US20040089540A1 - Mixed oxide material, electrode and method of manufacturing the electrode and electrochemical cell comprising it - Google Patents

Mixed oxide material, electrode and method of manufacturing the electrode and electrochemical cell comprising it Download PDF

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US20040089540A1
US20040089540A1 US10/344,083 US34408303A US2004089540A1 US 20040089540 A1 US20040089540 A1 US 20040089540A1 US 34408303 A US34408303 A US 34408303A US 2004089540 A1 US2004089540 A1 US 2004089540A1
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electrode
mixed oxide
approximately
oxide material
range
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Frederik Van Heuveln
Lambertus Plomp
Gerard Elzinga
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Energieonderzoek Centrum Nederland ECN
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Priority claimed from NL1015886A external-priority patent/NL1015886C2/nl
Priority claimed from NL1017632A external-priority patent/NL1017632C1/nl
Priority claimed from NL1018266A external-priority patent/NL1018266C1/nl
Application filed by Energieonderzoek Centrum Nederland ECN filed Critical Energieonderzoek Centrum Nederland ECN
Assigned to ENERGIEONDERZOEK CENTRUM NEDERLAND (ECN) reassignment ENERGIEONDERZOEK CENTRUM NEDERLAND (ECN) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ELZINGA, GERARD DOUWE, HEUVELN, FREDERIK HENDRIK VAN, PLOMP, LANBERTUS
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    • 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
    • Y02E60/13—Energy storage using capacitors
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    • Y10T29/00—Metal working
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    • Y10T29/49002—Electrical device making

Definitions

  • the invention relates firstly to a mixed oxide material with a high electron conductivity.
  • a material of this type is known from DE-C-196 40 926.
  • A denotes a metal cation selected from group IIa (alkaline-earth metals) or from the lanthanides from the Periodic System, or a mixture thereof; B represents a platinum metal cation, while C represents a metal cation selected from groups IVb, Vb, VIb, VIIb, VIIIb and IIb of the Periodic System of the Elements, or a mixture thereof.
  • ABO y an empirical formula ABO y , where y ⁇ 3 and where A comprises at least one metal selected from Na, K, Rb, Ca, Ba, La, Pr, Sr, Ce, Nb, Pb, Nd, Sm and Gd, and B comprises at least one metal selected from the group consisting of Cu, Mg, Ti, V, Cr, Mn, Fe, Co, Nb, Mo, W and Zr, where A and B cannot both be Nb and where the compound SrVO 2.5 is excluded.
  • the mixed oxide material according to the invention as described above may be such that both A and B are a single material; expediently, A and/or B comprise(s) a metal which is doped with another metal, the doping metals for A and B being selected from the options given above for A and B.
  • A is Sm x Sr (1-x) , with x lying in the range from approximately 0.4 to approximately 0.6.
  • A is Nd x Sr (1-x) , with x lying in the range from approximately 0.4 to approximately 0.6.
  • composition of B is composed of a plurality of metals, such as, in an advantageous embodiment, Co and/or Fe.
  • B comprises Co (1-x) Fe x , with x lying in the range from approximately 0.2 to approximately 0.6.
  • the invention also relates to an electrode for an electrochemical cell which can be produced from a material with a high electron conductivity which is characterized in that the electrode comprises a mixed oxide material according to the invention as defined above.
  • the invention also relates to a method for producing an electrode for an electrochemical cell, comprising the steps of providing a suitable substrate, and forming a cohesive layer of a mixed oxide thereon by applying a mixture of a mixed oxide, one or more binders and at least one solvent, followed by removal of the solvent and, if appropriate, followed by a heat treatment, which is characterized in that a cohesive layer which includes a mixed oxide material as defined above in accordance with the invention is formed on the substrate.
  • the substrate may be a strip of thin metal or an (optionally conductive) plastic.
  • the mixed oxide material according to the invention using a suitable binder and a solvent, will be brought into the form of a suspension or paste, after which a layer of the suspension or paste can be applied to the substrate by spreading, dipping, brushing or screen printing.
  • the method can also be carried out by the substrate being a matrix and by the mixed oxide being accommodated in the matrix and forming a cohesive unit therewith.
  • the paste or suspension described above can also be used to fill the matrix.
  • the substrate may also have a release property, so that the layer which comprises the mixed oxide material, after application on the substrate, is removed and is subjected to a heat treatment if appropriate.
  • a layer of mixed oxide material, optionally on a substrate, is obtained, the mixed oxide material being a material according to the invention with a high electron conductivity.
  • the invention also relates to an electrochemical cell which comprises at least two electrodes and an electrolyte and which is characterized in that at least one electrode is an electrode as defined above in accordance with the invention.
  • Both electrodes may be an electrode according to the invention; it is also possible for one of the electrodes to be selected from a carbon electrode, an RuO 2 electrode and an RuO 2 .xH 2 O electrode.
  • the mixed oxide material according to the invention can be used for numerous purposes, such as electrodes in electrochemical cells, heating elements and the like.
  • electrodes in electrochemical cells When used as an electrode in an electrochemical cell, this is understood, in its broadest sense, as meaning use of an electrode in combination with an electrolyte and other electrodes.
  • Electrodes of this type are used in processes for the electrochemical conversion and storage of electricity, as are found in electrochemical capacitors, also known as supercapacitors or ultracapacitors, batteries, in particular including rechargeable batteries of the alkaline type or the metal/air type, fuel cells, such as the polymer electrolyte fuel cell, electrolysis equipment and sensors.
  • An electrochemical capacitor (or supercapacitor or ultra-capacitor) is a device in which electricity can be stored and then removed again, in particular with a high power density (in W/kg and W/l), by using electrical double-layer capacitance or what is known as pseudo-capacitance which is linked to Faraday processes, such as redox reactions or intercalation processes.
  • Applications include, inter alia, the (short-term) storage and/or emission of peak power levels and the reduction of duty cycles of batteries, as arises, inter alia, in battery or hybrid or fuel-cell vehicles, in installations or equipment which ensure the quality of central or local power networks or supplies, and in optionally portable electronic equipment, such as laptops and mobile telephones.
  • An electrochemical capacitor of this type has two electrodes, an anode and a cathode, at which electrons are respectively released and collected. Furthermore, the capacitor includes an electrolyte, for example an aqueous or organic solution, and a separator, and the entire assembly can be fitted in a metal or plastic housing. At least one of the two electrodes may be an electrode according to the invention.
  • the charge which is positive at one electrode and negative at the other, is stored in the electrical double-layer capacitance at the interface of electrode and electrolyte, in the pseudo-capacitance resulting from highly reversible redox reactions or intercalation processes at this interface or in the bulk of the electrode material, or in a combination of double-layer capacitance and pseudo-capacitance.
  • the composition and microstructure of the electrode materials, the microstructure of the separator and the composition of the electrolyte partly, but not completely, determine the internal resistance R i (in ⁇ ) of the capacitor, which should preferably be as low as possible.
  • the quantities described partly, but not completely, determine the energy density of the capacitor (in Wh/kg and Wh/l) and the power density (in W/kg and W/l). For known technologies these are typically, respectively, a few Wh/kg and a few thousand W/kg.
  • E E (in J) and the power P (in W) of the capacitor with capacitance C (in F) and charged to voltage V (in V)
  • electrochemical capacitors with electrodes which have activated carbon as the most important constituent and which predominantly use electrical double-layer capacitance are known. It is important that the activated carbon forms a porous structure with a high specific surface area which is accessible to the electrolyte, in order to form a capacitance which is as high as possible, and with an electron conductivity which is as high as possible, in order to produce a resistance which is as low as possible and to utilize as much electrode material as possible. The highest energy and power densities are obtained in this way, which is a requirement for most applications.
  • Carbon electrodes which predominantly use double-layer capacitance can be used as anodes and as cathodes; in this way, it is possible to make symmetrical capacitors.
  • Carbon electrodes can be used in combination with an aqueous electrolyte, the permissible capacitor voltage being at most approx. 1.2 V and a low internal resistance being obtained, or in combination with an organic electrolyte, in which case the maximum voltage is approx. 2.4 V, but the internal resistance which can be obtained is generally less low.
  • these compounds In combination with aqueous electrolytes, such as for example KOH solutions, these compounds have a high effective capacitance in F/g based on redox reactions and can be used as anodes and as cathodes. They also have a good electrical conductivity.
  • Drawbacks of these compounds when used in (symmetrical) electrochemical capacitors are the limited operational voltage range and the very high costs of material of the desired purity. Considerable research is being undertaken into alternative pseudo-capacitance materials which are able to counteract- these drawbacks while still allowing the desired higher capacitance and energy density to be achieved.
  • metal hydroxides which may change into metal oxyhydroxides, such as in particular Ni(OH) 2 .
  • Ni(OH) 2 metal hydroxides
  • This compound is attractive in view of its low cost, its high specific capacitance and its favourable potential range, its conductivity is low and is dependent on the charge state.
  • the reversible charge/discharge reaction at an electrode of this material in an alkaline electrolyte can be represented by Ni(OH) 2 +OH ⁇ NiOOH+H 2 O+e, in which Ni(OH) 2 has a poor conductivity and NiOOH has a significant electrical conductivity, provided it is in the correct phase (the P phase).
  • Ni(OH) 2 and in particular the nickel constituent and, if appropriate, the nickel required for the preparation, are also believed to have disadvantageous properties for the environment and health. Consequently, requirements and regulations apply with regard to its treatment and processing, which entail additional costs. These also impose limitations on its application areas, for example to the applications and markets for which collection and/or reuse are regulated.
  • a (rechargeable) battery is a known item of equipment. It can be used to store electricity and then to release it again, in particular with a high energy density (in Wh/kg and Wh/l), by using electrochemical conversion of electrical energy into chemical energy and vice versa.
  • the structure of batteries of this type corresponds to the structure of electrochemical capacitors described above, although their design and operation may differ.
  • (rechargeable) batteries of the nickel-cadmium, nickel-zinc and nickel-iron type, of the nickel-hydrogen type, of the nickel-metal hydride type, and of the metal/air type, such as iron/air, zinc/air, aluminium/air and lithium/air are known. At least one of the two electrodes of batteries of this type can now profitably be replaced by an electrode according to the invention.
  • the nickel electrodes, the cadmium electrode and the air electrodes are suitable for this purpose.
  • (rechargeable) batteries of the NiCd, NiZn, NiFe, NiH 2 and NiMH type are known, in which the “nickel electrode” consists of the same Ni(OH) 2 compound and has the same action as that described above for electrochemical capacitors.
  • the same drawbacks in terms of the restrictions in electrical conductivity and the same problems with regard to the environment and health apply.
  • Batteries of the Fe/air, Zn/air, Al/air and Li/air types are also known, in which during the discharge oxygen is consumed at the air electrode by electrochemical reduction; batteries of this type are “mechanically recharged” by renewal of the anode.
  • Bidirectional air electrodes which, as well as reducing oxygen, are also able to evolve oxygen in the reverse process and therefore allow electrically rechargeable metal/air batteries, are also known.
  • the compounds which have been described above only enable moderate performance to be achieved, on account of limited conductivity and catalytic activity, and are often expensive.
  • the materials according to the invention make it possible to produce high-performance electrodes which do not have the above drawbacks, i.e. which are inexpensive to produce, do not have any restrictions in terms of the thickness which can be beneficially utilized, and do not cause any environmental problems.
  • an electrode for an electrochemical cell can be produced by using a compound comprising a perovskite of the type ABO 3 ⁇ , in which ⁇ 0, where A comprises a metal selected from the group consisting of Na, K, Rb, Ca, Ba, La, Pr, Sr, Ce, Nb, Pb, Nd, Sm and Gd, and B comprises a metal selected from the group consisting of Cu, Mg, Ti, V, Cr, Mn, Fe, Co, Nb, Mo, W and/or Zr, and in which there is no metal from the group consisting of Pt, Ru, Ir, Rh, Ni and Pd, and in which A and B cannot both be Nb, and SrVO 2.5 is excluded.
  • A comprises a metal selected from the group consisting of Na, K, Rb, Ca, Ba, La, Pr, Sr, Ce, Nb, Pb, Nd, Sm and Gd
  • B comprises a metal selected from the group consisting of Cu, Mg, Ti, V, Cr, Mn,
  • perovskites of the type ABO 3 ⁇ is also understood as meaning perovskites of the type either A1A2BO 3 ⁇ or AB1B2O 3 ⁇ or A1A2B1B2O 3 ⁇ , where ⁇ 0 and ⁇ in particular is within the limits indicated above.
  • Examples include Sm 0.5 Sr 0.5 CoO 3 ⁇ , Nd 0.5 Sr 0.5 CoO 3 ⁇ and Nd 0.4 Sr 0.6 CoO 0.8 Fe 0.2 O 3 ⁇ , although the invention is not restricted to these examples.
  • an electrode for an electrochemical cell by using a compound comprising a Brown-Millerite ABO (2.5 ⁇ ) , where ⁇ 0, and A and B are selected from the groups described above.
  • a high capacitance and/or conversion rate or catalytic activity and a good electrical conductivity can be achieved in particular for values for ⁇ of between ⁇ 0.2 and ⁇ 0.05 or between +0.05 and +0.3.
  • a compound of this type is SrCoO (2.5 ⁇ ) , although the invention is not restricted to this example.
  • an electrode may comprise more than one of the corresponding perovskites and/or Brown-Millerites.
  • electrodes of this type have a considerable porosity, in order to increase the active surface area with the eletrolyte.
  • an electrode of this type at least in the vicinity of the surface, comprises a porous structure which comprises at least 30% and preferably more than 70% of one or more of the abovementioned compounds.
  • the electrical conductivity is of the same high level as that of Pb 2 Ru 2 O 7
  • the capacitance in ⁇ F/cm 2 is of the same high level as that of Ni(OH) 2 .
  • the expensive ruthenium it is also possible, with an electrode according to the invention, although not necessary, to avoid the heavy metal lead.
  • the electrodes may also, although not necessarily, contain a binder for the purpose of forming a cohesive structure.
  • a structure of this type may, but does not have to, be arranged in a matrix. It is also possible, although not necessary, for the electrodes to have undergone a heat treatment or calcining treatment or a sintering treatment.
  • FIG. 1 shows results of measurements carried out on electro-chemical capacitors with a carbon electrode and, respectively, an Ni(OH) 2 (indicated by ⁇ ) electrode which is known from the prior art and an Sm 0.5 Sr 0.5 CoO 3 ⁇ electrode (indicated by ⁇ ) according to the present invention.
  • electrodes according to the invention up to greater thicknesses without employing additives, such as for example graphite, or conductive matrices, such as for example foamed metals.
  • additives such as for example graphite, or conductive matrices, such as for example foamed metals.
  • conductive matrices such as for example foamed metals.
  • a matrix with a lower conductivity than that of, for example, a foamed metal for example a matrix of a conductive plastic or a conductive polymer, so that reductions in weight and costs can also be achieved.
  • independent, relatively thick electrode layers for example by printing, casting or dipping, optionally onto other (electrical or electronic) components, and which have a high capacitance and do not use expensive precious-metal elements.
  • electrodes according to the invention can also be made as thin films, for example by printing, casting, dipping, painting or spraying, and can be used in this form.
  • the electrodes according to the invention are not restricted to asymmetric capacitors or to capacitors with the structure indicated; they can also be put to good use in symmetrical electrochemical capacitors, in batteries and in fuel cells, reversible fuel cells, electrolysis equipment and sensors.
  • an electrode comprising one or more compounds according to the invention may replace the known Ni(OH) 2 electrode in an alkaline battery, for example an NiCd or NiMH battery.
  • the composition of the electrode according to the invention is then selected in such a way that the capacitance lies within the potential range which is desired for the battery.
  • An electrode according to the invention is characterized by a specific oxygen non-stoichiometry, i.e. a specific range of values for ⁇ and/or ⁇ , and by the complete avoidance of precious-metal elements, in particular ruthenium and iridium, by a high pseudo-capacitance (of the same level as for Ni(OH) 2 ) and/or a high catalytic activity and/or a high conversion rate, by a high electrical conductivity (of the same level as for Pb 2 Ru 2 O 7 ), virtually irrespective of the charge state or polarization, by a high stability, on account of the absence of undesired phases, and by a useful voltage range.
  • a specific oxygen non-stoichiometry i.e. a specific range of values for ⁇ and/or ⁇
  • precious-metal elements in particular ruthenium and iridium
  • a high pseudo-capacitance of the same level as for Ni(OH) 2
  • an electrode according to the invention it is also possible to avoid the use of environmentally harmful elements, such as nickel and lead, which occur in electrodes according to the prior art.
  • an electrode according to the invention compared to those which are known in the prior art, can be less expensive, can have a higher round-trip efficiency, in particular at relatively high current intensities, can be produced more easily, can be use in the form of a thin film or a thick layer, and may optionally be enclosed in a matrix which may also comprise a lightweight, inexpensive plastic material of moderate conductivity.
  • an electrode according to the invention also permits designs other than those which are known in the prior art for capacitors, supercapacitors, batteries, fuel cells, electrolysers and sensors.
  • the electrode it is now possible for the electrode to be printed as a layer onto another component and, in this way, to add a function to this component. This component may, for example, form part of a photovoltaic solar cell or of an electrochromic window.
  • Electrode according to the invention produced by the application of a layer of suspension, ink or paste to a substrate.
  • the substrate may, for example, be a metal foil or a plastic film.
  • the suspension, ink or paste comprises one or more compounds according to the invention, a solvent, and possibly auxiliaries, such as dispersing agents, surfactants, wetting agents and the like.
  • the compounds according to the invention may in this case be added in the form of a powder with a high specific surface area.
  • the suspension, ink or paste may if appropriate also contain a binder.
  • the application is effected by means of spreading, painting, spraying, dipping, printing, casting, slip casting or rolling. After its application, the layer may firstly be dried, during which process solvent and auxiliaries are completely or partially removed.
  • the substrate bearing the layer which may have characteristic thicknesses of between approx. 2 ⁇ m and approx. 1 000 ⁇ m and which may have a porosity of between approx. 5% and approx. 40%, is used in a supercapacitor or battery.
  • this laminate was arranged in a Teflon® cell housing. Both electrodes were provided with approx. 50 ⁇ l of electrolyte, after which the cell housing was sealed. Two stainless steel pins provide contact between the current collectors and the outside of the cell. The internal resistance ESR of the supercapacitor obtained in this way was measured with the aid of impedance spectroscopy.
  • FIG. 2 shows the results for a cell in which a platinum reference electrode was also fitted in the separator.
  • the potential curve of the electrode during charging and discharging with a current of 0.25 A/g leads to an effective capacitance for the compound according to the invention of ⁇ 130 F/g.
  • Electrode produced by the application of a suspension, ink or paste in a matrix may be foamed metal or a metal mat, metal gauze, polymer foam, polymer gauze or some other porous structure.
  • the suspension, ink or paste comprises one or more perovskite and/or Brown-Millerite compounds according to the invention, and may furthermore contain constituents as described in Example 1.
  • the perovskite and/or Brown-Millerite compounds may in this case be added in the form of a powder with a high specific surface area.
  • the suspension, ink or paste may be applied using the methods described in Example 1. After the application, the steps as described in Example 1 may follow. Typical thicknesses of the electrode structure which is formed will lie between appox. 100 ⁇ m and approx. 1 500 ⁇ m.
  • FIG. 3 shows the results for a cell in which a platinum reference electrode is also incorporated in the separator.
  • the potential curve of the electrode during charging and discharging with a current of 0.37 A/g reveals an effective capacitance for the compound according to the invention of ⁇ 120 F/g.
  • Electrode produced by the application of a layer of suspension, ink or paste to a substrate comprises one or more perovskite and/or Brown-Millerite compounds according to the invention, a solvent and possibly auxiliaries, such as dispersing agents, surfactants, wetting agents and the like.
  • the perovskite and/or Brown-Millerite compounds may in this case be added in the form of a powder with a high specific surface area.
  • the suspension, ink or paste may also contain a binder.
  • the substrate is a smooth surface. The suspension is distributed over the surface by spreading, painting, printing or casting and is dried. Then, the tape which is formed is removed from the smooth surface as an independent electrode layer. If appropriate, for use in a capacitor, battery, fuel cell, electrolyser or sensor, it is also possible for heat treatments, calcining steps or sintering steps to be carried out on the tape.
  • One or more compounds according to the invention are packaged in powder form in an envelope of porous plastic material, which is inert with respect to the electrolyte which is to be used and is electrically insulating.
  • an envelope of porous plastic material which is inert with respect to the electrolyte which is to be used and is electrically insulating.
  • powder material, envelope and a wire or strip of metal are pressed together in such a manner that there is contact between the powder particles themselves and between the wire or strip and the powder.
  • the structure formed in this way is used as an electrode in an electrochemical cell.
  • the electrode was likewise used in the same way as in Example 1 in a laboratory supercapacitor, fitted with a Pt reference electrode and a counterelectrode.
  • the results of the charging and discharging experiments are shown in FIG. 4. At a charging and discharging current intensity of 200 mA/g, the mean capacitance is approx. 160 F/g.

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NL1015886A NL1015886C2 (nl) 2000-08-07 2000-08-07 Elektrode voor een elektrochemische cel.
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NL1018266A NL1018266C1 (nl) 2001-06-12 2001-06-12 Gemengd oxidemateriaal met hoog geleidingsvermogen voor elektronen; elektrode voor een elektrochemische cel die dit materiaal omvat; werkwijze voor het vervaardigen van een elektrode voor een elektrochemische cel en elektrochemische cel die tenminste een dergelijke elektrode omvat.
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US20040214070A1 (en) * 2003-04-28 2004-10-28 Simner Steven P. Low sintering lanthanum ferrite materials for use as solid oxide fuel cell cathodes and oxygen reduction electrodes and other electrochemical devices
US7265890B1 (en) * 2006-06-20 2007-09-04 Eclipse Energy Systems Electrochromic infrared tunable filter and emissivity modulator
WO2008133549A1 (ru) * 2007-04-27 2008-11-06 Obschestvo S Ogranichennoi Otvetstvennost'yu 'natsional'naya Innovatsionnaya Kompaniya 'novye Energeticheskie Proekty' Катодный материал для тотэ на основе кобальт содержащих перовскитоподобных оксидов переходных металлов
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US20110062017A1 (en) * 2006-07-22 2011-03-17 Elangovan S Efficient reversible electrodes for solid oxide electrolyzer cells
US20110114503A1 (en) * 2010-07-29 2011-05-19 Liquid Light, Inc. ELECTROCHEMICAL PRODUCTION OF UREA FROM NOx AND CARBON DIOXIDE
US20110136001A1 (en) * 2009-06-15 2011-06-09 Kensuke Nakura Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery using the same
US20110135810A1 (en) * 2009-12-03 2011-06-09 Marina Yakovleva Finely deposited lithium metal powder
US20110226632A1 (en) * 2010-03-19 2011-09-22 Emily Barton Cole Heterocycle catalyzed electrochemical process
US8313634B2 (en) 2009-01-29 2012-11-20 Princeton University Conversion of carbon dioxide to organic products
US8500987B2 (en) 2010-03-19 2013-08-06 Liquid Light, Inc. Purification of carbon dioxide from a mixture of gases
US8562811B2 (en) 2011-03-09 2013-10-22 Liquid Light, Inc. Process for making formic acid
US8568581B2 (en) 2010-11-30 2013-10-29 Liquid Light, Inc. Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide
US8592633B2 (en) 2010-07-29 2013-11-26 Liquid Light, Inc. Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates
US8658016B2 (en) 2011-07-06 2014-02-25 Liquid Light, Inc. Carbon dioxide capture and conversion to organic products
US8721866B2 (en) 2010-03-19 2014-05-13 Liquid Light, Inc. Electrochemical production of synthesis gas from carbon dioxide
US20140231241A1 (en) * 2011-10-25 2014-08-21 University Court Of The University Of St Andrews Method for effecting a photocatalytic or photoelectrocatalytic reaction
CN104040765A (zh) * 2011-10-12 2014-09-10 阿海珐 用于电化学电池的电极以及制造这种电极的方法
US8845878B2 (en) 2010-07-29 2014-09-30 Liquid Light, Inc. Reducing carbon dioxide to products
US8961774B2 (en) 2010-11-30 2015-02-24 Liquid Light, Inc. Electrochemical production of butanol from carbon dioxide and water
US20150122325A1 (en) * 2012-06-29 2015-05-07 Research & Business Foundation Sungkyunkwan University Producing method of mesoporous thin film solar cell based on perovskite
US9090976B2 (en) 2010-12-30 2015-07-28 The Trustees Of Princeton University Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction
US9659681B2 (en) 2013-11-01 2017-05-23 Samsung Electronics Co., Ltd. Transparent conductive thin film
CN114649527A (zh) * 2022-02-24 2022-06-21 南京工业大学 一种四相导体质子导体氧电极材料、制备方法及用途

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WO2004047207A3 (en) * 2002-11-15 2005-05-06 Battelle Memorial Institute Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrochemical devices
WO2004047207A2 (en) * 2002-11-15 2004-06-03 Battelle Memorial Institute Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrochemical devices
US7758992B2 (en) 2002-11-15 2010-07-20 Battelle Memorial Institute Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices
US20040214070A1 (en) * 2003-04-28 2004-10-28 Simner Steven P. Low sintering lanthanum ferrite materials for use as solid oxide fuel cell cathodes and oxygen reduction electrodes and other electrochemical devices
US7265890B1 (en) * 2006-06-20 2007-09-04 Eclipse Energy Systems Electrochromic infrared tunable filter and emissivity modulator
US8354011B2 (en) * 2006-07-22 2013-01-15 Ceramatec, Inc. Efficient reversible electrodes for solid oxide electrolyzer cells
US20110062017A1 (en) * 2006-07-22 2011-03-17 Elangovan S Efficient reversible electrodes for solid oxide electrolyzer cells
WO2008133549A1 (ru) * 2007-04-27 2008-11-06 Obschestvo S Ogranichennoi Otvetstvennost'yu 'natsional'naya Innovatsionnaya Kompaniya 'novye Energeticheskie Proekty' Катодный материал для тотэ на основе кобальт содержащих перовскитоподобных оксидов переходных металлов
US20100028766A1 (en) * 2008-07-18 2010-02-04 University Of Maryland Thin flexible rechargeable electrochemical energy cell and method of fabrication
US9484155B2 (en) * 2008-07-18 2016-11-01 University Of Maryland Thin flexible rechargeable electrochemical energy cell and method of fabrication
US8986533B2 (en) 2009-01-29 2015-03-24 Princeton University Conversion of carbon dioxide to organic products
US8313634B2 (en) 2009-01-29 2012-11-20 Princeton University Conversion of carbon dioxide to organic products
US8663447B2 (en) 2009-01-29 2014-03-04 Princeton University Conversion of carbon dioxide to organic products
US20110136001A1 (en) * 2009-06-15 2011-06-09 Kensuke Nakura Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery using the same
US20110135810A1 (en) * 2009-12-03 2011-06-09 Marina Yakovleva Finely deposited lithium metal powder
US10119196B2 (en) 2010-03-19 2018-11-06 Avantium Knowledge Centre B.V. Electrochemical production of synthesis gas from carbon dioxide
US20110226632A1 (en) * 2010-03-19 2011-09-22 Emily Barton Cole Heterocycle catalyzed electrochemical process
US9222179B2 (en) 2010-03-19 2015-12-29 Liquid Light, Inc. Purification of carbon dioxide from a mixture of gases
US8845877B2 (en) 2010-03-19 2014-09-30 Liquid Light, Inc. Heterocycle catalyzed electrochemical process
US9970117B2 (en) 2010-03-19 2018-05-15 Princeton University Heterocycle catalyzed electrochemical process
US8500987B2 (en) 2010-03-19 2013-08-06 Liquid Light, Inc. Purification of carbon dioxide from a mixture of gases
US8721866B2 (en) 2010-03-19 2014-05-13 Liquid Light, Inc. Electrochemical production of synthesis gas from carbon dioxide
US8524066B2 (en) 2010-07-29 2013-09-03 Liquid Light, Inc. Electrochemical production of urea from NOx and carbon dioxide
US8845878B2 (en) 2010-07-29 2014-09-30 Liquid Light, Inc. Reducing carbon dioxide to products
US8592633B2 (en) 2010-07-29 2013-11-26 Liquid Light, Inc. Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates
US20110114503A1 (en) * 2010-07-29 2011-05-19 Liquid Light, Inc. ELECTROCHEMICAL PRODUCTION OF UREA FROM NOx AND CARBON DIOXIDE
US9309599B2 (en) 2010-11-30 2016-04-12 Liquid Light, Inc. Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide
US8961774B2 (en) 2010-11-30 2015-02-24 Liquid Light, Inc. Electrochemical production of butanol from carbon dioxide and water
US8568581B2 (en) 2010-11-30 2013-10-29 Liquid Light, Inc. Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide
US9090976B2 (en) 2010-12-30 2015-07-28 The Trustees Of Princeton University Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction
US8562811B2 (en) 2011-03-09 2013-10-22 Liquid Light, Inc. Process for making formic acid
US8658016B2 (en) 2011-07-06 2014-02-25 Liquid Light, Inc. Carbon dioxide capture and conversion to organic products
CN104040765A (zh) * 2011-10-12 2014-09-10 阿海珐 用于电化学电池的电极以及制造这种电极的方法
US9469906B2 (en) * 2011-10-25 2016-10-18 University Court Of The University Of St Andrews Method for effecting a photocatalytic or photoelectrocatalytic reaction
US20140231241A1 (en) * 2011-10-25 2014-08-21 University Court Of The University Of St Andrews Method for effecting a photocatalytic or photoelectrocatalytic reaction
US20150122325A1 (en) * 2012-06-29 2015-05-07 Research & Business Foundation Sungkyunkwan University Producing method of mesoporous thin film solar cell based on perovskite
US10720282B2 (en) * 2012-06-29 2020-07-21 Research & Business Foundation Sungkyunkwan University Producing method of mesoporous thin film solar cell based on perovskite
US9659681B2 (en) 2013-11-01 2017-05-23 Samsung Electronics Co., Ltd. Transparent conductive thin film
CN114649527A (zh) * 2022-02-24 2022-06-21 南京工业大学 一种四相导体质子导体氧电极材料、制备方法及用途

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