FI63134C - ACKUMULATOR - Google Patents

Description

- 7νί “- 'Ί fftl« «ANNOUNCEMENT

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QgS & V C Patent granted on 11 04 1983 "Patent meddelat ^ T ^ (51) KtJk? Flm.a3 H 01 M 10/44 FINLAND — FINLAND (21) 3229/72 (¾¾) HtlumUpHvI — AndUmtap ^ l6.ll.72 (EN ) (23) AMwpttvA — GilllglMadag l6.ll.72 (41) Tullut KiUcImM - MtvK off «ncU | 19.05.7 3

Pltulti ·) t r * ki «terih» IUtll · / 44) Nlhttvllulpuon} »listen to the published date.

Patent- och ragimntynitM Anutkin udagd ock utUkritm publieurud (32) (33) (31) tuollnut- * flH prtork * 18.11.71 USA (US) 2ΟΟΟ7Ο Proof-Styrkt (71) Energy Development Associates, Inc., 1100 West Whitcomb Avenue,

Madison Heights, Michigan U8071, USA (US) (72) Philip Charles Symons, Birmingham, Michigan, Carmelo Joseph Amato, Livonia, Michigan, USA (US) 7M Berggren Oy Ab (5 * 0 Electric Battery - Battery

Several different electric batteries have so far been used or proposed for use as either a primary or auxiliary source of electrical energy. Electric batteries of the type capable of producing about 100 watts of electricity per kilogram of weight are generally classified as high energy density (H.E.D.) storage batteries, which, due to their small size and high energy capacity, are very satisfactory for use in various fixed or mobile power plants. Despite the incentive created by the general need to replace conventional fossil fuel internal combustion engines as the primary power source for vehicles due to pollution associated with such engines in densely populated urban areas, no satisfactory high energy density electric battery has been proposed to this invention. to make storage equipment commercially acceptable.

The constant and hitherto unfulfilled need has been to provide an economical electric battery with a high energy storage capacity and which allows a simple and fast recharging of the battery to return it to a fully charged state. Previous types of electricity storage devices in the industry have generally been too large in weight and / or size, slow to recharge, and deficient in many places due to the high toxicity and hazard associated with the chemical composition used to generate electricity and the relatively complex and critical adjustments required. to control their discharge in order to maintain their normal and efficient operation.

The present invention avoids the problems and disadvantages associated with prior art electric batteries by using readily available and relatively inexpensive materials that can be easily produced in a central device and physically fed into the system while recharging it with minimal time and effort.

The advantages and benefits of the present invention are achieved by a rechargeable electric battery comprising at least one cell having a normally positive electrode for reducing halogen brought into electrical contact therewith and a normally negative electrode having oxidizing metal in electrical contact therewith during electrical discharge of said cell. a storage tank adapted to contain a certain amount of halohydrate, an aqueous metal halide electrolyte, connecting means for connecting the cell and the storage tank, a recirculation device for recycling the electrolyte during the discharge of the cell and the storage tank, characterized in that it comprises means for adding oxidizing metal to the cell to at least partially replace the consumed metal and means for electrolyte formed during the discharge of the cell; to remove the core at least in part to maintain the volume of the electrolyte within predetermined limits.

Halogen is preferably chlorine.

The oxidizable metal is preferably zinc.

According to one embodiment of the invention, the means for adding oxidizable metal to the cell comprises an electrolyte slurry containing entrained oxidizable metal particles, which electrolyte is fed to a recycling device for conveying the particles into electrical contact with the negative electrode.

/ · 3 631 34

The negative electrode then preferably has a plurality of porous chambers intended to be filled with oxidizable metal particles by feeding a slurry of particulate metal and electrolyte to the electrode chambers.

In addition to the above, the decomposition of the halide hydrate is the dissolution of oxidized metal and reduced halogen in the electrolyte causing a continuous increase in volume during battery discharge from which portions of the electrolyte are removed at appropriate intervals to maintain total volume in a preselected operating range. Periodic electrolyte removal may suitably coincide with halogen hydrate and / or oxidizable metal refill cycles.

The invention also relates to an electric battery comprising at least one cell having a normally positive electrode for reducing halogen brought into electrical contact therewith and a normally negative electrode having oxidizing metal in electrical contact with said cell during electrical discharge. a storage tank adapted to contain a certain amount of halohydrate, an aqueous metal halide electrolyte, connecting means for connecting the cell and the storage tank, recycling the electrolyte of the recycling device to the and means for removing at least part of the electrolyte formed during the discharge of the cell to maintain the volume of the electrolyte; within predetermined limits, use as a power source for the vehicle engine.

In fixed installations, recharging of the electric battery can be accomplished simply by supplying a fresh supply of oxidizable metal and halide hydrate to the location of the power plant according to a suitable schedule consistent with the use of the electric battery. In mobile power plant systems, such as those used in vehicles, recharging or recharging the electric battery can well be performed at roadside stations, where the electric battery module parts can be replaced with recharged modules with very little time and effort. The spent modules, including the electrolyte containing the dissolved metal halide salt, can be regenerated at such service stations or a central processing plant to form an oxidizable elemental metal and halide hydrate for reuse when recharging the electric battery.

Other advantages and advantages of the present invention will become apparent upon reading the description of the preferred embodiments and considering it in conjunction with the accompanying drawings.

Figure 1 is a schematic representation of an electrical energy storage device electrically connected to a motor; Fig. 2 is a perspective view of an electrode formed of a plurality of recesses made to be re-charged with oxidizable metal; Fig. 3 is a schematic representation of a rechargeable electric battery installed in a vehicle according to an embodiment of the present invention; Fig. 4 is a schematic representation of a rechargeable electric battery installed in a vehicle according to another satisfactory embodiment of the present invention; and Figure 5 is a schematic representation of a rechargeable electric battery installed in a vehicle in accordance with yet another alternative satisfactory embodiment of the present invention.

The electrical energy storage system for the oxidizable metal and halohydrate essentially comprises an electrolyte consisting of a solution containing dissolved metal halide and dissolved and / or absorbed halogen gas adapted to be reduced upon electrical contact with the positive electrode during storage of the positive electrode. In addition to the above essential ingredients, various other additives and ingredients may be incorporated into the liquid electrolyte to bring about controlled changes in its physical and chemical properties to improve performance. The electrolyte preferably consists of an aqueous solution containing from about 0.1% by weight to * to a saturation concentration of a metal halide consisting of a metal selected from the group consisting of Group VIII of the Periodic Table (namely: Pe, Co, Ni, Ru, Rh, Pd, OS, Ir and Pt), lanthanum series metals (namely: Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). and actinium series metals (namely: Th, Pa, U, Np, Pu, Am,

Cm, Bk and Cf), in addition to the following metals: Zn, Se, Ti, V, Cr, Mn, Cu, Ga, Y, Zr, Nb, Mo, Te, Ag, Cd, In, Sn, Hf, Ta, W , Re, Au, Hg,

Tl, Pb, Bi, Li, K, and Na, Pb, Cs, Be, Mg, Ca, Sr, and Ba. Metals that react with water can be allowed to stabilize and used as amalgams (mercury solutions). Of the above metals, zinc is the more preferred metal, while iron, cobalt and nickel are preferred among the remaining listed metals. Preferred halogen components are chlorine and bromine, of which the chloride salts of the preferred metals are particularly suitable and form the preferred embodiment. Particularly satisfactory results are obtained using aqueous solutions containing zinc chloride as the metal halide.

Although metal halide concentrations as low as about 0.1% can be used in the aqueous electrolyte, it is recommended to use concentrations of at least about 5-50% and more usually about 10 to about 35% by weight. When zinc chloride is used as the metal halide, the maximum conductivity of the electrolyte is achieved at a concentration of about 25% by weight, so that the concentrations of this particular substance in the electrolyte, which range from about 10 to about 35%, are particularly satisfactory.

The electrochemical reaction that occurs during a battery discharge is represented by the following equation:

Zn ° - »Zn ++ + 2e

Cl2 ° + 2e - »2C1"

Cl2 · 8H2O - »Cl2 + 8H2O

The above equations apply to a battery in which the oxidizing metal i 6 631 34 is zinc, the halogen is chlorine and the hydrate is chlorohydrate which decomposes continuously supplying more chlorine to the aqueous electrolyte to replenish the reduced chlorine with a positive electrode and enters the electrolyte in the form of chloride ion. with. Because water is added to the electrolyte as a result of the continuous decomposition of the halide hydrate, the concentration of the metal halide salt in the electrolyte remains moderately constant throughout the discharge phase of the battery. The volume of the electrolyte will, of course, increase continuously, and such a volume in excess of a preselected amount may be removed from time to time and subjected to reprocessing to recover the elemental metal and the corresponding halide hydrate.

A typical closed system of an electrical energy storage device is shown schematically in Figure 1 and comprises an electrode region or package, denoted by the letter S, consisting of one or more cells each containing a positive and a negative electrode placed in a hydrate storage region of the transmission link, which is denoted by the letter H. The aqueous electrolyte is circulated, for example, by means of a pump P from the storage tank through the electrode region S and from there back to the tank to replenish the chlorine gas or other halogen gas consumed in the electro-zone during electric current generation. Since the decomposition of the halide hydrate is endothermic, it is desirable in some cases to use a heat exchanger 10 to supply heat to the electrolyte before it enters the hydrate tank H to facilitate decomposition or "melting" of the hydrate and absorption of the halogen gas into the electrolyte. The electric current produced according to the arrangement shown in Fig. 1 is connected to a load such as a motor M, which is controlled by a switch 12 mounted in series in the electric circuit.

The replenishment of the oxidizing metal and the halide hydrate and the removal of excess electrolyte must be carried out at regular intervals, depending on the particular design features of the battery. In structural configurations to which a larger pool of oxidizable metal can be added, replenishment of the oxidizable metal can be performed at less frequent intervals than replenishment of the halide hydrate. For example, in a typical vehicle device, the replenishment of an oxidizing metal such as zinc can be performed at the end of each twenty-hour discharge time, which corresponds to about 1600 km; while the halohydrate component can be replenished at shorter intervals, such as at the end of each four-hour discharge, which corresponds to about 320 road kilometers driven. i: 7 631 34 ri. The halogen hydrate replenishment period generally corresponds to the average refueling period for conventional gasoline-powered vehicles.

Refillation of the oxidizable metal can be accomplished by replacing the entire electrode package, replacing only the negative electrodes, or alternatively feeding a physically oxidizable elemental metal to the electrode region, e.g., in the form of plates, rods, or pieces placed in the electrode region. In the latter case, a plurality of recesses or grooves 16 are formed in the negative electrode 14 shown in Fig. 2, which may suitably consist of a conductive unreacted material such as graphite, on its second surface extending inwardly from one edge of the electrode to a point slightly apart from its opposite edge. A porous separating material 18 consisting of a chemically resistant non-conductive material, such as a polytetrafluoroethylene-coated glass cloth, is suitably attached or otherwise attached to the surface of the electrode 14. The porosity of the porous separator 18 is adjusted with respect to the metal particles fed to the electrolyte slurry so that it acts as a filter, causing the particles to remain in the grooves 16 according to the slurry flowing inwards from its free ends. The electrolyte slurry is pumped through the electrode region until substantially all of the grooves 16 of the negative electrodes 14 are filled with oxidizable elemental metal, which returns the storage device to a fully recharged state.

The replenishment of the halohydrate component can best be accomplished by physically removing the storage tank H and replacing it with a similar tank filled with the halogen hydrate. This constitutes a preferred method in that the simultaneous replacement of the tanks results in the removal of the increased amount of electrolyte that has developed during the previous discharge period.

In addition to the above, the addition of the halohydrate can also be carried out by feeding the halohydrate into the electrolyte in the form of small particles suspended in a slurry; as solid granules or compressed pieces which can be easily fed into the container H; as an assembled structure comprising an inert support frame serving as a support for a halide hydrate supported on and inside its surface; and in the form of small particles, the size of which allows them to be fluidized using the gaseous halogen of which the hydrate is composed, as a fluidizing and carrier medium. In any case, the hydrate replenishment is performed to provide a continuous supply of halogen gas to reduce it with a positive electrode during the discharge cycle of the storage device.

Periodic removal of the electrolyte, which may occur in conjunction with halogen hydrate and / or oxidizing metal replenishment cycles, is performed as described above during replacement of the hydrate storage tank, which is itself filled with electrolyte, to replace the spent halide hydrate. Alternatively, a collection vessel may be placed in the recycling system into which the collection of the generated electrolyte may be performed and which collection vessel may be emptied from time to time to keep its total volume within the limits required by the system. In installations where the halide hydrate is physically replenished directly in the storage tank H as shown in Figure 1, a suitable drainage system may be connected to the tank to remove the electrolyte before it is replenished with the halogenate.

It will be appreciated from the above that both fixed backup storage systems and mobile electricity storage systems perform a quick and simple recharging of the battery to fully recharge it without suffering any significant downtime or costly and time consuming recharging processes, such as were necessary. In accordance with the practice of this invention, regeneration of rechargeable components of a battery can be easily, efficiently and economically performed at a central or local service station where the collected effluent electrolyte is electrolytically treated to precipitate a metal component and regenerate halogen gas to form an aqueous medium. separated and recovered. Such central or local service stations can process the electrolyte by purchasing alternating current from electricity companies at a lower cost during load base times and using large-scale equipment, thus achieving optimum efficiency and economy.

A typical in-vehicle refillable electrical energy storage device is shown in Figure 3. As seen, the vehicle 30 is provided with a permanently installed electrode package space 22 and a hydrate tank 24 that are periodically refilled or replenished at roadside service stations. The electrode package space 22 is electrically connected to a traction motor 9 63134 26 which moves the vehicle. In the specifically shown embodiment, the service station is equipped with an electrochemical regeneration unit 28 which is operated by an alternating current purchased from the power plant and rectified by a rectifier 30 to supply direct current to the regeneration unit 28. A suitable cooling unit which implies an exothermic reaction. In the arrangement specifically shown in Figure 3, the oxidizable metal Zu and the halogen hydrate C

According to an alternative satisfactory arrangement shown in Figure 4, a vehicle 34 incorporating a rechargeable battery of the present invention is recharged by physically removing both the electrode pack 36 and the hydrate storage tank 38 at a suitable roadside service station, which equipment is replaced by a recharged electrode pack 36 ' . As in the previous case, the vehicle is driven by a suitable motor or electric device 40 mounted in a transmission connection relative to the ground.

As in the case of the embodiment shown in Figure 3, the arrangement schematically shown in Figure 4 is based on the purchase of electrical energy from a local power plant, which current is rectified to produce direct current by means of a rectifier 42. Alternatively, a suitable direct current can be supplied by means of an alternating or direct current generator. An electric current is used to keep the cooler unit M running to cool the electrolyte and also to provide the reverse polarity to the electrode region 36 'to recharge it. The halogen gas generated during recharging is transferred to a suitable hydrate generator 46 operatively connected to the cooling unit 44 and the halogen hydrate formed is easily returned to the hydrate tank 38 *. In this particular embodiment, the electrolyte is removed in conjunction with the removal of the entire storage battery system, which in turn is regenerated in situ to reprecipitate the oxidizing metal to the negative electrodes and to replenish the halogen hydrate in the hydrate tank.

Another alternative satisfactory embodiment of the rechargeable battery 10 631 34 is shown in the arrangement shown in Figure 5. The illustrated mobile vehicle arrangement comprises a vehicle 50 driven by a motor 52 connected by transmission to the wheels and comprising a fixedly mounted hydrate tank 5h 3 made to be replenished with a hydrate at a service station and a removable electrode pack 56 made completely replaceable by a supplemented electro pack 56 at a roadside service station. As in the previous embodiments, the commercially purchased electric current is converted to direct current by a rectifier, which in turn is used to recharge the discharged electrode stack 56 * by electroplating metal ions normally on the negative electrode. The cooling unit 60 also operates with commercially purchased electrical energy, supplying refrigerant to a hydrate generator 62, where the halide hydrate is regenerated and stored in a hydrate storage tank 64 at the roadside station. Physical replenishment of the vehicle hydrate tank 54 is accomplished by transferring the regenerated hydrate from the storage tank 64 directly to the tank 54.

While it will be appreciated that the invention disclosed herein is well designed to achieve the above benefits and advantages, it should be noted that the invention may be modified, altered and varied without departing from the spirit thereof.

Claims (6)

631 34 11 An electric battery comprising at least one cell having a normally positive electrode for reducing halogen brought into electrical contact therewith and a normally negative electrode having oxidizing metal in electrical contact therewith with said cell during electrical discharge, a storage tank adapted to contain a certain amount of halogen hydrate, an aqueous metal halide electrolyte, connecting means for connecting the cell and the storage tank, a recycling device for circulating the electrolyte through the connecting means between the cell and the storage tank to oxidize the metal to at least partially replace the spent metal and means for at least partially removing the electrolyte formed during the discharge of the cell in order to maintain the volume of the electrolyte in advance; within certain limits. Electric battery according to Claim 1, characterized in that the halogen is chlorine. Electric battery according to Claim 1, characterized in that the oxidizing metal is zinc. An electric battery according to claim 1, characterized in that the means for adding oxidizable metal to the cell comprise an electrolyte slurry containing entrained oxidizable metal particles, which electrolyte is fed to a recycling device for electrically contacting the particles with a negative electrode. An electric battery according to claim 1, characterized in that the negative electrode has a plurality of porous chambers intended to be filled with oxidizable metal particles by feeding a slurry of particulate metal and electrolyte to the electrode chambers. An electric battery comprising at least one cell having a normally positive electrode for reducing halogen brought into electrical contact therewith and a normally negative electrode having oxidizing metal in electrical contact therewith with said cell during electrical discharge, a storage tank adapted to contain a certain amount of halohydrate, aqueous metal halide electrolyte, connecting means for connecting the cell and the storage tank, a recycling device for recycling the electrolyte through the connecting means between the cell and the storage tank to replace the oxidizable metal at least in part and means for removing at least in part the electrolyte formed during the discharge of the cell in order to maintain the volume of the electrolyte in advance within certain limits, use as a power source for the vehicle engine.