FR2478377A1 - Anode passivation resistant non aq. battery - contg. vinyl! polymer dissolved in electrolyte cathode soln. - Google Patents

Abstract

Non-aq. battery comprises an active metal anode; a cathodic; and an electrolyte-cathode soln. having ionic conductivity comprising a solute dissolved in an active liq. cathode with a vinyl polymer dissolved in the electrolyte cathode. Passivation of the active metal anode during storage and operation of the battery is avoided.

Description

 The present invention relates to a non-aqueous cell comprising an active metal anode, a cathode collector and an electrolyte-cathode having ionic conductivity which comprises a solute dissolved in an active cathodic liquid and which contains in solution a vinyl polymer.

 The production of high energy batteries requires, among other things, the compatibility of an electrolyte endowed with advantageous electrochemical properties with very reactive anodic materials such as lithium, etc.

The use of aqueous electrolytes is made impossible in these systems because the anode materials are sufficiently active to react chemically with water. It was therefore necessary, in order to be aware of the high energy density that can be obtained by the use of these very reactive anodes, to direct research towards non-aqueous electrolyte systems.

The term "non-aqueous electrolyte" as used herein refers to an electrolyte that is formed from a solute such as, for example, a metal salt or a complex salt of Group IA, IIA, IIIA or VA elements of the Table.
Periodic, dissolved in a suitably chosen nonaqueous solvent. The term "Periodic Table" as used herein refers to the Periodic Table of the Elements reproduced on the front cover of the book "Handbook of Chemistry and Pilysics", 4th Edition, The
Chemical Rubber Co., Cleveland, Ohio, 1967-1968.

 A multitude of solutes are known, and the use of many of them has been suggested, but the choice of a suitable solvent has been particularly problematic. The ideal electrolyte for battery must be formed of a solvent-solute couple which has a wide range of existence in the liquid state, a high ionic conductivity and a very good stability. A wide range of existence in the liquid state, ie, high boiling point and low freezing point, is essential if the battery is to operate at temperatures other than normal ambient temperatures. High ionic conductivity is required if the battery is to be capable of high throughput.

The stability is imposed for the materials constituting the electrodes, the materials of constitution of the stack and the products of the reaction which takes place in the stack, so that the latter has a long shelf life when used in a primary or secondary battery.

 The literature has recently made known that certain materials are capable of acting both as an electrolyte carrier, that is to say as a solvent for the salt constituting the electrolyte, and as an active cathode for a non-aqueous electrochemical cell. . US Pat. Nos. 3,475,226, 3,567,515 and 3,578,500 each disclose that liquid sulfur dioxide or solutions of sulfur dioxide and a co-solvent assume this dual function in non-aqueous electrochemical cells.

Although these solutions play their dual role, they are not without presenting various disadvantages in service. The sulfuric anhydride is still present and, since it is a gas at ordinary temperatures, it must be retained in the stack as a liquid under pressure or dissolved in a liquid solvent. Handling and packaging problems are caused if sulfur dioxide is used alone, and an additional component and additional mounting operation is required if the sulfur dioxide is to be dissolved in a liquid solvent. As indicated above, a broad range of existence in the liquid state encompassing normal ambient temperatures is a desirable characteristic of an electrolyte solvent. Obviously, sulfur dioxide is insufficient in this respect at atmospheric pressure.

 U.S. Patent Application No. 439,521, filed February 4, 1974 in the name of GE Blomgren et al., Discloses a non-aqueous electrochemical cell comprising an anode, a cathode collector and an electrolyte-cathode, the latter being formed of a solution of a solute endowed with ionic conductivity dissolved in an active cathode (depolarizing), which consists of a liquid oxy-halide of a Group V element or Group VI of the Periodic Table.Although oxy-halides can be used effectively as a component of the electrolytecathode together with an active metal anode, such as a lithium anode, to form a battery of very high energy density, it has been observed that if the battery is kept for a prolonged period about 3 days or more, passivation of the anode occurs and undesirable voltage delays occur at the beginning of the discharge, as well as a large amount of internal resistance of the battery.

 U.S. Patent No. 3,993,501 discloses a way of minimizing or preventing undesirable voltage delays at the beginning of the discharge of non-aqueous cells, the electrolyte-cathode of which contains an oxyhalide, by forming an film of a vinyl coating polymer on the surface of the anode which is in contact with the electrolyte-cathode.

U.S. Patent Application Serial No. 015,938 discloses a non-aqueous cell comprising an anode of active metal such as lithium, a liquid electrolyte-cathode comprising a solute dissolved in a solvent which is an oxy-halogenide. an element of Group V or Group VI of the
Periodic Table 1 and elemental sulfur or a sulfur compound is incorporated in the electrolyte-cathode so as to substantially eliminate the initial voltage response time of the cell during discharge.

 It is an object of the present invention to substantially prevent passivation of the active metal anode into electrolyte-liquid cathode cells.

 Another object of the present invention is to find a liquid electrolyte-cathode battery in which a vinyl polymer is dissolved in the liquid electrolyte-cathode so as to substantially prevent passivation of the active metal anode during storage and the use of the battery.

 Another object of the present invention is to find an oxy-halide type electrolyte-cathode battery in which elemental sulfur or a sulfur compound is used in the electroly-cathode according to the teachings of the state patent application. No. 15,938, together with a vinyl polymer, so as to effectively prevent the passage of the active metal anode during storage and use of the battery.

 Other features and advantages of the present invention will become apparent from the detailed description which follows.

 The invention relates to a non-aqueous high energy density cell comprising an active metal anode; a cathodic collector; an electrolyte-cathode solution having ionic conductivity comprising a solute dissolved in an active liquid cathode (depolarizing), with or without a reactive or non-reactive co-solvent; and a vinyl polymer is dissolved in the electrolyte-cathode of the cell so as to minimize the duration of the voltage response time of the cell during the discharge. The concentration of the vinyl polymer in solution in the electrolytic cathode should range from about 0.25 to about 4.0 grams per liter of electrolyte cathode. Preferably, the concentration should be between 0.25 and 1.5 g / liter and it is very advantageously equal to about 0.5 g / liter. It is estimated that a concentration of less than 0.25 g / liter is unfit. to significantly reduce the duration of the voltage response time during the initial discharge, while a concentration higher than 4.0 g / liter n1 provides no real improvement in reducing the duration of the voltage response time of the initial discharge .

 The term "vinyl polymer" as used herein refers to polymers whose monomeric units are the same (i.e., homopolymers) or differ from each other (i.e., copolymers). .

As used herein, and as described in an article published by Akiya Kozawa and RA Powers under the title "rlectrochemical Reactions in Batteries" in the
Journal of Chemical Education, Vol. 49, pp. 587-591, published September 1972, a cathodic depolarizer is a cathodic reactant and, therefore, it is the material that undergoes electrochemical reduction at the cathode. The cathode collector is not an active reducible material and behaves as a current collector coupled with an electronic conductor to the positive terminal (cathode) of a battery. In other words, the cathode collector constitutes a site for the electrochemical reduction reaction of the active cathode material and the electronic conductor connected to the cathode terminal of a battery.

 An active liquid reducible cathodic material (depolarizer) may either be mixed with a conductive solute which is a non-reactive material, but which is added to improve the conductivity of liquid active reducible cathodic materials, or may be mixed with both conducting solute and a reactive or non-reactive co-solvent. A reactive co-solvent is a co-solvent that is endowed with electrochemical activity and therefore behaves like an active cathodic material, whereas a non-reactive co-solvent is a material that is electrochemically inactive and therefore can not behave as an active cathodic material.

 If a separator is used in the cell of the present invention, this separator must have chemical inertness and must be insoluble in the electrolyte-liquid cathode; it must also be porous enough to allow the liquid electrolyte to pass through and to contact the anode of the cell thus establishing a path for ion transfer between the anode and the cathode. An advantageous separator for use in accordance with the invention is a woven or non-woven glass fiber mat.

 Any compatible solid material that is substantially electrically conductive may be used as a cathode collector in the cells of the invention. It is desirable that there is as much contact area as possible between the electrolyte cathode and the collector. It is therefore preferable to use a porous collector, because such a collector provides a high surface area interface with the liquid electrolyte-cathode. The collector may be metallic and may be present in any physical form, for example in the form of a metal film, a web or a compressed powder.

However, preferably, a compressed powder manifold must be at least partially formed of a carbonaceous material or other material with a large specific surface area.

 The solute can be a single or double salt which gives a solution with ionic conductivity dissolved in the solvent. Preferred solutes are complexes of inorganic or organic Lewis acids and ionizable inorganic salts. The main utility conditions to be satisfied involve that the salt, whether simple or complex, is compatible with the solvent that is used and gives a solution that is endowed with ionic conductivity. In accordance with the Lewis concept or the electronic concept of acids and bases, many substances that do not contain active hydrogen can behave as acids or as electron-doublet acceptors. The basic concept is exposed in the chemical literature (see Journal of the Franklin Institute, volume 226 - July / December, 1938, pages 293-313, G.N.

Lewis).

 A suggested reaction mechanism for the manner in which these complexes function in a solvent is described in detail in U.S. Patent No. 3,542,602, wherein it is presumed that the complex or double salt formed between the acid of Lewis and ionizable salt produces an entity that is more stable than either component alone.

 Representative examples of Lewis acids that may be used in the present invention include aluminum fluoride, aluminum bromide, aluminum chloride, antimony pentachloride, zirconium tetrachloride, phosphorus pentachloride, and the like. , boron chloride, boron fluoride and boron bromide.

 Ionizable salts useful in combination with Lewis acids include lithium fluoride, lithium chloride, lithium bromide, lithium sulfide, sodium fluoride, sodium chloride, sodium bromide, sodium fluoride and the like. potassium, potassium chloride and potassium bromide.

 It is obvious to those skilled in the art that double salts of a Lewis acid and an ionizable inorganic salt can be used as is or that the individual components can be added separately to the solvent to form the resulting salt or ions in situ. . A double salt of this kind is, for example, one which is formed by combining aluminum chloride and lithium chloride to form lithium aluminum tetrachloride.

The present invention provides a non-aqueous electrochemical system comprising an active metal anode, a cathode collector and a liquid electrolyte-cathode in which a vinyl polymer is dissolved, said electrolyte-cathode comprising a solute dissolved in a reducible electrolyte solvent such as at least one oxyhalogenide of a Group V or Group VI
Periodic table and / or a liquid halide of a Group IV, V or VI element of the Periodic Table, in the presence or absence of a co-solvent. The reducible electrolytic active solvent assumes the dual function of solvent for the electrolytic salt and active cathode (depolarizing) for the cell. The term "electrolyte-cathode" is used herein to refer to electrolyte-containing solvents that can perform this dual function.

 The use of a single component of the cell both as a solvent for the electrolyte and as an active cathode (depolarizer) is a relatively recent advance, since it was initially considered in general terms that both functions were necessarily independent and could not be assumed by the same subject.

 In order for the solvent of the electrolyte to operate in a cell, it is necessary that it be in contact with both the anode and the cathode (depolarizing) so as to form between them a continuous ion channel. It was therefore generally accepted that the material constituting the active cathode should never be in direct contact with the anode and, as a result, it appeared that the two functions were mutually exclusive. However, it has recently been discovered that certain active cathode materials such as liquid oxy-halides do not chemically react appreciably with an active anode metal at the interface between the metal and the cathode material, thus allowing the material cathode to come into direct contact with the anode and act as the vehicle of the electrolyte.Although the theory on which the cause of inhibition of the direct chemical reaction is based is not fully understood at the time and it is not intended to limit the invention to any theory whatsoever, it appears that a direct chemical reaction is inhibited either by a naturally high energy of activation of the reaction, or by the formation of a thin protective film on the surface of the anode. A protective film on the surface of the anode should never be formed to a sufficient extent to result in a strong increase in anodic polarization.

 Although active reducible liquid cathodes such as oxy-halides inhibit the direct reaction of the active metal anode surfaces to a sufficient extent that they can act both as a cathode material and as an electrolyte carrier for nonaqueous piles, they effectively cause the formation, on the surface of the anode of active metal during the storage of the battery, particularly at high temperatures, of a film which is formed of a fairly dense layer of material crystalline. This crystalline layer obviously causes passivation of the anode and results in a voltage response delay during the initial discharge together with high values of internal battery resistance in the range of 11 to 15 ohms for one battery. normal type C.

 The degree of anodic passivation can be measured by observing the time required for the closed circuit voltage of the battery kept in the magazine to reach the desired level of voltage after discharge has begun. If this response time exceeds 20 seconds, anodic passivation should be considered excessive for most applications. It has been observed, for example, in batteries containing an oxy-lithium halide that after a charge has been applied to the terminals, the battery voltage falls immediately below the desired level of discharge, then increases speed which depends on the temperature, the thickness of the crystalline layer and the electric charge.

 The exact composition of this layer is not known. It was observed that the thickness and density of the crystalline layer, as well as the dimensions and shape of the crystals, varied with the duration of the storage and also with the storage temperature; for example, at low temperatures, there is a relatively low growth of the crystalline layer, compared to the highest growth of the layer at high temperatures, of the order of 700C. It has also been observed that when the oxyhalides such as thionyl chloride or sulphuryl chloride are saturated with SO2 and then placed in a lithium anode cell, a crystalline layer develops rapidly on the surface of the lithium, thus passivating this metal. .

 In accordance with the present invention, it has been discovered that anodic passivation can be substantially prevented by dissolution of a vinyl polymer in the liquid electrolyte-cathode.

(dans cette formule, A indique qu'il s'agit d'un radical libres.The vinyl polymer must remain stable in the electrolyte-liquid cathode and it must not significantly reduce the battery's capacity during storage and discharge and, in most cases, even increase battery capacity, for a long time. high speed discharge. Although it is not desired to limit the invention to any theory, it appears that one of the reasons why vinyl polymers, for example vinyl chloride polymers, are stable in the cell whose electrolyte-cathode is formed An oxy-halide, for example a lithium oxy-halide battery, can be explained as follows: one of the accepted mechanisms of degradation of polyvinyl chloride is dehydrochlorination, it is aa the scission of a chlorine atom and a hydrogen atom that form the HCl molecule. This process continues until the electronegativity of the remaining chlorine atom on the polymer is compensated by the conjugation energy (i.e. the formation of double bonds) in the polymer. Subsequent degradation is considered to occur by a mechanism of free radical formation, as follows

(In this formula, A indicates that it is a free radical.

 For most of the compounds that have been observed, the interaction or the interference with the degradation of a polymer can be explained by the formation of radicals of R-, RO-, ROO and atomic chlorine types. The reaction mechanism by which SO2Cl2 decomposes is likely to result in the formation of free radicals, ie Cl and SO2Cl, as described in Z.G. Szabo and T.

Bérces titled "The Mechanism of the Thermal Decomposition of Sulfuryl Chloride", Zeit. for Physikalische Chemie, new series 12: 168-195 (1952). Thus, according to the LeChatelier principle (chemical equilibrium), the stability of vinyl chloride polymers can be promoted in a medium such as that which exists in systems containing an oxy-halide. In other words, if the concentration of any of the degradation products increases, the reaction equilibrium is shifted in favor of the undegraded initial polymer.

Unsaturated polymeric materials capable of being dissolved in electrolytes-liquid cathodes according to the invention can be represented by the following general formula corresponding to the monomeric unit of the polymer.
~ CH2 = CRRy) in which R and Ry, in the same monomeric unit, have
xy the same values as in the other monomeric units (homopolymers) or R and R in the monomeric unit
xy of a polymer do not have the same value as in the monomeric unit of the second polymer (copolymers) and
Rx is chosen from a hydrogen atom, halo
genes such as chlorine and bromine and
alkoxy groups containing alkyl radicals of 1
at 5 carbon atoms (for example acetoxy); and
R is selected from halogens such as chlorine
and bromine and alkoxy groups containing
alkyl radicals having 1 to 5 carbon atoms
(for example acetoxy).

le chlorure de @ y > dans lequel le motif monomérique répond à la formule
(CH2 = C H-Cl) et le chlorure de vinylidène dans lequel le motif monomérique répond à la formule

Examples of suitable polymers are vinyl acetate, in which the monomeric unit has the formula

the y-chloride in which the monomeric unit corresponds to the formula
(CH 2 = C H-Cl) and vinylidene chloride in which the monomeric unit has the formula

An example of a copolymer would be the vinyl chloride copolymer and the vinyl acetate in which Rx is hydrogen in the monomeric unit of the two polymers and
R is chlorine in the monomeric unit of a polymer and y is an acetoxy group in the monomeric unit of the second polyamine
For use in the present invention, polymers must be capable of dissolving in the solvent or in the solvent and co-solvent of the electrolyte-cathode of the cell and must not decompose therein. Although not all of the materials in the above group have this characteristic, anyone skilled in the art can readily choose those who possess it by subjecting the vinyl polymer to a simple test to see if it dissolves in the solvent or solvent and cosolvent liquids of the electrolyte that is desired to use.

For example, polyethylene and polypropylene would not be suitable because they would decompose in the liquid oxyhalide.

 Vinyl polymers which can be used according to the invention can be selected from copolymers of vinyl chloride and vinyl acetate, for example containing 97% vinyl chloride and 3% vinyl acetate, 86 % vinyl chloride and 14% vinyl acetate or 86% vinyl chloride, 13% vinyl acetate and 1% interpolymerized diacid (0.70.8 carboxyl group), homopolymers of chloride vinyl and homopolymers of vinyl acetate.

 The effective range of concentrations of the vinyl polymer in the electrolyte-cathode can range from about 0.25 to about 4.0 g / liter, and preferably from about 0.25 to about 1.5 g / liter. A concentration of less than about 0.25 g / liter in the electrolyte-cathode would be unable to substantially prevent the passivation of the active metal anode, such as a lithium anode, in an oxy-halide-based system. lithium, while a concentration greater than about 4.0 g / liter would not provide further protection and could even reduce the battery's discharge capacity.

 The vinyl polymer can be dissolved directly in the electrolyte-cathode solvent of the cell by any conventional technique. Thus, a vinyl polymer such as a copolymer of vinyl chloride and vinyl acetate can be dissolved directly in the thionyl chloride before or after the addition of the ionic solute. An advantage of the direct addition of the vinyl polymer to the electrolytecathode covering the anode is that the amount of vinyl polymer added to the cell is better regulated. In addition, in the industrial production of batteries, it is easier to add the vinyl polymer to the electrolyte cathode than to coat the anode with a vinyl polymer film.

 Preferred oxy-halides for use in the present invention include sulfuryl chloride, thionyl chloride, phosphorus oxychloride, thionyl bromide, chromyl chloride, vanadyl tribromide, and selenium oxychloride.

Advantageous organic co-solvents for use in the present invention include the following classes of compounds: - trialkyl borates: eg trimethyl borate
(CH30) 3B (liquid range -29.3 to 670C) - tetralkyl silicates: for example tetra silicate
methyl (CH 3 O) 4 Si (boiling point 12 ° C.) - nitroalkanes: for example nitromethane CH 3 NO 2 (range
liquid -17 to 100.80C) - alkylnitriles: for example acetonitrile CH3CN (range
liquid -45 to 81.60C) - dialkylamides: for example dimethylformamide, HCON (CH3) 2
(liquid range -60.48 to 1490C) - lactams: for example N-methylpyrrolidone,

<tb> CH2-CH2-CH2-CO-N-CH3
<tb> (liquid range -16 to 2020C) - tetraalkylureas: for example tetrathiamine,
(CH3) 2N-CO-N (CH3) 2 (liquid range -1.2 to 1660C) - esters of monocarboxylic acids: for example acetate
ethyl (liquid range -83.6 to 77.060C) - ortho esters: eg trimethyl orthoformate
HC (OCH3) 3 (boiling point 1030C) - lactones: for example qamma-butyrolactone

<tb> CH2-CH2-CH2-O-CO
<tb> (liquid range -42 to 2060C) - dialkyl carbonates: for example dimethyl carbonate
thyle OC (OCH3) 2 (liquid range 2 to 900 ° C) - alkylene carbonates: for example propylene carbonate
lene

<tb> CH <SEP> (CH3) <SEP> CH2-O-CO-O <SEP>
<tb> (liquid range -48 to 2420C)
: nonoethers: for example diethyl ether (liquid range
-116 to 34.50C)
polyethers: for example 1,1- and 1,2-dimethoxyethanes
(respective liquid ranges -113.2 to 64.50C and -58 to 830C) cyclic ethers: for example tetrahydrofuran (range
liquid -65 to 67 ° C); 1,3-dioxolane (liquid range -95 to
780C) nitroaromatic compounds: eg nitrobenzene
(liquid range 5.7 to 210.80C) aromatic carboxylic acid halides: by
benzoyl chloride example (liquid range 0 to 1970C)
benzoyl bromide (liquid range -24 to 2180C) - aromatic sulfonic acid halides: for example
benzenesulfonyl chloride (liquid range 14.5 to 10C) - aromatic phosphonic acid dihalides: by
benzenephosphomyl dichloride (boiling point
2580C) - aromatic thiophosphonic acid dihalides
for example benzenethiophosphonyl dichloride
boiling point 1240 ° C. under a vacuum of 5 mm) cyclic sulfones: for example sulfolane

<tb> CH2-CH2-CH2-CH2-SO2
<tb> (melting point 220C); 3-methyl
sulfolane (melting point -1 C) alkylsulfonic acid halides: for example chlo
methanesulfonyl chloride (boiling point 1610C) alkylcarboxylic acid halides: for example
acetyl chloride (liquid range -112 at 50.90C); bromide
acetyl (liquid range -96 to 750C); propio chloride
nyle (liquid range -94 to 800C) saturated heterocyclic compounds: for example tetra
hydrothiophene (liquid range -96 to 1210C); 3-methyl-2
oxazolidone (melting point 15.9 C) - dialkylsulfamic acid halides: for example
dimethylsulfamyl chloride (boiling point 800C,
16 mm) - alkyl halogenosulphonates: for example chícrosulphonate
ethyl (boiling point 151QC) - heterocyclic carboxylic acid halides
for example 2-furoyl chloride (liquid range
-2 to 1730C) - pentagonal unsaturated heterocyclic compounds: by
example 3,5-dimethylisoxazole (boiling point
1400C); 1-methylpyrrole (boiling point 114 C)
2,4-dimethylthiazole (boiling point 1α4oc); furan
(liquid range -85.65 to 31.360C) - esters and / or halides of dicarboxylic acids: by
example ethyl chloride and oxalyl (boiling point
1350C) - halides of alkylsulfonic acids and halides
mixed carboxylic acids: for example
chlorosulfonyl and acetyl (boiling point 980C
under a vacuum of 10 mm) - dialkylsulfoxides: for example dimethylsulfoxide (range
liquid 18.4 to 1890C) - dialkyl sulphates: for example dimethyl sulphate
(liquid range -31.75 to 188.50C) - dialkyl sulfites: eg dimethyl sulfite
(boiling point 126 C) - alkylene sulfites: eg ethylene sulfite
glycol (liquid range -11 to 1730C) - halogenated alkanes: eg methylene chloride
(liquid range -95 to 400C); 1,3-dichloropropane (range
liquid -99.5 to 120.40C).

 Among the co-solvents indicated above, those which are preferred are nitrobenzene; tetrahydrofuran; 1,3-dioxolane; 3-methyl-2-oxazolidone; propylene carbonate; gamma-butyrolactone; sulfolane and ethylene glycol sulfite; dimethyl sulphite and benzoyl chloride. Among the preferred co-solvents, the best are nitrobenzene, 3-methyl-2-oxazolidine, benzoyl chloride, dimethyl sulfite and ethylene glycol sulfite, because they have a greater inertia. the battery components and because they have wide liquid ranges and in particular because they allow a very efficient use of cathode materials.

In accordance with the invention, these inorganic solvents such as liquid inorganic halides of Group IV, V and VI elements of the invention can also be used.
Periodic table, for example selenium tetrafluoride (SeF4), selenium monobromide (Se2Br2), thiophosphoryl chloride (PSCl3), thiophosphoryl bromide (PSBr3), vanadium pentafluoride (vu5), lead tetrachloride ( PbCl4), titanium tetrachloride (TiCl4), sulfur decafluoride (S2F10), tin bromide-trichloride (SnBrCl3), dibromide-tin dichloride (Sn3r2Cl2), tribromide-tin chloride (SnBr3Cl) ), sulfur monochloride (S2Cl2) and sulfur dichloride (SCl2). These halides, in addition to behaving as a solvent for the electrolyte in non-aqueous cells, can also act as an active reducible cathode, thereby contributing to the total active reducible material in these cells.

 Useful anode materials are generally consumable metals and include aluminum, alkali metals, alkaline earth metals and alloys of alkali metals or alkaline earth metals with each other and with other metals. The term "alloy" as used herein includes mixtures, solid solutions such as lithium-magnesium, and intermetallic compounds such as lithium mono-aluminide. Preferred anode materials are alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as calcium.

 In the preferred embodiment, the choice of the particular oxy-halide for a particular cell according to the invention should also consider the stability of the oxy-halide in question in the presence of the other components of the cell. and the temperatures at which the battery must operate. Therefore, an oxy-halide must be chosen so that it is stable in the presence of the other components of the stack.

 In addition, when it is desired to make the electrolyte solution more viscous or to convert it into a gel, a gelling agent such as colloidal silica may be added.

 The present invention is illustrated by the following examples, given without limitation.

EXAMPLE 1
Several 12.06 mm diameter stacks are made using a lithium anode, a carbon cathode collector, an insulated glass fiber separator and an electrolyte cathode of 1.5M LiAlCl 4 in sOCl 2 with lithium sulfide and 3% by volume of S2Cl2. In addition, some of the batteries are dissolved in the cathode electrolyte at the concentration indicated in Table I. A copolymer of vinyl acetate and vinyl chloride containing 97% by weight of chloride of vinyl and 3% by weight of vinyl acetate (sold under the trademark "VYNW" by the firm Union
Carbide Corporation) or a copolymer of vinyl acetate and vinyl chloride containing 86% by weight of vinyl chloride and 14% by weight of vinyl acetate (sold under the trade name "VYHH" by Union Car bide Corporation After storage for approximately 5 days at room temperature, the cells are subjected to open-circuit voltage measurements (TCO); internal resistance (ohms); the initial discharge voltage across a 75 ohm resistor after 1 second; short circuit intensity (ICC); the discharge capacity in ampere-hours (Ah) on a 75 ohm resistor; and the amp-hour discharge capacity on a 250 ohm resistor. The results thus obtained are reproduced in Table I. As shown in this table, the cells whose electrolyte-cathode contains the vinyl polymer have higher initial voltages after 1 second, greater short-circuit intensities. and a lower internal resistance. TABLE I "VYhit" in
electro
No ad- "VYNW" in catholyte electrolyte (g / 1) lyte-cathode
ditif 0.25 0.25 1.0 2.1 4.2 8.4 (0.5 g / 1)
Battery n 1 battery n 2 battery n 3 cell n 4 cell n 5 cell n 6 cell n 7 cell n 8
TCO (volts) 3.70 3.69 3.69 3.69 3.69 3.69 3.69 3.70
Resistance incernz (chms) 8.3 7.5 6.9 7.6 6.4 6.0 5.7 8.1
Tenaion after a second-75 ohm (volts) 2.8 2.9 2.9 3.2 3.1 3.2 3.2 3.0
ICC (Amps) 0.6 2.1 2.8 2.1 2.0 1.7 2.7 1.4
Ampere-hours 75 ohms 0.85 0.80 0.82 0.85 0.78 0.80 0.60 0.82
Ampere-hours 250 ohms - - - 1.36 1.32 1.26 1.22 -
EXAMPLE 2
Several 19.05 mm diameter stacks are made by following the procedure of Example 1, except that in all the stacks 0.5 g / liter of "VYNW" are dissolved in the electrolyte-cathode. The average open circuit voltage of the batteries is 3.69; the average internal resistance is 10.0 ohms; the average voltage after 1 second when discharging into a 75 ohm resistor is 2.83 volts; the average voltage after 5 seconds when discharging into a 75 ohm resistor is 3.19 volts; and the short circuit current is 1.2 amperes.

 In each batch tested, three, four or five cells were discharged continuously on a 75 ohm resistor or a 250 ohm resistor or intermittently discharged for 4 hours a day on a 75 ohm or 250 ohm resistor. ohms The average voltage, the average number of ampere-hours (Ah) up to a threshold of 2.7 volts and the average energy density in watts-hour per cubic centimeter (Wh / cm3) up to a threshold 2.7 volts are shown in the following Table II.

TABLE II
Average values
Ampere Voltage - Density of light
Hours (volts) hour Wh / cm3
Three batteries, continuous discharge sux terminals of a resistance of
75 ohms 17.4 3.25 0.76 0.52
Three batteries, intermittent discharge across a 75 ohm resistor for 4 hours /
day 18.5 3.25 0.80 0.55
Four batteries, continuous discharge across a resistance of
250 ohms 89.2 3.40 1.21 0.87
Five batteries, intermittent discharge across a 250 ohm resistor
4 hours / day. 101.4 3.40 1.38 0.98
EXAMPLE 3
Four test batches of five cells each were made, as in Example 2. After storage for one month at 710 C, the twenty cells marked an open circuit voltage of 3.72 volts; an average internal resistance of 12.8 ohms; an average voltage after 1 second after discharging across a 75 ohm resistor of 2.5 volts; and a short circuit current of less than 0.1 ampere.

 Each test batch of five cells was tested as shown in Table III, which reproduces the average voltage, the average number of ampere hours to a threshold of 2.7 volts, and the average energy density. in watts hours per cm3 up to a threshold of 2.7 volts.

TABLE III
Average values
Ampere Voltage - Energy Density
Test conditions Hours (volts) hour Wh / cm3
Trial Lot 1
Continuous discharge across a 75 ohm resistor 14.9 3.19 0.63 0.42
Trial Lot 2
Intermittent discharge across a 75-ohm resistor for half an hour a day 15.1 3.10 0.64 0.43
Trial Lot 3
Continuous discharge across a 250 ohm resistor 76.6 3.30 1.01 0.70
Trial Lot 4
Intermittent discharge across a 250 ohm resistor for 4 hours per day. 80.0 3.40 1.09 0.77
EXAMPLE 4
Several stacks were made as in Example 2. After storing at 200C for six months, the batteries marked an average open-circuit voltage of 3.71 volts; an average internal resistance of 12.5 ohms a mean voltage after discharge for one second across a resistance of 75 ohms of 1.9 volts and a short circuit current of less than 0.1 amperes.

 It goes without saying that the present invention has been described for explanatory purposes, but in no way limiting, and that many modifications can be made without departing from its scope.

Claims (8)

 1. - Non-aqueous battery, characterized in that Frena an anode an active state; a Pathodite collector; an electro-cathode solution having a unique conductivity comprising a solute dissolved in an active liquid cathode; with a vinyl polymer dissolved in the electrolyte-cathode.  2. Non-aqueous battery according to claim 1, characterized in that the monomeric unit of the vinyl polymer corresponds to the formula  Wherein R is selected from hydrogen, halogens  x and alkoxy groups whose alkyl radicals have 1 to 5 carbon atoms; and R y is selected from halogens and alkoxy groups wherein the alkyl radicals have 1 to 5 carbon atoms.  3. Non-aqueous battery according to one of claims 1 and 2, characterized in that the concentration of the vinyl polymer in the electrolyte-cathode is from about 0.25 to 4.0 g / liter of electrolyte.  4. Non-aqueous battery according to one of claims 1 and 2, characterized in that the vinyl polymer is chosen between copolymers of vinyl chloride and vinyl acetate and homopolymers of vinyl chloride.  5. Non-aqueous battery according to one of claims 1 and 2, characterized in that the electrolyte-cathode contains a material selected from lithium sulfide, sulfur monochloride and mixtures thereof.  6. - Non-aqueous battery according to claim 1, characterized in that the electrDlyte-cathode contains at least one liquid oxy-halide selected from thionyl chloride, sulfuryl chloride, phosphorus oxychloride, thionyl bromide. , chro aryl chloride, vanadyl tribromide and selenium oxychloride.  7. Non-aqueous battery according to claim 6, characterized in that the electrolyte-cathode contains an inorganic co-solvent.  8. Non-aqueous battery according to claim 6, characterized in that the electrolyte-cathode contains an organic co-solvent.