WO2015160751A1 - Système de pile à combustible de batterie hybride à électrode partagée - Google Patents

Système de pile à combustible de batterie hybride à électrode partagée Download PDF

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WO2015160751A1
WO2015160751A1 PCT/US2015/025673 US2015025673W WO2015160751A1 WO 2015160751 A1 WO2015160751 A1 WO 2015160751A1 US 2015025673 W US2015025673 W US 2015025673W WO 2015160751 A1 WO2015160751 A1 WO 2015160751A1
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Prior art keywords
cell
anode
alloy
hydrogen
cathode
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PCT/US2015/025673
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English (en)
Inventor
Kwo-Hsiung Young
Diana Wong
Jean NEI
Benjamin Reichman
Benjamin Chao
William C. MAYS
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Ovonic Battery Company, Inc.
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Priority claimed from US14/252,012 external-priority patent/US20150295290A1/en
Priority claimed from US14/251,962 external-priority patent/US9343735B2/en
Application filed by Ovonic Battery Company, Inc. filed Critical Ovonic Battery Company, Inc.
Publication of WO2015160751A1 publication Critical patent/WO2015160751A1/fr

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    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • H01M10/347—Gastight metal hydride accumulators with solid electrolyte
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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

Definitions

  • the invention relates to energy storage devices. More particularly, the invention relates to systems for storing energy and using that energy to provide continuous electrical power on demand and without a startup delay.
  • the present invention effectively combines a battery and a fuel cell into a single device capable of intermediate temperature operation.
  • the hybrid battery/fuel cell devices provide many advantages including higher energy/power density, lower initial cost, enhanced reliability, instant start, continuous operation, and power leveling capabilities.
  • Hydrogen is considered is a highly desirable fuel source in addressing the needs for global energy. Hydrogen is the most plentiful element in the universe (over 95%) and can therefore provide a virtually inexhaustible, clean source of energy for our planet.
  • a fuel cell is an energy-conversion device that directly converts the energy of a supplied gas, such as hydrogen, into electrical energy.
  • the base unit of the fuel cell is a cell having a cathode, an anode, and an appropriate electrolyte.
  • Fuel cells have many current and potential applications such as supplying power for transportation vehicles, replacing steam turbines and power supply applications of all sorts. Despite their seeming simplicity, many problems have prevented the widespread usage of fuel cells.
  • SOFC solid oxide fuel cell
  • PEM proton exchange membrane
  • the remainder of the materials used in the construction of the fuel cell need to be compatible with such an environment, which again adds to the cost of producing these systems.
  • the PEM itself is quite expensive and its low conductivity at temperatures below 80°C inherently limits the power performance and operational temperature range of the PEM fuel cell.
  • the PEM membrane is sensitive to high temperatures, and begins to soften at 120°C. The membrane's conductivity depends on water and dries out at higher temperatures, thus causing cell failure. Therefore, there are many disadvantages to the PEM fuel cell which make it somewhat undesirable for commercial/consumer use. Both type of fuel cells require a substantial preparation time and cannot be started quickly.
  • the conventional alkaline fuel cell operated at room temperature has some advantages over PEM fuels cells in that alkaline fuel cells have higher operating efficiencies, use less expensive materials of construction, and have no need for expensive membranes.
  • the alkaline fuel cell also has relatively higher ionic conductivity in the electrolyte, therefore, it has a much higher power capability.
  • conventional alkaline fuel cells still suffer from certain disadvantages.
  • Conventional alkaline fuel cells often employ expensive noble metals catalysts in both electrodes, which, as in the PEM fuel cell, are susceptible to gaseous contaminant poisoning.
  • the conventional alkaline fuel cell is also susceptible to the formation of carbonates from CO2 produced by oxidation of the anode carbon substrates or introduced via impurities in the fuel and air used at the electrodes.
  • Fuel cells are important to addressing global warming by eliminating carbon dioxide production, existing technologies cannot effectively store energy produced by the vast majority of alternative energy production devices.
  • Fuel cells like batteries, operate by utilizing electrochemical reactions. Unlike a battery, in which chemical energy is stored within the cell, fuel cells generally are supplied with reactants from outside the cell. Thus, fuel cells still require an externally supplied gas source.
  • the energy storage that accompanies alternative energy power generation systems is typically a battery system.
  • Each of these alternative energies represents a discontinuous source of electrical energy in that they are effective only as long as their power source is active.
  • solar energy sources function only in daylight hours, and have peak operating performance only in direct sunlight and in the absence of cloud cover.
  • Wind power is highly weather dependent and while many areas experience more regular winds, even these areas suffer low wind levels at least during some point of each day.
  • the provided intermediate temperature power cell of the present invention solves many of the issues of irregular power generation observed with alternative energy sources.
  • the intermediate temperature hybrid cell is capable of storing electrical energy in the form of hydrogen for later consumption during times of power need but low generation in addition to functioning as a battery. Further, the cell is capable of utilizing external hydrogen as fuel for continuous operation for long periods. The cell provides greatly improved reliability and simplicity that both reduces the cost and increases the lifetime of the system.
  • an intermediate temperature hybrid power cell including a cathode that includes: one or more cathode materials capable of absorbing and desorbing hydrogen, the cathode material including a mixed metal oxide capable of being oxidized by air; an anode formed of one or more anode materials, the anode material capable of reversible electrochemical and gas phase hydrogen charge; wherein the anode material and the cathode material are in electrochemical contact and wherein the anode and the cathode function as electrodes in a battery, a fuel cell, or both, at an intermediate temperature of 100 degrees Celsius to 700 degrees Celsius, optionally 200 degrees Celsius to 500 degrees Celsius.
  • Some embodiments further include a hydrogen storage alloy or hydrogen source, the hydrogen storage alloy or hydrogen source in gaseous contact with the anode.
  • the hydrogen storage alloy is optionally separated from the anode by a hydrogen gas transferring conduit or a proton conducting membrane.
  • An anode for use in an intermediate temperature hybrid power cell optionally includes two or more anode materials.
  • a second anode material is optionally capable of fast-rate hydrogen discharge at temperatures between 200 and 250°C.
  • a second anode material is a Fe-doped Mg alloy.
  • An anode material optionally includes or is solely formed from anode material particles of 0.1 to 2 micrometers in cross sectional dimension. Anode material particles are optionally spherical or substantially spherical.
  • an anode material includes a: BCC phase metal hydride alloy; Mg or Ca based MH alloy; Mg2 i based metal hydride alloy; ZrNi based metal hydride alloys; I-III alloy; rare earth metal based metal hydride alloy; or combinations thereof.
  • An anode material is optionally a BCC phase metal hydride alloy selected from the group consisting of V-Ti-Cr based alloy and a Laves-phase alloy.
  • An intermediate temperature hybrid power cell optionally includes a cathode material that is capable of multi-electron transfer (more than 1 electron transfer per transition metal atom).
  • the cathode material includes one or more nickel hydroxide materials.
  • An intermediate temperature hybrid power cell includes an electrolyte.
  • An electrolyte is optionally a solid electrolyte.
  • an electrolyte includes one or more perovskite-like materials.
  • An intermediate temperature hybrid power cell optionally includes a hydrogen source that is in gaseous contact with an anode material, a hydrogen storage material, or both.
  • the cathode of an electrochemical cell is in gaseous contact with an oxygen source, optionally raw atmospheric air or atmospheric quality air.
  • the resulting intermediate temperature power cell has the advantages of instant start, load matching, effectively storing energy from an alternative energy source, providing power generation in suboptimal weather and other conditions, low cost to both install and operate, and long expected lifetimes.
  • FIG. 1 is a schematic of a hybrid power cell according to one embodiment of the invention.
  • FIG. 2A is a schematic of a hybrid power cell according to one embodiment of the invention illustrating cell function in battery mode during charging
  • FIG. 2B is a schematic of a hybrid power cell according to one embodiment of the invention illustrating cell function in battery mode during charging
  • FIG. 2C is a schematic of a hybrid power cell according to one embodiment of the invention illustrating cell function during operation using both battery mode and fuel cell mode;
  • FIG. 3 A illustrates the round trip energy efficiency of a hybrid power cell operating in battery mode using NiMH technology at 25°C;
  • FIG. 3B illustrates the round trip energy efficiency of a hybrid power cell operating in battery mode using NiMH technology at 50°C;
  • FIG. 4A illustrates a cathode material associated into a functional cathode that is capable of being oxidized by air as well as functioning in proton transfer according to some embodiments in which the cathode material is associated with a binder material;
  • FIG. 4B illustrates a cathode material associated into a functional cathode that is capable of being oxidized by air as well as functioning in proton transfer according to some embodiments in which the cathode material directly associates with a solid electrolyte;
  • FIG. 4C illustrates a cathode material associated into a functional cathode that is capable of being oxidized by air as well as functioning in proton transfer according to some embodiments in which the cathode material is associated with a proton conducting substrate;
  • FIG. 5 illustrates PCT measurements of various active materials illustrating that improved performance is achieved at intermediate operating temperatures
  • FIG. 6 illustrates scanning electron microscopy of anode particles as used in some embodiments of the invention
  • FIG. 7 illustrates hydrogen desorption kinetics of Mgss.sAhjFes.s at 240°C as one exemplary hydrogen storage alloy
  • FIG. 8 illustrates the heat of hydride formation vs. Ni-content for several materials including those suitable for use at intermediate temperatures in a hybrid power cell;
  • FIG. 9 illustrates a bipolar plate design for a stack used in an intermediate temperature hybrid power cell according to one embodiment of the invention.
  • FIG. 10A illustrates a system employing an intermediate temperature power cell utilized in a first sub-stack and as second sub-stack that are arranged in a bipolar stack design and operable asynchronously wherein the first sub-stack 102 is being fueled/air-oxidized while the second sub-stack 104 is being used to power the load;
  • FIG. 10B illustrates a system employing an intermediate temperature power cell utilized in a first sub-stack and as second sub-stack that are arranged in a bipolar stack design and operable asynchronously wherein the first sub-stack 102 is used to power the load while the second sub-stack 104 is being fueled/air-oxidized;
  • FIG. 11A illustrates a system employing an intermediate temperature power cell utilized in a first sub-stack and as second sub-stack that are arranged in a bipolar stack design and operable asynchronously and operating in battery mode wherein the first sub-stack 102 and the second sub-stack 104 are being charged via an external power source such as a renewable energy source; and
  • FIG. 11B illustrates a system employing an intermediate temperature power cell utilized in a first sub-stack and as second sub-stack that are arranged in a bipolar stack design and operable asynchronously and operating in battery mode wherein the first sub-stack 102 and the second sub-stack 104 are both being used to power the load.
  • first,” “second,” “third” etc. may be used herein to describe various materials, elements, components, regions, layers, and/or sections, these materials, elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one material element, component, region, layer, or section from another material, element, component, region, layer, or section. Thus, a first "material,” “element,” “component,” “region,” “layer,” or “section” discussed below could be termed a second (or other) material, element, component, region, layer, or section without departing from the teachings herein.
  • hybrid power cell capable of full and efficient functionality at intermediate temperatures.
  • the hybrid power cell combines the elements of a fuel cell with that of a battery into a single device capable of both storing and instantly utilizing stored chemical energy.
  • the present invention is a significant step forward in addressing clean energy needs.
  • a hybrid power cell according to the invention is capable of functioning in a battery mode or a fuel cell mode in a single device and utilizing a single pair of electrodes.
  • the hybrid power cell optionally operates in an intermediate temperature range to improve battery energy and power performance while also eliminating the need for an air electrode with expensive catalysts within a fuel cell.
  • the hybrid power cell includes two operating modes: a fuel cell mode; and a battery mode.
  • Supplying fuel in the form of hydrogen gas and air when operating in the fuel cell mode serves to charge the anode with hydrogen while at the same time oxygen provided from air or other source simultaneously oxides the cathode (Ni(OH)2, for example) to a higher oxidation state (NiOOH), essentially charging the device for power generation when switched to battery mode.
  • Ni(OH)2 a higher oxidation state
  • NiOOH oxidation state
  • Table 1 Comparison of energy storage/generation for grid applications.
  • FIG. 1 A schematic of an intermediate temperature hybrid power cell according to one embodiment is shown in Fig. 1.
  • a cell 1 can function in either a battery mode, or a fuel cell mode and is capable of instant switching between the two modes.
  • energy optionally obtained from the grid or from another power source such as an alternative energy source is stored in a cathode 2 and a hydrogen storage alloy 4.
  • Energy can be fed back to the grid by the following reversible electrochemical reaction of Formula I:
  • a cell further includes an anode 6 in electrochemical contact with the cathode 2.
  • the anode is capable of reversible electrochemical and gas phase hydrogen charge.
  • a solid separator 8 Between the anode 6 and the cathode 2 is a solid separator 8.
  • the solid separator 8 is a proton conductor.
  • low pressure hydrogen gas can be supplied by several methods to charge the hydrogen storage alloy through a gaseous phase reaction.
  • the cathode is optionally oxidized by air or other oxygen source yielding continual usage and governed by the reaction according to Formula II:
  • An intermediate temperature hybrid power cell may be charged in multiple ways.
  • An intermediate temperature hybrid power cell may be charged by externally supplied electricity in battery mode (FIG. 2A) where electricity is optionally provided by grid or any alternative energy source.
  • an intermediate temperature hybrid power cell may be charged by externally supplied hydrogen and an oxygen source such as air in the fuel cell mode (FIG. 2B).
  • the cathode is oxidized into NiOOH, and hydrogen generated from the anode or an outside source is stored in the hydrogen storage canister.
  • the chemical energies stored in the cathode and hydrogen storage canister are converted into electricity through the proton-conducting solid electrolyte (FIG. 2C).
  • hydrogen from an outside source can be directly fed to the anode without the use of a hydrogen storage canister as a pressure buffer, which allows continuous operation in the fuel-cell mode.
  • NiMH nickel metal hydride
  • Table 2 Illustrative advantages of using the NiMH technology are illustrated in Table 2.
  • a cathode is made at least in part from a cathode material capable of absorbing and desorbing hydrogen.
  • a cathode material includes a mixed metal oxide capable of being oxidized by air.
  • a cathode material includes a metal oxide that is optionally modified chemically to provide multi-electron transfer extending beyond the customary one electron per metal atom capacity even in an aqueous electrolyte at ambient temperature.
  • a cathode material includes a high valence transition metal oxide illustratively ⁇ 2 ⁇ 7 , MnC , Fe203, C0O2, Ni0 2 ; a hydroxide from a transition metal illustratively Mn(OH)2, Fe(OH)3, Co(OH)3; an oxi-hydroxide from a transition metal, illustratively CoOOH or NiOOH; an oxide of mixed metal illustratively (Mn, Co, Ni)O x , (Mn, Al, Ni)O x , LiMn 2 0 4 ; a hydroxide of mixed metal illustratively (Mn, Co, Ni)(OH) x , (Mn, Al, Ni)(OH) x , (Li, Ni)(OH) x , (Li, Mn)(OH) x ; or other materials capable of multi-electron transfer such as HFeP04, HMnP0 4 , HFeS
  • a cathode material is a mixed metal oxide material, illustratively (Ni, Co, Zn)(OH)2.
  • a cathode material is optionally a particulate material that is spherical or substantially spherical. Processes for forming such a cathode material may be achieved by co-precipitation in a single reactor substantially as described in C. Fierro, et al., Journal of the Electrochemical Society, 153 (2006) A492. Briefly, mixed metal hydroxide is coprecipitated with other metals, optionally cobalt and zinc, by mixing a mixed metal oxide solution that is continuously fed into a reactor under strong stirring at constant pH and temperature as described in U.S. Patent No.
  • substrate as used herein relates to any electronically conductive network, foam, grid, plate or foil made from any electrically conductive material.
  • a substrate illustratively includes conventional nickel foils, plates and foams, as well as, carbon networks, fibers or particulate and cobalt oxyhydroxide networks.
  • a cathode material optionally contacts (e.g. by coating, layering, or other contact) an electrically conductive substrate to form a cathode.
  • a substrate for a cathode material optionally satisfies several parameters including sufficient malleability such that the cathode material can be adequately pressed onto the substrate material and bind thereto.
  • a substrate optionally has the ability to conduct protons such that the cathode material may be both exposed to an oxidizing gas such as air as well as transfer protons to and from the anode.
  • An intermediate temperature hybrid power cell further includes an anode.
  • An anode include an anode material capable of reversible electrochemical and gas phase hydrogen charge. As such, an anode may function by being supplied by hydrogen obtained from an external hydrogen source, a cathode material, an electrolyte, a hydrogen storage alloy, or any combination thereof.
  • An anode material optionally contacts (e.g. by coating, layering, or other contact) an electrically conductive substrate.
  • An anode material is optionally capable of both electrochemical and gas phase hydrogen charge/discharge at intermediate temperatures.
  • An intermediate temperature is optionally from 100°C to 700°C, or any value or range therebetween. Excellent results are obtained using sub-ranges.
  • an intermediate temperature is optionally from 200°C to 500°C.
  • an intermediate temperature is from 200°C to 250°C.
  • An anode material is optionally a metal hydride (MH).
  • MH metal hydride
  • Conventional MH alloys used in NiMH battery anodes are processed through melting, casting, and grinding.
  • Typical AB2 and AB5 alloys, for example, are very hard, and the resulting powder often has sharp and pointy corners necessitating a thick separator to prevent punch-through and direct shorts between the cathode and anode. This is the reason that Li-ion batteries have very similar power densities to the NiMH battery despite the much higher ionic conductivity in the NiMH electrolyte: the Li-ion battery separator is much thinner than the NiMH separator.
  • MH materials as used in the present invention are optionally formed so as not to suffer the complications of prior materials.
  • MH includes particles of MH material.
  • Particles of MH material optionally have a cross sectional dimension of 0.1 to 2 micrometers.
  • particles of MH are spherical or substantially spherical.
  • Anode materials are optionally formed by a gas atomization technique. Illustrative gas atomization techniques are described in K. Young, et al, Journal of ' Alloys and Compounds 2011, 509, 4896; and K. Young, et al., International Journal of Hydrogen Energy 201 1, 36, 3547. Typical anode material particles generated by this process produces spherically-shaped particles shown in FIG. 6.
  • An anode material optionally includes multiple anode materials.
  • an anode material includes 1, 2, 3, 4, 5, or more anode materials or alloys.
  • an anode material includes a: BCC phase metal hydride alloy illustratively a V-Ti-Cr based alloy and a Laves-phase alloy; Mg or Ca based MH alloy; Mg2Ni based metal hydride alloy; ZrNi based metal hydride alloys; I-III alloy; rare earth metal based metal hydride alloy; or combinations thereof.
  • BCC phase metal hydride alloy illustratively a V-Ti-Cr based alloy and a Laves-phase alloy
  • Mg or Ca based MH alloy Mg2Ni based metal hydride alloy
  • ZrNi based metal hydride alloys ZrNi based metal hydride alloys
  • I-III alloy rare earth metal based metal hydride alloy
  • an anode material is a BCC phase metal hydride alloy illustratively a V-Ti-Cr based alloy and a Laves-phase alloy.
  • a series of body- centered-cubic- (BCC) based MH alloys has a much higher hydrogen storage capacity.
  • PCT isotherms indicate that the BCC-based alloys have a very strong metal-hydrogen bond (Fig. 5) that illustrates improved performance at modestly elevated temperatures such as intermediate temperatures as are used by the hybrid power cell of the invention.
  • a second anode material is included either intermixed with a first anode material, contacting a first anode material, or otherwise in contact with a first anode material so as to be capable of hydrogen transfer from a first anode material to a second anode material.
  • a second anode material is optionally capable of fast-rate hydrogen discharge at temperatures between 200 and 250°C, where fast-rate in the context of a second anode material is defined as discharging 80% of its full capacity in 80 minutes or less.
  • a second anode material is optionally a Fe-doped Mg alloy.
  • an anode includes a single anode material that functions as both a hydrogen storage medium and for electrochemical charge/discharge.
  • an anode is a laminated composite material with two layers of different metal hydride (MH) alloy intimately connected to each other where a first MH alloy functions as an anode material, and a second MH alloy functions as a hydrogen storage material.
  • MH metal hydride
  • an anode material is associated with a hydrogen storage material via a proton conducting membrane or solid film such that hydrogen can be readily exchanged between a hydrogen storage alloy on one side of the film and an anode material located on the other side of the film.
  • a hydrogen storage alloy is separated from an anode material and housed externally thereto.
  • a hydrogen storage alloy is optionally housed in a hydrogen storage canister in gaseous contact with the cell or anode material portion thereof.
  • Adding an external hydrogen storage canister to the system has several advantages. First, MH alloy without the presence of catalytic NI has the highest storage capacity and the alloy can supply additional capacity to the electrochemically active anode material. Second, separation of hydrogen storage and anode MH alloys adds flexibility in to system design allowing separate optimized temperatures for the battery elements and hydrogen storage elements.
  • the hydrogen storage canister acts as a pressure buffer that prevents any high pressure fluctuations from rupturing the thin separator while acting as a hydrogen purifier that reduces the possibility of anode and electrolyte contamination.
  • the separation of the anode and hydrogen storage unit can allow the use of more catalytic anode material, such as Pt and Pd, if necessary.
  • Non-limiting exemplary hydrogen storage alloys include MgH 2 , VH 2 , TaH 2 , PdHo.7, Mg 2 NiH 4 , Mg88.8Ai2.7Fe 8 .5, FeTiH 2 , LaNi 5 H 6 , Ti 35 V 22 Cr 43 , Ti 2 Ni, CaNi 2 , LaNi 2 , and LaNi 3 , among many others.
  • Hydrogen storage alloys may be prepared in a number of conventional ways as per techniques known in the art illustratively as described in Young K. (2013) Metal Hydrides. In: Reedijk, J. (Ed.) Elsevier Reference Module in Chemistry, Molecular Sciences and Chemical Engineering. Waltham, MA: Elsevier.
  • a material for storing hydrogen is not a MH alloy.
  • a material for hydrogen storage is a metal-organic-framework (MOF).
  • MOFs are synthesized using organic linker molecules and metal clusters that self-assemble to form materials with well defined pores, high surface areas, and desired chemical functionalities.
  • Illustrative examples of MOFs for hydrogen storage include the fluorinated MOFs, optionally polymers of polynuclear silver(I)-triazolate clusters as described in U.S. Patent No. 8,343,260.
  • An MOF is optionally an activated carbon MOF such as those described in WO 2012/131483. Additional examples of MOFs include those described in U.S. Application Publication No.
  • non-MH alloys useful as hydrogen storage materials include the newly discovered inorganic compounds, such as Co-S, Co-P, Co-Si, and Co-B. While the progress of research on those inorganic compounds at room temperature is slow (limited to 1.6 wt.%), raising operation temperature to the intermediate temperatures of the present hybrid power cell increases the number suitable compounds.
  • An anode material, a cathode material, or both are optionally in each independently in contact with one or more gas diffusion layers.
  • a gas diffusion layer is optionally positioned between a gas flow and an active material. The presence of a gas diffusion layer improves performance in fuel cell mode by several mechanisms including providing a uniform diffusion path of the gas between the flow and the active material and moving excess water away from an active material while still retaining some water content under dry operating condition. Illustrative examples of a gas diffusion layer are illustrated in U.S. Patent No. 8,518,596.
  • An anode material is in electrochemical contact with a cathode material by an intermediate electrolyte. While typical metal hydride battery structures employ a classic potassium hydroxide alkaline electrolyte, the inventive cell optionally excludes KOH as an electrolyte.
  • a cell includes a solid electrolyte composition. Replacing liquid electrolyte with solid-state film enables the increase in cathode voltage, eliminates oxygen evolution, and increases the overall capacity. Increasing the operation temperature from room temperature to the intermediate temperature range increases the proton conductivity by a factor of at least 10.
  • a solid electrolyte optionally has a thickness that is less than 15 micrometers, optionally less than 10 micrometers, optionally 5 micrometers or less.
  • an electrolyte material examples include a perovskite-like solid electrolyte optionally as described in US Patent Application Publication No: 2012/0183835.
  • an electrolyte is a liquid electrolyte.
  • ABO3-6 perovskite where A is a rare-earth element or an element with a large radius and B is an element with a smaller radius, is capable of proton conduction as serves as one example of an electrolyte.
  • the structure of such an oxide if prepared under proper conditions, is prone to a large density of oxygen vacancies.
  • oxygen from the water occupies a vacancy, and the remaining two protons are then attached to two separate oxygen ions, which create a proton-conducting path substantially as described by R.A. Davies, et al., Solid State Ionics 1999; 126; 323.
  • the proton conductivity depends on the vacancy density and also the distance between neighboring oxygen ions.
  • Ni(OH)2/NiOOH type materials are optional cathode materials in a hybrid power cell.
  • a (Ni, Co, Zn)(OH)2 spherical powder produced by co-precipitation in a single reactor is used as a cathode material.
  • aqueous KOH solution limits the potential of the cathode to lower than 0.4 V vs. Hg/HgO.
  • solid electrolyte loosens the restriction in voltage and allows the use of Ni(OH)2 up to at least NiOOHo.33, which yields a 66% increase in capacity.
  • electrolyte is optionally a solid electrolyte.
  • An electrolyte is optionally a solid acid electrolyte.
  • Proton conductivity of solid acid at room temperature is low but is enhanced by several orders of magnitude at intermediate temperature. Without being limited to any particular theory, it is predicted that as temperature rises, water is generated by the following thermal decomposition reaction and contributes to the mobility of protons:
  • proton conductivity improvement in solid acid is related to a structural change at elevated temperature.
  • the oxyanions acquire higher rotational freedom in the crystal lattice, which results in disorder in hydrogen bonding between the oxyanion groups and enables protons to start hopping.
  • solid acids such as K3H(S0 4 )2, CsH2P0 4 , RbH2P0 4 , or LiH2P0 4 demonstrate high proton conductivity in the intermediate temperature range up to 10 S cm "1 .
  • mechanical durability of solid acid electrolytes is improved by incorporating solid acid into a thermally durable and flexible supporting material.
  • an electrolyte is an ionic liquid (IL) used alone or in conjunction with a polymer separator.
  • ILs are molten salts and by convention refer specifically to the salts which have melting temperatures (T m ) ⁇ 100°C.
  • ILs exhibit unique physicochemical properties, including low melting temperature, large liquid state range, high thermal stability (decomposition temperature, Tdec> 300°C), high chemical and electrochemical stability, low vapor pressure, nonflammability and high ionic conductivity. These unique characteristics are desirable for electrolytes in a variety of electrochemical devices such as batteries, super- capacitors, actuators, dye-sensitized solar cells and thermo-electrochemical cells.
  • ILs optionally include organic cations such as imidazolium, ammonium, pyrrolidinium and inorganic or organic anions such as tetrachloroaluminate (AlCLf), hexafluorophosphate (PF6 ⁇ ), tetrafluoroborate (BF 4 ⁇ ), bistriflylimide (Tf2N ⁇ ) and triflate (CF3SO3 ).
  • PILs Protic ILs
  • Ionic conductivity is of great importance for ILs to be considered as electrolytes, which is governed by the mobility of the ions and depends on the viscosity and the number of charge carriers. High ionic conductivities have been reported for ILs, from > 150 mS cm “1 at 25°C up to 470 mS cm "1 at 100 °C.
  • PILs exhibit conductivities in the range of 10 ⁇ 100 mS cm “1 at 25°C, such as methylammonium formate (MAF, 43.8 mS cm “1 ), ethylammonium nitrate (EAN, 39.6 mS cm “1 ), pyrrolidinium TFSA ([Pyr][TFSA], 39.6 mS cm “1 ) and diethylmethylammonium trifluoromethanesulfonate ([dema][TfO], 10 mS cm “1 ).
  • ionic conductivity of PILs generally increases with temperature.
  • the observed temperature dependence of ionic conductivity is not linear and conforms the empirical Vogel-Tammann-Fulcher (VTF) or Fulcher equation:
  • free-standing proton-conducting membranes based on PILs and are optionally used as an electrolyte for fuel cell applications in the intermediate temperature range of 100-200°C
  • free-standing proton-conducting membranes include [dema][TfO]/sulfonated polyimides (SPI), l-ethyl-3-methylimidazolium tetrafluoroborate (EtMeImBF4)/sulfonated poly(aryl ether ketone) (SPAEK-6F), and l-butyl-3 -methyl imidazolium triflate ([bmim][TfO])/Nafion.
  • [dema][TfO] has a high ionic conductivity of - 53 mS cm “1 at 150°C and ⁇ 10 mS cm “1 at room temperature.
  • a [dema][TfO] IL membrane and [dema][TfO]/SPI composite membranes exhibit good thermal stability (> 300°C) and high ionic conductivity (>10 mS cm "1 at 120°C).
  • Such fuel cells can successfully operate at 30 ⁇ 140°C, and a current density of 250 mA cm "2 is achieved at 120°C.
  • EtMeImBF4/SPAEK-6F composite membranes exhibit the highest ionic conductivity of - 23 mS cm "1 at 180°C and thermal gravimetric analysis (TGA) measurements show that decomposition commence at 310°C.
  • [bmim][TfO]/Nafion composite membranes were also reported to have high ionic conductivity (6 to 1 1 mS cm "1 at 150 to 180°C) and remain stable up to over 200°C.
  • Ionic liquid may optionally be used in combination with a solid electrolyte to increase the proton exchange efficiency at the anode/separator and cathode/separator interfaces.
  • the electronic resistivity of ionic liquid is not as important but the three- phase nature at interfaces has to be considered, i.e. ionic liquid should not flood the electrodes and block the movement of gas molecules.
  • an electrolyte includes or is molten salt, optionally one or more molten carbonates, which is similar to ionic liquids, with a protonic conductivities reported on the order of 10 1 S cm "1 .
  • a hybrid power cell includes a hydrogen storage alloy.
  • the hydrogen storage alloy is optionally intermixed with an anode material, physically contacting an anode material, separated from an anode material by a hydrogen conducting membrane or film, or is located remote from an anode material but in gaseous contact with the anode material.
  • FIG. 1 illustrates an embodiment where a remote hydrogen storage element is provided that includes a hydrogen storage alloy 4 in gaseous contact with an anode material 6 where gaseous contact is optionally controlled by a valve.
  • hydrogen can be readily transferred between an anode material and a hydrogen storage alloy such as in the condition of charging with power provided by an external power source (e.g. solar, wind, grid, or other).
  • an external power source e.g. solar, wind, grid, or other.
  • hydrogen can be readily transferred from a hydrogen storage alloy to an anode material in a discharge condition illustratively when the cell is functioning as a fuel cell.
  • a hydrogen storage alloy is optionally a Mg-based alloy capable of fast-rate discharge at temperatures between 200 and 250°C.
  • a hydrogen storage alloy is a Fe-doped Mg alloy that previously achieved 90% full capacity absorption (7.8 wt.%) at 240°C. US Patent Application 2005/0126663.
  • a hybrid power cell includes a hydrogen source.
  • a hydrogen source is in gaseous contact with a hydrogen storage alloy, an anode material, or both.
  • a hydrogen source is regulated by a valve that regulates the transfer of hydrogen to the hydrogen storage alloy the anode material, or both. When the valve is in the open condition it will supply hydrogen to the system or part thereof for charging or for operation as a fuel cell. When the valve is in the closed condition, the cell can operate in fuel cell mode using the hydrogen stored in the charged hydrogen alloy material or may simply function in battery mode.
  • a hydrogen source is optionally purified hydrogen.
  • a hydrogen source is optionally a rough hydrogen source.
  • an external hydrogen source will allow the hybrid power cell to function in fuel cell mode indefinitely.
  • hydrogen is supplied by the hydrogen source or the hydrogen storage alloy, or both, while the cathode is continually oxidized by a reaction with an oxygen source such as air.
  • An oxygen source is optionally connected to a cell via a conduit suitable for carrying gas.
  • a valve is present between an oxygen source and a cell body to allow for switching between fuel cell and battery modes.
  • a hybrid power cell according to the invention includes an oxidizing gas source in gaseous contact with a cathode material.
  • Oxygen is optionally supplied by a purified or substantially purified oxygen source.
  • An oxidizing gas source is optionally air.
  • the present invention when using particular cathode materials as described (e.g. mixed metal oxides) herein are capable of using air as an oxidizing gas to provide the necessary oxygen to oxidize the cathode material to a higher oxidation state (NiOOH) during a charging process.
  • NiOOH oxidation state
  • a hybrid power cell in the fuel cell mode is compatible with atmospheric-quality air.
  • the two main modes of operation for a hybrid power cell are fuel cell mode for periods when power generation via solar or wind is idle (or other low power input times), and battery mode for storing excess energy generated by solar or wind.
  • Fuel cell mode can be operated asynchronously using two sub-stacks as is traditionally done, but a single stack utilizing the direct reaction with oxygen in air simplify the overall system design may be used with the provided intermediate temperature hybrid power cell.
  • a hybrid power cell is optionally contained in a housing. Any housing suitable for containing a cell including the anode, cathode, and electrolyte may be used.
  • a housing optionally is in contact with an oxygen source and a hydrogen source, each independently via an intermediate valve.
  • the housing is optionally electrically connected to a power source such as an electrical grid, solar panel, wind power source, hydropower source, geothermal power source, or other alternative or green energy source.
  • a power source such as an electrical grid, solar panel, wind power source, hydropower source, geothermal power source, or other alternative or green energy source.
  • Known methods of including a rechargeable cell in a housing are operable.
  • the design of the intermediate temperature hybrid power cell can be assembled in a stack configuration.
  • a stack design at the device level relies in the type of electrolyte used for the electrochemical system.
  • a bipolar plate design for the stack shown in FIG. 9 is optionally used with solid electrolytes and ionic liquid-polymer gel electrolytes.
  • a mono-polar design is optionally used for an ionic liquid-based cell.
  • the bipolar plate design for the intermediate temperature hybrid power cell stack is optionally configured similar to conventional fuel cell stacks.
  • the active layers are optionally thicker, however, in order to accommodate the storage capacity of the battery-based materials may be sized to meet power requirements.
  • Table 3 Key parameters in the design of 1 kW battery/fuel cell stack.
  • the bipolar plates have multiple functions: they collect and conduct the current from cell to cell, quickly bring fuel and oxidant to the cell, and provide cooling as necessary to the stack.
  • the materials are compatible with the electrochemical environment and operating temperature.
  • Graphite-based bipolar plates are light and allow room to integrate cooling channels, and are optionally used for embodiments used in the lower end of the intermediate temperature range, e.g. 100°C to 300°C.
  • Metallic polar plates with special corrosion protective coatings such as CrN or a conductive polymer are optionally used at higher temperatures in the intermediate range such as 300°C to 700°C, which greatly reduces the weight and volume of the stack.
  • Separate cooling/heating plates with similar coatings can be integrated within the stack to minimize corrosion.
  • the gas diffusion layer acts as a landing for the fuel/oxidant (e.g. hydrogen and air) for even distribution to the active materials, and it must also be conductive of protons.
  • exemplary non-limiting GDL layers include a carbon cloth/paper material treated with a hydrophobic coating. The coating is stable at the cell operating temperatures.
  • Some specific illustrative examples of GDL include uncoated carbon fibers or high surface area carbon material with high temperature binder material such as polybenzimidazole (PBI). Surface treatments that improve conductivity/performance are optionally further included.
  • an intermediate temperature hybrid power cell excludes one or more noble metals.
  • the design of the inventive cell eliminates any need to adjust flow rates to match load response as the energy is stored locally in the electrodes.
  • the system illustrates a first sub-stack 102 and a second sub-stack 104 that are electrically connected via one or more switches 106 and also to a load 108.
  • the sub-stacks are connected to a fuel source 112 (such as for providing hydrogen or methane fuel) that is regulated for gaseous transmission to the first stack, the second stack, or both via an inlet valve 114 and optional outlet valve 116.
  • Solid lines signify gas flow whereas dashed lines signify no fuel flow.
  • An oxidizing gas 118 e.g. air or other oxygen source
  • valve 120 and optional outlet valve 122 Other features such as separate hydrogen storage can also be integrated.
  • the system can operate in two modes: fuel cell mode (FIG. 10A and B) and battery mode (FIG. 11A and B).
  • the stack includes two sub-stacks 102, 104 wired in parallel that operate asynchronously depending on the charge- discharge cycle of each sub-stack. While one sub-stack is fueling and charging via air oxidation, the other sub-stack has already been charged and provides power essentially as a battery, essentially as shown in FIG. 10A. There are no flow controls necessary to handle the load, but the timing of the charging sub-stack is controlled to match the discharge time of discharging sub- stack.
  • the system switches the load over to the newly charged sub-stack, and fuel and air are provided to charge the depleted stack as shown in Fig. 10B.
  • This asynchronous mode of operation allows the batch-mode battery charging process to be operated continuously, but it could also be possible to operate continuously using a single stack, where one end of the electrode is fueled/air-oxidized, which is fast enough for protons to move to the active layer-electrolyte interface to react and provide power thereby simplifying the system design.
  • the full stack or the individual sub-stacks can be utilized during battery-mode operation, which shows the stack charging via electricity generated by an outside source 124 in FIG. 11A and discharging in FIG. 11B.
  • Battery mode is useful to store excess energy from renewable energy sources such as solar or wind. Also, during periods of low sun or wind, the system can be switched to fuel cell mode to provide uninterrupted, continuous power.
  • the hybrid power cell as provided is its ability to handle dynamic loads and transients essentially as a battery. While there is an increased weight contribution from the storage materials to the stack, the materials are in a form that is electrochemically favorable for high power capability without the high cost of noble metals. There is also no need to adjust flow rates to match load response in this type of system, as the energy is stored locally in the electrodes.
  • Patents, publications, and applications mentioned in the specification are indicative of the levels of those skilled in the art to which the invention pertains. These patents, publications, and applications are incorporated herein by reference to the same extent as if each individual patent, publication, or application was specifically and individually incorporated herein by reference.

Abstract

L'invention porte sur une pile électrique hybride qui combine une batterie au nickel-hydrure métallique, un stockage d'hydrogène à l'état solide et des technologies de pile à combustible alcaline dans une pile unique fonctionnant à l'intérieur d'une plage de température intermédiaire ciblée. Une pile comprend une cathode qui est apte à utiliser de l'air atmosphérique brut en tant que source d'oxygène et une anode qui est apte à un stockage d'hydrogène en phase gazeuse et électrochimique réversible, l'anode et la cathode étant hautement fonctionnelles à des températures intermédiaires. La pile électrique hybride résultante permet de résoudre les problèmes antérieurs de stockage d'énergie connecté au réseau à haute capacité fiable nécessaire pour une plus grande adoption d'énergie renouvelable.
PCT/US2015/025673 2014-04-14 2015-04-14 Système de pile à combustible de batterie hybride à électrode partagée WO2015160751A1 (fr)

Applications Claiming Priority (4)

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US14/252,012 US20150295290A1 (en) 2014-04-14 2014-04-14 Shared electrode hybrid battery-fuel cell system
US14/251,962 US9343735B2 (en) 2014-04-14 2014-04-14 Shared electrode hybrid battery-fuel cell system
US14/251,962 2014-04-14
US14/252,012 2014-04-14

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JP2017220414A (ja) * 2016-06-10 2017-12-14 三菱電機株式会社 電力貯蔵デバイス
CN110247136A (zh) * 2019-05-28 2019-09-17 武汉环达电子科技有限公司 一种封闭式水下铝燃料电池能源系统
CN113067023A (zh) * 2021-03-05 2021-07-02 常州大学 一种高温复合质子交换膜及其制备方法

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JP2000036308A (ja) * 1998-07-16 2000-02-02 Toyota Motor Corp 燃料電池システム
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JP2017220414A (ja) * 2016-06-10 2017-12-14 三菱電機株式会社 電力貯蔵デバイス
CN110247136A (zh) * 2019-05-28 2019-09-17 武汉环达电子科技有限公司 一种封闭式水下铝燃料电池能源系统
CN113067023A (zh) * 2021-03-05 2021-07-02 常州大学 一种高温复合质子交换膜及其制备方法

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