NON-AQUEOUS CELL WITH ACTIVE METAL ANODE.

Description

TITLE NON-AQUEOUS CELL WITH ANODE OF A ACTIVE METAL. INV. DES KALNOKI-KIS TIBOR U.S. PRIORITY PATENT APPLICATION No. 52467 DATED JUNE 27, 1979 PATENT APPLICATION No. 147218 DATED MAY 6, 1980 Rome, the linens. / IC ι ( / A ·ύ Register A Protocol No. 23000 A / 80 MINISTRY OF INDUSTRY, COMMERCE AND CRAFTS Provincial Office of Industry, Commerce and Crafts of Milan COPY OF IRE UIT.III FOR DEPOSIT FOR SHORT SENDING INDIVIDUALS, AND In the year 19OO on the twenty-ninth day of June the Pitia UNION CANDIDE ΟΟΚίΌΗΛΤΙΟΝ ι kÉiqnocx of American nationality Ξ2 ..... jn New York, NY (USA) ΓΚ'ίΊΕΕηΤ-Ο'Α Via by proxy MODIANO & ASSOCIATI Sas di dr.ing. «. MODIANO C (Italian Patent and Trademark Agency) and with domicile for legal purposes in Milan - Via Meravigli Ifì at »· agent has presented to me, the undersigned: - Application in boi lo for the granting of a PATENT FOR INDUSTRIAL INVENTION having for II 7 OL 0I NON-AQUEOUS CELL WITH ACTIVE METAL ANODE. inventor designated ο: KAlJJÙKI-KI5 Tibor Priority of the patent application in: USAN of June 2, 19 19 and H. 1L721O of 6 May 1960. accompanied by: Description in duplicate of n. gj pages of writing. DttesokritutaletcaxtJooLxxTtRXRiptQix - Letter of appointment - ^g^TazuiWK.rtt2rimsrite <aT±.'Altoj:1i-)pr33rjr£,; • Priority documents and Italian translation. (with reservation,) - Authorization or deed of transfer, (with reservation) - Act of designation of the inventor. • Proof of payment on postal account no. 00668004 in the name of the Tax and Concession Registry Office Rome of L. 112,500© sent by the Post Office of Milan 23 on 25.6.1980 n. 035 - Boiled milk brand L. 2,000.* The application, descriptions and drawings listed above have been signed by the applicant and countersigned by me and stamped with the office seal. THE DEPOSITOR ..SS For copying in accordance with the final version (The UFEIC) Peter Meeei p. the Director (Salvatore Ravalli) The Whales) __ THE HEAD OF THE PATENT OFFICE 5K)) Baleni) Hon. MINISTRY OF INDUSTRY, TRADE AND CRAFTS Central Patent Office - R Ο KA The Company iixjBqrtteemtm UNION CARBIDE CORPORATION of American nationality With registered office / $,-* 1 !￢ﾀﾙ ￎﾽￂﾷ 1 L ￎﾌ ' : F ￂﾰ i ! f'O / t XX ￏﾊ Z, 't'G 0 6 0 A / 80 letters» 1” No” **· N· γ· (USA) & medium Agent MODIANO & ASSOCIATI Sas di Dr.Ing,G.MODIANO & C.(Italian Patent and Trademark Agency)S ............. ............................................................................! ί and with elective domicile for legal purposes in Milan j Via Meravigli 16, requests the granting of a patent for the invention entitled: CELIA NON ACQUOSA CON ANODE OF AN ALLOY METAL. Designated Inventor: KALNOKI-KIS Tibor U Γ'Ί.O.L,MI! / ·'·':> k -VifiCiUiSVpr '****· · ·*·>»'» 1. .L· ,£ . . J 2C.Ì S0 023060 ijwa «... • ... .LU— I— ftΪ : :t» Ih “·********** HtVW MFurttM Priority of patent application in: USA, N, 52467 of June 27, 1979 and N, 147216 of May 6, 1960. Attached documentation: a) Description in duplicate. b) Dj6»gjd3di^xxxxxx.-taoreiB>i»«dupii®exe»piSìpt->· d) Priority document ccn Italian translation (with reservation 1 e) Authorization or deed of transfer (with reservation). f) Act of designation of the inventor. g) Proof of payment of the required taxes. h) Revenue stamp of L. 2,000,... ... 1 Date OR. GìU.WO ...........................\ „ IH X Mt V. 71277 / ΰΟΗ ' (ΒΡ 12521-1-1)' •f AQUEOUS CELL WITH ACTIVE METAL ANODE. UNION CARBIDE CORPORATION, in New York, NY (USA) Designated Inventor: KALNOKI-KIS Tibor Deposited on 26 JUNE 1930 at No. 2 3 0 8 0 A / 80 There . ss, ia *sa, tr *et. if * r- # t= , SUMMARY Non-aqueous cell comprising an anode of an active metal, for example lithium, a cathode collector and a conductive cathode-electrolyte comprising a solute dissolved in a liquid cathode, such as an oxyhalide, and in which a vinyl polymer is dissolved in the cathode-electrolyte. B * SS * · SS | SS , DESCRIPTION The present invention relates to a non-aqueous cell in which an active metal anode, a cathode collector, an ionically conductive cathode-electrolyte comprising a solute dissolved in an active liquid cathode and in which a vinyl polymer is dissolved in the cathode-electrolyte are employed. The development of high-energy bacterial systems requires, among other things, the compatibility of an electrolyte possessing desirable electrochemical characteristics with highly reactive anode materials, such as lithium or similar materials. The use of aqueous dioxide trolytes is precluded in these systems, since the anode materials They are active enough to react chemically with water. Therefore, in order to realize the high energy density achievable through the use of these highly reactive anodes, it was necessary to turn to the research of non-aqueous electrolyte systems. The term nonaqueous electrolyte as used here refers to an electrolyte that consists of a solute, for example a salt of a metal or a complex salt of elements from Group IA, Group IA, Group IIIA, or Group VA of the Periodic Table, dissolved in a suitable nonaqueous solvent. The term Periodic Table as used here refers to the Periodic Table of the Elements given on the inside cover of the Handbook of Chemical and Physics, 8th Edition, The Chemical Rubber Co., Cleveland, Ohio, 1967-1968. Many solutes are known, and many have been suggested for use, but selecting a suitable solvent is particularly challenging. The ideal battery electrolyte should comprise a solvent-solute pair that has a wide liquid-state range, high ionic conductivity, and high stability. A wide liquid-state range—that is, a high boiling point and a low freezing point—is essential if the battery is to be operated at temperatures other than normal room temperature. High ionic conductivity is necessary if the battery is to have a high output capability. Stability is necessary for the materials that make up the electrodes, the construction materials, and the electrolyte. of the cell and the products of the reaction that occurs in the col, in order to achieve a long shelf life when used in a primary or secondary battery system* Recently it has been described in the literature that certain materials are able to act as a vehicle for an electrolyte, for example, as a solvent for the salt that constitutes the electrolyte, and as an active cathode for a non-aqueous electrochemical cell* U.S. Patents* Nos. 3,475,226, 3,567,515, and 3,578,500 each indicate that liquid sulfur dioxide or solutions of sulfur dioxide and a cosolvent can perform this dual function in nonaqueous electrochemical cells. While these solutions perform their dual function, they present several drawbacks when used. Sulfur dioxide is always present and, being a gas at ordinary temperatures, must be contained in the cell as a liquid under pressure or dissolved in a liquid solvent. If sulfur dioxide alone is used, handling and packaging problems arise, and if sulfur dioxide must be dissolved in a liquid solvent, an additional component is required and an additional assembly step is necessary. As indicated above, a wide liquid state range that includes normal room temperatures is a desirable characteristic in a solvent for an electrolyte.Obviously, sulfur dioxide is not suitable, in this respect, at atmospheric pressure. Patent application, USA serial number 439,521 in the name of of 0. B* Blomgren et al filed on February 4, 1974, describes a r non-aqueous electrochemical cell comprising an anode, a cathode collector, and a cathode-electrolyte, said cathode-electrolyte comprising a solution of an ionically conducting solute dissolved in an active cathode (depolarizer) wherein said active cathode (depolarizer) is a liquid oxyhalide of an element of Group V or Group VI of the Periodic Table. Although oxyhalides can be used effectively as a component of a cathode-electrolyte in conjunction with an anode of an active metal, for example, a lithium anode, to produce a high energy density cell of good characteristics, it has been observed that if the cell is stored for an extended period of time of about three days or more, passivation of the anode is noted, resulting in undesirable voltage delays at the onset of discharge together with high cell impedance. U.S. Patent 3,993,501 to T. Kalnoki-Kis describes an approach for minimizing or avoiding undesirable voltage delays at the onset of nonaqueous cell discharges employing an oxyhalide-containing electrolyte-atode by coating a vinyl polymer film on the surface of the anode that contacts the electrolyte-cathode. The disclosure made in this patent is incorporated herein by reference. U.S. Patent Application Serial Number 015*938 de- - 5 ~ refers to a non-aqueous cell comprising an active metal anode, for example lithium, a liquid cathode electrolyte comprising a solute dissolved in a solvent that is an oxalhalide of an element in Group V or Group VI of the Periodic Table, and in which elemental sulfur or a sulfur compound is incorporated into the cathode electrolyte so as to substantially eliminate an initial voltage delay of the cell during discharge. This description is included herein by reference. One of the objects of the present invention is to substantially prevent passivation of the metal anode and active in cells having a liquid electrolyte-cathode. Another object of the present invention is to provide a liquid cathode-electrolyte cell in which a vinyl polymer is dissolved in the liquid cathode-electrolyte to substantially prevent passivation of the active metal anode during storage and use of the cell. Another object of the present invention is to provide a cell system having an oxyhalide electrolyte-cathode employing elemental sulfur or a sulfur compound in the electrolyte-cathode as described in U.S. Patent Application Ser. No. 015,9J8 together with a vinyl polymer to effectively prevent passivation of the active metal anode. during storage and during use of the cell. The foregoing and further purposes will become more fully apparent from an examination of the following description. The present invention relates to a high-density non-aqueous cell comprising an active metal anode; a cathode collector; an ionically conducting electrolyte-cathode solution comprising a solute dissolved in an active liquid cathode (depolarizer) with or without a reactive or non-reactive cosolvent; and wherein a vinyl polymer is dissolved in the cell's cathode electrolyte to decrease the duration of the cell's voltage delay during discharge. The concentration of the vinyl polymer dissolved in the electrolyte The electrolyte-cathode concentration should be between approximately 0.25 grams per liter and approximately 4.0 grams per liter, referred to the electrolyte-cathode. Preferably, the concentration should be between 0.25 and 1.5 grams per liter, and more preferably approximately 0.5 grams per liter. A concentration below 0.25 grams per liter is considered ineffective in substantially reducing the duration of the voltage delay during the initial discharge while a concentration above 4.0 grams per liter demonstrates no effective improvement in further reducing the duration of the voltage delay at the initial discharge. The vinyl polymer materials suitable for use in accordance with the present invention are normally solid vinyl polymers or / such as for example homopolymers of vinyl chloride or vinylidene chloride, or copolymers containing vinyl chloride or vinylidene chloride having copolymerized therein at least one of the said monomers selected from the group consisting of vinyl esters, dibasic acids, diesters of dibasic acids and monoesters of dibasic acids. The term copolymers is used here to indicate mixed polymers or mixtures of polymers and also heteropolymers formed from two or more different monomers polymerized together (reference: Copolymer Chemical and Technical Dictionary, 3rd Edition, H. Bennett, editor, Chemical Publishing Company, 1974) General examples of suitable copolymers include combinations of vinyl chloride copolymerized with vinyl esters such as vinyl acetate and the like; vinyl chloride copolymerized with diesters of dibasic acids such as dibutyl maleate; vinyl chloride copolymerized with vinyl esters such as vinyl acetate and dibasic acids, or monoesters or diesters of dibasic acids such as maleic acid, dibutyl maleate, or monobutyl maleate. Specific examples are: a vinyl chloride / vinyl acetate copolymer containing 97% vinyl chloride - 3% vinyl acetate; a vinyl chloride / vinyl acetate copolymer containing 86% vinyl chloride - 14% vinyl acetate; a vinyl chloride / vinyl acetate / dibasic acid copolymer containing 86% vinyl chloride - 13% vinyl acetate - 1% maleic acid. Suitable vinyl polymeric materials suitable for use in the present invention are also described in U.S. Pat. 4· 141*870 cho is inserted here as a reference. As used here and as described in an article entitled Electrochemical Effects In Batteries by Akiya Kozawa and R.A. Powers in the Journal of Chemical Education - Vol. 49, pages 587-591, September 1972 Edition, a cathode depolarizer is the cathode reactant and, therefore, is the electrochemically reduced material at the cathode. The cathode collector is not an active reducible material and functions as a current collector and also as an electronic conductor for the positive terminal (cathode) of a cell. In other words, the cathode collector is a site for the electrochemical reduction reaction of the active cathode material and the electronic conductor to the cathode terminal of a cell. A liquid-active reducible cathode material (depolarizer) can be mixed with a conducting solute or a non-reactive material, which is added to improve the conductivity of liquid-active reducible cathode materials, or it can be mixed with a conducting solute and a reactive or non-reactive co-solvent. A reactive co-solvent is a product that is electrochemically active and therefore functions as an active cathode material, while a non-reactive co-solvent is a product that is electrochemically inactive and therefore cannot function as an active cathode material. A separator, if employed in the cell of the present invention -2 should be chemically inert and insoluble in the electrolyte-ca- All liquid θ must have a porosity such as to allow the liquid electrolyte to pass through the anode of the glue and come into contact with the anode of the sila, thus establishing an ion transport path between the anode and the cathode. A suitable separator for use in the present invention is a non-woven or woven glass fiber fabric. Any compatible solid product that is substantially the t electronically conductive will be useful as a cathode collector in the cell of the present invention. It is desirable to have the largest possible surface contact between the electrolyte-cathode and the collector. Therefore, it is preferred Use a porous collector because it will provide a high surface area interface with the electrolyte-liquid cathode. The collector can be metallic and can be present in any physical form, such as a metal film, a mesh structure, or a pressed powder. Preferably, however, a pressed dust collector should be at least partially composed of a carbonaceous material or other material having a high surface area. The solute can be a simple salt or a double salt that will form an ionically conducting solution when dissolved in the solvent. Preferred solutes are complexes of inorganic or organic Lewis acids and ionizable inorganic salts. The main requirements for use are that the salt, simple or complex, be compatible with the solvent to be used or that it form a solution that is ionically conducting. According to the Lewis concept or electronic concept of acids and bases, many substances that do not contain active hydrogen can act as acids or as electron pair acceptors. The fundamental concept is reported in the chemical literature (Journal of the Franklin Institute, Vol. 226 - July / Peooober, 1938, pp. 293-313 by G.N. Lewis). A suggested reaction mechanism for how these complexes function in a solvent is described, in detail, in U.S. Patent 3,542,602 where it is suggested that the complex or double salt formed between the Lewis acid and the ionizable salt forms an entity that is more stable than either component alone. Typical Lewis acids suitable for use in the present invention include: aluminum fluoride, aluminum bromide, aluminum chloride, antimony pentachloride, zirconium tetrachloride, phosphorus pentachloride, boron fluoride, boron chloride, and boron bromide. Among the ionizable salts useful in combination with Lewis acids are: lithium fluoride, lithium chloride, lithium bromide, lithium sulfide, sodium fluoride, sodium chloride, sodium bromide, potassium fluoride, potassium chloride, and potassium bromide. ' • . To those skilled in the art it will be obvious that double salts formed from a Lewis acid or an inorganic ionizable salt may be used as such, or the individual components may be used. can be added to the solvent, separately, to form the λ salt or the resulting ions in situ. Such a double salt, for example, is that formed by combining aluminum chloride and lithium chloride to obtain lithium aluminum tetrachloride. In accordance with the present invention, there is provided a nonaqueous electrochemical system comprising an active metal anode, a cathode collector, or a liquid cathode-electrolyte having a vinyl polymer dissolved therein, said cathode-electrolyte comprising a solute dissolved in an active deductible electrolyte solvent, such as at least one oxyhalide of an element in Group V or Group VX of the Periodic Table and / or a liquid halide of an element. Group IV, V, or VX of the Periodic Table, with or without a co-solvent. The active reducible electrolyte solvent performs the dual function of acting as a solvent for the electrolyte salt and as an active cathode (depolarizer) of the cell. The term electrolyte-cathode is used here to describe solvent-containing electrolytes that can perform this dual function. The use of a single cell component as an electrolyte solvent and as an active cathode (depolarizer) is a relatively recent development, since previously, it was generally considered that the two functions were necessarily independent and could not be performed by the same material. For a solvent electrolyte to function in a cell, it must come into contact with the anode and the cathode (depolarizer) in such a way as to form a contact between them. continuous Ionian course. ί · i Thus, it was generally assumed that the active cathode material should never directly contact the anode, and thus the two functions were mutually exclusive. However, it has recently been discovered that certain active cathode materials, for example liquid oxyhalides, do not react appreciably chemically with an active anode metal at the interface between the metal and the cathode material, thus allowing the active cathode material to contact the anode directly and act as a carrier substance for the electrolyte. While the theory regarding the cause of the inhibition of a chemical reaction is still being explored, The nature of the reaction is not fully understood at present and while the invention does not wish to be limited to any theory of the present invention, it appears that a direct chemical reaction is inhibited by an intrinsically high activation energy of the reaction or by the formation of a thin, protective film on the anode surface. A protective film on the anode surface need not be formed in such an amount as to result in a noticeable increase in anodic polarization. Although active reducible liquid cathodes, e.g. oxyhalides, prevent the direct reaction of active metal anode surfaces sufficiently or sufficiently to allow them to function as a cathode material and as a carrier for the electrolyte for non-aqueous cells, oxyhalides do, in fact, cause the formation of a surface film on the active metal anode during The cell's storage life, especially at high temperatures, consists of a rather thick layer of crystalline material. It turns out that this crystalline layer causes passivation of the anode, resulting in a voltage delay at the initial discharge, along with high cell impedance values ​​in the range of 11 or 15 ohms for a standard C-shaped cell. The amount of anodic passivation can be measured by observing the time required for the closed-circuit voltage of the stored cell to reach the desired voltage value after discharge has begun. If this delay exceeds 20 seconds, anodic passivation should be considered excessive for maximum application. What has been observed, for example, in lithium oxyhalide bonding systems is that, after the state When a load is applied across the cell terminals, the cell voltage immediately drops below the desired discharge value, then increases at a rate that depends on the temperature, the thickness of the crystal layer, and the electrical load. The exact composition of this layer is not known, but it has been observed that the thickness and density of the crystalline layer and also the size and shape of the crystals vary with the length of the storage period and also with the temperature during storage, for example, at low temperatures there is relatively little growth of the crystalline layer compared to the growth » 14 - greater than the layer at temperatures higher than approximately 0°C. Furthermore, it has been observed that when oxyhalides, for example thionyl chloride or sulfuryl chloride, are saturated with SO2 and then introduced into a lithium anode cell, a crystalline layer rapidly forms on the lithium surface and excellent passivation of the lithium is achieved. In accordance with the present invention, it has been found that anodic passivation can be substantially prevented by dissolving a vinyl polymer in the liquid cathode electrolyte. / The vinyl polymer must remain stable in the liquid electrolyte-cathode and must not significantly decrease the cell's capacity during storage and discharge, and in most cases will even increase the cell's capacity on high-rate discharge. ' . Although the While the applicant does not wish to be limited to any theory of the present invention, it appears that one reason why vinyl polymers, e.g., vinyl chloride polymers, are stable in an oxyhalide electrolyte-cathode cell system, e.g., in a lithium-oxyhalide cell system, can be explained as follows. One of the accepted mechanisms of degradation of a vinyl chloride polymer is deidrochlorination, i.e., the separation of a chlorine atom and a hydrogen atom to form H01. This process continues until the electronegativity of the remaining Cl atoms on the polymer is compensated by the conjugation energy. gallon (i.e., formation of double bonds) in the polymer. It is therefore assumed that further degradation occurs by a free radical mechanism such as the following: I . 1 I 1 1 II C„ 0_ ga CC*> C- C- C Cl H ι·ιι·»»· „here ι · · ι » ι · ι 3,000,000 — -CwC-C«CC«CCC (' indicates free radical) Many of the compounds which have been observed to interact with or interfere with the degradation of a polymer can be explained, for the most part, by the formation of radicals of the types R*, RO*, ROO', and atomic chlorine. The reaction mechanism by which SO2Clg decomposes is accepted to proceed by the formation of free radicals, namely, Cl* and SO2Cl' as described in an article entitled "The Mechanism of the Thermal Decomposition of Sulfuryl Chloride" by Z. G. Szabo and T. Böroes, Zeit.fiir Physikalische Chemie Houo Tolge 12:168-195 (1952). Thus, according to Le Chatelier's principle (chemical equilibrium), the stability of vinyl chloride polymers can be increased in an environment such as that experienced in oxyhalide systems. In other words, if the concentration of any of the degradation products is increased, the equilibrium of the ΐ reaction will be shifted in favor of the original, undegraded polymer. Polymers for use in the present invention must be capable of dissolving in the solvent or co-solvent of the cell electrolyte-cathode and must not decompose in the electrolyte-cathode. , -16r Although not all materials in the above group If they have this feature, anyone who is an expert in the sector can easily choose those materials that actually have these characteristics. J ' characteristics simply by examining the vinyl polymer to see if it will dissolve in the intended solvent of the liquid electrolyte or in the solvent or co-solvent to be used.. For example, polyethylene and polypropylene will not be suitable as they decompose into a liquid oxyhalide. ., s> (or V '· The effective concentration range of vinyl polymer in the cathode electrolyte can vary between 0.25 and about 4.0 ► grams per liter, preferably between about 0.25 and about 1.5 grams per liter. A concentration below 0.25 grams per liter in the cathode electrolyte would be ineffective in substantially preventing passivation of the active anode metal, such as lithium in a lithium oxyhalide system, while a concentration above about 4.0 grams per liter would not. would provide no additional protection or possibly even reduce the cell's discharge capacity. The vinyl polymer can be dissolved directly in the cell's electrolyte-atode solvent using any conventional technique. Thus, a vinyl polymer such as vinyl chloride-vinyl acetate can be dissolved directly in thionyl chloride before or after the addition of the solute. - 17 ionic. One benefit of adding the vinyl polymer directly to the cathode electrolyte instead of coating the anode is that it provides better control over the amount of vinyl polymer added to the glue. Furthermore, in commercial cellulose production, it is much easier to add the vinyl polymer to the cathode electrolyte than to coat the anode with a vinyl polymer film. Suitable oxyhalides for use in the present invention include sulfuryl chloride, thionyl chloride, phosphorus oxychloride; thionyl bromide, chromyl chloride, vanadium tribromide, and selenium oxychloride. lenio. Useful organic cosolvents intended for use in the present invention include compounds belonging to the following classes. Trialkyl borates: e.g., trimethyl, borate (OH 0)^B (liquid range: -29.3 to 67° θ)» « Tetraalkyl silicates: e.g., tetramethyl silicate, (CII.O) Si (boiling point 121°C). 4 Nitroalkanes: e.g., nitromethane, CH (liquid range: -17° θ to 100.8° C.) Al ohi 1 nit rili: for example acetoni*trile, CHCN ' (liquid range -45° C. up to 81.6° C.) Piai oh the aromas of: for example dimethylformamide,. BCON (CH^) 2 (liquid range -60.48 to 149°C) Lactams» for example N-methylpyrrolidone, . CH -CH -CH -CO-N-CH (liquid state range -16 to I etc. 3 202° C.) Tetr aàlohìl ureas: for example, tetramotllurea (CH^)^N-CO-N(CH^) (liquid range -1.2 to 166°C.) Esters of monocarboxylic acids» e.g., ethyl acetate (liquid range -83.6 to 77.6°C.) Orthoosteriis for example, trimethlorthoformate, HC(OCH ) (boiling point 103° C.) Lactones» for example, γ-(gamma)-butyrol a-itone, CH^-CH^-Clt^-O-CO (liquid range - 42® C up to 206® C.) Carbonate alcides: for example, dimoyl carbonate, OC(OCH ) J c (liquid state range 2 up to 90°C») Aichilen carbonates! for example, propllen carbonate Cyl(CH^) CH^-O-CO-O (liquid range -48® C to 242®C.) Monoethers! For example, diethyl ether (liquid range -116°C to 34.5°C.) Poly and yesterday: for example 1,1·^ and 1,2~dimethoxyethone (liquid state ranges -113.2 to 64.5°C and -58°C to 83®C, respectively) Cyclic ethers: for example, tetrahydrofuran (liquid range -65°C to 67°C) and 1,3-diiso3ane (liquid range -95°C to 78°C.) o U'·' \ a Nitroaromatìoi» for example, nitrobonzono (liquid state range 5t7°C up to 210.8°C.) Aromatic carboxylic acid halides » e.g., benzoyl chloride® (liquid range 0°C to 197°C) and benzoyl bromide (liquid range -24°C to 218°C.) Halides of aromatic sulfonic acids» e.g., bonzen sulfonyl chloride (liquid range 14.5°C to 251 6C.) Dihalides of phosphoric aromatic acids» for example, Bonzen phosphonyl dichloride (boiling point ?58°C.) iihalides of thiophosphonic aromatic acids» for example, Bonzen phosphonyl dichloride (boiling point 124°C at 5°C.) I------------------------------------------------r Cyclic sulfones» e.g., sulfolane, CIÌ^-OH^-CH^-CH^-SO^ (melting point 22°C)} 3-methylsulfolane (melting point -1°C.) Acid halides alkyl sulfones oi» for example, mothansulfonyl chloride (boiling point 161°C.) Alkyl carboxylic acid halides: for example, acotyl chloride (liquid range -112°C to 5θ.9°C), acotyl bromide (liquid range -96°C to 76°C), propionyl chloride (liquid range -94°C to 76°C). 80° C.). Saturated heterocyclic compounds» for example, tetrahydrothiophosphate (liquid range -96°C to 121°C) j 3-methyl-2-oxazolidone (melting point 15.9°C) Halides of dialkyl sulfamic acids » e.g., dimethyl sulfamyl <5' * Ύ - ώ chloride (boiling point 80°C l6mm.) «Alheliyl halogensulfonates» for example, ethyl chlorosulfonate (boiling point 151°C-). Halides of unsaturated heterocyclic carboxylic acids» e.g. 2-furoyl chloride (liquid range -2° C to 173°) Five-membered unsaturated heterocyclic compounds! for example, THE 3 f5“jàimethylisoxazole (boiling point 140°C) 1-M^tyl»pyrrole (boiling point 114 cC) 2,4-dimethylthiazole (boiling point 144°C) furan (liquid range - 85.65®θ to 31.36®C) 11· Esters and / or halides of dibasic carboxylic acids» e.g., ethyl oxide chloride (boiling point 135°C) * < Halides of sulfonic acids and mixed carboxylic acid halides! For example, chlorosulfonyl acetyl chloride (boiling point at 10 mm.) Dialkyl sulfoxides: e.g., dimethyl sulfoxide (liquid range 18.4°O to 189°C.) Bialcbyl sulfates! For example, dimethyl sulfate (liquid range -31.75 60* to 188.5°C.) Dialkyl sulfites» for example, dimethyl sulfite (boiling point 126°C)<. » Àlohilene sulfites for example, ethylene glycol sulfite (liquid range -11°C up to 173°C.) Some halogenated» for example, methylene chloride (range at liquid state -95 ÙC up to 40°C); 1,3-dichloropropane (liquid state range -99.5 ÙC» up to 120.4 ÙC.° Of the cosolvents listed above, the preferred ones are nitrohenzone; tetrahydrofuran; 1,3-dioxolane; 3-methyl-2-oxazolidone; propyl carbonate; γ-butyrolactone; sulfolane; ethylene glycol sulfite; dimethyl sulfite; or benzoyl chloride. Among the preferred cosolvents, the best are nitrobenzene; 3-methyl-2-oxazolidone; benzoyl chloride; dimethyl sulfite; or ethylene glycol sulfite, because they are more chemically inert than the battery components and have wide liquid state ranges, particularly because they permit highly effective use of the cathode materials. It is also within the scope of the present invention to use inorganic solvents such as liquid inorganic halides of elements of Groups IV, V and VI of the Periodic Table, for example, selenium tetrafluoride (SeP ), selenium monobromide (SeBr ), that is, 4 2 2. pure thiophosphoryl (pSCl), thiophosphoryl bromide (PSBr), vanadium pentafluoride (VP e), lead tetrachloride (PbCl), titanium tetrachloride (TiCl), disulfur decafluoride, tin trichloride-bromide (SnBrCl), tin bichloride-dibromide (SnBrCl), tin chloride-tribromide (SnBrCl), sulfur monochloride (Sgdg) or sulfur dichloride (Sgdg). These halides, in addition to functioning as an electrolyte solvent in non-aqueous environments, can also function as an active reducible cathode thus contributing to the overall active reducible material in such glues. Useful anode materials are, in general, consumable metals - and these include aluminum, the halide metals, alkali earth metals, and alloys of alkali metals or alkali earth metals with each other and with other metals. The term "alloy" as used herein and in the appended claims is intended to include mixtures, solid solutions such as lithium-magnesium, and intermetallic compounds such as lithium monoaluminide. Preferred anode materials are alkali metals such as lithium, sodium, and potassium and alkaline earth metals such as calcium. In the preferred embodiment, in selecting the particular oxyhalide for a particular cell according to the present invention, the stability of the particular oxyhalide should also be considered. oxyhalide in the presence of the other components of the cell and the operating temperatures at which the cell is expected to operate must also be considered. Thus, an oxyhalide must be chosen that is stable in the presence of the other components of the cell. Additionally, if you want to make the electrolyte solution more viscous or if you want to turn it into a gel, you can add a gelling agent such as colloidal silica. The following examples illustrate the present invention and are not to be construed in any way as limiting it. EXAMPLE .1 ' Several cells of 0.475 inch (12 mm) diameter were prepared using a lithium anode, a carbonaceous brass cathode, a non-woven glass fiber separator, or an electrolyte-atode. W, made up of 1.5 M LiAlO] in SOCl with lithium sulfide and a quantity of 1.5 M LiCl. . made up of 1.5 M LiCl by volume of S,Cl. Furthermore, a vinyl acetate / vinyl chloride copolymer containing 97% by weight of vinyl chloride and 14% by weight of vinyl acetate (obtained commercially from Union Carbide Corporation as VYNTf), or a vinyl acetate / vinyl chloride copolymer containing 86% by weight of vinyl chloride and 14% by weight of vinyl acetate (obtained commercially from Union Carbide Corporation as VTiIH) was dissolved in the electrolyte of some sweet cells in the concentration shown in Table 1. After storage.For approximately 5 days at room temperature the cells were tested for open circuit voltage (OCV); impedance (ohms); initial discharge voltage across a 75-ohm load after one second; short circuit current (SSC); discharge capacity in ampere-hours into a 75-ohm load; and discharge capacity in amper-hours into a 250-ohm load. The resulting data are shown in Table I. As is evident from the data shown, the cells employing vinyl polymer in the electrolyte-atode exhibited higher initial voltages after one second, higher short circuit currents, and lower impedances. t / υ \lP, «fe <fx ►f—( vO 'M « O m «fe -.f-Ì CN rrt V o 4» -rt © CN r»4 ©<r » . fe r* fe ». *. | co 00 © 1 Cn \O r> CO r~* cn ». r t. m co O CN r- vo cn *. * . CN © rrt Oc o CO CO o TTM( with CN faith. faith. faith NO CO rM © r“f Oc co CN or*( © . f'- COR- fe . fe fe »1 fe and NO CO CM © rM oc m © oo CN rrt CO cofer. ferrofe CO CN © rrt Oc CN CO Oc Oc 00 1 CO CO CN CN © -t Oc © CO in Oc rrt 00 fek fe fe fe fe CO fe CN CM © om faith with CD OO 1 r* faith V· ·- 1 CO oo o © &s § C> fl Ct Ά & Λ fl p O · . ife © fl ft ° g 21 | C) - td *^· •rt oow ω ι J3 w O Φ E3 Kt © rrt q. • or 1 Λ X! fl 17 LO OO fl (X P-© fl O © fe > © W fl m fl «n M c_ / I?t V* to O < fe «d <N - 25 EXAMPLE 2 Some cells with a diameter of 0.75 inches (19.1mw) were prepared. As in Example 1 except for the fact that in all cells 0.5 grams per liter of VYNW were dissolved in the electrolyte-cathode; the average impedance was 10.0 ohms; the average voltage after 1 second when discharged into a 75-ohm load was 2.33 volts; the average voltage after 5 seconds when discharged into a 75-ohm load was 3.19 volts; the short-circuit current was 1.2 amperes, Three, four, or five cells in each test lot were continuously discharged into either a 75-ohm or a 250-ohm load, or discharged intermittently for four hours a day into either a 75-ohm or a 250-ohm load. Average ampere-hours up to an average watt-hour for 2.7 volts are shown in Table II. The average voltage, cut-off at 2.7 volts, and energy density per cubic inch (wh / in 3) up to a cut-off of $ Average reading © —, in CM Oh m CM #» cn © © *ar> cn cn *vm CM r* rr· rl n* eo ΟΊ © ri rl CO «-i faith p < r •h tn o 0 owk „8? SUB y tì +» or P e.rt cn « or •β s co +» I © Γί tt Ο cn β 0 ο tì fi Ο © 0(¾ P or P <D •ri lA 0 d r- o ι © ri f—ί © CJ <· tì O BQ •ri £r\ +> CM (4 ooo fi <? & 4* 4» you .© © , Λ © m fs m +, oj © EXAMPLE 3,. Four test batches of five cells each were prepared as in Example 2. After storage for 1 month at 71°C, the twenty cells * they recorded an average open circuit voltage of 3.72 volts; an average impedance of 12.8 ohms; an average voltage after 1 second when discharged into a 75-volt load of 2.5 volts; and a short-circuit current of less than 0.1 ampere. Each batch of five cells · under test was tested as shown in Table 3 and the average voltage, average ampere-hours up to hour interruption at 2.7 volts and average energy density in watts-hour per pollioe oubioo up to interrupt time are illustrated in Table 3 Table III· » r here av - 2& cj © I P © »4 (3 © $ ࢢ! are C *rH -G 3: o\ r L0 rH * r* mc** *s On rH CN rH rH fi fi / : C? : / the I (X s <n rH 3V to VD © © », 4K » © © ri rH SMALL TABLE © if •P ri ©V © © rH 9*4 en<r •s ·% ·> ·» cn in tn in Hey rH <£> r »> ♦ © *4- ΜΊ o ft rH rH o © — © by •ri o •ri H Sg gR or Pi *rt * gg JPfl Is S ? •po ►U © d gl A •H © ! β ·& .8 8h g » H g 1S< O ir· ft © , Pi -p ft « © •ri © Pi •d -P © for 3 £ ΐ o Ο © UN U +' ί%il I Cl I <n 3 o β s •ii ft & cj a , ri ? p 0 •d ej •4 co •p (8Xj3 * *· Example 4 Several cells were prepared as in example 2. After storage at 20° C for months, the cells showed an average open circuit voltage of 3.71 volts; an average impedance of 12.5 ohms; an average voltage after one second, when discharged into a 75-ohm load, of 1.9 volts; and a short circuit current of less than 0.1 ampere. While the present invention has been described with reference to many particular details thereof, it is not intended that these details are intended to limit the scope of the present invention. »< / n>

Claims

1. CLAIMS 1. A non-aqueous cell comprising an active metal anode; a cathode collector; an ionically conductive electrolyte-cathode solution comprising a solute dissolved in an active liquid cathode j θ wherein a vinyl polymer is dissolved in the electrolyte-eathode.

2. A non-aqueous cell as claimed in claim 1 wherein the vinyl polymer is selected from the group consisting of homopolymers of vinyl chloride or vinylidene chloride, and comopolymers containing vinyl chloride or vinylidene chloride having at least one monomer copolymerized therein, selected from the group consisting of vinyl esters, dibasic acids, diesters of dibasic acids, and monoesters of dibasic acids.

5. A non-aqueous cell as claimed in claim 1 wherein the vinyl polymer is selected from the group consisting of vinyl chloride / vinyl acetate copolymers, vinyl chloride / vinyl acetate / dibasic acid copolymers, and vinyl chloride homopolymers.

4. A non-aqueous cell according to claim 1, 2 or 3 wherein the concentration of the vinyl polymer in the electrolyte-atode ranges from about 0.25 to 4.0 grams per liter of the electrolyte. 5» A non-aqueous cell according to claim 1, 2 or 3 wherein the concentration of the vinyl polymer in the cathode electrolyte ranges from about 0.5 to 1.5 grams per liter of the electrolyte.

6. A non-aqueous cell as claimed in claim 1, 2 or 3 wherein the cathode electrolyte contains a product selected from the group consisting of lithium sulfide and sulfur monochloride and mixtures thereof. 7* A non-aqueous cell as claimed in claim 1, 2 or 3 wherein the cathode electrolyte contains at least one liquid oxyhalide selected from the group consisting of thionyl chloride, sulfuryl chloride, phosphorus oxychloride, thionyl bromide, chromyl chloride, vanadyl tribromide and selenium oxychloride, 8. A non-aqueous cell as claimed in claim 7 wherein at least one liquid oxyhalide is selected from the group consisting of thionyl chloride and sulfuryl chloride.

9. A non-aqueous cell as claimed in claim 1, 2 or 3 wherein the anode is selected from the group consisting of lithium, sodium, calcium, potassium and aluminum.

10. A non-aqueous cell as claimed in claim 7 wherein the electrolyte-cathode contains an inorganic co-solvent.

11. A non-aqueous cell as claimed in claim 7 wherein the electrolyte-atode contains an organic co-solvent.

12. A non-aqueous cell as claimed in claim 7 wherein the anode is lithium and the liquid oxyhalide is thionyl chloride.

13. A non-aqueous cell as claimed in claim 7 wherein the lithium anode is: 1»liquid lithium oxyhalide sulfuryl chloride.

14. A non-aqueous cell as claimed in claim 1, 2, or 3 wherein the solute is a complex salt of a Lewis acid and an inorganic ionizable salt. The Authorized Representative: 1Ìg7 G. Modiano t ACT OF DESIGN OF THE INVENTOR KALNOKI-KIS Tibor The Authorized Representative: MODIANO & ASSOCIATI Sae dì %r. / (f- <3· , / Mì,w <£ p. ,.--XApeTT'farchi) Vtógi'feriiv ΓαϊΓΰ / MILANO