WO2012007727A1 - Pile à combustible - Google Patents

Pile à combustible Download PDF

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Publication number
WO2012007727A1
WO2012007727A1 PCT/GB2011/001073 GB2011001073W WO2012007727A1 WO 2012007727 A1 WO2012007727 A1 WO 2012007727A1 GB 2011001073 W GB2011001073 W GB 2011001073W WO 2012007727 A1 WO2012007727 A1 WO 2012007727A1
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WIPO (PCT)
Prior art keywords
fuel cell
ammonium
anode
urea
membrane
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PCT/GB2011/001073
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English (en)
Inventor
Shanwen Tao
Rong LAN
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University Of Strathclyde
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Publication of WO2012007727A1 publication Critical patent/WO2012007727A1/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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • H01M8/222—Fuel cells in which the fuel is based on compounds containing nitrogen, e.g. hydrazine, ammonia
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
    • C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • C08J5/2281—Heterogeneous membranes fluorine containing heterogeneous membranes
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • 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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for using a fuel cell, in particular a fuel cell comprising a cation exchange membrane, which consumes urea, ammonia, or a salt of these compounds as fuel to generate electricity.
  • the invention also provides a method of powering an apparatus by harnessing the electricity generated from operating a fuel cell according to a method of the invention.
  • Fuel cell technology is now well recognised as having the potential to help address the energy crisis as the world's finite supply of fossil fuels becomes exhausted. Thus the application of fuel cell technology is likely to play a pivotal role in combating both the looming energy crisis and also climate change.
  • a fuel cell is an electrochemical apparatus that generates electricity from fuel and oxidant supplied to it.
  • the fuel is consumed and electrons are generated on the anode side.
  • the electrons generated are forced through an external circuit to the cathode where they react with the oxidant, typically oxygen present in air.
  • the anode and cathode are separated by an electrolyte but connected by an external circuit through which the electrons generated flow from anode to cathode, thereby allowing electrical power to be harnessed.
  • PEMFCs employ an acidic proton-conductive polymeric membrane, typically a cast or extruded film of appropriate thickness to provide mechanical barrier properties (so as to separate the cathode and anode) yet allowing rapid transport of protons.
  • the most well known membrane used in PEMFCs is DuPont's NafionTM, a poly-sulfonated perfluoropolymeric material described in US Patent No. 3,718,627 (to Grot et a/.).
  • the second category into which many fuel cells fall does not rely on the passage of protons through the electrolyte but rather the passage of hydroxide anions.
  • the "classic" alkaline fuel cell was developed by Francis Bacon (and so is sometimes referred to as the Bacon fuel cell) and comprises a liquid alkaline electrolyte, such as potassium hydroxide, typically saturated within a porous non-electrolytic support.
  • a solid membrane i.e. a hydroxide anion exchange membrane
  • alkaline fuel cell is used primarily in the art to refer to Bacon fuel cells. Given this, there appears to be less consensus as to how to refer to "solid-state alkaline fuel cells” although alkaline membrane fuel cells (AMFCs) is an accurate description.
  • PEMFCs use hydrogen as the fuel from which protons and electrons are generated at the anode, since the ability to generate protons at the anode is a requirement in PEMFCs - direct methanol fuel cells for example generating protons, electrons and carbon dioxide at the anode from methanol and water - the ability to provide a on-board hydrogen storage facility persists as a challenge and as a limitation to the use of fuel cells in transport applications.
  • Hydrogen can be stored in low molecular weight compounds such as ammonia, methane and methanol, which molecules contain 17.6, 25.0 and 12.5 wt% hydrogen respectively. Hydrogen can also be stored in urea. Notably the energy density of liquid ammonia in particular is very high.
  • hydrogen- and nitrogen containing compounds may be used directly in fuel cells comprising a PEM, and in which a fuel-side catalyst serves to produce protons and electrons from the fuel, the protons passing through the PEM to the cathode.
  • alkaline fuel cells comprise an electrolyte interposed between cathode and anode constituted by an aqueous alkaline solution, e.g. potassium hydroxide present as a solution within a porous matrix.
  • aqueous alkaline solution e.g. potassium hydroxide present as a solution within a porous matrix.
  • urea as a fuel source for fuel cells appears to have been even less reported than has ammonia.
  • US Patent No. 7, 140, 187 (infra) describes a method and apparatus for generating energy from a composition comprising urea and water.
  • the urea is used to provide either ammonia or hydrogen which are either oxidised to form water and energy or the ammonia is reformed to nitrogen and hydrogen the hydrogen component of which is then oxidised to form water and energy.
  • Mention is made of the oxidation of urea in an urea fuel cell either at a temperature of about room temperature to about 200°C or in a solid oxide fuel cell or molten carbonate fuel cell operating at a temperature between about 700°C and about 1000°C.
  • Urea is a non-toxic low-cost industrial product which is widely used as fertiliser. It can be synthesised from ammonia produced from natural gas or coal in large quantities.
  • AdBlue a 32.5% urea solution developed by Europe's AdBlue urea-selective catalytic reduction (SCR) project, is available worldwide to remove NO x generated by diesel powered vehicles. Despite the widespread availability of urea, there is currently no technology able to generate electricity from urea or AdBlue.
  • the present invention is based upon the surprising finding that a fuel cell comprising a solid membrane capable of permitting and based on the principle of transport of ammonium ions may be operated through the direct use of urea, ammonia, or a salt of either of these as the fuel.
  • This finding is surprising not only given the sparsity of reports of direct fuel cells based on these substrates and the emphasis, where ammonia has been used, on its use as an indirect fuel for fuel cells using PEMFC technology, but also the more recent disclosures of alkaline fuel cells or fuel cells based on solid alkaline membranes for operation of the fuel cells.
  • the present invention is based upon the use of cation exchange membranes as an electrolyte for the transport of ammonium ions been the anode and cathode of a fuel cell, as opposed to the transport of protons, upon which principle all PEMFCs are based.
  • the invention is of particular utility in relation to the use of ammonium or urea salts since these non-hazardous materials may be easily manipulated in either solid form, or dissolved or otherwise manipulated in liquid media.
  • the invention is of particular utility in relation to the use of urine since this natural product provides an abundant supply of fuel that may be used according to the present invention.
  • an anodic catalyst comprises nano-sized metal, metal alloy, metal oxide, metal carbide or metal nitride particles, or mixtures of the foregoing.
  • a method of operating a fuel cell that comprises a solid cation exchange membrane, the method comprising contacting an anode in the fuel cell with urine, an ammonium salt or a urea salt and contacting the cathode with an oxidant whereby to generate electricity.
  • a method of operating a fuel cell that comprises a solid cation exchange membrane, the method comprising contacting an anode in the fuel cell with ammonia, urea, or an ammonium or a urea salt and contacting the cathode with an oxidant whereby to generate electricity, wherein the anode comprises nano-sized metal, metal alloy, metal oxide, metal carbide or metal nitride particles or is absent an elemental metallic catalyst.
  • the invention provides a method of powering a device comprising carrying out a method of operating a fuel cell according to the first or second aspects of the present invention, and using the electricity generated thereby to power to the device.
  • the invention provides the use an ammonium salt, a urea salt or urine as a direct fuel for a fuel cell that comprises a cation exchange membrane.
  • the invention provides use of a cation exchange membrane in a fuel cell for which the direct fuel is an ammonium salt, a urea salt or urine.
  • Fig. 1 (a) shows a schematic diagram of the operating principal (working mechanism) of a direct aqueous ammonia fuel cell of the present invention showing ammonium ions passing across the cation exchange membrane.
  • Fig. 1 (b) shows a schematic diagram of the operating principal (working mechanism) of a direct ammonium carbonate fuel cell of the present invention showing ammonium ions passing across the cation exchange membrane.
  • Fig. 2 shows the fuel cell performance at the temperature indicated of a fuel cell (Cell A) , the preparation of which is described below, using as fuel a 35 wt% ammonia solution, 1 M ammonium carbonate solution and urine.
  • Fig. 3(a)-(c) and Fig. 4(a)-(b) show the fuel cell performance at room
  • Cell B a fuel cell (Cell B), the preparation of which is described below, using a variety of fuels.
  • Fig. 5(a)-(c) and Fig. 6(a)-(c) show the fuel cell performance at 40 °C of a fuel cell (Cell B), the preparation of which is described below, using a variety of fuels.
  • Fig. 7(a)-(c) and Fig. 8(a)-(c) show the fuel cell performance at 60 °C of a fuel cell (Cell B), the preparation of which is described below, using a variety of fuels.
  • Fig. 9(a)-(c) and Fig. 10(a)-(c) show the fuel cell performance at 80 °C of a fuel cell (Cell B), the preparation of which is described below, using a variety of fuels.
  • Fig. 11 (a)-(d) and Fig. 12(a)-(c) show the fuel cell performance at room temperature (20 °C) of a fuel cell (Cell C), the preparation of which is described below, using a variety of fuels.
  • Fig. 13(a)-(d) and Fig. 14(a)-(c) show the fuel cell performance at 80 °C of a fuel cell (Cell C), the preparation of which is described below, using a variety of fuels.
  • the various aspects of the present invention each arise from the recognition that fuel cells that comprise solid cation exchange membranes, and operated using ammonia, urea, or an ammonium or urea salt supplied directly to the fuel cell as the reactant fuel operate by transfer of ammonium ions across the cation exchange membrane.
  • direct fuel is meant herein the material that is actually supplied to the fuel cell.
  • typical fuel cells comprises an anode and a cathode in electrical communication through an external circuit, the anode being provided with a catalyst capable of catalysing the oxidation of the fuel and the cathode being provided with a catalyst capable of catalysing the reduction of the oxidant.
  • fuel cells are provided with an electrolyte, in the present invention a solid cation exchange membrane, serving to separate physically the oxidation and reduction reactions that take place at the anode and cathode.
  • the electrolyte membrane is a solid, it together with the electrodes and associated catalysts make up what is referred to in the art as a so-called membrane electrode assembly (MEA).
  • MEA membrane electrode assembly
  • the electrode material of the MEA comprises carbon (e.g. carbon cloth, felt or carbon paper) in or on which the catalyst is applied. However, this may be omitted, with an electrode formed of a metal/metal-containing compound (e.g. a metal oxide) absent carbon.
  • carbon e.g. carbon cloth, felt or carbon paper
  • a metal/metal-containing compound e.g. a metal oxide
  • FIGs 1 (a) and (b) Schematic diagrams of the operation of direct ammonia and direct urea fuel cells of the invention, based on use of the ammonium ion as electrolyte, are depicted in Figs 1 (a) and (b) respectively.
  • the working mechanism of fuel cells of the invention based on the transport of ammonium ions is slightly different from those that use hydrogen as the fuel.
  • ammonium ions are produced as a consequence of the disproportionation of ammonia in aqueous solution, or may be provided in the form of an ammonium salt.
  • urea or urea salts are employed as fuel, ammonium ions are generated by disproportionation of ammonia generated upon hydrolysis of the urea.
  • the OCV of a fuel cell is higher than 0.82 V, as is shown in Fig. 2.
  • urea or a urea salt is used as fuel
  • its hydrolysis whereby to provide ammonia and carbon dioxide serves to provide ammonia, and thus ammonium ions by disproportionation in aqueous media in situ that transfer across the membrane in the form of ammonium ions.
  • the hydrolysis of urea is driven by the consumption of ammonia in this way during operation of the fuel cell.
  • a characteristic feature of the present invention is the use of a solid cation exchange membrane.
  • the methods of the present invention are thus distinguished from methods in which an alkaline electrolyte is present in solution or as a liquid.
  • solid cation exchange membrane is meant a solid electrolyte membrane capable of permitting transport of cationic ammonium ions from a first face of the membrane to a second face of the membrane.
  • Such membranes are approximately 1 to 500 pm thick, e.g. about 10 to 250 pm thick.
  • a large number of appropriate solid membranes are suitable such as commercially widely available cation exchange polymers and resins used in industrial water purification, metal separation and catalytic applications, as well as cation exchange membranes, including sulfonated fluoropolymers, such as NafionTM, used in PEMFCs.
  • cationic exchange membranes may be used without pre-conversion to an ammonium-ion containing form. This may be for one of two reasons.
  • the cation exchange resin may be available, e.g. commercially in an ammonium-containing form.
  • An example of this is the ammonium salt of polystyrene sulfonate, available commercially from Aldrich Chemical Co. (and which may be made from the reaction between sulfonated polystyrene and ammonia solution).
  • the cation exchange resin it may be possible for the cation exchange resin to be capable of conducting ammonium ions without initially comprising ammonium ions itself.
  • a cation exchange membrane which does not comprise ammonium ions, may be used as a or the solid cation exchange membrane according to the various aspects of this invention is constructed, this is not particularly limited.
  • materials from which existing PEMs are made, and which thus serve as electrolytic membranes for proton transport may be used.
  • electrolytic membranes for proton transport There are a very wide variety of such membranes and these have been reviewed by B Smitha ef al. (J. Membrane Sci., 259 10-26, (2005)).
  • the membrane may comprise a cation exchange polymer comprising covalently bound anions and associated cations.
  • sulfonated polymers including copolymers
  • fluoropolymers such as sulfonated perfluorinated polymers
  • archetypal sulfonated perfluorinated polymers being Nafion itself.
  • useful sulfonated fluoropolymers may be defined as copolymers of (i) a first monomer that comprises a sulfonate group and is partially or perfluorinated and (ii) a second monomer that is partially or perfluorinated, for example wherein the first monomer is a sulfonate-terminated perfluorovinyl ether and the second monomer is tetrafluoroethylene.
  • sulfonated polymers examples include £>/s(perfluoroalkylsulfonyl) imide (PFSI), sulfonated ⁇ , ⁇ , ⁇ -trifluorostyrene-grafted PTFE, styrene-grafted poly(vinylidine fluoride) and sulfonated poly(ether ketone) (SPEEK) as well as Nafion itself, which is a copolymer of a sulfonate-terminated perfluorovinyl ether and tetrafluoroethylene.
  • PFSI perfluoroalkylsulfonyl imide
  • SPEEK sulfonated poly(ether ketone)
  • sulfonated polymers may be in either acid or salt form (i.e. comprising sulfonic acid group or sulfonate salt such as sodium or potassium salt). Whether in acidic or salt form, such sulfonated polymers may be regarded and are described herein as permanently charged polymers.
  • Either the acidic or salt form, or a mixture, of cationic exchange membranes, e.g. of sulfonated polymeric cationic exchange membranes may be used as a or the material for the ammonium containing membrane according to this invention. In this case when the fuel cell is operated and ammonium ions are either generated (e.g.
  • ammonium ions will gradually substitute the protons (e.g. of sulfonic acid groups) or other cations (e.g. sodium or potassium ions of sulfonate esters).
  • ammonium ion-containing membranes As an alternative to constructing the membrane from a cation exchange membrane that does not contain ammonium ions as cations, it is possible to generate ammonium ion-containing membranes by treating cation exchange membranes with either gaseous or aqueous ammonia or by immersion in an ammonium salt solution. This may be achieved as described hereinbelow, and/or by R Halseid et al. (infra). For example cation exchange membranes may be immersed in an ammonium chloride solution for a period between about 1 hour and about 7 days, e.g. about 24 to about 48 hours, followed by optional washing with deionised water. Typically the solid cation exchange membrane will comprise at least a proportion of ammonium ions as cations within the membrane.
  • the cations will be ammonium ions, typically at least 10% or 20%. Generally at least 50% of the cations will be ammonium ions and in some embodiments substantially all, for example 80 to 100% or 95% to 100% of all cations will be ammonium ions. The co-existence of other ions such as protons, or sodium or potassium ions may be tolerated in the membrane.
  • the membrane will consist essentially of ammonium ions.
  • the membrane will comprise little or no hydrogen ions, for example associated with the acidic form of sulfonated polymers. For example, in such embodiments, the less that 10% of the cations within the solid membrane will be hydrogen ions, typically less than 5%, for example between about 0%, or 0.5% and 2% hydrogen ions.
  • the membrane need not be a cation conductor comprising only ammonium ions as the cations initially present.
  • a mixed cation- conducting membrane that includes ammonium ions can be used.
  • a membrane containing NH 4+ /H + , NH + /Na + or NH 4+ /H + /Na + (for example mixed cation NafionTM) can be used as electrolyte for the present invention.
  • Inorganic NH 4 + ion-conducting materials may also be used as the solid cation exchange membrane.
  • Such materials include ammonium (or ammonium/hydronium) ⁇ -alumina; ammonium (or ammonium/hydronium) ⁇ '-alumina, ammonium (or ammonium/hydronium) ⁇ ''-alumina.
  • solid cation exchange membranes may be constituted by blends of different polymers.
  • the membrane may be a homogeneous ammonium exchange membrane (made only from ammonium ion exchanging material) or a heterogeneous cation exchange membrane (made from ammonium ion exchanging and non-exchanging materials).
  • a satisfactory combination of function e.g. ammonium ion conductivity
  • mechanical properties may suitably be provided by providing a mixture of materials, one or more of which provides the desired ammonium ion-conducting functional property and one or more further components of which provide appropriate mechanical strength or other polystyrene properties.
  • solid cation exchange membranes useful in the present invention may be provided that are heterogeneous ammonium ion exchange membranes, comprising mixtures of ammonium ion- conducting polymers, such as those described hereinbefore, and other polymers not having such ammonium ion conducting properties, e.g. neutral polymers such as PVC, polyvinyl alcohol) PVA, PEG, polyvinyl benzene) (PVB), high density polyethylene (HDPE) or low density polyethylene (LDPE), PTFE and PVDF.
  • the neutral polymers may be PVC, polyvinyl alcohol) PVA, PEG, polyvinyl benzene) (PVB), PTFE and PVDF.
  • an inorganic ammonium ion conducting material including those discussed infra
  • such a material can be mixed with an organic material such as PVDF, PTFE, PVA, high density polyethylene (HDPE) or low density polyethylene (LDPE) to form a composite then casting a membrane to conduct ammonium ions.
  • an organic material such as PVDF, PTFE, PVA, high density polyethylene (HDPE) or low density polyethylene (LDPE)
  • neutral polymer a polymer without anions (or cations) covalently bound to the polymer.
  • ammonium ion conducting membranes produced by blending cation exchange resin or polymers, and PVA in w/w ratios from about 20:80-80:20 (typically from about 40:60 to about 60:40 e.g., about 50:50) have suitable membrane strength and ammonium ion transport capabilities.
  • the invention provides a solid cation exchange membrane comprising a blend of a cation exchange polymer (e.g. a cation exchange polymer at least a proportion of the cations within the membrane are ammonium ions, for example, wherein at least 5%, typically at least 10%, 20% or 50% and in some embodiments substantially all, for example 80 to 100% or 95% to 100% of all cations are ammonium ions) and PVA in w/w ratios from about 20:80-80:20 (typically from about 40:60 to about 60:40, e.g. about 50:50).
  • a cation exchange polymer e.g. a cation exchange polymer at least a proportion of the cations within the membrane are ammonium ions, for example, wherein at least 5%, typically at least 10%, 20% or 50% and in some embodiments substantially all, for example 80 to 100% or 95% to 100% of all cations are ammonium ions
  • PVA in w/w ratios from about 20:
  • ammonium ion exchange membrane As an alternative to or in addition to the use of permanently charged polymers, e.g. having covalently bound anions such as sulfonate/sulfonic acid groups, it is also possible as the ammonium ion exchange membrane to use solid polymeric materials doped with ammonium salts, for example, ammonium chloride, nitrate, sulfate, acetate, oxalate, bicarbonate, carbonate or carbamate, e.g., according to certain embodiments, ammonium carbonate or ammonium hydrogen carbonate.
  • ammonium salts for example, ammonium chloride, nitrate, sulfate, acetate, oxalate, bicarbonate, carbonate or carbamate, e.g., according to certain embodiments, ammonium carbonate or ammonium hydrogen carbonate.
  • polymers such as poly(sulfone-ether)s, polystyrene, vinyl polymers, such as polyvinyl chloride) (PVC), poly(vinylidene fluoride) (PVDF), poly(tetrafluoroethylene) (PTFE) and poly(ethyleneglycol) (PEG) may be doped with ammonium salts in this way, e.g. by casting a liquid mixture of one or more polymers and one or more ammonium salts such as ammonium carbonate or ammonium hydrogen carbonate, onto a glass plate and evaporating the solvent(s).
  • PVC polyvinyl chloride
  • PVDF poly(vinylidene fluoride)
  • PTFE poly(tetrafluoroethylene)
  • PEG poly(ethyleneglycol)
  • ammonium salts such as ammonium carbonate or ammonium hydrogen carbonate
  • the membrane may also comprise an inorganic material, such as titanium or silicon dioxide, e.g. as particles therefore dispersed through the membrane.
  • an inorganic material such as titanium or silicon dioxide, e.g. as particles therefore dispersed through the membrane.
  • PVA-Ti0 2 material described by CC Yang (J Memb. Sci., 288, (2007), 51 -16).
  • the present invention is, because the fuel cell relies upon ammonium ion exchange instead of proton exchange, the use of this non-acidic electrolyte lessens the dependence on, and indeed can avoid the use of, noble metal catalysts in the construction of the anode and cathode in the fuel cells. This is because other catalysts, that cannot withstand exposure to the strong acidic environment in PEMFCs, can be used in the generally more benign environment of membranes transferring ammonium ions.
  • platinum- and palladium-based (particularly platinum-based, including platinum- and platinum/ruthenium-based) catalysts can be used as the both the anode and cathode when practising the methods according to the present invention, such expensive and rare metal can be avoided according to the present invention, with the electrodes made instead of non-precious catalysts such as nickel and silver.
  • Appropriate materials which may be used as the catalyst at the anode include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, rhodium, platinum, palladium, tantalum, tungsten, bismuth, tin, antimony, lead, and metal alloys, oxides, nitrides or carbides of any of the foregoing, such as metal nitrides, e.g. chromium nitride or cobalt molybdenum nitride (e.g. C0 3 M0 3 N), molybdenum carbide, platinum and platinum/ruthenium.
  • metal nitrides e.g. chromium nitride or cobalt molybdenum nitride (e.g. C0 3 M0 3 N), molybdenum carbide, platinum and platinum/ruthenium.
  • the anode catalyst may be a composite material comprising nickel, zinc and phosphorus, optionally with one or more other metals, such as iron, cobalt, tin or aluminium, upon which is deposited a single noble metal selected from palladium, platinum, rhodium, ruthenium, iridium, gold or silver, or a binary alloy of any of the foregoing, as described in WO 2008/116930 (Acta SpA).
  • the catalyst present at the cathode may be made of similar materials as those from which the anodic catalyst may be manufactured; particular materials that may be suitable include copper, nickel, nickel-containing alloys, aluminium-containing alloys, nickel-containing oxides such as lithium nickel oxide, lithium manganese oxide and lithium cobalt oxide; chromium nitride, molybdenum carbide, silver, silver-containing alloys such as nickel-silver alloys and manganese dioxide, for example, nickel, nickel- containing oxides such as lithium nickel oxide, lithium manganese oxide and lithium cobalt oxide; chromium nitride, molybdenum carbide, silver and manganese dioxide.
  • manganese dioxide understood by those skilled in the art to refer to Mn (IV) oxide, other manganese oxides, or mixtures of manganese oxides may also be used, such as Mn (lll/IV) oxide and Mn (ll/lll) oxide.
  • EMD electrolytic manganese dioxide
  • the anodic or cathodic catalyst may be a catalyst free of a platinum group metal and of the type described in WO 2009/124905 (Acta SpA).
  • macrocyclic N4-chelates of transition metals on porous carbon materials may be heat-treated in the presence of a nitrogen- or sulfur-containing compound and an electronic conducting porous carbon support whereby to provide supported catalysts, in particular where the N4-chelates used are a blend of an iron (II) or iron (III) phthalocyanine and a copper (II) or cobalt (II) phthalocyanine.
  • Non-precious metal composite catalysts such as cobalt-polypyrrole- carbon (Co-PPY-C) can also be used as cathode in the fuel cell (see R. Bashyam, Nature, 443 (2006) 63-66).
  • Electrodes in perovskite, K 2 NiK 4 , spinel or other structure such as La 2 Ni0 4+5 etc. are widely used as electrodes for solid oxide fuel cells and molten carbonate fuel cells. Since ammonium- conducting membranes are much less acidic than conventional acidic proton exchange membranes, the skilled person will be able to readily assess the suitability of such oxides, and use these as appropriate, in accordance with the present invention. Some of these oxides can thus be used as both anode and cathode catalysts in accordance with the present invention.
  • the catalysts can be used in the form of powders, mesh, foam or powders with a conducting medium such as carbon powder, carbon paper, carbon clothes, nickel foam see (F Bidault et al. (Inter. J. Hydrogen Energy, 34 (2009) 6799-6808); and 35 (2010) 1783-1788)).
  • a conducting medium such as carbon powder, carbon paper, carbon clothes, nickel foam see (F Bidault et al. (Inter. J. Hydrogen Energy, 34 (2009) 6799-6808); and 35 (2010) 1783-1788)).
  • the anode may be formed by mixing, with carbon, nano-sized particles comprising the catalytic materials described above, including nano-sized particles of metals, metal alloys, metal oxides, metal carbides and metal nitrides. Mixtures of such nano-sized particles may also be used.
  • the anode may be formed from such nano-sized particles without carbon (for example by omitting the carbon from the ink used for the anode described in the preparation of Cell A below).
  • nano-sized particles is meant herein particles having sizes in the range of 1 to 100 nm, for example 1 to 10 nm, since such small particles sizes increase the specific surface area available for catalysis of a given amount of material.
  • nano-sized metal particles are nickel particles of approximately 2 nm in diameter (for example about 1 to 3 nm in diameter) as measured by TEM.
  • Such nanoparticles may be prepared generally in accordance with the teachings of S Lu ei al. (infra). Sizes may be established by use of transmission electron microscopy. The procedure described by Lu et al. may be varied by inclusion of Na 3 C 6 H 5 0 7 -2H 2 0 when preparing the nano-sized nickel particles. We find the particles may be dried at room temperature.
  • the anode may be formed of nano- sized particles of metals, e.g. nano-sized particles elemental metal such as nickel (optionally and typically mixed with carbon), we have also found an elemental metallic catalyst is not required.
  • noble metal catalysts such as ruthenium, rhodium, palladium, osmium, iridium and platinum be reduced or avoided, as discussed infra, in the construction of, inter alia, the anode of the fuel cells, but elemental iron, cobalt, nickel, copper, silver and gold, or combinations thereof, or combinations of any of the foregoing metals with ruthenium, may also be reduced or avoided.
  • the cathode may be constituted by a mixture of carbon and nano-sized manganese dioxide particles.
  • the cathode may be formed from such nano-sized particles without carbon (for example by omitting the carbon from the ink used for the cathode described in the preparation of Cells A and B below), Appropriate particles can be prepared in accordance with the teachings of C Xu et al. (J. Power Sources, 180 (2008) 664-670).
  • the resultant manganese dioxide particles provide advantageously higher surface area over manganese oxide prepared by other methods.
  • no elemental metallic catalyst is required at the cathode. That is to say, not only may the use of noble metal catalysts, such as ruthenium, rhodium, palladium, osmium, iridium and platinum be reduced or avoided, but elemental iron, cobalt, nickel, copper, silver and gold, or combinations thereof, or combinations of any of the foregoing metals with ruthenium, may also be reduced or avoided. Also, we have found that not only may metallic catalysts be avoided at the cathode, but also metal-containing catalysts may also be omitted at the cathode whilst still permitting operation of fuel cells according to the present invention.
  • noble metal catalysts such as ruthenium, rhodium, palladium, osmium, iridium and platinum be reduced or avoided, but elemental iron, cobalt, nickel, copper, silver and gold, or combinations thereof, or combinations of any of the foregoing metals with ruthenium, may also be reduced or avoided.
  • metallic catalysts
  • the present invention relies upon the direct supply to the cation-conducting membrane of ammonium ions. These may be supplied as the ammonium ions present in ammonium salts, which may be supplied in solid or liquid (e.g. aqueous) form. Typically urea, urea salts (such as the commercially available urea phosphate) and ammonia will be supplied as aqueous solutions of any convenient concentration. Accordingly the present invention is distinct from prior art in which the use of these chemicals as fuels is described where one of these compounds is initially reformed, e.g. to provide hydrogen, which is the fuel that is supplied to and consumed directly by the fuel cell.
  • ammonia is used as the fuel with which the fuel cell is fed this may be provided as an aqueous solution of ammonia, for example at concentrations of from about 0.001 M to that at which the solution is saturated.
  • Aqueous solutions of the ammonia may be generated from a source of liquid ammonia if this is convenient. This may be mixed with water whereby to provide the desired aqueous ammonia. The water may be provided from an outside source or generated within the fuel cell itself.
  • solutions of ammonium salts such as ammonium chloride, nitrate, sulfate, acetate or oxalate may be used.
  • ammonium salts comprising an ion that yields carbon dioxide, such as ammonia bicarbonate, ammonium carbonate and ammonium carbamate, may be used in accordance with this invention.
  • Concentrations of ammonium or urea salts, or urea may range from about 0.001 M to that at which the solution is saturated, or even higher, thereby providing aqueous slurries, pastes or gels of the salts.
  • the fuel supplied to the fuel cell is an aqueous solution of an ammonium salt, e.g.
  • urea is used as a fuel
  • concentration at which it may be used there is no particular upper or lower limit to the concentration at which it may be used; any convenient concentration could be used, for example from about 0.001%, 0.01% or about 1% w/v, or about 10% w/v, up to the concentration at which an aqueous solution of urea is saturated.
  • formulations other than solutions of urea could be employed such as slurries, pastes or gels (typically with water as continuous phase) with these being manipulated into the fuel cell by use of a suitable pumping apparatus.
  • urea As is known commercial urea is often accompanied by certain contaminants and the term "urea" is not intended to require the presence of urea in the absence of these contaminants, which can include one or more of ammonia carbamate, carbonate, bicarbonate, formate and acetate.
  • a particularly convenient aspect of the present invention is that there are preexisting commercial distribution networks that exist for the supply of urea and ammonium bicarbonate for use in agriculture as a fertiliser and as an additive to trap nitrous oxide in automobiles.
  • Ammonia is also a commonly used industrial and agricultural chemical that can be handled safely.
  • An example of a commercially available urea solution, suitable for use according to the present invention is that available commercially as a 32.5% solution in water sold under the trade name AdBlue, a pure aqueous solution of urea used in commercial diesel vehicles for the removal of nitrous oxide.
  • urea fuel cells can use urine as the fuel.
  • urine a product of human/animal excretion
  • an energy source for every adult producing 1.5 litres of urine per day, containing 2wt % urea, 11 kg of urea is produced each year. This is equivalent to the energy in 18 kg of liquid hydrogen that can be used to drive a car for 2700 km.
  • the present invention thereby also allows a method of removing the primary nitrogen-containing and principal solid component - urea - from urine, whilst generating electricity, providing twin environmental benefits.
  • Suitable apparatus for delivery in the case of ammonia by way of steel or stainless steal conduits, such as tubes, will be evident to those skilled in the art.
  • those skilled in the art will be aware of how to construct apparatus that allow manipulation of solutions of ammonia salts or of urea or urea salts, for example.
  • the fuel may be introduced by gravity feed or by pumping.
  • the oxidant may be any convenient oxygen-containing species. Conveniently, and typically, the oxidant may be oxygen itself, and may be conveniently supplied within air. Alternatively, purified oxygen may but need not necessarily be used. The oxidant may be gaseous or liquid. In theory, the effect of carbon dioxide in air at the cathode is negligible.
  • the present invention may be used to operate a single fuel cell or a fuel cell stack.
  • a fuel cell stack is a plurality of fuel cells configured consecutively or in parallel, so as to yield either a higher voltage or allow a stronger current to be drawn.
  • the present invention contemplates the use of fuel cell stacks in practising the methods and according to the other embodiments of the present invention.
  • the present invention is of use in allowing generation of electricity for supply to a variety of devices, which may be stationary or non-stationary.
  • the device may or may not, but typically does, comprise the fuel cell, or fuel cell stack, operated according to the present invention.
  • Stationary devices may be non-portable devices such as fixed machinery or, more typically, portable devices such as mobile telephones, digital cameras, laptop computers or portable power packs where use of the present invention may allow the replacement or complementing of existing battery technology.
  • the methods may be used to power non- stationary devices such as vehicles, e.g. cars.
  • Further examples of specific embodiments of the invention include under-water vehicles such as submarines, and rocket and other aeronautical applications.
  • the invention can also be used to clean up municipal waste water and generate electricity. Based on this invention, it is possible to develop renewable and sustainable urine fuel cells.
  • the invention thus provides for direct urea or urea salt, or ammonia or ammonium salt fuel cells, which may be use low-cost non-noble catalysts such as nickel, silver and manganese oxides such as Mn(IV)oxide, or even no catalyst at all.
  • non-noble catalysts such as nickel, silver and manganese oxides such as Mn(IV)oxide, or even no catalyst at all.
  • high power density need not be a determinative requirement if the cost of the cell itself is low.
  • High power can be achieved by using enlarged fuel cell area or stacks with increased numbers of single cells.
  • the methods of the present invention may be practised at temperatures as low at about ambient temperature (about 20 to 25 °C) up to about 150-250 °C, Typically the methods are practised at temperature in the range of about 5 to about 250 °C, e.g. 15 to about 150 °C. In certain embodiments the method may desirably be practised at temperature more than about 20°C, more than about 50°C or more than about 80 °C.
  • poly-tetraflurorosulfonic acid polymer film (NafionTM 211 membrane from DuPont, thickness about 25.4 ⁇ ) was treated with an organic base such as gaseous or aqueous ammonia to replace the H + groups by NH + groups of the polymer film.
  • Ammonia gas is difficult to handle on account of its toxicity and for ease of handling the NAFIONTM film was immersed for 30 minutes in a 35 wt% ammonia solution (Fisher Scientific Co)
  • the thus-treated membrane can be stored in ammonia solution for future use.
  • the NH 4 + -form membrane can be washed with water several times before using for an MEA.
  • Ammonium salts such as (NH 4 ) 2 C0 3 , NH 4 HCO3, NH 4 N0 3 , (NH 4 ) 2 S0 4 , NH 4 CI, (NH 4 ) 3 P0 4 etc may also be used to generate NH + -containing cation exchange polymer membranes from other cation exchange membrane.
  • the reaction or ion exchange can happen in situ by passing a solution of ammonia, urea, or urea or ammonium salt over the membrane even after the MEA has been made.
  • Polytetraflurorosulfonic acid polymer film (NAFIONTM from DuPont) was treated as described above with aqueous ammonia to react the free sulfonic acid groups and create quaternary ammonium groups.
  • the resultant NH 4 + -form membrane was used as an electrolyte.
  • the membrane electrode assembly (MEA) was fabricated with Mn0 2 /C (20 wt% Mn0 2 ) cathode and nickel anode. These were manufactured as follows:
  • an ink was made by mixing carbon (Carbot Vulcan XC72R; 20 mg), deionised water (20 ml), isopropanol (6 ml), (NH 4 ) 2 C0 3 (5 mg) and 5% Nafion solution (Aldrich; 100 ⁇ ) in an iced ultrasonic bath (Fischer Scientific Ltd) for 30 minutes.
  • the thus- obtained ink was sprayed or coated on a Carbon paper (E-TEK, Toroy 090), and dried under vacuum at 80 °C for 1 hour whereby to provide a carbon electrode.
  • Mn0 2 was prepared from KMn0 4 , Mn(CH 3 COO) 2 and carbon (Cabot Valcun XC72R) a co-precipitation method as described by C Xu et a/., (J. Power Sources, 180, 664-670 (2008)). The thus-prepared Mn0 2 was then incorporated into the mixture described above with a weight ratio of Mn0 2 to carbon of 50:50 by weight (although this could range from about 5 to about 95 wt%).
  • nano-sized nickel particles were prepared from NiCI 2 .6H 2 0 and KBH 4 according to the method of S Lu ef a/., (Proc. Natl. Acad. Sci. USA, 105, 20611 -20614 (2009)). Some trisodium citrate was added into aqueous NiCI 2 solution in order to obtain nano-sized nickel particles (nickel particle size about 2 nm) as observed with TEM. The thus-prepared nickel particles were then incorporated into the mixture described above with a weight ratio of nickel particles to carbon of 50:50 by weight (although this could range from about 5 to about 95 wt%).
  • a Nafion 211 membrane (treated as described above) was put between two carbon electrodes on carbon paper as prepared above and hot-pressed at 80 °C for 20 seconds.
  • the loading of the cathode and anode were 20 mg/cm 2 and 10 mg/cm 2 respectively.
  • Carbon paper (Toroy 090, E-TEK) was thereby used as current collector for the cell.
  • Ammonia solution, urine solution and 1 M NH 4 HC0 3 aqueous solution were used as the fuels for the fuel cell tests and air as the oxidant supplied to the cathode.
  • the air was passed through water at room temperature before entering the fuel cell. In principle, water is, however, not required at the cathode.
  • a Solartron 1287A electrochemical interface incorporated with a CorrWare/CorrView software was used to measure fuel cell performance.
  • Fig. 2 shows the fuel cell performance for Cell A when operated with 35 wt% aqueous ammonia, 1 NH 4 HC0 3 and human urine/air.
  • a maximum power density of 2.5 mW/cm 2 was achieved at room temperature when 35 wt% ammonia aqueous solution was used as fuel. It will be noted that the OCV of Cell A is higher than the theoretical 0.82V when 35 wt% ⁇ 3 ⁇ 2 0 solution is used because the concentration of 35 wt% ⁇ 3 ⁇ 2 ⁇ is much higher than 1M.
  • Cell B was prepared as described above for Cell A except no nano-sized nickel particles were added to the anode.
  • CorrWare/CorrView software was used to measure fuel cell performance.
  • Cell C was prepared as described above for Cell A except no nano-sized nickel particles were added to the anode and no Mn0 2 was added to the cathode
  • CorrWare/CorrView software was used to measure fuel cell performance.

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Abstract

L'invention concerne un procédé de fonctionnement d'une pile à combustible qui comprend une membrane d'échange de cations solide, le procédé comprenant la mise en contact d'une anode dans la pile à combustible de l'urine, un sel d'ammonium ou un sel d'urée et la mise en contact de la cathode avec un oxydant afin de produire de l'électricité.
PCT/GB2011/001073 2010-07-16 2011-07-18 Pile à combustible WO2012007727A1 (fr)

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GB2511743A (en) * 2013-03-11 2014-09-17 Craig Mclean-Anderson Electrochemical cells
WO2016094498A1 (fr) * 2014-12-10 2016-06-16 Novek Ethan Procédé intégré de capture de carbone et production d'énergie
CN113224331A (zh) * 2021-05-08 2021-08-06 中北大学 一种碱性体系直接尿素燃料电池阳极催化剂及其制备方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2511743A (en) * 2013-03-11 2014-09-17 Craig Mclean-Anderson Electrochemical cells
WO2016094498A1 (fr) * 2014-12-10 2016-06-16 Novek Ethan Procédé intégré de capture de carbone et production d'énergie
US9624111B2 (en) 2014-12-10 2017-04-18 Ethan Novek Integrated process for carbon capture and energy production
CN113224331A (zh) * 2021-05-08 2021-08-06 中北大学 一种碱性体系直接尿素燃料电池阳极催化剂及其制备方法

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