène étant régulée par l'amplitude de la tension ou l'intensité du courant.
EP02735315A 2001-05-23 2002-04-27 Procede de stockage reversible d'hydrogene et reservoir d'hydrogene Withdrawn EP1395517A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10125546A DE10125546B4 (de) 2001-05-23 2001-05-23 Verfahren zum reversiblen Speichern von gasförmigem Wasserstoff und Vorrichtung zur Durchführung des Verfahrens
DE10125546 2001-05-23
PCT/EP2002/004690 WO2002094711A1 (fr) 2001-05-23 2002-04-27 Procede de stockage reversible d'hydrogene et reservoir d'hydrogene

Publications (1)

Publication Number Publication Date
EP1395517A1 true EP1395517A1 (fr) 2004-03-10

Family

ID=7686133

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02735315A Withdrawn EP1395517A1 (fr) 2001-05-23 2002-04-27 Procede de stockage reversible d'hydrogene et reservoir d'hydrogene

Country Status (5)

Country Link
US (1) US7306862B2 (fr)
EP (1) EP1395517A1 (fr)
JP (1) JP4005511B2 (fr)
DE (1) DE10125546B4 (fr)
WO (1) WO2002094711A1 (fr)

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CA2529427C (fr) * 2004-12-17 2011-03-15 University Of New Brunswick Synthese, recharge et traitement de materiaux pour le stockage de l'hydrogene au moyen de fluides supercritiques
JP4061556B2 (ja) * 2005-08-12 2008-03-19 株式会社新潟Ｔｌｏ 水素量センサーおよび水素貯蔵装置
FR2913417B1 (fr) * 2007-03-06 2009-11-20 Ceram Hyd Procede et unite de stockage d'hydrogene
FR2916906B1 (fr) * 2007-05-28 2009-10-02 Ceram Hyd Soc Par Actions Simp Membrane echangeuse protonique et cellule comportant une telle membrane
FR2928492B1 (fr) 2008-03-06 2011-10-21 Ceram Hyd Materiau pour un dispositif electrochimique.
FR2931142B1 (fr) 2008-05-15 2010-08-20 Commissariat Energie Atomique Procede de fabrication d'un reservoir d'hydrogene a hydrures metalliques
US8177941B1 (en) * 2009-02-04 2012-05-15 United States of America as represented by the Sectretary of the Navy Hydrogen fuel storage and recovery system
US8117824B1 (en) * 2009-02-04 2012-02-21 The United States of America as represented by the Secterary of the Navy Pollution free engine using hydrogen as a fuel
US8980416B2 (en) * 2009-02-17 2015-03-17 Mcalister Technologies, Llc Architectural construct having for example a plurality of architectural crystals
US8147599B2 (en) 2009-02-17 2012-04-03 Mcalister Technologies, Llc Apparatuses and methods for storing and/or filtering a substance
US20100284903A1 (en) * 2009-05-11 2010-11-11 Honda Patents & Technologies North America, Llc New Class of Tunable Gas Storage and Sensor Materials
US8257295B2 (en) 2009-09-21 2012-09-04 Alcon Research, Ltd. Intraocular pressure sensor with external pressure compensation
DE102011012734B4 (de) * 2011-02-24 2013-11-21 Mainrad Martus Verfahren zur reversiblen Speicherung von Wasserstoff und anderer Gase sowie elektrischer Energie in Kohlenstoff-, Hetero- oder Metallatom-basierten Kondensatoren und Doppelschichtkondensatoren unter Standardbedingungen (300 K, 1atm)
CA2845078A1 (fr) 2011-08-12 2013-02-21 Mcalister Technologies, Llc Construction architecturale ayant une pluralite de mises en oeuvre
US8617399B2 (en) 2011-08-12 2013-12-31 Mcalister Technologies, Llc Dynamic filtration system and associated methods
WO2013025654A2 (fr) 2011-08-12 2013-02-21 Mcalister Technologies, Llc Filtre de distribution de fluide présentant des milieux filtrants en spirale et systèmes et procédés associés
US8764966B2 (en) 2011-11-10 2014-07-01 GM Global Technology Operations LLC Electrochemical process and device for hydrogen generation and storage
US8840578B2 (en) * 2011-12-09 2014-09-23 Alcon Research, Ltd. Multilayer membrane actuators
US9339187B2 (en) 2011-12-15 2016-05-17 Alcon Research, Ltd. External pressure measurement system and method for an intraocular implant
US9295389B2 (en) 2012-12-17 2016-03-29 Novartis Ag Systems and methods for priming an intraocular pressure sensor in an intraocular implant
US9528633B2 (en) 2012-12-17 2016-12-27 Novartis Ag MEMS check valve
US9572712B2 (en) 2012-12-17 2017-02-21 Novartis Ag Osmotically actuated fluidic valve
US9534296B2 (en) 2013-03-15 2017-01-03 Mcalister Technologies, Llc Methods of manufacture of engineered materials and devices
JP6024588B2 (ja) * 2013-05-13 2016-11-16 トヨタ自動車株式会社 水素吸蔵装置
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AT513486B1 (de) * 2013-07-04 2014-05-15 Universität Linz Verfahren zum Laden und Entladen eines Wasserstoffspeichers
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Also Published As

Publication number Publication date
DE10125546B4 (de) 2005-12-29
US7306862B2 (en) 2007-12-11
JP2004526659A (ja) 2004-09-02
US20050016866A1 (en) 2005-01-27
DE10125546A1 (de) 2002-12-05
WO2002094711A1 (fr) 2002-11-28
JP4005511B2 (ja) 2007-11-07

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