AU779270B2 - Dismantable, re-chargeable, re-cycleable 'wet' chloride battery system - Google Patents

Description

I Following Provisional Application on a Chloride 'wet' cell battery system the following is a detailed description of the slightly 'wet' Chloride cell. Two different positive ions are in separate compartments separated by the metallic cathode with a inert internal surface facing the anode (which is at the centre of the cell) being Gold or Platinum electroplated to a thickness of up to Ix um.

(micron) so no oxidation occurs from this surface when cell is recharged. This system has basically a central anode compartment separated by the coated cathode with a outer cathode compartment. The JO0 assembled cell is filled with metallic chloride solution in cathode compartment with Ammonia and Potassium Hydroxide (or Sodium Hydroxide) and the anode compartment is filled with Ammonium Chloride solution and Potassium Hydroxide (or Sodium Hydroxide). Potassium Hydroxide eliminates any remote possibility of NC13 (Nitrogen Tri- 5 chloride) forming and metal ions elinate N2H4 (Hydrazine) formation.

The outer wall of the cell is of preferably machinable plastic or castable oolymer resin. Inside this a capacitor strip is wrapped.

This capacitor strip is of two strips of copper foil less than .lx mm. thich filled with Barium Titanate and Alumina grit (for a spacing of less than 50 The capacitor strip runs off the battery cell and is only active when battery circuit is closed and when charged this pushes metallic ions in the outer cathode compartment towards cathode to reduce to metal on cathode. During re-charging the impressed voltage (which is larger in magnitude than cell discharge voltage) in terms of over-voltage or 'larger' voltage difference charges capacitor in reversed polarity so this tends to pull oxidized metal ions away from cell cathode towards capacitor strip so oxidation of metallic cell cathode occurs with metallic ions released into outer cell cathode compartment and inert noble metal 2 coating of Platinum or Gold on internal surface stopping any metal oxidation from internal cell cathode surface or release from internal cell cathode surface of metal in the anode compartment. The depletion of positive metallic ions in the outer cathode compartment on discharge is replaced by dissolved Ammonia forming a Ammonium positive ion. In the anode compartment on discharge, anode metal is oxidized and Ammonium ions lose hydrogen ions and go to dissolved Ammonia. The hydrogen ion from the Ammonium ion in the central anode compartment during discharge releases hydrogen from the dissoc- .IO iated Ammonium ion which then goes (the Hydrogen) out of anode compartment as gas and forms hydrogen ions on the outer cathode surface in the cathode compartment where hydrogen ions combine with dissolved Ammonia to form Ammonium ion which replaces positive ion in cathode compartment during discharge. During re-charging when :I5 cathode compartment outer surface oxidizes and anode compartment S: surface has metal ions from anode compartment deposited by reduction and Ammonia formed from discharge forms Ammonium ion from Hydrogen outer cathode surface in cathode compartment. (Note the hydrogen gas to hydrogen ion reaction has a zero voltage result and can be reversed without any applied voltage.) The following cell reaction and half cell reactions occur: Ma Ma++ 2e- EaO +x volts (1) Mc++ 2e- Me Eco +y volts (2) Ma Mc++ Ma++ Me Ecell o (x y)volts (3) NH.I c- NH3(aq) H- c- NH3(aq) 4/2H2(q) (4) Anode Compartment on Anode surface.

NH3(aq) 1/2H2(g) NH3(aq) H+ e- NH4 e- Cathode Compartment on Cathode surface.

These half cell reactions and define cell's work- 3 ings. Reaction is the cathode reaction on discharge which is ion reduction to metal or deposition of metal on cathode outer surface. Reaction is the anode reaction on discharge which is metal oxidation. Reaction is the full cell reaction and the comb-ined E.M.F.'s from reaction and give the output voltage of the cell. On discharge Ammonium Chloride as in reaction (4) becomes dissolved Ammonia in anode compartment and chloride ion becomes associated with metal ion formed by oxidation of anode and Hydrogen is released and goes to cathode/cathode compartment. On .IO discharging Reaction states that dissolved Ammonia combines with hydrogen ions from hydrogen (from anode/anode compartment) to form Ammonium ion that becomes associated with chloride ion as metal ions in cathode compartment leave solution and are deposited by reduction on external surface of cathode. Reaction and a5 occur in reverse with imposed over-voltage during re-charging process which can be rapid and down to 20 Minutes. The following systems are of some of the combinations of substances of metals that can be usedin this type of cell during discharge. (left side cathode and right side anode) FeCl3/Fe:Ni/NiCl2 Eo +.591 Volts FeC13/Fe:Cd/CdC12 E o +.744 Volts FeCl3/Fe:Co/CoCl2 E o +.641 Volts CuCl2/Cu:Sn/SnCl2 Eo +.4768 Volts CuC12/Cu:Zn/ZnCl2 Eo +1.1028 Volts CuCl2/Cu:Fe/FeCl3 Eo +.7499 Volts FeCl3/Fe:Sn/SnCl2 Eo +..2246 Volts The prefered system for weight,cost,re-chargeability in terms of a reasonable over-voltage that will not destroy inert noble metal coating on internal surface of cathode and energy to weight ratio -4and also energy to volume ratio is system the Cu-Fe cell which can have up to a 3x amp-hour rating on a 1.5 volt size cell at metal chloride concentrations of up to and over lOx Molar solution strength as wet pastes. The cell has two cells in series ,one on top of each other in the cell. (Summary of Invention) This invention is a re-chargeable battery system based on a 'half' 'D' unit which builds in multiples to larger batteries and even to a 12 Volt battery which has enough storage capacity to be even used as a car battery. So a basic unit of this 'wet' Chloride system is polymer resin enclosure (preferably castable polymer resin) with a double Copper strip filled with di-electric material such as Bare ium Titanate so that strip is electrical in parallelto battery output and is only active as a capacitor strip when battery is in 'closed' circuit under load and this capacitor strip then forces ions *5 in outer cathode compartment to cathode of Cooper cathode where reduction of Copper Chloride paste/solution occurs and the potential in the inner anode compartment of Iron electrode gives oxidation of Iron to Ferrous Chloride and hence electricity generation or release at about 1.5 volt for the two part cells connected in series and on top of each other forming the single cell battery. Ammonia also helps the exchange by going to Ammonium Chloride in the Cathode compartment as Hydrogen from the anode compartment is circulated to cathode compartment and becomes a Hydrogen ion (at zero volts potential) and hence Ammonium ion forms as part of dissolved Ammonium Chloride and and the Ammonium Chloride in anode compartment goes to Ammonia and Ferrous Chloride as Iron anode oxidizes and Hydrogen goes to cathode compartment and the reverse Hydrogen circulation path exists during cell re-charging as Copper Chloride is formed in cathode compartment during voltage 5 impressed oxidation and Ferrous Chloride goes to Iron and Ammonium Chloride in anode compartment during re-charging as voltage impressed reduction. Cell releases high currents and these currents are considerably higher than a basic non-re-chargeable 'dry-cell' so as cell units heat up a pressure relief valve exists for safety in the cell if the minute amount of gas become too pressurized. With these basic units larger battery units can be made of a basic 6x volt lantern battery or even a 12x volt car battery but cooling fans are incorporated in battery in closed circuit activation to .IO cool cell with motor fan being a compact disc electric motor with radial windings. The Platinum inert metal film resists oxidation S during re-charging and is not removed as a protective barrier as long as re-charging applied voltage potentials are not too high and this inert metallic barrier gives good electrical conductivity to .5 of inside surface of cathode to anode compartment. (End of summary of invention) Figure 1 is a horiz-ontal cross-section of cell with S 1 the cathode compartment solution which is originally Ammonia solution and Copper(ll) Chloride solution. Item 2 shows the anode compartment originally containing Ammonium Chloride solution. The inert noble metal coating 3 being electroplated and up to Ix um.

(micron) thick. Item 4 is the hollow Iron anode with irregular faces cut into outer anode surface (for retainment of electroplated metal during re-charging and greater surface area for faster discharging). Item 5 is the Copper cathode with irregular faces cut into outer surface (for retainment of deposited metal during discharge and greater surface area for faster deposition during discharge) with inert noble metal film electroplated on inside smooth surface.

A preferably machinable plastic or castable polymer resin 6 encloses cell or is a barrier to cont-ain cell solutions. Copper foils 6with Barium Titanate and Alumina grit 8 for spacing is between foils and forms external capacitor Strip 7 and is coated with epoxy resin 7a and in outer cathode compartment around periphery of cathode compartment and moves ions to outer cathode surface during discharge and pulls ions away from outer cathode surface during recharging. The noble metal film (preferably Platinum) has a very high Eo potential and resistsoxidation during re-charging and does not break-down in cell as long as excessive re-charge over-potentials are not applied and protects inside of cathode (exposed to .IO anode compartment) while still giving electrical conductivity in cell and exposure to anode compartment. Figure 2a is a schematic circuit diagram showing the connection of the capacitor strip 11 in parallel with the resist-ance load 12 accross the battery cell 9 so that capacitor strip 11 is only active when circuit is closed by [5 connection or switch 10. Figure 2b is a detailed drawing of a i/2x cell which is 33mm. in Diameter and 28mm. high with 1 the S cathode compartment and 2 the anode compartment and 3 inert metal coatina on the internal surface of cathode 5 and 4 the hollow Iron anode. Item 6a is the machinable (castable) plastic bottom of 1/2x cell casing (preferably P.T.F.E. PolyTetraFluoroEthylene) and 6b is the machinable (castable) plastic top of 1/2x cell casing pushed onto bottom and sealed by rubber washer (thin) 18. Capacitor strip 7 is coated in epoxy resin and isolated from chemical of cathode compartment and is around outer periphery of cathode compartment. The anode compartment is initially packed with 9.5 mls.

(milli-litres) of paste with 12.0 grams of Ammonium Chloride having about .5 mls. of free water and greater than .06 gms. of Potassium Hydroxide (any Alkali metal Hydroxide is acceptable but Potassium Hydroxide is prefered). The cathode compartment is initially packed 7 with 10.5 mis. of Ammonical Copper Chloride paste with excess Copper Chloride with about .5 mis. of free water and greater than .06 gms. of Potassium Hydroxide (KOH the prefered Alkali metal Hydroxide). So in each 1/2x cell .11 mole of divalent metal is exchanged (Cu and Fe) and each cell can give out about 16,200J.

of electrical energy with a top temperature of cell reaching 1200C during a short circuit with most of the 2x mls. of free water being distilled off cell thus stopping cell reaction and water vapour escaping through relief valve 22 and H20 vapour from cathode IO compartment going through gauze channels 28 to relief valve system 22. The capacitor strip that is in parallel to battery circuit and is only active when battery is active in closed circuit and connected to cathode by 13 which is also coated with epoxy resin with negative side of capacitor strip being connected by 14 to base Cop- 15 per plate 16 (about .4mm. Copper plate) with indent to contain solder. Two connections 15 from anode to base Copper plate 16 secure cell to base Copper plate and connections 15 are sealed by epoxy resin with indents 17 in base plate 16 and also in casing 6a and thus solder connections firmly hold 1/2x cell. Rubber seal 18 and Top of plastic casing bottom 6a seal top with connections 26 from cathode (sealed by epoxy resin) with 2x connections balancing load and pulling down on top casing 6b when connections 26 are soldered to top Copper plate or positive surface (about .4mm. thick Copper) 25 with indents in Copper plate 25 and casing 6b to hold leads 26 and top 6b securely when top 6b is pressed firmly and leads 25 soldered thus firmly sealing 1/2x cell. rings at base and top of cathode on outer side seal cathode. Rubber seal 23 at top of 1/2x cell seals cell and relief valve 22 (spring and plate) with Stainless Steel gauze 400# 28 is 400 gauze openings per in- -8ch) allows gas like Hydrogen to pass from anode compartment to cathode compartment and visa versa. Gas vent from cell 24 is open when internal pressure of cell exceeds 40x P.S.I. (pounds per square inch) when cell is hot, usually from short circuiting and allows the about Ix ml. of free water in each 1/2x cell to escape thus stopping cell reaction. Plastic insert 29 presses against gauze 28 and sealing rubber washer 23 and is pressed by hollow Copper anode 4 which seals against plastic insert by thin rubber washer 20 with rubber washer 19 sealing base if Iron hollow anode. So anode is IO isolated from cathode compartment by rubber washers 20 and 19 and very fine gauze 28 with cathode isolated from anode compartment by rubber rings and fine gauze 28 at top of 1/2x cell. Holes in anode 21 of up to 1.0mm. diameter allow interflow of Hydrogen from anode compartment to cathode compartment through gauze at top of 15 cell and vertical holes in cathode (Cu) at up to 1.6mm. in Diameter ~with some holes in side of cathode 27 connecting to vertical holes 31 of cathode and this is the inter-connection of particularly Hydrogen from cathode compartment to anode compartment and visa-

S.

versa as well as H20 vapour release as cell heats up to top temper- S 20 ature of 120oC. Up to 1.6mm. x 1.6mm. circular grooves are cut in anode 30b and 30a the cathode grooves. These grooves are easily cut in a metal Lathe. Figure 2c shows the Iron anode 4 with groove with up to Ix mm. diameter holes through to hollow centre of anode.

A combination of these holes and grooves in anodeand cathode lead to better retainment of metal granules deposited during electrochemical reaction of battery and re-charging in case metal granules are dislodged if battery is bumped suddenly. Holes to centre of anode and some holes to vertical holes of cathode allow for Hydrogen transfer from anode to cathode during discharge and Hydrogen -9transfer from cathode to anode during re-charging. The increased surface area of grooves and holes of cathode and anode allow for very rapid discharge and re-charge of up to lOx amps output (Discharge) and lOx amps input (re-charge) due to increased area for interaction and very wet pastes that react electro-chemically. Figure 2d shows the cell assembly on 2x (1/2x) cell units 32 stacked one on top of each other, positive surface to negative surface with negative surface underneath connecting thin stainless steel base plate 34 and positive surface on top contacting thin stainless steel plate positive surface 33. Plastic bushes at top of battery 35a (top bush) and 35b (bottom bush) electrically isolate battery from two casing halves of thin stainless steel .3mm.) with 36a at top screwing into bottom half thin stainless steel half casing 36b. Threads in 36a and 36b are course and of high pitch and easily rolled into this thin casing. The complete cell with casing weighs about 120 grams total. Figure 3a is a brief crosssection of the disc D.C. motor required to cool a 6x volt lantern battery made from 4x cell bateries previously described in Provisional application PQ3756 of the 1/11/99 and can be a generator or motor. To operate at up to lOx amp discharge continuous duty disc motor blows air through 6x volt lantern battery. The electric motor is very simple and not much explaination is required.

A thin aluminium circular disc 39 with centre drilled out is fixed by spokes to central bush 40 to shaft of motor 41. The 300x winding loops on athin Aluminium disc of 50mm. outside diameter and inside diameter forms the armature of the 6v. D.C. motor with windings 38 inside flat pole face permanent magnets of Ferrite (Fe304) (1,200 gauss) with magnets 37a,37b of opposite pole facing inwards towards windings on both sides of Aluminium disc. Windings IO0 are from .3mm. Copper enamel wire and motor idles at 3,000 R.P.M.

consuming up to 12x watts of electrical power. Plastic bushes 42 fixed to shaft electrically isolate shaft from Copper commutator connector plate 43. Commutators 44a,44b of opposite charge connect to Copper connector plate 43 through bronze roller in same design as in Figure 12g of application 55,344/98 by this inventor. Current flow in winding loops is by 45 with magnetic field lines 46 from permanent magnets facing towards two opposite faces of aluminium disc/ring 39. The 6V. motor cools 6V. lantern battery that can I0 deliver up to 60 watts of power for 18 minutes and battery (lanttern is a 3 Amp-hour battery holding about 1/60 of a Kilowatt Hour of Energy. Figure 3b is a cross-section of lantern battery with 4x cell batteries 47 in series with 6V. lantern battery enclosure 48 and 6V. cooling motor 50 connected in parallel and 15 only active when battery circuit is closed. Blown air flowing through battery to cool cells 49 is shown. Figure 3c is a vertical cross-section of 6V. lantern battery with 47 the 4x 'D' cells and 48 the lantern battery enclosure with 50 the 6V. motor in closed circuit. With 49 the blown air to cool cells by fan blade plate 56. Figure 3d is a schematic of circuit diagram involving the 6V. lantern battery with 4x cells in series 47 with switch 51 to close circuit and cooling motor 50 in parallel with the resistance load 52 on the battery such that motor 50 is only active when circuit is closed circuit. Figure 4 shows a block 160mm. wide and 200mm. high and 220mm. long containing 72x cells with 9x parallel series of 8x cell batteries giving a maximum of 90 amps at 12 volts for 18 minutes requiring only 18minutes to re-charge with the assembly being essentially a car battery of II 27x Amp-Hour that can store up to 1/3x of one Kilo-Watt Hour of energy. The two disc motors in base 55a and 55b side by side have a Aluminium disc of 100mm. outside diameter and 40mm. inside diameter diameter holes) with 150x winding loops on each disc of each motor of .6mm. diameter Copper enamel wire so that each motor can deliver up to 50 watts of air blown power at around 3,000 R.P.M..

The blown air 54 cools the 72x cells 53 of the 9x parallel series of 8x cells. Again the two disc 12 volt air cooling motors are in parallel to resistance load on the car battery and IO motors are only active when battery circuit is closed as in Figure 3d. Other battery systems can be constructed but they are similar to systems of Figure 3 and Figure 4 based on the cell which is based on the 1/2x cell of Figure 2b.

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Claims (3)

1. 2. A Dismantable,rechargeable, re-cycleable 'wet' Chloride battery 14 cell as claimed in claim 1 where a combination of half unit cells adding to form in series double half cell units as cells form a series of cells to give a 6x Volt Lantern battery as 4x 'D' cell battery units of each 1.5x Volts combines a disc D.C. electric disc motor comprising a Aluminium disc with loops through and around said disc running radially on disc with permanent magnets of opposite pole faces facing windings on each side of disc to give combined rotation affect of motor armature that drives a fan blade plate to cool units of 6x Volt lantern battery assembly with this IO 6x Volt motor in parallel to battery circuit resistive load and motor is only on or active when battery circuit with resistive load Sis closed thus cooling 6x Volt lantern when battery is releasing o• high current flows with motor design parameters being typically a oooo• rotating Aluminium disc for armature of about 50mm. outside dia- 5 meter and 20mm. inside diameter where typically about 300x radial •e ~windings of about .3mm. Copper enamel wire winding loops are made S with said armature spinning at about 3,000 R.P.M. between Barium oooo Ferrite magnets of about 1,200x gauss field strength with motor of output of up to about 12x watts with essential features of the compact motor being plastic bushes that armature rotates in and Copper connector plates that current is transfered to rotating windings through by bronze roller commutator electrical power tran- sfer means.
2. 3. A Dismantable,rechargeable, re-cycleable 'wet' Chloride battery cell as claimed in claim 1 where a combination of half unit cells adding to form in series double half cell units as cell battery units of 1.5x Volts of 8x in series to give a 12x Volt car battery which combines with a disc D.C. electric disc motor comprising a Aluminium disc with permanent magnets of opposite pole faces facing 15 wings on each side of disc to give combined rotation affect of motor armature that drives a fan blade plate to cool 1.5x Volt units of 12x Volt car battery assembly with this 12x Volt motor in parallel to battery circuit with resistive load and motor in parallel to battery circuit resistive load and motor is only on or active when battery circuit with resistive load is closed thus cooling 12x Volt car battery when battery is releasing high current flows with motor design parameters being typically a rotating Aluminium disc for armature of about 100mm. outside diameter and about 40mm. inside diameter with central hole of this diameter and where typically about 150x radial windings of about .6mm. Copper enamel wire winding loops loops are made with said armature spinning at about 3,000 R.P.M. between Barium Ferrite magnets of about 1,200 gauss field strength with motor of output of up to 15 about 50x watts and multiples of this motor are applied to 12x Volt car batteries of different sizes of more numerous parallel series of 8x of 1.5x Volt cells with essential features of the compact motor being plastic bushes that armature rotates in and Copper con- nector plates that current is transfered to rotating windings thro- ugh by bronze roller commutator electrical power transfer means.
3. 4. The Dismantantable,rechargeable, re-cycleable 'wet' Chloride battery cell with half cell unit,internal components, multiple full cell assemblies and Disc electric motor and motors as herein described with reference to accompanying drawings. GEORGE ANTHONY CONTOLEON 11TH.,OCTOBER,2004. APPLICANT DATE