WO1992010864A2 - Configurations de batteries a metal/oxygene - Google Patents

Configurations de batteries a metal/oxygene Download PDF

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Publication number
WO1992010864A2
WO1992010864A2 PCT/GB1991/002212 GB9102212W WO9210864A2 WO 1992010864 A2 WO1992010864 A2 WO 1992010864A2 GB 9102212 W GB9102212 W GB 9102212W WO 9210864 A2 WO9210864 A2 WO 9210864A2
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WO
WIPO (PCT)
Prior art keywords
oxygen
electrolyte
cell
metal
battery
Prior art date
Application number
PCT/GB1991/002212
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English (en)
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WO1992010864A3 (fr
Inventor
Handel Meirion Thomas
Original Assignee
Rolls-Royce And Associates Limited
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Publication date
Application filed by Rolls-Royce And Associates Limited filed Critical Rolls-Royce And Associates Limited
Publication of WO1992010864A2 publication Critical patent/WO1992010864A2/fr
Publication of WO1992010864A3 publication Critical patent/WO1992010864A3/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/64—Heating or cooling; Temperature control characterised by the shape of the cells
    • H01M10/647—Prismatic or flat cells, e.g. pouch cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
    • H01M10/6567—Liquids
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
    • H01M10/625—Vehicles
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
    • H01M10/6561—Gases
    • H01M10/6562—Gases with free flow by convection only
    • 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

  • This invention relates to metal/oxygen battery constructions, both the construction of individual cells and of a stack of such cells electrically connected together in series externally of the cells.
  • Metal/oxygen batteries are also known as metal/air batteries, and in this specification use of the former term should be taken to include the latter, except where the context requires otherwise. Such batteries are becoming well known as, e.g., small emergency sources of power for use at sea or on land.
  • the reader is referred to the following United States patent specifications: Niksa et al, US4925744; Hunter et al, US4942100; Hoge, US4885217; Strong et al, US4871627; and Ha len et al, US4626482.
  • Such batteries rely on the combination of waterproof sheet-like gas-permeable oxygen cathodes and consumable metal anodes in an aqueous electrolyte.
  • cathode material comprises several layers of different sheet materials laminated together by hot rolling.
  • the innermost layer, in contact with the electrolyte, comprises a non-woven web of carbon fibre. This is bonded to a nickel mesh which acts as a current collector, which in turn is bonded to another carbon fibre web layer.
  • the outermost layer, on the oxygen side of the cathode, is a microporous layer of TEFLON (RTM).
  • RTM microporous layer of TEFLON
  • the carbon fibre webs are impregnated with a carbon/TEFLON/silver catalyst slurry which is dried before the hot rolling process.
  • aluminium alloy anodes as disclosed in the above-mentioned prior art are particularly advantageous to use.
  • aluminium/oxygen batteries can give a very high energy density and a power density which is adequate for many applications.
  • Known chemical optimisation of the cells includes the use of an alkaline electrolyte, particularly potassium hydroxide, to achieve formation of aluminium hydroxide precipitate instead of a passivating gell in the space between the anode and the cathode.
  • Known physical optimisation includes:
  • a related object is to provide a submersible vehicle making use of such improved batteries.
  • a further object is to provide simple but efficient cooling of a multi-cell metal/oxygen battery when situated in a submersible vehicle.
  • Another object of the invention is to improve the supply of oxygen to individual cells in metal/oxygen batteries.
  • a further object of the invention is to enable the sharing of electrolyte between cells in multicell metal/ oxygen batteries in order to maintain a common level of electrolyte while also substantially maintaining electrical isolation between cells.
  • the present invention provides a metal/oxygen battery construction having a plurality of separate elecrolyte-holding cells each containing metal anode means and oxygen cathode means, each cell having an electrically non-conducting housing comprising opposed faces and a rim region, each housing having aperture means in at least one of the opposed faces, to which aperture means the cathode means are sealingly secured, the faces of adjacent housings being sealed to each other in confronting fluid-tight manner so as to define therebetween oxygen feed means and electrolyte drainage channel means, both the oxygen feed means and the electrolyte drainage channel means communicating with the cathode means.
  • the oxygen feed means comprises an oxygen supply space in direct communication with the cathode means, and at least one oxygen feed channel leading to the oxygen supply space.
  • each cell contains a metal anode plate located between two oxygen cathodes and each face of the housing has an aperture with a corresponding one of the cathodes sealingly secured thereto, the oxygen supply space being adjacent to confronting cathodes of adjacent housings.
  • the oxygen feed channels between the adjacent housings are connected to an an oxygen delivery manifold.
  • the oxygen supply spaces, the oxygen feed channels and the electrolyte drainage channel means are defined by depressions in the adjacent confronting faces of the housings.
  • the oxygen permeable sheetlike cathodes are substantially waterproof, there is inevitably some seepage of electrolyte through them and out of the cells, hence the need for an electrolyte drain.
  • the lowest portion of the drain incorporates electrolyte drainage means for transport of the seepage away from the sealed areas between the housings.
  • the drainage means comprises electrolyte recirculation means for injecting drainage electrolyte back into the interior of an adjacent cell.
  • the rim regions of the housings may be advantageous to make with a stepped configuration rather than a plain cylindrical or outwardly tapered shape.
  • This stepped configuration may occupy only part of the periphery of the housings if the heat dissipation obtained by such an arrangement is sufficient.
  • the invention provides a submersible vehicle comprising a hull, pressurised oxygen supply means, a multi-cell metal/oxygen battery, power conditioning means and propulsion means, at least the battery being contained in free-flooded compartment means whereby the battery operates at ambient pressure and circulation of water around the battery effects cooling of the cells. Such circulation of the water around the battery may be forced or unforced.
  • the pressurised oxygen supply means is also contained in the above-mentioned free-flooded compartment means.
  • the free-flooded compartment means has at least one removable vehicle external wall portion to allow removal and replacement of the battery and/or said at least part of the oxygen supply means.
  • the pressurised oxygen supply means may comprise a pressurised oxygen tank, an oxygen supply manifold for distribution of oxygen to the cells comprising the battery, an oxygen supply pipe extending between the tank and the manifold, and flow control means in the supply pipe, the flow control means comprising isolating valve means to allow disconnection of an aft portion of the supply pipe from the oxygen tank, vent/fill valve means to allow venting and filling of the tank from outside the vehicle and flow regulator means between the isolating valve means and the manifold for control of flow of oxygen to the manifold.
  • the pressurised oxygen tank is integral with the hull of the vehicle and an aft portion of the oxygen supply pipe with associated flow control means is disconnectable from the tank for removal from the vehicle together with the battery, the free-flooded compartment means being to ithe rear of the tank and forward of the power conditioning equipment.
  • a third aspect of the invention provides a metal/oxygen cell construction comprising an electrically non-conducting housing for holding therein anode means, oxygen cathode means and an electrolyte, the housing comprising opposed faces and a stepped rim region for providing the cell with an enlarged external surface area for enhanced transfer of heat to the environment.
  • a metal/oxygen battery comprises a plurality of cell housings whose faces are sealingly engaged to each other to form a stack of cells, thereby restricting the surface area of the housings available for radiative and convective dissipation of heat generated by electrochemical reactions within the cells.
  • the stepped rim region considerably increases the surface area available for heat exchange with the environment.
  • This aspect of the invention is particularly intended for use in the above-described battery powered submersible, the stepped rim region being exposed to the water in the free-flooded compartment means.
  • the stepped rim region comprises a plurality of steps.
  • the stepped rim region may comprise only a portion of the circumference of the housing.
  • the invention provides a metal/ oxygen battery cell construction in which an electrically non-conducting housing contains metal anode means and oxygen cathode means in fixed spaced-apart relationship to each other, each housing comprising opposed faces thereof and a peripheral rim region, the cell interior comprising an electrolytic reaction region containing the anode and cathode means, a precipitate collection region for retaining reaction product particles precipitated from the reaction region, and electrolyte circulation channel means for facilitating circulation of electrolyte within the cell without disturbing the precipitated particles, the channel means having intake means and exit means adjacent different parts of the reaction region, the channel means between the intake means and the exit means extending around at least part of the periphery of the precipitate collection region.
  • the exit means is situated such that the part of the channel means leading thereto extends through the precipitate collection region from the periphery of the cell towards the reaction region.
  • the exit means should be shielded from deposition of precipitate particles thereinto from the reaction region.
  • the extremities of the reaction region are near the peripheral rim region of the housing and the channel means comprises a central channel portion extending centrally through the precipitate collection region from the periphery of the cell to an exit situated directly beneath and centrally of the reaction region and two peripheral channel portions each extending from a respective intake near an extremity of the reaction region, around a part of the periphery of the precipitate collection region, and joining the central channel portion at the periphery of the cell.
  • the precipitate collection region comprises a plurality of elongate baffles extending widthwise between the opposed faces of the housing and lengthwise from the rim region towards the reaction region, the baffles being spaced from each other to define compartments open near the reaction region into which the precipitate is deposited during normal operation of the cell.
  • the part of the channel means leading to its exit extends through the precipitate collection region, that ' part of the channel means is defined between adjacent baffles and may be shielded from deposition of precipitate particles thereinto by baffle means located between the exit of the channel means and the reaction region.
  • the present invention provides a metal/oxygen battery construction having a plurality of separate electrolyte-holding cells each containing metal anode means and oxygen cathode means, adjacent cells being connected together in electrical series, each cell having an electrically non-conducting housing comprising opposed faces and a rim region, each housing having aperture means in at least one of the opposed faces, to which aperture means the cathode means is sealingly secured, confronting faces of adjacent housings being sealed to each other in fluid-tight manner so as to define therebetween oxygen feed means and electrolyte drainage channel means, both the oxygen feed means and the electrolyte drainage channel means communicating with the cathode means, the oxygen feed means being connected to an an oxygen supply manifold for distribution of oxygen to the cells comprising the battery, the electrolyte drainage channels being connected to electrolyte recirculation means for injecting drainage electrolyte back into the interiors of the cells.
  • connections between the oxygen supply manifold and the oxygen feed means are used to provide the required electrolyte recirculation means.
  • This is achieved by using the flow of oxygen between the oxygen supply manifold and the oxygen feed means to entrain electrolyte from the drainage channels into mixed electrolyte/oxygen flow which is then passed into the tops of the housings and empties into the interiors of the cells where the mixed electrolyte/oxygen flow separates into its constituent components, an oxygen head space thereby being created in each cell, from which head space oxygen passes to the oxygen feed means and thence to the cathode window means.
  • the oxygen head space is created in the upper closed end of a dip tube within each cell, the dip tube having a lower open end for the injection of the recirculated elecrolyte into the main body of electrolyte within the cell.
  • the oxygen feed means defined between the confronting faces of adjacent housings comprises an oxygen supply space in direct communication with the cathode means, and an oxygen feed channel connected to the oxygen supply space and to the oxygen head space.
  • the electrolyte recirculation means comprises oxygen feed lines each having one end connected to the oxygen supply manifold and the other end connected to a mixed oxygen/ electrolyte flow line at a 'T' junction, the oxygen feed line being the stem of the *T' and the oxygen/ electrolyte flow line being the cross-bar of the 'T*, one side of the cross-bar being connected to an electrolyte drainage channel through non-return valve means and the other side of the cross-bar being connected to an oxygen head space in the interior of the cell.
  • drainage electrolyte from each drainage channel is recirculated to only one of the two adjacent cells, that is, the first of the two cells in a designated direction lengthwise along the stack of cells, comprising the battery.
  • the drainage channel on the outer face of the last cell in the stack is connected to the drainage channel on the outer face of the first cell in the stack, the latter drainage channel being connected to the electrolyte recirculation means. This ensures that there is a nominally correct amount of seepage returned to each cell.
  • a sixth aspect of the invention is directed to ensuring that the electrolyte level in different cells remains substantially similar in spite of differing leakage rates through the cathodes, and differing rates of recirculation of drainage electrolyte back into the cells, provision therefore being made for the interiors of adjacent cells to be connected for the interchange of electrolyte in such a way that no substantial shunt currents occur between cells. This may be achieved by connecting the interiors of adjacent cells through capillary tubes.
  • Figure 1 is a schematic diagram showing a propulsive system for a submersible vehicle incorporating a metal/ oxygen battery
  • Figure 2 is a pictorial view of a multi-cell metal/- oxygen battery according to the present invention, one end cell of the battery being shown with half the front wall of the cell removed to reveal internal structure;
  • Figure 3 is an end elevation of a typical one of the metal/oxygen cells in the battery shown in Figure 2, the cell again being shown with half the front wall of the cell removed to reveal internal structure;
  • Figure 4 is an enlarged detail of the top part of the cell shown in Figure 3;
  • Figure 5 is an enlarged detail of the bottom part of the cell shown in Figure 3;
  • Figures 6A and 6B are top and bottom portions respectively of a sectional view taken on the line joining points ABCDEF in the cell of Figure 3;
  • Figure 6C is an enlargement of the portion of Figure 6A within the outlined box
  • Figure 7 is a view on arrow VII in Figure 3.
  • Figure 8 is a view on arrow VIII in Figure 3.
  • the designs shown in the above-mentioned drawings are based on the use of a particularly simple form of aluminium/oxygen battery technology in which circulation of the electrolyte within individual cells relies on convection currents produced by the heating effect of the electrolytic reaction within the cell.
  • the preferred elecrolyte is potassium hydroxide and the reaction product is a precipitate of aluminium hydroxide particles. Since circulation of the electrolyte is not forced, the precipitate particles are more likely to fall towards the bottom of the cells instead of being entrained in the circulation of the electrolyte. This keeps the cathode/anode space relatively free of reaction products and thereby facilitates maintenance of the maximum power output of the cell for a longer period during operation of the cell.
  • This type of cell has a high energy density and a power density which is suitable for many applications, such as emergency or stand-by power or electrically powered vehicles.
  • FIG. 1 shows how such an aluminium/oxygen battery can be integrated into the power system of a ship, such as a remotely controlled undersea survey vehicle.
  • a pressure vessel or oxygen tank 101 capable of holding gaseous oxygen at a pressure of two hundred atmospheres or higher, is linked through an oxygen supply line 102 to the battery 103, which comprises a number of individual cells 105.
  • the cells 105 are externally linked together in electrical series so that two electrical output lines 107 and 109 are connected respectively to the anode of the first cell of the battery and the cathode of the last cell.
  • the electrical output lines 107 and 109 are connected in parallel to power conditioning equipment 111.
  • This comprises two units, namely a constant voltage output DC/DC converter 113 for supplying power to vehicle services such as guidance and manoeuvring systems, and a variable output DC/DC converter 115 for powering an electric motor and gear unit 117 which drives a propeller 119.
  • a constant voltage output DC/DC converter 113 for supplying power to vehicle services such as guidance and manoeuvring systems
  • a variable output DC/DC converter 115 for powering an electric motor and gear unit 117 which drives a propeller 119.
  • the oxygen tank 101 forms part of the hull of the vessel, because the tank 101 must be very strong anyway to perform its oxygen containment function. Provision can be made for the tank 101 to have a duct 126 on its axial centreline through which electrical cables or other services can pass. Overall longitudinal stiffness of the vehicle can be provided by suitable chassis members (not shown), which also provide further fore-and-aft access for services.
  • the battery 103 is contained in a free-flooding compartment 127 within the hull so that the battery operates with its immediate surroundings at ambient seawater pressure and with circulation of water around the battery to effect cooling of the cells.
  • Such circulation of the water around the battery may be forced, using pumps or the like, or unforced, utilising merely natural circulation induced by passage of the vehicle through the water.
  • compartment or compartments aft of the battery compartment containing the power conditioning equipment 111 and the motor unit 117, may be dry or oil-filled as a matter of design choice, according to the type of electric motor chosen for unit 117.
  • This aft space may also contain the steering and trim gear and their controls (not shown) .
  • the oxygen supply line 102 extends between the tank 101 and an oxygen distribution manifold 200 on top of the battery with connections 201 to the individual cells 105.
  • the supply line 102 includes two isolating valves 121,123, a vent/fill valve 125 to allow venting and filling of the tank 101 from outside the vehicle, and two flow regulators R1,R2 in series between the isolating valve 123 and the manifold 200.
  • Rl is for lowering the oxygen pressure from the very high tank pressure to an intermediate value
  • R2 is for reducing it further to a lower battery supply pressure.
  • the aim is to control the battery supply pressure to a constant 24.9 mbar, approximately, above the pressure of the seawater in the compartment 127.
  • the regulators Rl, R2 automatically adjust themselves with reference to the pressures in compartment 127 and supply line 102.
  • a low pressure relief valve (not shown) is also fitted to the supply line 102 near the battery, say in the oxygen manifold, to protect the battery cells from being overpress ⁇ rised in the unlikely event of one or both of the regulators Rl,R2 failing.
  • valve 121 can be opened while valve 123 is closed, to allow filling and venting of the oxygen tank independently of the connection to the battery 103.
  • the oxygen supply line 102 at least up to its isolating valve 123, can be included in an extended free flooded compartment 127.
  • the battery 103 and any attached equipment can be removed from the vehicle through a removable hull panel or door 129 comprising a wall of the compartment 127.
  • the battery and its associated oxygen flow control devices can be contained in respective adjacent free-flooding compartments.
  • valve 123 Disconnect the oxygen manifold 200 from the battery. Fill a new battery with electrolyte.
  • each working cell 105 comprise an aluminium alloy anode 205, a pair of oxygen cathode panels 207A,207B, one panel on each side of the anode but spaced apart therefrom, a supply of oxygen and an alkaline electrolyte (not shown), preferably a 3.5 mole solution of potassium hydroxide.
  • a suitable stackable cell housing for accomodating the electrolyte, the anode and the cathodes.
  • the cell housing 203 comprises two similarly featured half-housings or shells 209A,209B, see particularly Figures 7 and 8 in addition to Figures 2 and 3.
  • Each shell is moulded from, for example, epoxy resin reinforced with a glass fibre filler, though other suitably rigid non-corroding and non-conducting materials could be used at the option of the designer.
  • a suitable thickness for the specified material is 2mm.
  • the shells 209A,B are moulded with integral top and bottom block portions 211A,B and 213A,B respectively,
  • the blocks have smooth plane mutually parallel front and back faces which are continuous with the plane radially outturned edges 215A,B of the thin shell portions.
  • top and bottom block portions of the shells when bonded together on their faces to form top and bottom structural blocks 211,213 for " the complete cell, also provide a convenient location for fluid ingress and egress holes to and from the interiors of the cells and for helping to define oxygen supply and electrolyte drainage channels between the cells. They further provide convenient sites for connections to external oxygen and electrical connections.
  • a complete cell housing is made by gluing confronting plane edges 215A,B of the two halves of the housing together after fitting the components of the cell into the two halves.
  • An epoxy glue may be used. After gluing the two halves together, a suitable total thickness for the housing is about 25mm. After the glue has cured, the various holes are bored in the top and bottom blocks 211,213 as required.
  • Each smooth front and rear end face 217A,B of a housing is moulded complete with a cross-shaped depression 219A,B.
  • the depressions in confronting cell walls are in registration with each other, so forming between adjacent cells a central oxygen chamber 221, an oxygen supply channel 223 leading to the chamber 221 from the top of the battery and an electrolyte drain channel 225 leading from the chamber 221 to the bottom of the battery for draining off the inevitable electrolyte seepage through the cathodes 207A,B.
  • the cathode sheets or panels 207A,B fit within and are coextensive with the laterally extending arms of the cross-shaped depressions 219A,B, except for a triangular area of the oxygen chamber 221 below the cathode panels, which connects with the electrolyte drain channel 225.
  • the major components which are fitted into a cell before bonding together of the shells as mentioned above comprise the anode plate 205, two anode support posts 230,231 (one on each side of the cell), four lateral restraint posts 240 - 243 (two on each side of the cell) for restraining the anode against lateral moveme 0nts, the two panels of laminated cathode material 207A,B (one on the front face of the cell and one on its rear face) which confront the central anode 205, the baffle members 250 in the bottom half of the cell, and the electrolyte dip tube 260, which is instrumental in returning electrolyte seepage to the cell interior.
  • each anode support post 230,231 has a threaded end which is screwed into a threaded hole in the top edge of the anode.
  • the top of each post 230,231 also has a threaded end which passes through the top block 211 and is secured by a nut 265 against movement.
  • the posts 230,231 are provided with an insulating coating layer 270, which may comprise polyethylene, P.V.C., or the like.
  • the restraint posts 240 - 245 underneath the anode likewise have upper threaded ends which are screwed into threaded holes in the lower edge of the anode. At their lower ends the restraint posts are provided with forwardly and rearwardly projecting bosses 275 which contact the front and rear internal faces of the cell housing for lateral restraint of the anode,
  • the cathode current collector cables 285A,B are soldered or otherwise electrically bonded to a copper strip 290 (see particularly Figures 2 and 6C), which runs the width of the cathode panels 207A,B.
  • This copper strip is in turn soldered or otherwise electrically bonded to a nickel mesh 300 forming part of the laminated construction of the cathode panels.
  • the copper strip 290 and the ends of the cables 285 connected to it are embedded in the cell wall and are not in direct contact with the electrolyte within the cell.
  • the cables 285 emerge through the cell wall and are connected to the top of the anode posts 230,231 of the next cell along the battery in order to connect adjacent cells in electrical series.
  • the two cathode panels 207A,B each cover a trapeizoidal aperture defined by edges 295A,B moulded into the shells 209A,B. Each aperture is the same shape as, but slightly bigger than, the anode plate 205 within the cell.
  • Each cathode panel 207A,B is a laminated construction comprising a thin inner layer of carbon fibre web material 301, a thick layer of carbon fibre mat material 302, the nickel alloy mesh 300 adhered between the two carbon fibre layers to collect the electrical current, and an outer covering of waterproof but oxygen permiable microporous plastic 303.
  • the thickness of the fibre mat layer 302 is such that the outer plastic layer 303 of each cathode is in approximately the same plane as the surfaces of the housing surrounding the cross-shaped depressions 219A,B.
  • the inner web material 301 is hydrophillic for absorption of the electrolyte into the cathode. This provides intimate contact between the electrolyte and the oxygen permiating into the outer layers of the cathode.
  • the carbon fibre mat material 302 is impregnated with a mixture of catalytic silver particles combined with activated carbon and polytetrafluoroethylene, the latter constituent rendering the mat hydrophobic.
  • the complete multilayer cathode material is a proprietory product of Alupower Inc., of New Jersey, U.S.A. Alternatively, other known cathode materials having similar properties may be substituted, such as those disclosed in the previously mentioned prior patents.
  • the cathode panels 207A,B are assembled into the shells 209A,B by peeling a peripheral edge portion of the carbon fibre mat material away from its supporting nickel mesh 300 and gluing or otherwise bonding that edge portion of the mat over the outside of the edges 295A,B of the trapeizoidal aperture.
  • the parted peripheral strips of nickel mesh having been previously bonded to the copper strips 290A,B along their top edges, are bonded to the inside of the edges 295A,B of the trapeizoidal aperture.
  • each cathode panel confronts the central anode plate 205 across an electrolyte gap, where production of aluminium hydroxide precipitate occurs as a byproduct of the electricity production.
  • the anode plate gradually erodes and it should therefore be sufficiently thick to enable the cell to operate for a desired length of time despite the erosion.
  • Controlled circulation of the electrolyte within the cell must be established in order to ensure that depleted electrolyte between the anode and the cathodes is replaced by fresher electrolyte.
  • the design of the cell ensures very slow natural circulation of the electrolyte, caused by the heat of reaction between the anode and cathodes.
  • the circulation is sufficiently slow to ensure that the aluminium hydroxide particles produced in the interelectrode gap do not remain in suspension, but drop to the bottom of the cell as sediment. If the particles remained in suspension between the electrodes, they would inhibit the cell reaction.
  • the sediment is collected in a sump construction defined by two sets of stainless steel strip baffle members 250 in the bottom half of the cell. These baffle members completely span the internal gap between the flat inner faces of the shells 209A,B and are bonded thereto. Besides providing the cell walls with a degree of fore-and-aft stiffening, they define sump compartments 320 - 325, which are open at the top near the cell reaction region, but closed at the bottom to retain the sediment.
  • the vertically oriented baffle members which help define the compartments, help control sediment movement laterally of the cell due to rolling vehicle motion. Once the sediment has settled in the sump compartments, it tends to become compacted, thereby enhancing the useful life of the cell.
  • the baffle members 250 are made of a heat conducting material to assist cooling of the sediment, because this is thought to aid the compaction process.
  • the useful life of the cell ends when the sediment level reaches the top of the sump compartments.
  • the stainless steel baffle members 250 are positioned and shaped so as to leave a free path for the thermally induced natural circulation of electrolyte around a channel 330 defined between the periphery of the cell and the sump compartments and then up a central channel 331 defined between the two sets of baffle members.
  • the central channel is prevented from being filled with sediment by an inverted V-shaped deflector baffle 335 held between the bottom of the anode plate and the top of the central channel.
  • electrolyte warmed in the reaction region rises upwards towards the top of the cell, cools at the cell periphery, and simultaneously is pushed outwards and downwards around the cell periphery by newly warmed and rising electrolyte so that it enters the peripheral circulation channel 330, where it cools further and sinks to the bottom of the cell, so in turn pushing electrolyte up the central channel 331 back to the reaction region.
  • the volume of electrolyte in the sump compartments is not too great compared with the volume in circulation within the cell.
  • normal molecular diffusion and gradual filling of the compartments with sediment ensures eventual use of the electrolyte in the sump compartments.
  • the sump compartment volumes should not exceed that necessary for containment of the reaction products produced by complete consumption of the anode plate.
  • the oxygen supply line 350 to the cell comprises a tapping from the oxygen manifold 200.
  • the oxygen supply line 350 first passes around the outside of the cell to a point near the bottom, where it makes a T-junction with an electrolyte return pipe 351.
  • the bottom end of this pipe is connected to an electrolyte drain tube 352 through a non-return valve 353 or equivalent device to ensure electrolyte flows only in the direction of the arrow.
  • the electrolyte drain tube 352 is connected to a small drilling 354 within block 213 at the bottom of the cell. Through another drilling 355, the drilling 354 receives the cathode seepage electrolyte which collects in the drain channel 225.
  • the pressure of the oxygen in the supply line 351 is less than that exerted by a column of seepage electrolyte of a certain height collected in the drain channel 225.
  • electrolyte is passed through the valve and entrained in the flow of oxygen past the T-junction through a short, very small diameter section of tube 356 to form an oxygen/electrolyte mixture, This then passes up the electrolyte return pipe 357 from the T-junction to the top of the cell.
  • a small diameter tube 358 is connected to a small diameter tube 358 at the top of the cell, which passes through a small diameter laterally oriented drilling in the top block 211 of the cell.
  • the end of the small diameter tube 358 projects into a small chamber formed in the interior of the block by a large diameter vertical through-drilling 360, the top end of the drilling being sealed by a plug 361.
  • the 358 is bent downward within the chamber, so that in combination there is formed a separator for the oxygen/electrolyte mixture coming from the electrolyte return line.
  • the electrolyte therefore drips from the free end of the tube 358 into the top of the electrolyte dip tube 260, which is connected to a sleeve insert 362 projecting from a narrower part of the vertical drilling 360 at its lower end.
  • the oxygen exhausts from the oxygen/electrolyte separator chamber by means of a vent 370, which is a continuation of the small diameter lateral drilling containing the tube 358.
  • This vent connects with a further fore-and-aft oriented drilling 375 which leads to the oxygen supply channel 223 formed between adjacent cells, and thence to the outside of the cathode panels 207A,B.
  • drilling 360 which forms the oxygen/electrolyte separator already referred to
  • a drilling 380 which provides a means of filling the cell with electrolyte after the cell has been assembled into the battery stack.
  • the top end of the drilling 380 is sealed off with a plug 381.
  • a third vertical drilling 390 has its top end sealed with a plug of microporous material 391 which is waterproof, but permeable with regard to hydrogen so that any hydrogen created in the cell reactions can be vented into the free-flooded chamber surrounding the battery and hence safely disposed of as mentioned previously.
  • Figure 8 shows the bottom block 213 of the cell having a vertical drilling 400 connecting with the interior of the cell and sealed by a plug 401.
  • the plug is removable so that electrolyte can be drained from the interior of the cell as required.
  • vent valves in the top and bottom blocks 211,213, connected to the oxygen supply channels 223 and the elect #rolyte drain channels 225 formed between the adjacent cells by the cross-shaped depressions 319A,B when the cells are stacked together. These are provided for the purpose of purging the channels and the oxygen chambers 221 of air when the battery is connected up to the oxygen supply before use.
  • the oxygen manifold is installed on the top blocks 211 of the battery as shown and connections are made to the oxygen supply line 350 for each cell.
  • the battery's electrical connections are also made on the blocks 211, As best shown in Figures 3,4 and 7, the two cathode collector cables 285A,B. on each side of each cell are joined together (optionally by means of a connector block 440 as alternatively shown in Figure 2) and a short cable 286 carrying their combined currents is connected to the top of the anode post 230 of the next adjacent cell along the battery stack so as to connect the cells together in series.
  • an expansion bladder (not shown) is a necessary means of coping with small short term electrolyte volume changes caused by changes in cell temperature. It is also necessary for absorbing the long term electrolyte volume increase due to the net influx of oxygen atoms into the aluminium hydroxide precipitate in the cells.
  • Such an expansion bladder may conveniently be connected to the interior of an end cell in the battery stack through a capillary tube and functions to maintain a pressure in the cells which is exactly the same as the ambient pressure.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)

Abstract

Les éléments d'une configuration de batterie à métal/oxygène contiennent chacun un électrolyte d'hydroxyde de potassium, une plaque d'anode en métal et une paire de panneaux de cathode perméables à l'oxygène et disposés de chaque côté de l'anode. Chaque élément possède un boîtier non électroconducteur comportant des faces opposées et une zone marginale périphérique, une ouverture étant ménagée dans chacune de ces faces opposées pour permettre la fixation étanche à celle-ci des panneaux de cathode et l'obturation de l'ouverture. Les faces des boîtiers sont appliquées l'une contre l'autre de manière étanche aux fluides afin de définir entre elles des voies d'amenée d'oxygène et d'évacuation d'électrolyte, lesquelles voies communiquent avec les cathodes à l'extérieur des éléments.
PCT/GB1991/002212 1990-12-12 1991-12-12 Configurations de batteries a metal/oxygene WO1992010864A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9026927A GB9026927D0 (en) 1990-12-12 1990-12-12 Metal/oxygen battery constructions
GB9026927.5 1990-12-12

Publications (2)

Publication Number Publication Date
WO1992010864A2 true WO1992010864A2 (fr) 1992-06-25
WO1992010864A3 WO1992010864A3 (fr) 1993-04-01

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EP (1) EP0561938A1 (fr)
AU (1) AU9080891A (fr)
GB (1) GB9026927D0 (fr)
WO (1) WO1992010864A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0700110A1 (fr) * 1994-08-05 1996-03-06 Electric Fuel (E.F.L.) Limited Batterie refroidie du type zinc/oxygène
WO1997014190A1 (fr) * 1995-10-10 1997-04-17 Stn Atlas Elektronik Gmbh Accumulateur d'energie electrique independant de l'air exterieure
US6197445B1 (en) 1998-03-06 2001-03-06 Rayovac Corporation Air depolarized electrochemical cells
TWI418079B (zh) * 2011-07-04 2013-12-01 Delta Electronics Inc 電池模組
CN108365282A (zh) * 2018-04-25 2018-08-03 上海交通大学 铝空气电池循环及沉淀回收装置

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US3052201A (en) * 1948-12-11 1962-09-04 Union Carbide Corp Mounting for heavy duty battery
US3390014A (en) * 1960-05-11 1968-06-25 Eisler Paul Secondary electric batteries having plurality of thin flexible intermediate bipolar plates
US3551208A (en) * 1966-12-12 1970-12-29 Yardney International Corp Cell with displaceable electrode
DE1915598A1 (de) * 1968-04-25 1969-11-13 Energy Conversion Ltd Elektrochemisches Element
US3861958A (en) * 1969-10-17 1975-01-21 Inst Francais Du Petrole Process and devices for recovering electrolyte leaks in a fuel cell
FR2075986A1 (fr) * 1970-01-08 1971-10-15 Gulf Energy & Environ Systems
US3834944A (en) * 1973-09-10 1974-09-10 Yardney International Corp Multi-cell metal-fluid battery
US4152492A (en) * 1978-07-31 1979-05-01 The United States Of America As Represented By The Secretary Of The Navy Water cooled bipolar battery apparatus
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EP0265242A2 (fr) * 1986-10-22 1988-04-27 Alcan International Limited Batterie multicellulaire du type métal-air
EP0311275A2 (fr) * 1987-09-25 1989-04-12 Alcan International Limited Batterie métal-air à électrolyte circulant
JPH01186768A (ja) * 1988-01-19 1989-07-26 Meidensha Corp 電解液循環形二次電池の電極構造
WO1992005598A1 (fr) * 1990-09-18 1992-04-02 Alcan International Limited Pile d'aluminium

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0700110A1 (fr) * 1994-08-05 1996-03-06 Electric Fuel (E.F.L.) Limited Batterie refroidie du type zinc/oxygène
WO1997014190A1 (fr) * 1995-10-10 1997-04-17 Stn Atlas Elektronik Gmbh Accumulateur d'energie electrique independant de l'air exterieure
US6197445B1 (en) 1998-03-06 2001-03-06 Rayovac Corporation Air depolarized electrochemical cells
US6436571B1 (en) 1998-03-06 2002-08-20 Rayovac Corporation Bottom seals in air depolarized electrochemical cells
TWI418079B (zh) * 2011-07-04 2013-12-01 Delta Electronics Inc 電池模組
CN108365282A (zh) * 2018-04-25 2018-08-03 上海交通大学 铝空气电池循环及沉淀回收装置
CN108365282B (zh) * 2018-04-25 2023-12-26 上海交通大学 铝空气电池循环及沉淀回收装置

Also Published As

Publication number Publication date
AU9080891A (en) 1992-07-08
WO1992010864A3 (fr) 1993-04-01
GB9026927D0 (en) 1991-04-03
EP0561938A1 (fr) 1993-09-29

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