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WO2015010823A1 - Structure d'accumulateur et procédé de fabrication - Google Patents

Structure d'accumulateur et procédé de fabrication Download PDF

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Publication number
WO2015010823A1
WO2015010823A1 PCT/EP2014/062083 EP2014062083W WO2015010823A1 WO 2015010823 A1 WO2015010823 A1 WO 2015010823A1 EP 2014062083 W EP2014062083 W EP 2014062083W WO 2015010823 A1 WO2015010823 A1 WO 2015010823A1
Authority
WO
WIPO (PCT)
Prior art keywords
particles
storage medium
storage
solid electrolyte
functionalizing
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.)
Ceased
Application number
PCT/EP2014/062083
Other languages
German (de)
English (en)
Inventor
Marco Cologna
Carsten Schuh
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.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of WO2015010823A1 publication Critical patent/WO2015010823A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
    • Y02E60/36—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

Definitions

  • the invention relates to a storage structure for a solid electrolyte battery and to a method for the production thereof.
  • Solid electrolyte batteries are based on the principle of action of solid electrolyte fuel cells, which by an additional Buffalo of at least one memory element to a
  • Solid electrolyte battery can be extended.
  • Generically known solid electrolyte fuel cells for example, oxide ceramic fuel cells, also referred to in the art as SOFC (Solid Oxide Fuel Cell), are known from the international publication WO 2011/019455 AI, in which the concept of SOFC-derived solid electrolyte - Batteries is discussed in more detail.
  • SOFC Solid Oxide Fuel Cell
  • Such solid electrolyte batteries operate at an operating temperature above 500 ° C, at which the solid electrolyte has a sufficient ion conductivity for oxygen ions.
  • a valve provided for operating a solid electrolyte rechargeable battery storage medium as a component of at least ⁇ a memory element of the solid electrolyte battery environmentally usually summarizes particles comprising one to form
  • the memory structure typically comprises a gas-permeable porous microstructure, that is a skelettarti ⁇ gene structure of the storage medium with a high open porosity.
  • the object of the invention is to specify a storage structure by which an agglomeration of the memory material particles is further reduced compared to known memory structures.
  • a memory structure for a Festelekt ⁇ rolyt battery in which a functionalized metallic phase is stored.
  • a total proportion of the functional tional initiateden metallic phase in the memory structure lies in a range of about 0.5 to 3monyspro ⁇ center.
  • the functionalizing metallic phase is preferably incorporated in the surface area of the storage structure, but may also extend into deeper areas of the storage structure, which is also referred to in the art as a bulk.
  • Functionalization in the general sense is understood as meaning an improvement in the reaction kinetics of reaction processes by introducing functionalizing material that is not primarily involved in an ongoing reaction. Depending on the type of functionalizing material, this functionalization also acts catalytically on the reaction kinetics.
  • a functionalizing metallic phase causes an increase in the reaction rate of the redox reactions occurring during operation of the solid electrolyte battery.
  • This increase in the reaction rate in a memory structure which has been functionalized according to the invention is manifested by an increased current density, given a constant proportion by weight of the storage medium in comparison to a conventional, non-functionalized storage structure.
  • a solid electrolyte battery provided with the means according to the invention provides a short-term higher electrical power than solid electrolyte batteries with memory structures known in the prior art.
  • the memory structure functionalized with the agents according to the invention can advantageously be produced with a reduced weight proportion of the storage medium with a constant charge capacity.
  • the invention is further achieved by two adjacent methods for producing a storage structure for a solid electrolyte battery.
  • a main body of the memory structure is infiltrated with a chemical precursor of a functionalizing metallic compound. Subsequently, a Temperaturbe ⁇ treatment of the body by means of an adjustable Tempe ⁇ temperature and an adjustable period of time is provided.
  • the base body is produced, for example, in a customary sintering method and preferably consists of oxide dispersion-strengthened particles of the storage medium, which are embedded in a coarse-grained ceramic matrix.
  • the Par Tikel of the storage medium are functionalized before the base ⁇ body of the memory structure is produced.
  • particles of the storage medium are infiltrated with the chemical precursor of the functionalizing metallic compound, followed by temperature treatment of the infiltrated particles by means of an adjustable temperature and an adjustable period of time.
  • the main body of the storage structure is made of the functionalized particles as described above.
  • Further advantageous embodiments of the invention are Ge ⁇ subject of the dependent claims.
  • Particularly suitable functionalizing substances are metals or metal compounds have been found which contain an element from a group of transition metals, alkaline earth metals, lanthanides and / or the boron group, in particular cerium, aluminum, barium, nickel, copper, magnesium and / or molybdenum or a connection of said elements.
  • the functionalizing metalli ⁇ cal phase is a separate phase, before so for example next to a storage medium and an inert material in the storage structure.
  • Fig. 1 is a schematic representation of an exemplary
  • Fig. 2 is a schematic representation of a microstructure ei ⁇ ner memory structure according to a first embodiment; a schematic representation of a microstructure ei ⁇ ner memory structure according to a second embodiment and FIG. 3.
  • FIG. 1 shows an exemplary structure diagram for illustrating an operation of a solid electrolyte battery, as far as it is relevant to the description of the present invention. Due to the schematic representation will be Therefore, not all components of such a solid electrolyte battery considered.
  • a solid electrolyte battery consists DA rin that at one - arranged in the drawing below and symbolized with a circled plus sign - positive electrode, also referred to as the air electrode 16, a process gas, in particular air, via a gas supply 14 to ⁇ is guided during discharge - according to a circuit shown in the right-hand side of the air - oxygen is extracted from the air.
  • the oxygen used in the form of oxygen ⁇ ion 0 2 ⁇ by a voltage applied to the positive electrode of the solid electrolyte 18, to a - in the drawing, arranged above and with a circled minus sign symbolic ized - negative electrode 20, which is also referred to as a storage electrode.
  • a gaseous redox pair for example a hydrogen-steam mixture with a porous storage structure 2 in combination.
  • a dense layer of the active storage medium were present at the negative electrode 20, the charge capacity of the solid electrolyte battery would be quickly exhausted.
  • a storage structure 2 made of porous material containing an oxidizable material as a storage ⁇ medium, preferably in the form of metal or metal oxide, at ⁇ game as iron and iron oxide and / or nickel and nickel oxide contains ⁇ .
  • Redox pair for example, a mixture of H 2 / H 2 0, the transported through the solid electrolyte 18 oxygen ⁇ ions are transported after their discharge at the negative electrode in the form of water vapor through pore channels of the porous storage structure 2, which includes the active storage medium , Depending on whether a discharge or charge is present, the metal or the metal oxide is oxidized or reduced and the oxygen required for this purpose by the gaseous Redox couple H 2 / H 2 0 delivered or transported to the solid electrolyte 18 and the negative electrode 20 back.
  • the ⁇ ser mechanism of oxygen transport through a gasförmi ⁇ ges redox couple is therefore called a shuttle mechanism, the gaseous redox couple as shuttle gas.
  • the diffusion of the oxygen ions through the solid electrolyte 18 requires a high operating temperature of 600 to 900 ° C of the described solid electrolyte battery. Said operating temperature range is also responsible for an optimal composition of the gaseous redox couple H 2 / H 2 0 advantageous in equilibrium with the storage medium. At such an operating temperature, not only the electrodes 16 and 20 and the electrolyte 18 are exposed to a high thermal load, but also the memory structure 2, which is the
  • Storage medium includes. With the steady cycles of oxidation and reduction, the active storage medium tends to become too internal and / or coarsened. Sintering means that individual particles fuse progressively by diffusion processes with each other, remove both the reactive surface as well as the time required for the gas trans port ⁇ continuous open pore structure in more advantageous to ⁇ manner.
  • Roughening means that individual grains grow at the expense of other grains, with the number density and reactive surfaces of the grains detrimentally decreasing.
  • the redox couple H 2 / H 2 0 can no longer reach the active surface of the active storage medium, so that even after Sectionentla ⁇ tion of the memory, the internal resistance of the solid electrolyte battery is very high, which prevents further technically meaningful discharge ,
  • FIG. 2 shows a greatly enlarged representation of a microstructure of a memory structure according to the invention according to FIG first embodiment of the invention.
  • the introduction according to the invention of a functionalizing metallic phase into the storage structure takes place in this first exemplary embodiment after the manufacture of a main body of the storage structure.
  • the base body is first manufactured, processed in the participating components in ⁇ example in the form of powder mixtures to slip processed and formed into corresponding ceramics.
  • redox-active storage medium SM is stored, for example in the form of particles in a ceramic matrix of a body.
  • the memory structure then includes
  • Inert material particles IN and storage medium particles SM are Inert material particles IN and storage medium particles SM.
  • the storage structure comprises a storage medium SM which consists of particles of any particle size and which is represented by hatched circular grain cross sections in the drawing. In the drawing, the grain cross sections are shown in the same size for simplicity.
  • the storage structure further comprises particles
  • Inertmaterial IN which are arranged with respect to the particles of Spei ⁇ chermediums SM both intragranular and intergranular in the structure, are thus arranged within and / or between the particles of the storage medium SM.
  • Inertmaterial IN serves to prevent mutual sintering and / or coarsening of the particles of the active storage medium SM.
  • the particles of the inert material IN are inert to the running redo reactions and
  • the inert material IN is present in belie ⁇ biger form, for example in the form of particles of any size or in the form of - whiskerförmigen particles - not shown.
  • Inertmaterials IN are pores. Through the formed offe ⁇ ne porosity shuttle gas, in particular H 2 / H 2 0, to flow in the desired manner by the memory structure.
  • a charging or discharging process causes a reduction or oxidation of the particles of the active storage medium SM, which increases its oxidation state during the oxidation and in the course of Reduk ⁇ tion its oxidation state again lowered. Oxidation and reduction processes are associated with a continuous volume change of the particles of the active storage medium SM.
  • ODS particles oxides dispersion-strengthened
  • storage material SM intragranularly arranged inert material IN
  • iron or iron oxide particles are used, which are fine-grained
  • Yttrium-stabilized zirconia also called YSZ
  • YSZ is currently used as the intergranular inert material IN for forming the ceramic matrix, preferably in a composition also designated 8YSZ with a concentration of 8 mol% Y 2 O 3 in ZrO 2 .
  • a support structure (not shown) can also counteract coarsening of the storage medium SM.
  • the support structure has a skeletal morphology, in particular in the form ei ⁇ nes fürdringungsgePolges in order to ensure a high degree con ⁇ tact area for interaction with the storage medium.
  • Morphologies such as rod arrays or derglei ⁇ chen possible.
  • the memory structure is functionalized with a metallic connection, as described below.
  • a chemical precursor of the functionalizing material which is typically present as an organometallic salt, is first dissolved in a suitable solvent.
  • suitable organo-metallic salts are nickel (11) nitrate as hexahydrate, cerium (III) nitrate as
  • a suitable polar solvent for example, what ⁇ ser, or dissolved in a nonpolar solvent, for example ethanol.
  • the porous storage structure is then infiltrated with the dissolved chemical precursor and dried. Subsequently, the storage structure is temperature-treated to cause a thermal decomposition of the above-mentioned organo-metallic salt.
  • the functionalized metallic phase FP formed by the infiltration and decomposition of the organometallic salt remains close to the surface of the storage structure or, alternatively or additionally, deeply penetrates or diffuses into the storage structure.
  • the storage structure shown in Fig. 2 is characterized by a substantially uniform distribution of the particles of the metallic phase FP both between the particles of the inert material IN as well as between particles of the storage material.
  • the uniform distribution of the particles of the metallic phase FP can be formed either in a near-surface layer of the memory structure or extend into the depth of the memory structure.
  • a thin, porous layer of the functionalizing metallic phase FP is formed on the surface of the memory structure.
  • inhomogeneously distributed islands of the functionalizing metallic phase are formed in a near-surface region of the memory structure.
  • metallic phase FP is by a set process control of infiltration or the selected temperature and increased duration of the temperature treatment, a deeper infiltration and / or diffusion of the functionalized metallic phase FP in the memory structure causes.
  • the steps of the infiltration and heat treatment ⁇ above are repeated until a desired proportion by weight of the functionalizing phase, typically between 0.5 and 3 percent by weight is reached in the storage structure.
  • Fig. 3 is a greatly enlarged illustration of a micro structure of an inventive storage structure according to a second embodiment of the invention in which the particles of the functionalizing metallic phase FP in contrast with the aforementioned first embodiment is substantially exclusively on the surface of particles of the storage medium ⁇ around SM are formed.
  • the functionalization is already applied during the production of the particles of the storage medium SM, ie before the production of the basic body.
  • the particles of the storage medium are functionalized in a manner analogous to the previously described method.
  • the particles of the storage medium SM are infiltrated with a dissolved chemical precursor and dried.
  • An ⁇ closing the particles of the storage medium SM are tempe ⁇ raturbehandelt to cause thermal decomposition of the organo-metallic salt.
  • the functionalized particles of the storage medium SM are then stored in the ceramic matrix of the base ⁇ in order to obtain the finished memory structure.
  • FIG. 3 shows the functionalized particles of the storage medium SM in the finished storage structure, wherein the particles of the metallic phase FP are stored in the surface region of the particles of the storage medium SM, whereas between the inert particles IN, in contrast to FIG. 2, no particles of the metallic phase FP are stored.
  • An introduction of the functionalizing metallic phase FP in the finished base body of the memory structure according to the first embodiment shown in Fig. 2 has advantages for the cases in which the functionalization is to act at least partially on the reaction kinetics with the shuttle gas.
  • a directed near-surface functionalization can be achieved.
  • the functionalizing metalli ⁇ specific phase FP acts in this first embodiments of a coarsening and / or sintering of the particles of the Inertmaterials IN, wherein a disadvantageous change in the porosity of the inert material IN is counteracted.
  • a disadvantage of the first embodiment compared with the second embodiment may be that the metallic phase FP in the first embodiment is not completely in contact with the particles of the memory material SM and thus a comparatively higher proportion of functionalizing metallic phase FP is required to increase the reaction kinetics of the storage material SM.
  • An introduction of the functionalizing metallic phase into the particles of the storage medium prior to the fabrication of the storage structure according to the second embodiments shown in FIG. 3 has advantages for the cases in which the functionalization is to act mainly on the reaction kinetics of the redox reaction taking place with the participation of the storage medium , With the second embodiment, a preference of the functionalization on the particles of the storage medium can be achieved.
  • the functionalizing metalli ⁇ specific phase FP is according to this second embodiments, in direct contact with the particles of the storage material SM.
  • This direct contact increases the reaction kinetics of the Spei ⁇ chermaterials SM and also counteracts a coarsening and / or sintering of the particles of the storage material SM.
  • this second embodiment requires a lower proportion of material of functionalizing metallic phase FP in comparison with the first embodiment.
  • a disadvantage of the second embodiment over the first embodiment may be that the functionalizing metallic phase FP in the second embodiment does not contribute to the counteracting of coarsening
  • a functionalizing phase FP increases the rate of reaction taking place in the loading ⁇ operating the solid electrolyte battery redox reactions.
  • This increase in the reaction rate in accordance with the invention a functionalized memory structure makes compared to a conventional, non-functionalized storage structure at a constant proportion by weight of the storage medium SM in particular by an increased current density ⁇ noticeable.
  • a solid electrolyte battery provided with the agents according to the invention provides a short-term higher electrical output than conventional solid electrolyte batteries having memory structures known in the prior art.
  • the functionalized with the invention with ⁇ stuffs memory structure can be manufactured advantageously with a reduced weight percentage of the storage medium at constant charge capacity.
  • the active principle of the functionalizing materials varies with the material used. Some of the materials used increase the rate of redox reactions by catalytic action on the oxidation or reduction of water or iron.
  • nickel is known as a catalyst for many processes involving a reduction of water. Other materials in turn reduce the coarsening by a sintering inhibiting or de-wetting effect (Dewetting Agents).
  • Dewetting Agents dewetting Agents
  • ⁇ influences advantageously film formation, migration of the oxygen ions, diffusion mechanisms, ENTRANCE friendliness making and decomposition mechanisms of the shuttle gas in the depth of the storage structure and / or education.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une structure d'accumulateur pour une batterie à électrolyte solide, structure dans laquelle est insérée une phase métallique de fonctionnalisation présentant une teneur totale dans la structure d'accumulateur allant de 0,5 à 3 % en poids. L'insertion, selon l'invention, d'une phase métallique de fonctionnalisation provoque une augmentation de la vitesse des réactions redox occurrentes lors du fonctionnement de la batterie à électrolyte solide.
PCT/EP2014/062083 2013-07-22 2014-06-11 Structure d'accumulateur et procédé de fabrication Ceased WO2015010823A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013214284.6 2013-07-22
DE102013214284.6A DE102013214284A1 (de) 2013-07-22 2013-07-22 Speicherstruktur und Verfahren zur Herstellung

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WO2015010823A1 true WO2015010823A1 (fr) 2015-01-29

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PCT/EP2014/062083 Ceased WO2015010823A1 (fr) 2013-07-22 2014-06-11 Structure d'accumulateur et procédé de fabrication

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WO (1) WO2015010823A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2119276A (en) * 1982-04-26 1983-11-16 United Technologies Corp Steam reforming utilizing iron oxide catalyst

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2403655C9 (ru) * 2005-04-21 2011-04-20 Члены Правления Университета Калифорнии Инфильтрация исходного материала и способ покрытия
US20110033769A1 (en) 2009-08-10 2011-02-10 Kevin Huang Electrical Storage Device Including Oxide-ion Battery Cell Bank and Module Configurations
KR101849976B1 (ko) * 2011-04-08 2018-05-31 삼성전자주식회사 전극 활물질, 그 제조방법, 이를 포함한 전극 및 이를 채용한 리튬 이차 전지
DE102011084181A1 (de) * 2011-09-27 2013-03-28 Siemens Aktiengesellschaft Speicherelement für eine Festelektrolytbatterie

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
GB2119276A (en) * 1982-04-26 1983-11-16 United Technologies Corp Steam reforming utilizing iron oxide catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
C. D. BOHN ET AL: "Stabilizing Iron Oxide Used in Cycles of Reduction and Oxidation for Hydrogen Production", ENERGY & FUELS, vol. 24, no. 7, 15 July 2010 (2010-07-15), pages 4025 - 4033, XP055142587, ISSN: 0887-0624, DOI: 10.1021/ef100199f *
ROMERO E ET AL: "Molybdenum addition to modified iron oxides for improving hydrogen separation in fixed bed by redox processes", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 37, no. 8, 20 December 2011 (2011-12-20), pages 6978 - 6984, XP028910750, ISSN: 0360-3199, DOI: 10.1016/J.IJHYDENE.2011.11.066 *

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