FR2494915A1 - ELECTROCHEMICAL CELL - Google Patents

Abstract

Electrochemical cell comprising an anode arrangement and a functionally related cathode arrangement. The cathode arrangement consists at least partially of a mixture of a halogen component and an oxygen-containing organic component selected from the group comprising ethers, alcohols, ketones, vinyl and polyvinyl esters, salts, anhydrides, propylene oxide, poly(N-vinylpyrrolidone), propylene carbonate, triphenylphosphine oxide and mixtures of the same.

Description

 The present invention relates to the conversion of chemical energy into electrical energy, and it relates more particularly to a new and improved cathode material usable in the cells and batteries of electric cells, hereinafter generally called electrochemical cells.

 One of the fields of use of the present invention is the supply of electrical energy to inaccessible devices such as implanted pacemakers. However, the present invention is applicable to a wide variety of batteries and electrochemical cell elements. It applies in particular to battery cells intended to provide a relatively high specific voltage and energy with a great long life under conditions of low current consumption.

 In some cases, the batteries according to the invention can be assembled and encapsulated in a dry atmosphere, conveniently by operating in "dry" rooms or enclosures having a relative humidity of less than about two percent, by using substantially anhydrous components and / or dried. All the batteries and battery tests which will be described here have been prepared and carried out in practically watertight enclosures which, necessarily necessarily hermetic, nevertheless used substantially anhydrous components. In their industrial embodiments, electrochemical cells according to the invention may preferably be contained in hermetically sealed enclosures such as envelopes of welded stainless steel provided with suitable electrical crossing members intended to come into electrical contact with components of the cell as known per se. The assembly of such batteries is preferably carried out in a "dry room".

 The present invention is based on the discovery that certain organic compounds containing oxygen (which will be described by name later) are particularly interesting, when they are mixed with iodine, bromine or certain interhalogens such as IBr and the like (which will be collectively referred to as halogens in the following), as cathode materials in electrochemical cells. These compounds are interesting in that they form with the halogens electrically conductive mixtures, that is to say mixtures in which the electrical conductivity is much higher than that of the halogen alone. their composition by relating it to the initial time when the constituents are mixed together, because in some cases reaction products differing from the initial constituents which form the mixture. In such mixtures, and preferably under substantially anhydrous conditions, the halogen can be readily used to form the electrochemically active component of the cathode material.

The preferred halogen is iodine. The preferred oxygen-containing organic compounds are: polyoxyethylene (PEO) such as water-soluble lesins POLYOX, ethanol, propylene oxide and vinyl acetate. POLYOX is a trademark used by the firm UNION
CARBIDE CORPORATION to designate the polyoxyethylene that it markets. Organic substances in the form of polymers, monomers (polymerizable and non-polymerizable) and mixtures of polymers and monomers can be adopted to constitute the organic compound containing oxygen. The term "polymer" should be understood to include all organic substances containing two or more monomer units.

 The preferred anode for producing electrochemical cells using the above-mentioned mixtures as cathode materials is lithium. However, it is permissible to use any metal or alloy suitable for forming a lonically conductive halide, such as, for example, silver, calcium, magnesium, sodium, lithium-maonsium alloys, lithium-calcium and the like. Monovalent metals are preferred.

 In their preferred form, the batteries according to the invention can be arranged so as to form electrolytes in situ, and they will be described here as such. For example, when the electrochemically active ingredients are lithium and iodine, a solid electrolyte of lithium iodide is formed between the anode and the cathode after manufacture of the battery. Alternatively, the electrolyte may be preformed in whole or in part.

For example, the following arrangement can be used: Li / Li1 (L2O3) /PEO.nI2. Such an arrangement may be desirable to modify the rate of spontaneous discharge. Suitable alumina dispersions are described in the publications of C.C. Liang, J. Eiectrochem.

Soc. 120, p. 1289 (1973); CC Liang and LH Barnette,
J. Electrochem. Soc. 123, p. 453 (1976), and in United States patent 2-eric No. 3713897, documents to which reference may usefully be made on this subject.

 Another variant that can be made to these batteries to make it part of their functional arrangement is the use of an anode coated with poly (2-vinylpyridine) (P2vP) or another polymeric material such as those described. to the United States patent of ar N 3957533, or of a self-supporting body in poly (2-vinylpyridine) such as that described in the patent of the United States of America N-4,182,798. to these last two patents on this subject.

The characteristics and advantages of the invention will emerge more fully from the detailed description which is given below by way of nonlimiting example with reference to the appended drawings, in which
Fig. 1 is a schematic representation of an electrochemical test cell using the improved cathode materials according to the invention;
Fig. 2 is a schematic representation of a sealed cell comprising a poly (2-vinylpyridine) body; and
Figs. 3 and 4 are graphs representing the variation of the voltage as a function of the discharge capacity (Q) for test cells according to the invention.

 The invention does not aim at any particular configuration of cells or batteries, but it extends to any combination of constituent elements producing an electrochemical cell or battery in which the cathode material is of the improved type which is described here. Consequently, the invention is not limited to a particular arrangement or to a particular structural configuration of electrochemical cells. In the material arrangement, the only condition required is that the anode and cathode means of the cell or battery, including the cathode material according to the invention, be placed in a relationship of mutual cooperation in the broadest sense. In order to obtain substantially anhydrous or substantially nonaqueous batteries, these are assembled and encapsulated in a dry atmosphere, preferably by operating in a dry room or enclosure having a relative humidity of less than about 2%, this using substantially anhydrous and / or dried components.

In the description below, the stacks chosen as exemplary embodiments of the invention are flat cylindrical stacks with flattened parts in the form of a disc, as shown in the figures. It should be understood that any configuration for the battery and its constituent elements is satisfactory for the implementation of the invention. In the figures, the cathode material is designated by the reference 12, while the anode, preferably lithium, is designated by the reference 14. The anode and the cathode are both in contact with inert current collectors 16 and 18 respectively, which can be made of metal such as Hastelloy or stainless steel. In the battery shown, the lithium anode is shaped and welded by ultrasound, its welding being carried out peripherally around the current collector 18 of so as to prevent the collector and the cathode material 12 from coming into contact. The electrochemically active constituents, namely the cathode 12, the anode 14 and the current collectors 16 and 18, are enclosed in a non-conductive and chemically inert casing 20 in the form of a cup which can be made of a plastic material such as for example Kynar, trademark of Pennwalt
Corporation designating a polyvinylidene fluoride, housing which includes a sealed cover 22 of the same material. These two organs can be welded to each other by ultrasound or assembled in a leaktight manner in another way. These organs can be made of other inert insulating materials such as Halar, trademark of the firm Ai Lied Chemical Corporation designating an ethylene-chlorotrifluoroethylene copolymer, and Tefzel, trademark of the company EI Du Pont de Nemours, Co. designating a copolymer of ethylene and tetrafluoroethylene. Stainless steel conductors 24 and 26 which are molded in the elements 20 and 22 of the housing serve to come into electrical contact with the current collectors 16 and 18. In order to seal the battery, the whole assembly, as shown in Figure 2, is enclosed in a stainless steel envelope 30 with glass-metal seals 32 and 34 surrounding the electrical conductors 24 and 26, ogre known per se. The envelope 30 may conveniently be formed, as shown, of two cup-shaped parts which are welded together.

 The cell of FIG. 2 comprises a body or a film 36 of polymer formed by poly (2-vinyl pyridine) carried by the active surface of the anode 14, the active surface being that which normally comes into contact with the cathode from the stack, at least initially.

 Batteries of the type described above do not require an electrolyte during manufacture. Consequently, an electrolyte is not shown individually in the figures. However, after assembly, it actually forms an electrolyte in situ. The electrolyte is formed between the cathode and the anode, usually taking the form of a layer, under the effect of the reaction between the metal of the anode and the iodine contained in the cathode. For example, in a battery comprising an anode in it thium and iodine in the cathode, an electrolyte of lithium iodide will be formed.

 According to the invention, iodine or another halogen, or mixtures of such halogens, and a selected organic constituent containing oxygen or a mixture of such constituents are mixed directly with one another in various proportions to form the material of the invention. cathode 12. In most cases, the mixture is preferably heated to relatively average temperatures, of the order of 125 ° C. This is particularly desirable when the organic component containing oxygen is a polymeric compound. On the other hand, a non-polymer such as tetrahydrofuran (THF) may not require heating when mixing with the halogen.

PCLYOX, which is a preferred polyoxyethylene, is heated with iodine for about an hour at around 1250C to obtain good results
Certain precautions are necessary when mixing various organic constituents with the halogen. For example, mixtures of starch and iodine and certain mixtures of polyoxyethylene and iodine decompose violently above temperatures of about 125C.

 As a particulate material, the iodine can be used either as coarse particles or as divided particles, such as those obtained when the iodine has been ground to powder. The use of finely divided iodine is preferred.

The organic constituent containing oxygen can be chosen from the group formed by the following compounds
ethers such as poly (vinyl methyl ether),
tetrahydrofuran (THF), diethyl ether,
butyl methyl ether, polyoxyethylene (PEO)
polyoxypropylene (PPO) and polyvinylbu
tyral;
alcohols such as poly (vinyl alcohol), e-
thanol, phenol, methylcellulose and friend
Don;
ketones such as acetone, poly (me-
thylvinylketone) and methyl ethyl ketone;
esters such as vinyl esters and po
following lyvinyls: poly (viny succinate
le), vinyl acetate and poly (viny acetate
the);
acids such as poly (acrylic acid)
(PAA),
acetic acid and oxalic acid;
salts such as sodium salts and
ammonium salts of poly (acrylic acid) and
sodium acetate;
anhydrous such as acetic anhydride; and
the following specific compounds:
propylene oxide;
poly (N-vinylpyrrolidone)
propylene carbonate
triphenylphosphine oxide (TPP).

In addition, the above-listed compounds can be mixed together or else be mixed with other materials, such as:
polyoxyethylene + poly (2-vinylpyridine) for example in equal proportions (number of oxygen atoms equal to number of nitrogen atoms), then mixed with iodine in the ratio of 8 moles of iodine (12) by mole of oxygen + nitrogen, and
polyoxyethylene + triphenylphosphine oxide, as above.

The organic compounds containing oxygen of the invention can be broadly characterized as being compounds containing no nitrogen in the sense that if nitrogen is present there, it is not the same so that the nitrogen contained in the compounds of cathode materials of the pyridine type, such as for example poly (2-vinylpyridine) and the like. In these latter compounds, nitrogen is present in the compound so as to be able to have electrons in common with a halogen such as iodine. This situation must be distinguished from that of the kinds of compounds of the present invention, such as for example the ammonium salts of acids of the type described above, in which nitrogen is incapable of sharing the electrons with a halogen such as iodine.
Semen, in the case of the oxygen-containing compounds of the invention, it is believed that oxygen is involved in the sharing of electrons with halogen. An exception to this rule is that poly (N-vinylpyrrolidone) contains active nitrogen in addition to active oxygen.

 The viscosity is likely to play a significant roll in certain applications to prevent any appreciable segregation of the various constituents of the cathode. This viscosity may vary from that of solids to that of liquids, depending on the particular combination of cathode and the use for which it is intended. One can act on the viscosity by adding either a thinning solvent or a thickening agent (which will be referred to hereinafter generally as viscosity adjusting agents) to the cathode material, depending on whether one wishes to increase the viscosity or reduce it . Mention may be made of thinning solvents such as chloroform and orthodichlorobenzene as examples of inert solvents which may be used. Alternatively, a compound containing oxygen according to the invention or a mixture of compound may be used as a thinning solvent containing oxygen according to the invention. As examples of compounds according to the invention which are advantageous as thinning solvents, mention may be made of ethanol, acetone, tetrahydrofuran and diethyl ether. Examples of inert thickeners include fumed silica (Si02), finely divided aluminum iodide (A1I3), finely divided alumina (A1203), laminated silicates such as montmorillonite, iodide finely ground lithium, hydrocarbon polymers such as, for example, po; lystyrene, polybutene, poly (alpha-methylstyrene) and styrene-butadiene elastomers. As an alternative, an oxygen-containing compound according to the invention or a mixture of oxygen-containing compounds according to the invention can be used as thickener the invention. Examples of compounds according to the invention which are useful as thickening agents include polyoxyethylene, p & yoxypropylene and poly (N-vinylpyrrolidone).

EXAMPLE I
Batteries of the type shown in Figure 1 were made for testing purposes. These cells included lithium anodes and used as cathodes mixtures of iodine and the various compounds listed in Table I below. The active surface of the anode was 5.1 cm 2. The cathode materials were prepared by heating mixtures of iodine and each additive compound together in a sealed glass vial in an oven oscillating at 125 ° C for one hour, unless otherwise noted. The conductivities of the cathode materials are shown in Table 1. The mixtures were prepared so that the ratio of the number of iodine molecules (I2) to that of the oxygen atoms in the additive was initially 8, 0.All in all, the reports are all expressed under these same conditions, unless otherwise indicated. All of the batteries were cathodically limited with 200mAh stoichiometric iodine capacity. All the cells of this example were assembled with the interposition of a sheet of poly (2-vinylpyridine) 0.08 mm thick between anode and cathode as shown in FIG. 2. The cells were discharged at 37-C in a resistive load of 10 kilohms.

All of the batteries had no-load voltages of approximately 2.8 volts.

The average delivered capacity (until reaching a cut-off voltage of 100 mV, unless otherwise indicated), determined on the best two of three identical batteries, is presented in Table 1 for each class of additive compounds containing oxygen . Table I
IODINE CATHODES WITH OXYGEN CONTAINING COMPONENTS: CONDUCTIVITY AND BATTERY PERFORMANCE
Compound Class Conductivity No-load voltage Cjapacity Consumption rate
containing oxygen from the initial cathode avg. avg. issued cathodic mation
(ohm -1 cm-1) (volt) (mAh) average (%) polyoxyethylene ethers (PEO) 1.79 x 10-4 2.80 172 86
polyoxypropylene (PPO) 1.98 x 10-4 2.80 176 88
PEO / PPO copolymer 0.7 / 0.3 - 2.80 178 89
tetrahydrofuran (THF) 1.27 x 10-4 2.87 130 65
poly (vinyl butyral) 4.13 x 10-4 2.80 148 74 alcohols poly (vinyl alcohol) (PVA) 1.826 x 10-3 2.94 158 79
methylcellulose - 2.77 153 77
phenol 5.0 x 10-6 2.80 146 73
starch - 2.83 180 90
ethanol 5,496 x 10-5 2.80 180 90 methyl ethyl ketone ketones 1.5 x 10-4 2.80 160 80 poly (vinyl succinate) esters - 2.78 162 81
poly (vinyl acetate) 5.38 x 10-6 2.78 164 82
vinyl acetate 4.17 x 10-6 2.78 182 91 poly (acrylic acid) acids (PAA) - 2.71 169 80
acetic acid 3.7 x 10-6 2.73 166 83
oxalic acid - 2.69 168 80 salts sodium salt of PAA - 2.76 155 78
PAA ammonium salt - 2.78 176 88
sodium acetate 2.1 x 10-4 2.95 159 80 anhydrides acetic anhydride 6.5 x 10-5 2.79 178 89 various poly (N-vinylpyrrolidone 2.7 x 10-5 2.79 186 93
triphenylphosphine oxide (TPP) 2.7 x 10-5 2.78 130 65
EXAMPLE II
Mixtures of iodine and polyoxyethylene (PEO) were prepared over the range of starting compositions ranging from 0.50 to 40.0 molecules of iodine (I2) per oxygen atom of the PEO. The PEO used in these mixtures was
POLYOX supplied by Union Carbide Corporation. The water content of the PEO, determined by Karl's analysis
Fischer, was 0.21%.

 Table II below indicates the variation in electrical conductivity and density with the composition, these quantities being measured on pressed pellets of mixtures prepared in sealed glass ampoules and heated in an oscillating oven under the conditions specified. As described in Example 1, three identical cells with cathodic limitation were produced with stoichiometric iodine capacity of 200 mAh for each composition indicated in Table 2. For each composition, an additional group of cells devoid of foil sheet was produced. P2VP between anode and cathode but identical to the others for the rest. These batteries were discharged at 37XC in resistive loads of 10 kilohms. The capacities delivered above a cut-off voltage of 100 mV (unless otherwise indicated) are given in Table 3. Figures 3 and 4 show the average discharge curves respectively obtained for batteries with and without P2VP sheet.

Table 2
CATHODE MATERIAL (I2 / PEO) - PREPARATION AND PROPERTIES
Composition Preparation Conductibility Volu mass
(I2 / O) Temp. (C) Duration (h) (ohm -1 cm-1) mique (g / cm)
0.5 100 1.0 2.0 x 10 4 2.62
1.0 100 1.0 4.8 x 10 4 3.54
2.0 100 1.0 3.9 x 10-4 4.35
8.0 125 1.0 7.3 x 10 5 4.77
20.0 125 1.0 4.5 x 10-6 6 4.80
40.0 125 1.0 2.0 x 10 7 4.88
Table 3
BATTERY PERFORMANCE BASED ON CATHODE COMPOSITION (I2 / PEO) *
Composition Capacity Consumption rate - Overall volume Cathode capacity delivered (% of specific *** electrode)
(12 / O) (mAh) total iodine) (cm) (mAh / cm3)
WITH P2VP SHEET 0.5 58 (12) 29 (6) 0.625 93 (19)
1.0 97 (17) 49 (8) 0.450 216 (38) 2.0 128 (7) 64 (4) 0.373 343 (19) 8.0 171 (1) 86 (1) 0.339 505 (3) 20, 0 182 (8) 91 (4) 0.335 544 (24) 40.0 177 (1) 88 (1) 0.331 534 (2)
theoretical 0.327 610
WITHOUT P2VP SHEET 0.5 52 (12) 26 (6) 0.586 89 (20)
1.0 72 (7) 36 (4) 0.411 175 (17) 2.0 ** 141 (6) 71 (3) 0.334 422 (17) 8.0 ** 155 (2) 78 (1) 0.300 516 ( 7) 20.0 t 143 (12) 72 (6) 0.296 83 (41) 40.0 ** 177 (17) 59 (9) 0.292 400 (58)
theoretical 0.289 692
Standard deviations are given in parentheses.

** 100 mV cut-off voltage not reached.

*** Including the volume of the P2VP sheet, if present.

EXAMPLE III
Batteries of the type described in the previous examples were produced with I2 / O ratios of 8.0 and / or 20.0 and preparation temperatures below 125 C. Oxygen-containing compounds were used. different molecular weights with iodine to make cathode materials. The heating time was 1 hour, except for that of the examples which was prepared by simply mixing the components at room temperature. The deviations studied and the consumption rates obtained on groups of three batteries are indicated in Table 4 below. All of these cells included a sheet of poly (2-vinylpyridine) 0.08 mm thick sandwiched between the anode and the cathode. They were discharged at 37-C in resistive loads of 10 kilohms.

 No significant changes in cathode consumption were observed by varying the molecular weight (PM). It has been observed that the batteries discharge satisfactorily even when the cathode had not been heated at all during its preparation.

Consequently, although heating is desirable during preparation of the cathode, it is not essential.

Table 4
TEMPERATURE OF PREPARATION / PERFoR: THESE BATTERIES ACCORDING TO PM OF PEO Temperature of Composition Consumption rate preparation of cathode Type of cathode cathode (c) (I2 / O) of PEO (%) 25 20 POLYOX 87 100 8 POLYOX 91 100 8 PM = 5000 000 * 90 100 20 PM = 600 0008 91 100 8 PM = 20 20 OOO * 90 supplied by Polysciences, Warrington, Pa, USA

EXAMPLE IV
Six variants of cathode material were produced from mixtures of PEOs with molecular weights of 20,000 and 5,000,000 in different proportions to form the oxygen-containing component.

The PEO proportions of the two molecular weights were varied from 0 to 100% in 20% increments. The initial ratio of I2 molecules to O atoms was set at 20 in each case. PEO compounds were purchased from Polysciences, Warrington, Pa, U.S.A.

Each mixture was made up and then heated for 1 hour at 125 ° C as described above. Stacks were constructed in groups of three, each comprising a 0.08 mm thick sheet of poly (2-vinyloyridine) sandwiched between the anode and the cathode. All the batteries were discharged at 37C in loads of 10 kilohms. The average capacities delivered by these groups of batteries are summarized in Table 5 below.

Table 5
PERFORMANCE OF MIXTURE CELLS OF TWO DIFFERENT PM PEOs
Composition of the PEO mixture
(% of PEO at PM = 20,000, remains in Consumption rate
PEO at PM = 5,000,000) of the cathode (%) 86
20 90
40 86
60 88
80 90
100 90
EXAMPLE V
Mixtures of iodine and compounds were prepared
oxygen-containing organics, and we have them themselves
mixed with a nitrogen-containing compound.
fe the constituents in a glass ampoule sealed in an oven oscillating at 1250C for one hour in the case of 2-ethylpyridine and aniline, or for 24 hours in the case of poly (4-vinylpyridine). These materials were studied as cathodes in cells with a stoichiometric iodine capacity of 200 mAh, as for those described in Example I. Three identical cells were studied for each cathode, with a starting composition of 8 molecules of iodine by sum of nitrogen and oxygen atoms, as indicated in Table 6. The cells were discharged as described in Example I. The capacities delivered above 100 mV are indicated in Table 6 below .

Table 6
PERFORMANCE OF YARNS WITH MIXTURE OXYGEN / NITROGEN CONSTITUENTS
WITH P2VP SHEET WITHOUT P2VP SHEET
Organic compounds Composition of capacity - Consumption rate - Capacity - Consumption rate
the cathode vrée average mation of vrée average mation of
(I2 / O / N) (mAh) the cathode (%) (mAh) the cathode (%)
POLYOX, 8 / 0.5 / 0.5 143 71.5 147 73.5 2-ethylpyridine
POLYOX, 8 / 0.5 / 0.5 167 83.5 173 86.5 poly (4-vinylpyridine)
PEO (PM = 20,000) è, 8 / 0.5 / 0.5 139 29.5 165 82.5 poly (4-vinylpyridine)
POLYOX, 8 / 0.5 / 0.5 170 85 aniline * supplied by Polysciences, Warrington, Pa, USA

Claims (27)

- R E V E N D I C A T I O N S  1. An electrochemical cell comprising anodic and cathodic means in functional cooperation, characterized in that the cathodic means comprises, at least in part, a mixture of a halogen constituent chosen from iodine, bromine, iodine bromide and mixtures thereof and an organic constituent containing oxygen chosen from ethers-oxides chosen from poly (vinyl methyl ether), tetrahydrofuran, diethyl ether, butyl methyl ether, poly (oxyethylene), poly (oxypropylene), polyvinyl butyral and their mixtures; the alcohols chosen from poly (vinyl alcohol), ethanol, phenol, methylcellulose, starch and their mixtures; ketones; vinyl and polyvinyl esters; salts; anhydrides; propylene oxide; poly (Nvinyl-pyrrolidone); propylene carbonate; triphenylphosphine oxide, and mixtures thereof.  2. Battery according to claim 1, characterized in that the halogen component is iodine, at least in part.  3. Battery according to claim 1, characterized in that the oxygen-containing component is polyoxyethylene, at least in part.  4. Battery according to claim 1, characterized in that the anode means comprises lithium.  5. Battery according to claim 1, characterized in that the anode means comprises a monovalent metal.  6. Battery according to claim 1, characterized in that the organic constituent containing oxygen of the cathode means is substantially in the form of polymer.  7. Battery according to claim 1, characterized in that the organic constituent containing oxygen of the cathode means is substantially in the form of monomer.  8. Battery according to claim 1, characterized in that the organic constituent containing oxygen of the cathode means comprises a mixture of polymer and monomer.  9. Battery according to claim 1, characterized in that the cathode mixture contains more halogen component than component containing oxygen.  10. Cathode material for electrochemical cells, characterized in that it is produced by a combination formed essentially of a halogen component and of polyoxyethylene.  11. Cathode material according to claim 10, characterized in that the halogen component is iodine, at least in part.  i2. Cathode material according to claim 10, characterized in that the proportion of the halogen component is greater than the proportion of polyoxyethylene.  13. Battery according to claim 1, characterized in that it comprises a viscosity adjustment agent contained in the mixture of the cathode means.  14. Electrochemical cell comprising anode and cathode means in functional cooperation, characterized in that the cathode means comprises, at least in part, a mixture of a halogen component chosen from iodine, bromine, iodine bromide and mixtures thereof and an organic constituent containing oxygen chosen from poly (vinyl methyl ether), tetrahydrofuran, diethyl ether, butyl methyl ether, polyoxyethylene, polyoxypropylene, polyvinyl butyral, poly (Inyl alcohol), methanol, phenol, methylcellulose, starch, acetone, poly (methylvinyl ketone), methyl ethyl ketone, vinyl and polyvinyl esters, poly (vinyl succinate), poly (vinyl acetate), vinyl acetate, poly ( acrylic acid), acetic acid and oxalic acid, sodium salts and ammonium salts of polyacrylic acid), sodium acetate, acetic anhydride, propylene oxide, poly (N -vinyl-pyrrolidone), propylene carbonate, triphenyiphosphine oxide and mixtures thereof.  15. Battery according to claim 14, characterized in that the halogen component is iodine, at least in part.  16. Battery according to claim 14, characterized in that the oxygen-containing component is polyoxyethylene, at least in part.  17. Battery according to claim 14, characterized in that the anode means comprises lithium.  18. Battery according to claim 14, characterized in that the anode means comprises a monovalent metal.  19. Battery according to claim 14, characterized in that the organic constituent containing oxygen of the cathode means is in the form of polymer.  20. Battery according to claim 14, characterized in that the organic constituent containing oxygen of the cathode means is in the form of monomer.  21. Battery according to claim 14, characterized in that the organic constituent containing oxygen of the cathode means comprises a mixture of polymer and monomer.  22. Battery according to claim 14, characterized in that the cathode mixture contains more of the halogen component than of the oxygen-containing component.  23. An electrochemical cell according to claim 14, characterized in that the halogen component of the cathode material is iodine at least in part.  24. An electrochemical cell according to claim 14, characterized in that the cathode material comprises polyoxyethylene forming the organic component, and in that the proportion of halogen component is greater than the proportion of polyoxyethylene.  25. Battery according to claim 14, characterized in that it comprises a viscosity adjusting agent contained in the mixture of the cathode means.  26. Cathode material, characterized in that it comprises, at least in part, a mixture of a halogen constituent chosen from the group formed by iodine, bromine, iodine bromide and their mixtures and an organic constituent containing oxygen chosen from the group formed by the ethers-oxides chosen from the group formed by poly (vinyl methyl ether), tetrabydrofuran, diethyl ether, butyl methyl ether, polyoxyethylene, polyoxypropylene, polyvinyl butyral and their mixtures ; the alcohols chosen from the group formed by poly (vinyl alcohol), ethanol, phenol, methylcellulose, starch and their mixtures; ketones; vinyl and polyvinyl esters; salts; anhydrides; propylene oxide; poly (N-vinylpyrrolidone); propylene carbonate; triphenylphosphine oxide, and mixtures thereof.  27. Cathode material, characterized in that it comprises, at least in part, a mixture of a halogen constituent chosen from the group formed by iodine, bromine, iodine bromide and their mixtures and an organic constituent containing oxygen chosen from the group formed by poly (vinyl methyl ether), tetrahydrofuran, diethyl ether, butyl methyl ether polyoxyethylene, polyoxypropylene, polyvinyl butyral, poly (vinyl alcohol), methanol, phenol, methylcellulose, starch, acetone, poly (methylvinyl ketone), methyl ethyl ketone, vinyl and polyvinyl esters, poly (vinyl succinate), poly (vinyl acetate), vinyl acetate, poly ( acrylic acid), acetic acid and oxalic acid, sodium and ammonium salts of poly (acrylic acid), sodium acetate, acetic anhydride, propylene oxide, poly (Nvinylpyrrolidone), propylene carbonate, triphenylphosphine oxide and their mixtures.  28. Cathode material according to any one of claims 26 and 27, characterized in that it comprises a viscosity adjusting agent.