MXPA98009807A - Non flammable electrolytes / auto extinguishable for bater - Google Patents

Abstract

The present invention relates to novel fire retardant electrolyte compositions, such compositions comprising a lithium salt dissolved in a fire retardant solvent selected from the group consisting of phosphates, phospholanes, cyclophosphazenes, silanes, fluorinated carbonates, fluorinated polyethers and mixtures of the same, the electrolyte composition optionally contains a CO2-generating compound, fire retardant batteries and incendive-retardant conductive films are also provided with such compositions, as well as methods of making such a film

Description

NON FLAMMABLE ELECTROLYTES / AUTO EXTINGUISHABLE FOR BATTERIES REFERENCE TO GOVERNMENTAL CONCESSION The present invention was made with government support. The government of the United States has certain rights over the invention.

TECHNICAL FIELD The present invention relates generally to batteries. More particularly, the invention relates to a fire retardant electrolyte composition and batteries made to contain the composition. Also within the scope of the present invention are the conductive layers comprising the fire retardant electrolyte composition.

BACKGROUND OF THE INVENTION Recently, "solid-state" batteries with high energy density have been developed using metallic lithium as the anode. Metallic lithium is a preferred anode material for batteries "because its thermodynamics and kinetic qualities are superior to those of other materials. Lithium is a good conductor of electricity and heat "and has an electrochemical equivalence of 3.86 Ah g- and a normal electrode potential of -3.5 V. In addition» lithium is soft and malleable »since it can be stuccoed into thin sheets. Nevertheless. it is well known that lithium reacts with water and other reagents (see »for example» Linden »D.» Ed. »Handbook of Batteries and Fuel Cells» McGraw-Hill »NY» 1984). Typically, the liquid electrolyte solvent used in lithium batteries is a dipolar aprotic solvent. The aprotic solvents are used due to the absence of labile hydrogen atoms that can react with lithium to release hydrogen. The dipolar solvents »that is to say» those that have a strong dipole moment in the molecule »are used because they have substantial solvation energies for the electrolyte salt» which results in a better dissolution of the salt »and because they have a more dielectric constant high for the solvent »that is» better ionic dissociation. Solvents such as procyancarbonate ("PC") »ethylene carbonate (" EC ")» diethylcarbonate (tcEC ")» 1 »2-di ethoxyethane» and methylformate have been used in lithium batteries in either pure form or In solvent mixtures, such solvents provide high conductivities in the presence of suitable lithium salts, however, the chemical stability and safety of such solvents has recently been questioned (see, for example, Bowden et al. (1992) "Rechargeable Lithium Batteries". »A Survey of the Published Literature» in Proc. Fourth Int'l Rechargeable Battery Seminar). Improved liquid organic electrolytes with higher conductivities than solvents are needed to meet the energy requirements for various consumer applications, especially at low temperatures. In addition »commercially available lithium cells» with a pure lithium anode »are currently available only as primary cells and are not recommended for use in secondary cells. 'This limitation is due to the reactivity of the electrolyte system with the metallic lithium. EKisten at least two inconvenient effects that arise from the reaction of lithium with the electrolyte in a lithium cell: the exothermic release of heat "and the formation of a passive film on the surface of the anode. The release of heat is a problem "because under some circumstances it could lead to an explosive release of energy and reactive materials" thus creating a danger to the operator and the device that the cell is energizing. It has been known that highly exothermic reactions occur when primary lithium batteries are subjected to temperatures above recommended levels or when some rechargeable cells are subject to unusual or severe recharging conditions (see »for example» Ebner et al. (1982). ) in Proc. 30th Power Sources Symp. »P 119). It has been known that primary lithium cells that use "for example" a thionylchloride system lithium »suffer from high exothermic reactions when subjected to temperatures above or below the recommended temperatures. In the case of secondary cells, subjecting the cells to unusual or severe lithium recharge and deposition conditions in a highly porous film at the anode has led to similarly disastrous results. Pasquariello et al. (1993) Proc. Sy p. Lithium Batteries 93-24: 106. In addition to the intrinsic reactivity of lithium to the electrolyte, the lithium in the rechargeable cells will be deposited to form a dendritic layer, which improves the reactivity of lithium (Pasquariello et al. Supra). It has been shown that the formation of passivation films in lithium is a reason for the loss of capacity of lithium cells in repeated cycles (Shen et al. (1934) Capacity Decline Studies of Rechargeable Lithium Batteries »McGraw-Hill» NY) . The film can isolate the anode from the electrolyte »thereby providing a high path of impedance and degradation in cell development. In addition »metallic lithium tends to" deposit "on the surface of the film rather than on the lithium anode; the deposited lithium is electrically isolated from the anode and is not available for subsequent discharges. The problem of lithium reactivity to the electrolyte has been handled in several ways. One approach is the use of a carbon intercalation compound such as LiCβ or iC ^ a with a liquid or polymer electrolyte. One drawback of such an approach is the loss of capacity density (0.37 Ah g - * - compared to 3.86 Ah g-: t- for lithium) and voltage (3.4 v compared to 3.5 V for lithium). However, commercial cells that have adopted such an approach are available. The first versions of such a cell had an anode LiCi = J »a LiCoO ^ cathode, which used EC: DEC (in a 1: 1 mixture). with a salt of lithium hexafluorophosphate (LiPF ^) as electrolyte. Such a cell has shown 1200 cycles at 100% depth of discharge "while retaining 7754 of its capacity. Megahead (1994) J. Power Sources 51:79. The energy densities of approximately 90-110 Pkg- * (210-260 Pd -3). depending on the configuration of the cell »have been achieved using this cell. Megahead »supra.

More recently »manu versions of this cell have been made with LiCß instead of LiC = t» since the anode has achieved a cycle performance comparable with the improved energy density. Although the performance of the cell is adequate, the improvement and energy density that could be obtained by using Li co or anode significantly provides the Li recharge character that is improved. The replacement of lithium with LiCß increases the temperature of initiation of the exothermic behavior at 120 ° C from 100 ° C for an ilMnOj cell, after 25 cycles as measured by accelerated scale calorimetry. Von Slacken and others (1994) Proc. Seventh Int'l Meeting on Lithium Batteries »p. 12. In addition »the heat capacity of the reaction was lower (1.7-2.0 cal 0K- versus 2.8 cal ° K-1 for Li | Mnoa). However, as the cycle is cycled, the lithium anode becomes more strongly exothermic (Von Slacken and others supra) J presumably due to the formation of a more porous electrode structure and therefore a greater area of surface. A second approach to reduce the problem of lithium reactivity to the electrolyte is to replace the electrolyte with a polymeric material. Such an approach would reduce the scale of reaction by imposing a transport constraint on the reaction. However, the conductivity of polymer electrolytes is at least an order of magnitude lower than that of liquid electrolytes, resulting in lower specific power and power batteries. In addition such an approach requires the use of alternative battery manufacturing techniques. Consequently »there is still the need to provide safe primary and secondary lithium batteries. Such batteries require an electrolyte that is chemically stable with respect to lithium "substantially non-flammable, and compatible with the existing electrode and battery manufacturing technology. The present invention provides such batteries. The new batteries do not show the drawbacks shown by previous batteries such as combustion under conditions of overload »accidental rupture» accidental short circuit »and the like.

BRIEF DESCRIPTION OF THE INVENTION Accordingly, a primary object of the invention is to solve the aforementioned need in the art by providing a lithium battery containing a fire retardant electrolyte composition. Another object of the invention is to provide such a battery comprising an anode »a cathode and a fire retardant electrolyte composition. Still another object of the present invention is to provide such a hateria in which the electrolyte composition comprises a lithium salt dissolved in a solvent selected from the group consisting of a phosphate, a phospholane, a cyclophosphohalene, a silane, a florinated carbonate, an fluorinated polyether "and mixtures thereof. Another object of the invention is to provide a battery comprising a fire retardant electrolyte composition as mentioned above, wherein the composition further includes a compound generating CO, -,. Still another object of the invention is to provide a fire retardant electrolyte composition comprising a lithium salt dissolved in a solvent selected from the group consisting of a phosphate »a phospholene» a cyclophosphorethane »a silane» a fluorinated carbonate »a fluorinated polyether »Or mixtures thereof. This is described above. and wherein the fire retardant electrolyte composition optionally includes a polymeric film-forming material. Another object of the present invention is to provide a fire retardant electrolyte composition as described above and »optionally» containing a CO-generating compound. Another object of the invention is to provide a conductive fire retardant film generally formed of a composition of a lithium salt 'or a single ion which conducts the polymer electrolyte dissolved in a solvent of fire retardant electrolyte as described above »an amount of a film-forming polymeric material such as poly (inylidene fluoride) effective to improve the mechanical strength of the resultant electrolyte composition» and »optionally» a C0a generating compound. In this way »thin but highly conductive films can be formulated having physical fire retardant properties. Additional objects "advantages and novel features of the invention will be set forth in part in the following description" and in part will become apparent to those skilled in the art upon examination of the following "or can be learned by practice of the invention. In a primary aspect of the invention »batteries comprising an anode are provided, a cathode and a fire retardant electrolyte composition "including a lithium salt dissolved in a solvent" wherein the solvent is a phosphate having the structure co or shown in formula (I) wherein R "Ra and R3 are independently selected from the group consisting of (a) C -C3 terminally substituted with O at 3 halogen atoms and containing O to 3 ether linkages" (b) Si (R - *) 3 and < c) B (0R - *), -., wherein the R- * are independently C -Cβ alkyls containing from O to 3 ether or C ^ -C ^ * alkoxy bonds and optionally wherein two or more compounds of structure (I) are linked by an ether linkage, a phospholane having the structure as shown in formula (II). where Rs is selected the group consisting of oxy or of a pair of electrons and, when Rs is a pair of electrons »Rß is CA-Cß alkyl terminally substituted with 0 to 4 halogen atoms and containing 0 to 3 bonds of ether »a cyclophosphazene having the structure as shown in formula (III)» R "7 I (III) CN = PJ I RT where n is an integer from 3 to 6 and R" 7 and Rβ are independently selected from the group consisting of hydrogen. halogen and ~ ORs where R? is C-C6 alkyl terminally substituted with 0 to 3 halogen atoms and containing 0 to 3 ether bonds "with the proviso that when one of the R * 7 or Re is -ORs the other is halogen" a silane which has the structure co or is shown in formula (IV), wherein R3-0, R3-3- »R ta and R3-3 are independently selected from the group consisting of (a) CA-Cß alkyl terminally substituted with 0 to 3 halogen atoms containing from O to 3 ether bonds and (b) -OR3- * wherein R3 - * is a C ^ -C ^ alkyl terminally substituted with 0 to 3 halogen atoms and containing O to 3 ether linkages and optionally wherein two or more compounds of the structure (IV) are linked by a siloxane bond »a fluorinated carbonate having the structure as shown in formula (V).

OR il (I) R - = - 0-C-0-R3-tS where R3-3 and R3-6 are independently selected from the group consisting of (a) a perfluorinated or partially fluorinated C ^ -C ^ Q alkyl containing from O to 3 ether bonds and (b) -OR3- " Wherein R3- "7 is a perfluorinated or partially fluorinated alkyl containing from 0 to 3 ether linkages or wherein R3-s and R3- * 3 are bonded to form a C or C-, C-, perfluorinated or partially-alkyl bond. fluorinated, a fluorinated polyether having the structure as shown in formula (VI) i (VI) ^ O- (C-CF30) «- (CFa0) -R = wherein R1T and R3-5"are independently a perfluorinated or partially fluorinated C ^ -C ^ alkyl or R20 and R3" 3- are independently selected from the group consisting of -F and perfluorinated or partially fluorinated Cx-CAO alkyl Yxyy are independently selected so that the polymer has a number average molecular weight on the scale of about 400 to about 10,000"or mixtures of such phosphates" fosanoes "cyclophosphazenes, silanes, fluorinated carbonates and fluorinated polyethers" and wherein the The fire retardant electrolyte composition optionally includes a film-forming polymeric material In other aspects of the invention, fire retardant electrolyte compositions and fire retardant conductive films comprising the solvents as described above are provided. of electrolyte fire retardants and the accompanying films described The batteries can be used and claimed here, eg a solid state Li ^ C ^ / electrolyte / LiCoOa »Li electrolite / Tis ^» or battery Li / electrolyte / VβO;,.; -, or in electrochemical devices such as fuel cells, supercapacitors, »electro-chemical devices and sensors» or the like.

BRIEF DESCRIPTION OF THE FIGURES Figure 1 shows the potential profile for the battery described in example 6 when going through a cycle. Figure 2 shows the exothermic behavior for the metallic lithium strips submerged in the triethyl phosphate (47.5% v / v): the diethyl ethoxyethyl phosphate mixtures (47.554 v / v): di-tert-butyl dicarbonate (S%) v / v> (solid line) and for the electrolyte used in a commercial primary lithium battery (dotted line) as described in example S.

DETAILED DESCRIPTION OF THE INVENTION The practice of the present invention will employ "unless otherwise indicated, conventional techniques of synthetic chemistry," "electrochemistry," and polymer chemistry that are well within the skill of the art. Such techniques are fully explained in the literature. See »for example» Encyclopedia of Chemical Technology by Kirk-Othmer »in Modern Synthetic Reactions» by House »'in the text of C.S. Marvel and G.S. Hiers ORGANIC SYNTHESIS »Collective Volume 1» or similar. All patents »patent applications and publications cited herein, whether supra or infra, are hereby incorporated by reference in their entirety.

Definitions: Before describing the present invention in detail, it will be understood that this invention is not limited to particular salts, methods or syntheses, solvents. or similar »as they may vary. It will also be understood that the terminology used herein is for the purpose of describing only the particular modalities "and is not intended to be limiting. It should be noted that "as used in the specification and appended claims" the singular forms "a" and "the" include plural referents unless the content clearly dictates otherwise. Thus. for example, the reference to a "fire retardant electrolyte composition" includes mixtures of such a composition. The reference to "a solvent" includes more than one solvent. The reference to a "CO 2 generator" includes the mixtures of the generators. of CO ^ and similar. In this specification and the following claims the reference will be made to a number of terms that will be defined to have the following meanings: The terms "fire retardants" and "non-flammable" are used interchangeably herein to indicate a reduction or removal of the tendency of a fuel material to be burned »that is to say» a "fire retardant" material is one that has a lower ignition susceptibility or »once the ignition has started» lower flammability. In this way »a fire retardant electrolyte composition is one in which the basic flammability has been reduced to be measured by accelerated scale calorimetry (ie» for example »Von Slacken and others» supra) »or by one of the normal flare or salver impurity tests accepted by the technique »other normal tests of reduced flammability» for example »ASTM D2863 (limiting oxygen index) (see» for example »Test for Flammability of Plastic Materials for Parts in Devices and Appliances »Underwriters Laboratories» Northbrook »IL» 1991; National Fire Codes »National Fire Protection Assos.» Quinsy »MA» 1992; Standard Test Method for Heat and Visibility S oke Rel ase Rates for Materials and Products »American Society for Testing and Material »Philadelphia» Pa. »1991, see also» "Fire Retardants" in Encyclopedia of Polymer Science and Engineering »Vol. 10» page 930-1022, 2nd ed. »John Wiley and Sonds »NY, 19BS). The terms "CO 2 generator compound" and "COa generator" are used interchangeably to refer to a chemical source of carbon dioxide. A C0a generator typically produces C0- ,. with the decomposition. The COja generators that are preferred for use in the claimed electrolyte compositions are those that do not produce the decomposition of the byproducts that are incopatible, either chemically or electrochemically being the electrolyte or other battery materials. The test cells of such CO2 generators in addition to the flame retardant electrolytes have improved the discharge-recharge cycle properties in a manner consistent with the report of Aurbach et al. (1994) J. Elestroche. Soc. 141: 603. The term "alkyl" as used herein refers to a group of branched or saturated unbranched hydrocarbons having from 1 to 24 sarbone atoms such as methyl or ethyl. niproyl »isopropyl, n-butyl »isobutyl» t-butyl, ostyl »decyl» tetradecyl »hexadesyl» eisosyl »tetrasosyl and the like. Preferred alkyl groups herein contain from 1 to 12 carbon atoms. The term "lower alkyl" refers to an alkyl group of one to six carbon atoms. The term "alkenyl" refers to a branched or unbranched hydrocarbon chain containing from 2 to 24 carbon atoms and at least one double bond. "Lower alkenyl" refers to an alkenyl group of 2 to 6 »more preferably 2 to 5 carbon atoms. The term "fluorinated lower alkenyl" refers to an alkenyl group of one to six carbon atoms in which at least one hydrogen atom, and optionally all the "hydrogen atoms" are replaced with fluoride atoms. The term "alkoxy" as used herein refers to an alkyl group bond through a single terminal ether linkage.; that is, an "alkoxy" group can be defined as -OR where R is an alkyl as defined above. A "lower alkoxy" group refers to an alkoxy group that is one to six, most preferably one to four, carbon atoms. The term "aryl" is used herein to refer to monocyclic aromatic thiols of 5 to 7 carbon atoms "and is typically phenyl. Optionally, such groups are substituted with one to four »more preferably one to two» lower alkyls »lower alkoxy. hydroxy and / or nitro substituents. The term "aralkylene" is used to refer to the portions containing alkylene and aryl monocyclic species "typically containing less than about 12 carbon atoms in the alkylene moiety" and wherein the aryl substituent is linked to the structure of interest to through the alkylene linking group. Exemplary aralkylene groups have the structure -. { CHa) _, - Ar where j is an integer on the scale of 1 to 6. "Halogen" refers to fluorine »chlorine» bromine or iodine »and is usually related to the substitution of halogen for a hydrogen atom in a organic compound "Haloalkyl" refers to an alkyl portion in which one or more of the hydrogen atoms is replaced by a halogen atom. Of the halogens "is generally preferred to fluoro. The term "lower haloalkyl" refers to an alkyl group of one to six carbon atoms in which at least one hydrogen atom "and optionally" all hydrogen atoms "are replaced with a halogen atom. The term "perhalogenated" refers to a compound in which all hydrogen atoms were replaced with fluoride atoms "while the phrase" partially halogenated "refers to a compound in which less than all of the hydrogen atoms They were replaced are fluoride. In this manner, a perfluorinated alkyl is a branched or unsaturated saturated hydrocarbon group as defined above in which all hydrogen atoms were replaced by fluoride atoms. "Optional" or "optionally" means that the circumstances described below may or may not occur "and that the description includes examples in which such a circumstance occurs and examples in which it does not occur. For example the phrase "optionally includes a polymeric film-forming material" means that the polymeric film-forming material may or may not be present and that the description includes both examples when the polymeric film-forming material is present and the example of when the material polymeric film former is not present In one embodiment of the invention a battery comprising an anode is provided: a cathode of a fire retardant electrolyte composition comprising a lithium salt dissolved in a solvent including low flammability. self-extinguishing »that is to say» fire retardant »solvents that are chemically stable to lithium Such fire retardant solvents include phosphates» sfoianos »cislofosfaseno» silanes and mixtures of such solvents Various fire retardant solvents which are useful in the invention described and claimed in the present you find somersia They are available or can be synthesized using conventional techniques well known to those skilled in the art of synthetic organic chemistry or which can be found in relevant texts. The fire retardant phosphate solvents that are useful in the invention include those having the structure as shown in the formula (I > wherein R 'R53 and R3 are as defined above and optionally wherein two or more compounds of structure (I) are linked via an ether linkage. Commercially available phosphate solvents include, for example, tri-ethyl phosphide (Aldrich) and triethyl osphate (Aldrich). Alternatively, triethylphosphate, a well-known flame retardant and plasticizer (see, for example, U.S. Patent No. 3,909,484 to Beavon; Nametz (1967) Ind. Eng. Chem. 59:99; and Larsen and others (1979 J. Fire Retardant Chem. 6: 182) can be manufactured from diethyl ether and phosphorus pentoxide by a metaphosphate intermediate as described in U.S. Patent Nos. 2,430,569 and 2,407,279 to Hull et al. In this way, tri- (methoxyethyl) phosphate, tris- (methoxyethoxy-ethyl) phosphate and tris- (1 »1" 1"-trifluroethyl) -phosphine can be synthesized by conventional synthetic techniques. Reuptations of osphoryl chloride are 2- (2-methoxy) ethoxy-ethanol and 1-l "-trifluoroethanol, respectively" in the presence of pyridine. The fire retardant phospholane solvents that are useful in the invention include those having the structure as shown in formula (II). wherein R3 and Rβ are as defined above. Commercially available phospholanes include Antibaze® 19 and Antibaze ™ * 1045 (Albright and ilson). Such phospholanes can be synthesized by a person skilled in the art using conventional synthetic techniques (see, for example, U.S. Patent Nos. 3,788,991 and 3,849,368 of Anderson et al.). For example »phospholanes they can be synthesized from the corresponding 2-chloro-l »3» 2-dioxaphospholane-2-oxide by reaction with ethanol 2-methoxyethanol »2» 2 »2-trifluoroethanol, 2-acetylethanol and 2-methoxyethoxyethanol, respectively. Alternative methods to prepare phospholane have been reported by Kluger et al. (1969) J. "Am. Chem. Sos. 91: 6066 and Taira et al." (1984) &T. Org. Chem. 49: 4531. it can be prepared by the re-allocation of 2-chloro-l, 3'-2-dioxaphosphine with ethanol. The insecticide-containing osphazene retarding solvents which are useful in the invention include those which have the structure shown in formula (III). where R "7» Ra and n are defined as above, such synosophosphenes can be prepared, for example, by the reaction of luorophosphazenes with alkoxy alcohols, thus cyclotriphosphazenes. they can be prepared by the reaction of hexafluorotrichialophosphazene with 2-methoxyethanol under suitable conditions to achieve tri- and mono- "substitution respectively. The fire retardant silane solvents which are useful in the invention include those having the strut as shown in formula (IV).

R3-0 i (IV) ^ -Si- 3-3 | R3-3 wherein R3-0 »R3-3-, R3-53 and R3-3 are defined as above.

Among the preferred silane solvents are the commercially available silane compounds (for example Aldrich) co or tetramethyl orthosilicate, tetraethyl orthosilicate, tetrabutyl orthosilicate and the like. Furthermore, the siloxane-based and phosphazene-based solvents for the electrolyte compositions can be synthesized by functionalizing the hydromethyl siloxanes and cyclotriphosphazene with ether derivatives. The hydrosiloxanes can be functionalized by the reaction are alcohols in the presensia of a base or by hydrosilylation with allyl ethers. The fluorinated carbonate fire retardant solvents which are useful in the invention include those having the structure co or shown in the formula (V), (V) wherein R3-85 and R3-6 are defined as above. Such fluorinated carbonates can be synthesized by one skilled in the art using conventional synthetic techniques as described in, for example, U.S. Pat. No. 3,455,954 to Prager »European Patent Publication No. 0557167, Johnson et al. (1973/74) J. Fluorione Che. 3: 1-6 »Moore et al.» 975) J. Fluorine Chem. 5: 77-81 »Walker et al. (1975) J. Fluorine Chem. 5: 135-139, and Hudlicky (1982) J.

Fluorine Chem. 20: 649-653 »the descriptions of which are incorporated herein by reference. The fire retardant fluorinated polyether solvents that are useful in the invention include those having the strusture shown in formula (VI) Hae (VI) R3-TO- (C-CF520) J < - (CF_O) and -RJ Ras¬ n where R3-3 »Ri ?, 580 and R533- are defined as above. Fluorinated polyethers having the formula (VI) are commercially available as, for example, FOMBLIN? * (Aldrich) or Galden ** (PCR Inc., Gaineville, FL). Alternatively, such fluordinated polyethers can be prepared using the method described by Sianesi et al. (1994) in Organofluorine Chemistry: Principles and Applications, Banks et al., Eds. »Plenum Press» NY »431-467 (and references cited herein). One skilled in the art can also prepare such fluorinated polyethers using well-known methods of commercially available polyether dressing such as those described in "for example" Persian et al. (1985) J. Am. Chem. Soc. 107: 1197- 1201 »Gerhardt and others. (1981) J. Chem. Soc., Perkin Trans. 1: 1321 »Gerhardt et al. (1979) J. Poly. Sci., Polyrn. Che. Ed. 18: 157, Gerhardt et al. (1978) J. Org. Che. 43: 4505, and Gerhardt et al. (1977) J. Chem. Soc., Chem. Commun. 8: 259. Optionally »at least one of R3-, R13 and R3» or Rß, or H &at least one of R3-0, R3-3-, R3-2 and R3-3 is modified to contain in the sai-phaon A substituent group having the structure -R! a :: 3-0-C (0) -0-Ri33, wherein 5 »3 and R533 are independently Cx-C6 alkyl or wherein 33 and R533 are linked to form an alkylene bridge C ^ -C, -, thereby forming a homo- (i.e., phosphate phosphate dimer) or heterodimeric solvent (i.e., phosphatosilane dimers). In one embodiment of the invention, a fire retardant electrolyte composition is prepared by dissolving a lithium salt in a fire retardant solvent. Preferred lithium salts include compounds of the formula Li-A, wherein A is an anion which may be Cl 'CF-SO-, CIO. * »BF ^, Br, I» SCN, AsFβ, N (CF_SO-) a »PFβ, SbFβ, 0 (CO) R: L» where R 3 - is H. alkyl, aryl. alkenyl »halogen, haloalkyl» or the like. Preferred salts include »for example» LiPF6, LiAsF6 »LN (O_CF3) _ and mixtures thereof. The solutions of lithium salts in the fire retardant solvents are prepared to achieve approximately 0.2 M to 2.0 M lithium »preferably 0.5 M to 1.5 lithium. The term "lithium salt" also refers to including single ion-conductive polymer electrolytes as described in commonly assigned U.S. Patent No. ,061,581 to Narang et al. "As well as in the US patent application. with serial number 08 / 372,216"entitled" Single ion-conductive solid polymer electrolytes "" of the inventors Narang et al. "filed on January 13, 1995. The descriptions of both aforementioned documents are hereby incorporated by reference . In this manner, a flame retardant electrolyte composition can be prepared by dissolving a single ion conducting polymer electrolyte in one of the solvents described above to achieve about 0.2M to 2μM lithium, preferably 0.5M to 1.5M of lithium. Single ion-conductive polymer electrolytes that are contemplated specifically for use herein include those having the structure as shown in the < SAW ) n where: R-a-- and jjaa are individually selected from the group consisting of the portions that have the estrustura (CH_) "A (OCH-CH-) vx (OCF-CFß) -iSO_R5 where R34S is -OM, -N < M) SO_CF_ -N (M) C (0) CF_O-C (M) (SO_CF _) _ and M is an alkali metal, preferably lithium, or one of R53 ** and R3 = s has the structure < CH2) X1 (OCH-CH-) v (OCFsCF_) ^ SO- 3 * and the other is selected from the group consisting of hydrogen, lower alkyl, halogen, lower alkyl, lower alkenyl, fluorinated lower alkenyl, aryl and aralkylene.; xl and zl can be the same or different and are integers on the scale from 1 to 100 inclusive; and l is an integer on the scale from 0 to 100 inclusive; and n is an integer indicating the number of mere units in the polymer. The additional single ion conductive polymer electrolytes contemplated for use in the invention described and claimed herein include copolymers containing the first mer units having the structure as shown in formula (VIII).

(VIII) and the second mer units having the structure as shown in the structure as shown in the formula (IX) wherein: R3 * 7 and 3E * are independently selected from the group consisting of hydrogen, lower alkyl, lower-butxi-CORR33- and - (CH-2) _x-0-R33- wherein R33- is lower alkyl or alkyl lower fluorinated and is not an integer in the esaala from 1 to 6 inclusive; R_a is - (CH_) Ic ^ (OCH_sH_) v ^ (? SF_CF -) _ ^ SO_R36 where Saß is defined as above; Bao is - (sH -)? A (OCHaCH-) v_CH_ or COOR33 where R3SS is lower alkyl or fluorinated lower alkyl; and x2 »x3» x4 »x5 and» 2 »y3» y4 »y5» z2 »z3» and z4 can be the same or different and are integers on the scale from 1 to 100 inclusive. In sosesuensia, the position of fire retardant elestrolite can be formulated with a lithium salt of the formula Li-A or a single ion conductive polymer electrolyte as described above. In addition, a high dielectric constant solvent such as ethylene carbonate, propylene carbonate, dimethylaarbonate, diethoxyethane, diethylcarbonate, dimethoxyethane, dipropylcarbonate, ethoxyethoxyethylether or mixtures thereof can be added to the fire retardant electrolyte composition. Such formulations have been shown to have conductivities at room temperature greater than 1 x 10-3 S / cm. The fire retardant electrolyte compositions can also be formulated with a CO_ generating compound. The incorporation of a CO_ generating compound provides improved batch cycle properties. For example, a battery containing a C0_-generating compound is capable of being charged, discharged and recharged in a greater number of such cycles. Such CO_-generating additives can be selected so that any decomposition of the by-products is compatible chemically and electrochemically with the electrolyte and other battery materials. Examples of such examples include dicarbonates »esters» peresters »dioxalates» aayl peroxides »peroxodisarbonates» Diels-Alder adducts of carbon dioxide and mixtures thereof. A preferred CO-generator is di-tert-butyl dicarbonate ("DTBD"). Electrically strong electrolyte films having conductivities greater than 10 ~ S crn-3 can be formed from a combination of: a solvent electrolyte as described and claimed herein or mixtures of such solvent electrolytes; a polymeric film-forming material such as polyvinylidene fluoride ("PVdF"), polyacrylonitrile »vinylidene fluoride and hexafluoropropylene copolymers. or similar »preferably PVdF; a lithium salt of the formula Li-A »where A is co or defined above» or a single ion conductive polymer electrolyte as described in serial number 0B / 372 »216» incorporated by reference above; optionally »a high dielectric constant solvent such as propylene carbonate (" PC "), ethylene carbonate (" EC "), di ethoxyethane (" DME "), and ethoxyethoxyethylether (" MEE "); and »'optionally' a C_ generating compound. It may be necessary to add a glyme (ie, dimethoxyethane (C ^ H or 0S), diglyme (Cß HM 03), trigly a (Cß H ß O ^, tetraglim (C10 H__ -) and so on) to form a bond The homogeneous polymer electrolyte is PVdF, such compounds will not only typically serve as solvents but also as additional plasticizing agents It will be appreciated that the conductive compositions formulated with the electrolyte materials present are also useful in the manufacture of fuel cells, sensors »Supercapacitors» electro-economic devices »and the like, using manufacturing techniques well known to those skilled in the art» or available in the relevant literature.

Manufacturing methods: A preferred method of manufacturing conductive compositions containing the new electrolytes is a technique of pressure in salor to form the films. Such a method typically involves: Ca) forming a gel electrolyte composition to the binarose (i) a lithium salt or a heterologous conductive polymer elestrolite (ie, a polysiloxane of the formula (I) or a copolymer which contains mere units (II) and (III)) »with (ii) an effective amount of fire retardant solvent and (iii) an amount of PVdF or an alternative material effective to improve the mechanical strength of the composition; (b) heating the resulting combination at a temperature and for an effective time to form a fluid sol; (c) pressurizing the fluid solution; (d) cooling the solution and íe) releasing the film provided in this manner. The alternative methods of manufacturing such as the successive somposiations will be apparent to experts in the field, or can be deduced from the relevant literature.

Industrial Applicability: Fire retardant electrolyte compositions are useful in a variety of sontextos. An important utility is in the manufacture of batteries. The batteries formulated are the new electrolyte compositions comprising a positive electrode, an anode "a negative electrode" or "cathode" and an electrolyte composition. The anodes and cathodes can be made of materials commonly used in primary and / or secondary batteries. The anode is typically metallic lithium. Alternatively, a carbon-based material such as petroleum coke or graphite, interlase metal oxide, such as tungsten or iron oxides, or other intercalation materials, such as TiS, can be used as the anode. The cathode is generally of a material that is lithium such as LiCoO-, LiMn-O ^ or LiNiO; however, alternative materials can also be used »ie. VßOAa, MnO_, FeS-, or similar. It will be appreciated that conductive compositions formulated with the novel electrolyte compositions of the invention are also useful in the manufacture of fuel seals, "sensors", supercapacitors, "electrochromic devices" and the like. using manufacturing techniques well known to those skilled in the art »or available in the relevant literature. The following examples are intended to provide those skilled in the art with a complete arrangement and description of how to make and use the novel electrolyte compositions of the invention and are not intended to limit the scope of what the inventors regard as their invention in any way. Efforts have been made to determine the accuracy with respect to the numbers used (ie »quantities» temperatures »etc.). but of course some experimental errors and deviations will be allowed. Unless otherwise stated, "the parts are parts by weight" the temperatures are in degrees centigrade "and the pressure is atmospheric or near-atmospheric. All reagent chemicals and the like are commercially available or are otherwise synthesized using conventional techniques well known in the art.

Experimental technique of measurement and measurement: A. Isicochemical characterization of solvents and electrolytes. Dielectric constant: The dielectric constant, e »of the fire retardant solvents was determined in an electrochemical cell containing two platinum electrodes. The electrodes having a diameter of 0.8 cm »an area of 0.50 cm3» and an interelectrode spacing of O.l cm »giving a volume sample of 0.05 cm3. A Hewlett-Packard HP 4192A LF impedance analyzer was used to measure the capacitance C of the cell when it was filled with the candidate, and it was calibrated using e = \ b_ »where b_ is the cell lattice. Two samples were used: conosid dielectric constants »water and trisloromethane» to salify the selda and calculate b_. Visosity: A Cannon-Ubbelohde viscometer was used to measure the viscosities of fire retardant solvents. The quinematic viscosity »+++ was calculated using ++++++ where fov is the calibration constant of the viscometer and +++ is the time measured for a fixed volume of solvent to flow through the capillary of the viscometer. Water and 1-propanol were used as standards to determine bv. The dynamic viscosity was calculated by +++++ where +++ is the density of the sample. Electrical conductivity: The conductivity cells were manufactured from high density polyethylene; Two nickel plates were used as electrodes. The exposed area of the Ni plates was 0.2 c 53; the spacing of the interelectrode was 1 c. The conductivities of the solutions prepared from the fire retardant solvents and lithium hexafluorophosphate (LiPfß) were measured using the AC imperancia method. Typically »saturated solutions were prepared; generally »these were of approximately 0.5 M. The conductivity k» will be by ksb ^ / - where ^ is the cell constant and R "is the real component of the AC impedance at high frequency (10 KHz). The cell constants were obtained by measuring the conductivities of the normal aqueous CK1 solutions of two concentrations. In the cases where k > 5 S crn-3 »the solutions of the solutions prepared using other salts, that is to say of lithium bis (trifluoromethanesulfonate) (iNíCF-SOa) -)» and the concentration dependence of the conductivities of the LiPFß solution is also they measured The conductivities were measured in LiPFβ solutions of 1 mol dm ~ 3, or in cases where LiPFe was poorly soluble in the solvent, saturated LiPF6 solutions were used. B. Electrochemical characterization Cyclic voltammetry: The cyclic voltammograms of the different electrodes were obtained in a three-electrode cell under an argon atmosphere. The electrodes were vitreous carbon, working electrode, platinum somo counter-electrode, and lithium as the reference electrode. In some cases »to test the stability of the solvent in the Li» the Li was used as working electrodes and counter electrodes. Cell test: Fire retardant electrolytes that had certain acceptable solvent properties as described above were tested in a variety of electrochemical cells; i. LiJ cells i. The experiments of DC twig / dessarga were conducted in a high density polyethylene cell are a work of nickel »lithium leafthrower» and lithium reference electrode to determine the stability of metallic lithium in the solvent. The lithium is electrodeposited on the nickel electrode at a constant current density of 1 mA crn-53 for one hour; the total load that was passed was 3.6 C cm-ß. Then the cell was cycled through the removal of electrodeposition (discharge) and electrodeposition (charge) alternating from 1.2 C cm -3 Li of the nickel electrode to a constant current density of 1 A crn-3 for 20 minutes or »during the electrodeposition removal procedure» until the nickel electrode potential reached +1.0 V towards the LijLi - * -. It was believed that the cell had fallen when the load was passed during the stage the removal phase of the electrodeposition »Q.ß? _» Was less than 50% of the load that was passed during the electrodeposition stage. Qß? _. The parameters of interest are the number of cycles before the fall »Nov» and the cycle efficiency »G.ß ^» which is calculated as S Q ¿, # = Qßß < a? s / Q «" a1- .. ífav and O. * *, * "provide a measure of the reactivity and an indication of the character of the solvent cycle with Li. ii. LijLi cells. Solvents approved in cells containing lithium anodes and cathodes and a lithium reference electrode. A sorne density of 3 mA c -53 and a half-cycle time of 30 minutes were used to cycle through the cell »although the effect of current density and charge / discharge time (ie depth) of discharge "were also parameters that were noted, an overpotential of 2.V was considered at any Li electrode as an indicator of failure.The objective of such tests was to measure the lithium figure of Merit (" FOM ") in the solvent of interest and judge from this the suitability of the solvent for use in secondary cells iii Primary cells Li The high density polyethylene cells described above were used to test the electrolytes with the cathodes used in the commercial primary cells The cathode materials used were iron disulfide (FeS_) and manganese dioxide (Mn0_) .The cathodes were prepared by mixing 85% by weight of FeS_ or Mn0_ and 5% by weight of black carbon with 10% by weight. of PVdF binder subsequently pressing on the mixture of nickel sheet substrates (O.5 cm3 to 2 cm3. The Cathodes were d at 90 ° C overnight. The cells were assembled from such cathodes, the lithium sheet anodes and the lithium reference electrode inside a dry box filled with argon. The assembled cells were removed from the dry box and discharged at various densities of sorte using a Maccor battery tester. The objective of such tests was to compare the electrochemical development of the solvents are that of the commercial primary cells. A Energizer? * Glass cell (LijFeS-2) (Eveready Battery Co.) was used as the baseline. iv. Secondary lithium cell. The purpose of such tests was to determine whether non-flammable electrolytes could be used in secondary lithium »ie" rechargeable "batte. The experiments were car out using a cell with a lithium anode or a carbon anode »a LiCoO intercalation cathode- or LiMn_0» a lithium reference electrode. A C0a or CO generador generator was used to improve the lithium cycle character. The cathodes and the cell were prepared as described above. The cells were subjected to a galvanostatic cycle at various current densities between the cell voltage limits 4.2 V (load) and 3.5 V (discharge).

C. Flammability tests FeS_ Two tests were used to determine the flammability of the fire retardant solvents. The first was differential scanning calorimetry ("DSC") in which samples of solvents were heated with and without lithium to expose the potential thermal hazards associated with the solvent either in itself or in contact with materials • they may be present in a cell. The second technique was acceleration scale calorimetry ("ARC"). The ARC is an adiabatic calorimeter in which the heat emitted from the test sample is used to increase the temperature of the sample. The ARC is conducted by placing a sample in a sample pump inside an insulating cover. In an ARC analysis, the sample is heated to a pre-selected initial temperature and held for a period of time to achieve thermal equilibrium. Subsequently, an investigation is conducted to measure the scale of heat increase ("self-heating") of the sample. If the self-heating scale is less than the pre-set scale after the programmed time interval (typically 0.02 ° C min_x) »the sample temperature is classified to a new value» and the search sequence of the wait salor is repeated. Once the scale of self-heating higher than the current value was measured, the salinity wait search session is abandoned; The smooth heating supplied to the calorimeter is subsequently required to maintain the adiabatic condition between the sample and the cover. The heat generated from the reassessment within the sample increases its temperature and pressure »thus increasing the scale of the reaction. See »for example» Townsend and others »(1980) Thermochi. Act 37: 1. this technique provides information for the thermal risk assessment »material handling procedures» and can provide additional information about the activation energies »storability» and other fundamental thermokinetic parameters that are not available when using other techniques.

EXAMPLE 1 Synthesis of Ethanol (2.3 gm) and pyridine (3.95 gm) were dissolved in 5 ml of benzene and the solution was cooled to 0 ° C in an ice bath. Then 2-chloro-3'-2-dioxane-5-oxide (5,985 gm) (Aldrich) in benzene (2 ml) was added dropwise to the solution to form a reassessment mixture. The reaction mixture was then poured at room temperature for 1 hour and heated to reflux for another hour. The product was distilled and redistilled. The properties of the product corresponded to those previously reported (Kluger et al., Supra, Taira et al., Supra.) The final distillate was used to prepare the electrolyte fire retardant compositions or the fire retardant gel polymer electrolyte films used in the batteries.

EXAMPLE 2 Synthesis of Tris- (methoxyethoxyethyl) phosphate A solution containing 7.44 gm of 2-methoxyethoxyethanol (Aldrich) and 7.7 gm of 4-di-methylaminopyridine ("DMAP") (Sigma) was prepared in 25 ml of benzene and cooled to 0 ° C in a low ice bath. an atmosphere of Ar. Phosiloyl chloride (3.06 gm) (Aldrich) in 5 ml of benzene was added dropwise to the solution which was poured at room temperature for 3 hours and put under reflux overnight. The reaction mixture was filtered further »and the chloroform (100 ml) was added and the mixture was washed with brine (50 ml). The washed organic phase was dried with anhydrous NaHSO and evaporated by rotating until it dried, yielding 7.68 gm of product (96.6% of product). The ^ H-NMR of the residue did not state that the reassignment had come to an end. The TLC chromatography on the ethyl acetate showed two manshas, one of which corresponded to DMAP and the other corresponded to the product. The residue was chromatographed on silica gel using ethyl acetate co or eluent. The product was recovered in the second »third and fourth 40-ml fractions that were combined. The combined eluent was dried in vacuo to yield 4.5 gm (56% yield) of tris-methoxyethoxyethyl phosphate which was used to prepare the insendium-retardant electrolyte compositions or the polymer electrolyte films of the fire retardant employed in the batteries.

EXAMPLE 3 Synthesis of Tris- (2-methoxyethoxy) tri luorofosfaceno The 2-methoxyethanol (2.28 gm) (Aldrich) was added dropwise to 20 ml of a suspension of 1.32 gm NaH (from 60% w / v suspension in mineral oil (Aldrish) in tetrahydro uran ("THF") » The resulting solution was poured at room temperature for 1 hour and added dropwise to a solution of hexafluorophosphenyne (2.49 gm) (Aldrish) in 20 ml of dry THF. at room temperature overnight and then put under reflux for 6 hours.The solvents and other volatile materials were removed by rotary evaporation.The residue was dissolved in chloroform and filtered to remove the salts, then the chloroform was removed by evaporation The residue was passed through a flash chromatography column containing a flash chromatography silica gel using ethyl acetate as eluent, a fraction was collected and the product isolated. To remove the ethyl acetate by rotary evaporation. The final produst was used to prepare the electrolyte to insendium retarder or electrolyte films of fire retardant gel polymer used in the batteries.

EXAMPLE 4 Synthesis of tris-ethoxysarbonyl ethyl phosphate The 2-hydroxyethyl ethylcarbonate (H0C_H ^ -O-C (O) -O- CH_CH3) was prepared in the following manner. Chloroethylformate was added. O.l moles) to a mixture of ethylene glycol (31 g, 0.5 moles) and pyridine (7.9 g, 0.1 moles) in THF (SO ml) by drops at 0 ° C under an inert atmosphere. The mixture formed in this manner was stirred overnight at room temperature. The THF was evaporated and the residue was dissolved in methylene chloride and washed several times with an aqueous saturated sodium chloride solution to remove ethylene glycol and salt. The organic layer was dried overnight in anhydrous. The solvent was distilled, and the pure product was distilled at about 50 ° C under reduced pressure.

A solution containing 4.02 gm of (2- hydroethyl) ethylcarbonate and 7.7 g of DMAP in 25 ml of benzene was prepared and cooled to 0 ° C in an ice bath under an argon atmosphere. The sphoryl chloride (3.06 g) in 5 ml of benzene was added dropwise to the solution which was then stirred at room temperature for 3 hours and put under reflux overnight. The reaction mixture was then filtered, chloroform (100 ml) was added and the mixture was washed with brine (50 ml). The washed organic phase was dried with anhydrous NaSO 4 and rotary evaporated to dryness, obtaining 7.6S gm of product (a yield of 96.6%). - ^ H-NMR of the indicated residue to which the reaction was directed to complete. TLC chromatography in ethyl acetate showed two spots, one of which corresponds to the produst. The residue was chromatographed on silica gel as described in Example 2. The eluate was brazed under vacuum to obtain 3.9 gm (57% yield) of tris- (ethoxycarbonyloxyethyl) phosphate which was used to prepare the electrolyte retarder compositions. of fire or gel polymer electrolyte films fire retardants used in batteries.

EXAMPLE 5 Synthesis of 4-dimethylethoxysilyl-2-butylene carbonate A solution of dimethylethoxysilane (3 gm) (Aldrich) »1-ethenyl ethylene carbonate (2.28 g) (Aldrich) and 200 mg Pt / C in 15 ml of THF was put under reflux for 18 hours under argon and He cooled. The term of the reaction was confirmed by ^ H-NMR. After filtering the substitution mixture, the solvent was removed by rotary evaporation and the residual liquid distilled in vacuo. The fractions were collected during the distillation step d: 35 ° C »2 drops; 2: 90 ° C-0 ° C, 0.8 ml; 3: 125 ° C »3 ml). The product (2.7 gm) was recovered in the third fraction and used to prepare the fire retardant electrolyte suspensions or the fire-retardant gel polymer electrolyte films used in the batteries.

EXAMPLE 6 Preparation of a lithium battery that are triathylphosphate This example describes the preparation of a battery comprising a metallic lithium anode »a LiMn-O ^ cathode and a fire retardant electrolyte. The fire retardant electrolyte was prepared to have the following co-position: LiPFß (1.0) (Aldrich) in tr? Ethylphosto ("TEP") (Aldrich) containing 10% (v / v) of di-ethylpyrosarbonate (Aldrish) as a C0a generator. The electrolyte solution was embedded in a separator of 25.4 micrometers thick (Celgard1 *). The mixed sactode was prepared from 85 parts of LiMn ^ O ^ »5 parts of black acetylene and 10 parts of PVdF dispersed in propylenecaronate; ethylenecarbonate (1: 1 v / v). The mixed cathode paste formed in the heating up to 170 ° C was applied in the aluminum sorbent collector and heated by pressure (approximately 4540 kg of pressure for 1 min at 120 ° C-130 ° C to form a film. The cathode was filled with the liquid electrolyte, the anode, the separator and the cathode were coated to form a battery having a total thickness of about 381 microns.Figure 1 shows the potential profile for the battery and each individual electrode in the cycle.

EXAMPLE 7 Full cell test A. primary batteries. Primary cells of LiJFeS; -, and LiJ nO- were constructed with lithium reference electrodes to evaluate the development of non-flammable electrolytes. The body of the cells was made of polypropylene. Solvents were tested including triacylphosphate ("TEP"), Dimer TEP »methoxyethyldiethyl phosphate (" MTEP ") and mixtures thereof as indicated in Table 1.

TABLE 1 SUMMARY OF PRIMARY CELL TESTS Li | Fes and Li | Mn0-2 Capacity Current Capacity Capacity Capacity (hr) Capacity Capacity Type of anode cathode discharge EODV = real energy Teip. Electrolyte cell (• A / c? 2] _ (lAh) dAh) 1.0V (.Ah) (iH) f'C) Li | FeS2 LiPF6 in PET 1 M 0.24 -10 11.8 79.3 9.6 12.6 23 Li | FeS2 LiPF6 in TEP 1 M 0.50 -9 11.8 35.5 8.9 11.4 23 Li | FeS2 LiPF6 in PET 1 M 1.50 -9 11.8 8.9 6.7 7.6 23 Li | FeS2 LiPF6 in TEP 1 M 2.00 -9 11.8 2.9 2.9 3.0 23 Li | FeS2 LiPF6 in TEP t DTBD (5%) 1 M 0.50 -9 11.8 35.9 9.0 12.8 23 Li | FeS2 LiPF¿ in TEP díiero 0.5 H 0.24 -10 11.8 100 12.0 16.8 23 Li [FeS2 LiPF¿ in MTEP 1 M 0.50 -10 11.8 42.0 10.5 13.5 23 Li | FeS2 LiPF6 in PET (47.5%) + 0.50 -12 11.8 37.2 9.3 11.9 23 MTEP (47.5 *) * DTBD (5%) 1 M Li | FeS2 LiPF6 in PET (47.5 *) + 0.60 -12 11.8 24.2 7.3 8.0 23 HTEP (47.5%) + DTBD (5%) 1 M Li | FeS2 LiPF6 in PET (47.5%) t 0.60 -12 11.8 30.8 9.2 12.2 40 MTEP (47.5%) + DTBD (5%) 1 M Li | FeS2 LiPF6 in TEP (47.5%) + 1.0 -12 11.8 7.3 3.6 3.3 23 MTEP (47.5%) + DTBD (5%) 1 M Li | FeS2 LiPF6 in TEP (47.5%) t 1.0 -12 11.8 11.8 5.9 6.4 40 MTEP (47.5 %) t DTBD (5%) 1 M LijMn02 LíPF¿ in TEP 1 M 0.24 -6 11.8 47.8 5.8 15.3 23 Li | Mn02 LiPFé in TEP 1 M 0.50 • 6 11.8 25.1 6.3 15.2 23 Li [Hn02 LiPF6 in PET (47.5%) t 0.50 -6 11.8 17.6 4.4 10.8 23 MTEP (47.5%) + DIBD (5%) 1 M Li | Hn02 LiPF6 in PET (47.5%) + 0.50 -6 11.8 20.5 5.1 14.1 40 MTEP (47.5%) t DIBD (5%) 1 M Li | Mn02 LiPF6 in TEP (47.5%) + 1.0 -6 11.8 8.3 4.1 11.0 40 MTEP (47.5%) * DIBD (5%) 1 M In addition, there is also I investigated the effect of added di-tert-butyl dibicarbonate ("DTBD") (Aldrich). The 1M LiPF-6 was the salt used in such tests. The measurements were conducted at different discharge current densities and temperatures. The results of the typical systems selected are shown in Table 1. For the LiJFeSa system, the discharge current densities were applied on the scale of O.24 to 2. O Ma cprs. Satisfactory results were obtained in the current density of 1.0 mA c -3 and lower. The cell voltages for most of the tested cells were very stable and close to 1.5 V during the entire discharge process until the theoretical capacity of the Li ano coil was reached or indicated by a potential dianode that increased rapidly. At 40 ° C »the cell shows better development, presumably due to the higher conductivity and lower viscosity of the electrolyte. Similar results were obtained for the Ox \ MnO ^ system. B. Sislo tests (Li Li Li). The reliability of using fire retardant electrolytes in a rechargeable lithium metal battery was assessed by studying the cyclic character of lithium between two lithium electrodes. The DC cycle tests of the Li | Li cells with lithium reference electrodes were conducted in PET »Dimer TEP» MTEP, Trimetoxyethyl Phosphate ("TMEP") »and mixtures thereof are salts including (LiPF6, Li iCFaSO ^» 3 »LiCF-3SOa» and LiAsF, ... A current density of 3 A-2 and half-cycle period of 30 min were the conditions used in such experiments. higher for any Li electrode. The results of such tests are presented in table 2.

TABLE 2 SUMMARY OF CYCLE TESTS FOR LifLi CELLS Salt Density and Tietpo Current 1/2 Tetp Nuts, Solvent Concentration ítA / ct? -) cycle cycles Í'C) TEP LiPF61 M 1.0 20 160 23 TEP LiPF61 M 3.0 30 15 23 TEP LiPF61 M LÍC030.1 M 3.0 30 8 23 TEP LiAsF 1 M 3.0 30 13 13 TEP Li Trilato 1 M 3.0 > , 30 6 23 TEP Li Itida 1 M 5.0 30 2 23 TEP Ditero LiPF¿ 0.5 M 1.0 20 2 23 MTEP LiPF61 M 3.0 30 15 23 TMEP LiPF60.5 M 1.0 20 100 23 TEP t PC 5% LiPFé 1 M 3.0 30 9 23 TEP + DTBD at 1% LiPFé 1 M 3.0 30 8 23 • TEP r DIBD at 5% LiPF61 H 3.0 30 48 23 TEP + DTBD at 5% LÍPF61 M 3.0 30 50 40 TEP + DTBD at 5% LiPF61 M 3.0 30 51 60 TEP (66%) t ditero LÍPFé 1 M 1.0 20 52 23 TEP (34%) TEP (63%) t ditero LÍPF61 M 1.0 20 335 23 (32%) + DIBD (5%) TEP (45%) t TMEP LiPFé 0.75 M 3.0 30 6 23 (50%) + DIBD (5%) MTEP + 5% DTBD LiPF61 M 3.0 30 19 23 TEP (47.5%) i MTEP LiPF61 M 3.0 30 14 23 (47.5%) + DTBD (5%) + DIBD (5%) Under the test conditions »the cell hesha are so posicion electrolita of 1 M LiPF in TEP it can be subjected to a cycle 15 times. This system is equivalent to a full cycle of the total capacity of the Li electrode. The addition of 5% DTBD improved the cycle character to 4B cycles »or three lithium cisions. Such improvement can be attributed to the decomposition in situ of the dicarbonate to produce carbon dioxide, thereby passivating the surfaces of the lithium electrode.

EXAMPLE 8 Material Safety: Acceleration Scale Calorimetry In order to determine the potential explosive hazard of fire retardant electrolyte composites »the thermal characteristics of the solvent mixture TEP (47.5% v / v), MTEP (47.5% v / v) and DTBD (5% v / v) were evaluated in an aerobic environment on an acceleration scale calorimeter (ARC) as described above. Figure 2 shows the self-heating scale as a function of temperature for the metallic lithium strips immersed in the TEP mixture: MTEP: DTBD and for the electrolyte used in a commercial primary lithium battery. In both cases, the electrolyte contains a 1 M salt (LiPFß for the flame retardant electrolyte and LiCF3S03 for the commercial battery electrolyte) and a metallic lithium strip (10 mg). The total weight of the solution was approximately 2.1 gm for both mixtures. The results shown in Figure 2 show that both electrolytes exhibit an exothermic behavior starting at approximately 160 ° C. The flame retardant electrolyte system exhibits a maximum self-heating scale of 0.38 ° C min-1 to 17B ° C. In contrast, the commercial electrolyte shows a higher exotherm with a maximum self-heating scale of 1.76 ° C min -1 to 191 ° C. The flame retardant electrolyte shows a second small exotherm between 200 ° C-23 ° C, but the total salor released during these two exotherms is less than that released during the single exotherm of the commercial battery electrolyte.

EXAMPLE 9 Preparation of a lithium battery containing PET and ethylene carbonate A solution of lithium bis (tri luoromethanesulfonate) imide (LiN (CFaSOa)) was prepared in a solvent system composed of ethylene carbonate: TEP (1: 1) .The ambient temperature conductivity of this solution was 2. 82 x 107-3 S cpt - * - by analyzing the AC impedance. A battery comprising a metallic lithium anode, a cathode iMn ^ O ^ and a fire retardant electrolyte can be made according to the procedure of example 6 by substituting the ethylene carbonate: TEP solvent system for the PET. The potential profile for the cycle is foreseen and each individual electrode in the cycle will be similar to the one described in figure 1.

EXAMPLE 10 Preparation of a lithium-containing battery A battery comprising a metallic lithium node, a cathode and a fire retardant elestrolite can be made according to the procedure of example 9 by substituting prepared as described in Example 1 for PET in the ethylene carbonate: TEP solvent system. It is anticipated that the potential profile for the battery and each individual electrode in the cycle will be similar to that described in Figure 1.

EXAMPLE 11 Preparation of a lithium battery containing Tris- (methoxyethoxyethyl) phosphate A battery comprising a metallic lithium anode, a Li n ^ O ^ cathode and a fire retardant electrolyte can be made in accordance with the procedure of example 3 by replacing the tris- (methoxyethoxyethyl) phosphate prepared as it is dispersed therein. Example 2 for PET in the ethylene carbonate: TEP solvent system. It is anticipated that the poten- tial profile for the battery and each individual electrode in the cycle will be similar to that described in Figure 1.

EXAMPLE 12 Preparation of a lithium battery containing tris- (2-methoxyethoxy) tri luorofos asino A battery that contains a metallic lithium anode, a cathode Li n ^ O ^ and a fire retardant electrolyte can be made according to the procedure of example 9 by substituting the tris- (2-ethoxyethoxy) trifluorophosprasene prepared as it is dissolved in the Example 3 for PET in the ethylcarbonate: TEP solvent system. It is anticipated that the potential profile for the battery and each individual electrode in the cycle will be similar to that described in Figure 1.

EXAMPLE 13 Preparation of a lithium battery containing triphosphate (ethoxycarbonyloxyethyl) A battery comprising a metallic lithium anode, an indole cathode and a fire retardant electrolyte can be made according to the procedure of example 9 by substituting the tris-ato (ethoxycarbonyloxyethyl) prepared as described in example 4. for PET in ethylene carbonate: TEP solvent system. It is anticipated that the potential profile for the battery and each individual electrode in the cycle will be similar to that described in Figure 1.

EXAMPLE 14 Preparation of a lithium battery that is 1,1-Dimethyl- (1-ethylene-carbonate) -ethoxysilane A battery comprising a metallic lithium anode, a cathode i30m and a fire retardant electrolyte can be made according to the procedure of example 9 by substituting the 1-l-dimethyl- (1-ethylene-di-carbonate) -ethoxysilane prepared as described in Example 5 for the PET in the ethylene carbonate: TEP solvent system. It is anticipated that the potential profile for the battery and each individual electrode in the cycle will be similar to that described in Figure 1, EXAMPLE 15 Preparation of a lithium battery containing Perfluoropropylene Carbonate A battery comprising a metallic lithium anode, a cathode iMn ^ O ^ and a fire retardant elestroll can be made according to the procedure of example 9 by replacing the per-loropropylene carbonate which can be prepared from the propylene carbonate using the method described in European patent publication Mo, 0557167 for PET in ethylene carbonate: TEP solvent system. It is anticipated that the potential profile for the battery and each individual electrode in the cycle will be similar to that described in Figure 1.

EXAMPLE 16 Preparation of a lithium battery containing a Perfluoropolieter A battery comprising a metallic lithium anode, an indole cathode and a fire retardant electrolyte can be made according to the procedure of example 9 by substituting the Galden1 * HT90 perfluoropolyether (formula weight = 460) (Harris Specialty Chemicals »PCR Division) for PET in ethylene carbonate: TEP solvent system. It is anticipated that the potential profile for the battery and each individual electrode in the cycle will be similar to that described in Figure 1.

EXAMPLE 17 Preparation of a lithium battery having a carbon anode and containing a non-flammable electrolyte This example describes the preparation of a battery comprising a carbon anode, a cathode iMn ^ O ^ and a fire retardant electrolyte. An electrolyte solution of 1.0 M LiPFß in ethylene carbonate: TEP (1: 4 v / v) is coupled in a separator of 2.54 microns thick (Celgars® 2500). The carbon anode is prepared from a compound of 90 parts of coke carbon (Ucar carbon) and 10 parts of PVdF in a propylene carbonate: ethylene carbonate (1: 1 v / v). The compound is combined at about 170 ° C for about 5 minutes and then pressed in heat (730 Kg / cm23 »120 ° C-130 ° C for one minute) in a copper current collector. After drying, the anode is refilled with the electrolyte solution. The cathode is prepared from 82 parts of LiMn ^ O ^ »12 parts of black acetylene and 6 parts of PVdF dispersed in propylene carbonate: ethylene carbonate (1: 1 v / v). The cathode mixture is mixed at 170 ° C for about 5 minutes and then applied in an aluminum current collector by heat pressure as above. After drying, the cathode is refilled with the liquid electrolyte. The anode »separator and cathode are extratified to form a battery having a total thickness of about 381 microns.

EXAMPLE 13 Fabrication of a Fire Retardant Electrolyte Film Containing TEP In a dry box »LiPFβ (1 gm)» PVdF (2 gm) and TEP (6 gm) were mixed and heated to 120 ° C until a clear fusion was obtained. The heat fusion was poured into a mold and subjected to pressure. After cooling to room temperature »a free-standing film was formed. The conductivity of the film was determined by the AC impedance. The conductivity at room temperature was 1.76 x lO-3 S cm-3.

EXAMPLE 19 Preparation of a fire retardant Elestrolite film containing TEP and ethylene carbonate A conductive film comprising LiPF6 > PVdF and a fire retardant electrolyte can be made according to the procedure of example 13 by replacing a solvent system composed of ethylene carbonate: TEP (1: 1) for the PET.

It is anticipated that the AC impedance is for the film will be similar to the one measured in example 18.

EXAMPLE 20 Manufacture of a fire retardant electrolyte film containing A conductive film comprising LiPFs, PVdF and an insendium retardant electrolyte can be made according to the procedure of example 19 by substituting prepared as described in Example 1 for the PET in the ethylene carbonate: TEP solvent system for the PET it is anticipated that the AC impedance for the film will be similar to that measured in example 19.

EXAMPLE 21 Fabrication of a fire retardant electrolyte film containing Tris- (methoxyethoxyethyl) os ato A sputtering film containing LiPFß »PVdF and a fire retardant Etherlite can be made according to the procedure of Example 19 by substituting the Tris- (ethoxy-ethoxyethyl) phosphate prepared as described in Example 2 for the TEP in the ethylene carbonate. : TEP solvent system for the PET is anticipated that the AC impedance for the film will be similar to that measured in example 19.

EXAMPLE 22 Fabrication of a fire retardant Electrolyte film that is 2-methoxyethoxytrifluorophosphazene A conductive film comprising LiPFβ »PVdF and a fire retardant electrolyte can be made according to the procedure of example 19 substituting the 2-ethoxyethoxytritluorophosphazene prepared as described in example 3 for the PET in the ethylene carbonate: solvent system of TEP for the PET it is foreseen that the impedance AC for, the film will be similar to the one measured in example 19.

EXAMPLE 23 Fabrication of a Fire Retardant Electrolyte Film Containing Tris- (Ethoxycarbonyl Toxyl) Phosphate A conductive film comprising LiPF ^ »PVdF and a Fire Retardant Electrolyte can be made according to the procedure of Example 19 by substituting the tris- (ethoxycarbonylethoxyl) phosphate prepared as described in Example 4 for the PET in the ethylene carbonate: TEP solvent system for the PET is anticipated that the AC impedance for the film will be similar to that measured in example 19.

EXAMPLE 24 Fabrication of an Insendium Retardant Electrolyte Film Containing 1, 1-Dimethyl- (1-ethylene-carbonate) -ethoxysilane A conductive film comprising LiPFs »PVdF and a fire retardant electrolyte can be made according to the procedure of example 19 by substituting the 1,1-dimethyl- (1-ethylethylene carbonate) -ethoxysilane prepared as described in example 5 for PET in the ethylene carbonate: TEP solvent system for the PET is anticipated that the AC impedance for the film will be similar to that measured in example 19.

EXAMPLE 25 Manufacture of a fire retardant electrolyte film containing perfluoroprolenesarbonate A conductive film comprising LiPFß »PVdF and a Fire Retardant Electrolyte can be made according to the procedure of Example 19 by substituting the perfluoropropylene carbonate that can be prepared from the propylene carbonate using the method described in European Patent Publication No. 0557167 for The PET for PET in the ethylene carbonate: TEP solvent system for the PET is anticipated that the AC impedance for the film will be similar to that measured in example 19.

EXAMPLE 26 Fabrication of an Insendium Retardant Electrolyte Film Containing Perfluoropolyether A film comprising LiPF6, PVdF and a fire retardant electrolyte can be made according to the procedure of example 19 by replacing the perfluoropolyether Galden.RTM. HT90 (formula weight = 460) (Harris Specialty Chemicals, PCR Division) for the PET in the ethylene carbonate. : solvent system of TEP. It is anticipated that the AC impedance for the film will be similar to that measured in example 17.

EXAMPLE 27 Manufacture of a fire retardant electrolyte film containing a polymethylsiloxane are pendant groups "S •? •"! "" • • • • • - and - ** - < »* -" » Polyisoxane with lithium triflate (polyethylsiloxane with pendant groups of C3HßOC.aF.4S? 3i) was synthesized according to the following scheme and procedure: CI- ^ CHCiL-.Br + CF-, - o '> CHss = OHCH, 3OC, - .F.4S0.2F 10 CFa-SOa (1) (2) (3) CH. CH. * i: (3) HSiCl. Cl-Si-Cl C3He0C3F < lSO3F (4) (5) twenty (6) CH_ 30 I (6) + (CH,). , SiOSi (CH3) 3 (CH3) 3Si0- (SiO) "- Si (CH3) 3 (7) CH3 i (7) + 2 LiOH > CH3 3SiO- (SiO) "- SI (CH3 3 + LiF THF / Ha |" s3Hosos3F ^ so3F (8) (a) Preparation of fluorosultone (2): In a 500 ml parr pressure reactor equipped with a magnetic stirrer 50 ml of fresh sulfur trioxide was prepared by distillation of fuming sulfuric acid, stirring was introduced continuously to tetrafluoroethylene at a pressure of 2.19 kg / cm3 The exothermic reaction took place The volume of the liquid content gradually increased according to At the end of the reaction, the crude product was purified by distillation.A colorless liquid product was collected at a temperature of 42-43 ° C. 162.9 g of fluorosultone (2) were obtained. 3): In a 250 ml neck bottle 3 equipped with a magnetic stirrer and covered with aluminum foil, 63.44 g (0.50 mole) of silver fluoride and 100 ml of anhydrous diglyme were combined.The bottle was cooled to -78 ° C and 90.04 g (0.50 moles) of fluorine Osultone (2) was added by dripping. A clear solution was produced after 1 hour at room temperature. The bottle was again cooled to -78 ° C and 60.49 g (0.50 moles) of allyl bromide (1), added by dripping. The reaction was heated to 45-50 ° C for 16 hours. The mixture was then filtered to remove the AgBr. The filtrate was poured into 100 ml of water and the oil layer that formed was washed three times with water and dried with O2. Distillation gave 79.16 g (3) 76.1%, bp 120-121 ° C. The identity of the product was confirmed using AH NMR spectroscopy (^ -H NMR (CDCl /?): 4.60 (d, 2H, CH3 = sHCHJst0-); 5.34-5.47 (m, 2H »CH> = CH-); 5.89-5.93 (m, 1H, CH5-t = CHCHsaO-)). (c) Preparation of (5): In a high pressure reactor, 72.69 g (0.35 mole) of (3), S0? .53 g (0.70 mole) of dichloromethylsilane (4) and 0.46 g (1.1 mole) were combined. of sapid chloroplatinic acid. The reactor was sealed and filled with argon at a pressure of 3.65 kg / cm 3 and then heated to 70-90 ° C for 22 hours. After cooling to room temperature, the product was transferred under the inert atmosphere to a frasso using a double-pointed needle. The unreacted dichloromethylsilane was removed under reduced pressure. To the distillation gave 85.89 g (5), 76%, bp 68-71 ° C / 0.80 m Hg. The identity of the product was confirmed using AH NMR spectroscopy (* • _? NMR < CDC13 / < S): 0.82 (s, 3H, CH ^ Si-); 1.15-1.25 (n.2H »BiCH" CEU, CH ..-)? 1.9-2.0 (m. 2H »SiCH, -, CH-, sH.3-); .1-4.2 (t »2H, SiCH ^ CH-.CH ^ OCF)). (d) Preparation of (6): < 5) (85.3 g »0.27 moles) were taken in anhydrous ether (50 ml), and the resulting solution was added to a mixture of water (50 ml) and ether (50 ml) by dropwise dripping. At the end of the addition, the reaction was able to continue overnight. The oily layer was separated from the aqueous layer. The aqueous layer was extracted with ether (40 ml x 3), and the ether extract was combined is the oil layer product., washed with water until the water phase became neutral to the pH paper, dried with anhydrous gSO, filtered, and the solvent was removed from the filtrate by the rotary evaporator. The resulting colorless liquid residue was further dried at room temperature under 0.1 at vacuum torr for 4 hours to yield 70.68 g of cyclosiloxane (6) (99%). The identity of the intermediate (6) was confirmed using a spectroscopy (^ -H NMR (CDCl3 / 6): 0.05- O.OT (m, 3H.CH -. Si-); 0.25-0.35 (m 2H »SiCH-, CHTOCH" -)? 1.85-1.90 (broad, 2H, SiCH3CH30-) 4.0-4.5 (broad, 2H, SiCH ^ CH-2CH ^ Q)). (e) Preparation of (7): Cyclosiloxane (6) (350 g, 1350 mol) 1 and hexamethyldisiloxane (42.4 g, 0.261 mol) were added to a round-bottomed flask with 10 drops of concentrated sulfuric acid and allowed to stand overnight. An additional 10 drops of concentrated sulfuric acid were added and the mixture was stirred for 24 hours. The mixture was then taken into the methylene slurry and washed with water (2 x 500 ml) and then a saturated NaCl solution containing a small holiness of NaHCO 3. The solution was dried with MgSO 4 before removing the solvent by evaporation. (f) Preparation of (8): The sulfonyl-polysiloxane fluoride (7) (59.B0 g, 0.22 moles) was taken in 270 L THF. The THF solution, the aqueous solution of lithium hydroxide (10.67 g of anhydrous LiOH »0.44 mol, in 150 ml of water) was added by dripping for 6 hours. Theoretically, 2 moles of lithium hydroxide are required to convert each group of sulfonyl fluoride to lithium sulfonate. However, »lithium hydroxide absorbs moisture because it is hygroscopic. A slight excess of LiOH was added until the solution became neutral using a pH meter as monitor. Absence of absorption of iS > F NRM at 123.5 ppm due to -S03F confirmed that all fluoride sulfonyl groups were converted to lithium sulfonate. THF and water were evaporated by rotation. The residual white solid was dried at 50 ° C under 0.1 at torr vacuum overnight. The resulting crude product was dissolved in 200 ml of acetone. The mixture was filtered in order to remove the LiF, and then the filtrate was concentrated. The acetone solution was added dropwise to 600 ml of dry ether with stirring. The polymer product precipitated. The polymer product 88) was then dried at 70-80 ° C under 0.05 at torr vacuum for 2 days' and the pure product (8) was obtained in 93% yield. The identity of the product (8) was confirmed using the spectroscopy ^ -H RMM (.D ^ O / á) 0.21 (broad, 3H »CH3Si-); 0.70 (broad, 2H »SiCH3-CH.3CH.3-); 1.80 (broad, 2H »SiCH-aCH ^ OE -) 4.10 (broad» 2H »SiCH3CHßCH-20C3F._1S03Li) i iS» F NMR (D30 / ppm): -5.61 (S »- FaCH.3SO.3Li) ü -39.03 (S, -CF3sFaS03Li)). (g) Preparation of the fire retardant film: > The lithium triflate polysiloxane (1 gm) »PVdF (2 g) and a mixture of 1 part propylene carbonate» 5 1 part ethylene carbonate and 2 parts triethylphosphate (6 gm) were mixed and heated to 120 ° C until He obtained a clear fusion. The melt was pressurized by heat, then cooled to room temperature to produce a free-standing "clear" film. The conductivity of this film was measured by the AC impedance. The conductivity at room temperature was 7.85 x 10- • * S cm-1.

EXAMPLE 28 * Manufacture of an electrolyte retarding film of insendium which are a polymethylsiloxane are pendant groups of C ^ H ^ OC ^ F .. SO-2N (Li) C (Q) CF, A polymer sonductor of a single ion of lithium-olisiloxane triflate having the general structure is synthesized according to the following scheme and procedures.

O) (10) (a), preparation of (9): Cyclosiloxane (6) prepared according to the procedure described in example 27 (35.5 gm, 117 mmol) was dissolved in THF (40 ml) and added at -7 ° C under stirring a mixture of a ony (17.2 g, 0.9 ml) in THF (220 ml). The mixture was stirred at -78 ° C for about one and a half hours, then heated to 0 ° C for about two hours. Stirring was continued at 0 ° C for about one hour. The mixture could be warmed to room temperature and then stirred overnight. The mixture was sonsentró in vacuo and placed in methanol (150 ml). The lithium hydroxide (9.9 gm »236 mmoles in 75 ml of water) was added. The mixture was concentrated, then methanol (150 ml) was added followed by 10 ml (120 mmoles) of 12 N hydrochloric acid in 20 ml of methanol. The product was purified by flash chromatography on silica gel (methylene chloride: ethyl acetate 1: 1): (b) Preparation of (10): Sodium hydride (14.5 gm »363 mmol» 60% in oil) was added , washed with 3 x 60 ml of pentane, in 3 portions to a mixture of (9) (3B.5 gm, 129.6 mmol) in 550 ml of dimethoxyethane. 5 The mixture was heated to 50 ° C and the stirring was continued for 2.5 hours. The suspension formed in this way was cooled to -70 ° C and the trifluoroacetic anhydride (29.3 ml, 207.5 mmol) was added for 30 minutes. The mixture formed in this manner was stirred with a mechanical stirrer at about -25 ° C for 2.5 hours until all the solid dissolved. The mixture could be warmed to room temperature and stirred overnight. The crude product mixture was concentrated in vacuo and the residue was taken up in 80 l of CH3C13: ethyl acetate (5: 1) and dried. purified by flash column chromatography on silica gel (CHaCl3: ethyl acetate 1.1) to yield the corresponding pure sodium salt (10). The latter was converted to lithium salt (10) by treatment in the IR120 (+ -) ion exchange resin previously treated with water, then with an aqueous solution of LiOH. The yield of the product was greater than 80%. (c) .Preparation of the Insendium Delay Film: A sonic film can be made according to the procedure of example 27 substituent (10) for (8). It is foreseen that the AC impedance for the film will be similar to that measured in example 27.

Claims (1)

1. NOVELTY OF THE INVENTION CLAIMS 5 1.- A battery that comprises an electrolyte that has a conductivity greater than 10-3 S crn-3 at room temperature "and that includes a compound that generates C03 as a fire retardant gas, when it decomposes. 2.- The battery in accordance with the claim 10 1 »further characterized in that the electrolyte which produces the insedent retarding gas comprises a dicarbonate, ester, perester, dioxanate» acyl peroxide, peroxodicarbonates, or diels-alder dioxide carbon dioxide, or mixtures of the same. 15 3.- The compliance battery is the claim 1, further characterized in that the electrolyte which produces the fire retardant gas comprises di-tert-butyl dicarbonate. 4. The battery according to claim 20 1 »further characterized by at least one of the following: (A) the electrolyte includes a silane; (B) the electrolyte includes a phosphate; (C) the electrolyte includes a halogenated carbonate; (D) the electrolyte includes a cislophosphasen; (E) the electrolyte includes a phospholane; (F) The electrolyte includes a fluorinated polyether. 5. The battery according to claim 4, further characterized in that the electrolyte that produces the fire retardant gas comprises a dicarbonate, ester, perester, dioxalate, acyl peroxide, peroxodicarbonate, or Diels-Alder adducts of sarbon dioxide, or mezslas of the 5 same. 6. The battery according to claim 4, further characterized in that the electrolyte that produces the fire retardant gas comprises di-tert-butyl dicarbonate. 'lO 7.- The battery in accordance with the claim 4 »further characterized in that the silane comprises: i R3-1 - Si-R -55"15 | t R 3 where R1 ° iRliiRA3 and * 3 are independently selected from the group consisting of (a) C ^ -C ^ alkyl terminally substituted are 0 to 3 atoms of halogen and containing O to 20 3 ether bonds and (a) -O? - * wherein R - * is C 1 -C 4 alkyl, terminally substituted with 0 to 3 halogen atoms and containing 0 to 3 ether linkages, and optionally wherein 2 or more compounds of the struence (IV) they are linked by a siloxane bond. 25 8.- The battery in accordance with the claim 4 »further characterized in that the phosphate has the following structure: wherein R» R2 and 3 are independently selected from the group consisting of (a) C ^ -C ^ alkyl terminally substituted with 0 to 3 halogen atoms and containing Or to 3 ether bonds, (b) Si (R - *) 3 and (c) B (OR - *) .-, where the R- * s 10 independently select C ± -C3 alkyl containing from 0 to 3 ether or alkoxy bonds of C ^ -C ^, and optionally wherein 2 or more compounds of structure (I) are linked via an ether linkage . 9.- The battery of soundness with the claim 15 4, further characterized because the halogenated sarbonate has the * following structure: f O II Wherein R "and R ß are independently selected from the group consisting of (a) perfluorinated or partially fluorinated C ^ -C ^ Q alkyl containing from O to 3 ether bonds and (b) -O? 3-" 7 wherein R1"7 is a perfluorinated or partially fluorinated alkyl containing from O to 3 ether bonds or Wherein R - * - 5 * and Riß are linked to form a perfluorinated or partially fluorinated C -C 10 alkyl bridge, and wherein the halogenated carbonate may have multiple sarfoonate groups. 10. The battery according to claim 4, further sarasterized because the sislofoefaseno has the following structure: wherein n is an integer from 3 to 6 and R * 7 and Rβ are independently separated from the group consisting of hydrogen, halogen and -ORs where * »is a C, -C.sub.4 alkyl terminally substituted with O to 3 halogen atoms and which are of O to 3 ether atoms, with the proviso that when one of R "7 or Rβ is -ORs" the other is halogen 11.- The battery in accordance with claim 4, characterized further because the phospholane has the following structure: wherein R = is selected from the group consisting of oxy or a pair of electrons and, when Rs is a pair of electrons, Rs is an alkyl of C ^ terminally substituted with 0 to 3 halogen atoms and containing 0 to 3 ether bonds. 12.- The battery of sonformidad are the reivindisasión 4 »sarasterizada in addition because the fluorinated polyester has the following structure: Rao RAßO- (C I-CFj-, 0)" - (CFa0) v- * -6 »Rsaa. wherein R a and R 1"are independently a C 1 -C 4, perfluorinated or partially fluorinated alkyl, R 5 and R 3 * are independently selected from the group consisting of -F or a perfluorinated or partially fluorinated CA-CιO alkyl. , yxyy are independently selected are values that are from 5 to 150. 13. The battery according to claim 4, further characterized in that the fluorinated polyester has an average molecular weight of between about 400 and 10,000.