MXPA97005253A - Electrolyte and cell electrolit - Google Patents

Abstract

The present invention relates to an electrolyte having ionic conductivity, which can be used in electrolytic cells, especially in rechargeable batteries (also referred to in the literature as secondary batteries), electrochromic displays and sensors, to oligomers of electrolyte precursors and to a combination of these electrolyte oligomers having ionic conductivity with appropriate support matrices. It also refers to processes to prepare certain electrolytes and articles of the same

Description

ELECTRÓLITO AND ELECTROLYTIC CELL The present invention relates to an electrolyte having ionic conductivity, which can be used in electrolytic cells, especially in rechargeable batteries (also referred to in the literature as secondary batteries), electrochromic exhibitors and sensors, to oligomers of electrolyte precursors and to a combination of these electrolyte oligomers having ionic conductivity with appropriate support matrices. It also refers to. processes to prepare certain electrolytes and articles thereof. Several disadvantages are known in electrolytic cells, which comprise, like the electrolyte, a solution of a conductive salt in a polar solvent. (In the present specification and claims, "conductivity" is related to "ionic conductivity", not "electronic conductivity"). Cells containing liquids of rather low viscosity may be subject to leakage. Cells containing volatile liquids have potential problems with solvent loss as vapor. Liquid electrolytes of this type can also be subject to overload instability.

In contrast, an electrolytic cell containing a non-volatile electrolyte, somewhat viscous, or with a solid electrolyte, is convenient in the construction of electrolytic cells, rechargeable batteries, electrolytic capacitors, and the like, since manufacturing ease is increased, and Unusual configurations and sizes can be prepared with relative ease, while avoiding the aforementioned problems with liquid electrolytes. For best results, the electrolyte, possibly in combination with a support matrix, must exhibit good mechanical properties, such as a light weight with retention of the structure over a range of temperatures. Another convenient property is the ease of manufacture, such as by molding, extrusion or thermoforming. Many attempts have been made to prepare solvent-free electrolytes, these electrolytes will maintain the attractive conductive properties at room temperature, along with other of the convenient features listed herein, but no system has proven completely satisfactory. One problem is that, in order to compete with liquid electrolytes, the conductivity of the solid electrolyte must be high enough to provide useful electrolyte cells.

It is known in the art that polymers of ethylene oxide (PEO) have attractive properties as substrates for ionic conductors, but require plasticizers or solvents, such as propylene carbonate or ethylene carbonate to function properly. Several references to such polymers have one or both ends capped with a free radical polymerizable functionality, such as an (et) acryloyl group; these polymers can then be polymerized in a solidified form, usually with entanglement or formation of a three-dimensional network. Bauer et al. , U.S. Patent No. 4,654,279, discloses a two phase interpenetrating network of a mechanical support phase, which is an interlaced network and an ionic conductive phase, which is a liquid 1,2-poly (alkylene oxide) in complex with a suitable metal salt.

Although it supplies self-supporting films, the '279 polymers will be prone to the known degradation of the combination of the metal / poly (alkylene oxide) ion in recycling and exposure to overvoltages. Also, poly (alkylene oxide) will be sensitive to water. In addition, the combination is not capable of being extruded or molded into thermoplastic objects, and requires thermosetting conditions that immobilize the network to the subsequent thermal process.

Selvaraj et al. , J. Electrochem Soc., 142, 366 (February 1995), teaches a poly (meth) acrylate with short side chains of eteroxy (approximately five units of ethylene oxide per chain) as suitable, when it forms a complex with an appropriate lithium salt, such as a water-insoluble, non-interlaced, conductive polymer, where no plasticizing solvent is present. However, this polymer is described as having a glass transition temperature (Tg) of -26.52C and a molecular weight of 240,000. The ionic mobility within a matrix having a relatively high glass transition temperature will be insufficient to obtain the desired high conductivity, below room temperature. Noda et al. , U.S. Patent No. 5,527,639, discloses a polymer with lithium salt impurities, obtained by entanglement of an organic compound of the general formula (using its notation): Z - [(A) m- (Ep) -Y] k where Z is the residue of an active hydrogen compound, selected from certain alcohols, amines and phenols, A is - [- CH2-CH-0) - I CH2-O- (CH2-CH2-O) n-R, where n is an integer from 0 to 25 and R is CI-C2Q alkyl, alkenyl, aryl or alkaryl; E is at least one of - (R2-0) -, R2 being an alkylene having two or more carbon atoms, Y is an active hydrogen or a polymerizable functional group, k is an integer from 1 to 12, m is an whole from 1 to 250, and p is an integer from 1 to 450. Noda prefers a molecular weight of the organic compound below 50,000. Noda teaches that its interlaced polymer will be useful as a component of an electrode or the electrolyte of a galvanic cell. Noda reveals a good storage capacity for such galvanic cells, but reveals in no more than the qualitative language the extension of the improvement in the conductivity at low temperature for the lithium ion in complex. Noda requires that its organic compound be interlaced, which is not required by the oligomers of the present invention. The organic Noda compound further differs in structure from the oligomers claimed in the present invention. M. atanabe, Makrom, Symp. 105, 229 (1996) has disclosed, without experimental details, a macromonomer: CH2 = CH-C00-CH2-CHR4- (0-CH2-CH2) w-0-C2H5 where R4 is -CH2-0-CH2-CH2-0-CH2-CH2-0-CH3. which is reported to dissolve lithium trifluoromethanesulfonimide and then polymerize photochemically to conductive films. At Li / 0 ratios of 0.02-0.08, the conductivity at 802C was 10 ~ 3O ~ 1cm ~ 1, at 302C it was 10 ^ 0-\ "1 Y a ° ac was 10-SQ-icpT1- These polymers they do not appear to be oligomeric in nature and, therefore, should be less versatile than the combinations of the present invention The inventor has discovered a novel oligomer useful in such lithium batteries (or another based on a salt of a conductive metal), to which the oligomeric lithium or other conductive metal salt can be added at the time of formation or mixing then for improved conductivity and for improved resistance to conductivity degradation in recycling or exposure to overvoltage. of lithium salt (or other conductive metal) / oligomer with a mixed composition of the matrix polymer, this matrix is a compatible or miscible mixture of two acrylic polymers, at least one of which may also contain a salt that aids in the uctivity The term "conductive metal salt" in this specification refers to a component of a mixture of an oligomer, as described herein, and a salt (or a mixture of salts) that is soluble or miscible, with the oligomer, to form a conductive mixture. As Gray, "Solid Polymer Electrolytes", Editors VCH, 1991, describes on page 116, "Polymer electrolytes are formed when the salt consists of a polarization cation and a large delocalized charge anion, to minimize the grid power. " Highly preferred as cations are the lithium salts described herein, but other cations may be used, as long as the salt meets the solubility criteria and the oligomer / metal salt mixture is stable with respect to oxidation and / or reduction in the work potential. Other cations may be those of alkali metals, such as sodium, potassium and the like; examples of these salts are sodium tetraphenyl bride, sodium iodide, sodium thiocyanate, potassium thiocyanate, rubidium iodide, and the like. Other cations may also be employed, such as alkaline earth metal cations, such as magnesium, calcium and the like (as exemplified by calcium iodide, calcium bromide, magnesium perchlorate, magnesium trifluoroethylsulfonate, and the like), aluminum (as exemplified by lithium aluminum tetrachloride); and zinc (as exemplified by zinc bromide, zinc iodide, zinc chloride, and the like). This list is not exhaustive, other soluble metal salts may also be useful, for example manganous bromide, lanthanum perchlorate, cupric trifluoroethyl sulfonate, and the like. Certain organic cationics can also be employed, such as "metal cations", for the purposes of this invention, such as the tetraalkylammonium salts, as exemplified by tetraethylammonium tetrafluoroboride, tetrapropylammonium hexafluorophosphide, tetrabutylammonium perchlorate, tetramethyl trifluoromethylsulfonate. -onium, tetramethylammonium bromide, tetraethylammonium phthalate, and the like. In the following description and explanation, the term "conductive lithium salt" refers to a highly ionizable lithium salt, with a large counter ion, which is highly soluble in polar media. This description excludes, for example, LiF, LiCl and Li S04, but include, for example, LiC104, LiBF4 and LiN (CF3S02) 2. The conductive metal salt / oligomer mixture can be mixed with the matrix composition to give a compatible mixture, or it can be encapsulated or combined between layers of the matrix composition or preferably it can be applied to the surface of a thin film of the matrix composition. Preferably, the salt in both the salt / oligomer A and the matrix B is a lithium salt with a large anion, more preferably (due to the solubility) LiN (CF3S02) 2. The conductive metal salt / oligomer mixture can be mixed with the matrix composition to give a compatible mixture, or it can be encapsulated or combined between layers of the matrix composition or it can preferably be applied to the surface of a thin film of the matrix composition. Preferably, the salt in both the salt / oligomer A as the matrix B is a lithium salt with a large anion, more preferably (due to the solubility) LiN (CF3S02) 2. These compositions are useful in electrolytic cells, such as batteries with suitable anodes and cathodes based on lithium. Other known anodes and cathodes may also be used, if their electrochemistry is compatible with the conductive metal salt selected for use in the electrolyte. Also, a resource for producing certain salt / oligomer combinations was discovered, and also a method for preparing an oligomer article, as applied to a thin film or sheet of the matrix composition, the article being employed as the electrolyte component of the composition. an electrolytic cell, such as a battery that can be recharged. More specifically, an oligomer, preferably non-crystalline, has been discovered of the formula: Rl-X - [(A) q- (Br)] - Z, wherein: (a) Ri is C? _C? 2 alkyl, C 1 -C 2 alkoxyalkyl, aryl or aicaryl C -Cj, or - (CH 2) m-COOR 3, where m is 1 or 2, and R 3 is C 1 -C 2 alkyl; (b) -X- is -0-, -S-, -S (0) -, -S (0) 2-, -, -NH-, -NR3-, NH-C (0) -NH-, -NR3-C (O) -NR3-, -NH-C (0) -0-, -NR3-C (0) -0-, (>) R3CC (0) OR3, (>) HC-C (O) OR3, (> C) - (C (O) OR3, (>) HC-C (0) R3, (>) C- (CO (0) R32, -PH-, PR3-, -P (OH) -0-, -P (OR3) -0-, -P (O) (OH) -O-, -P (O) (OR3) -0-, -0-P (OH) - 0--0-P (OR3) -0-, -OP (O) (OH) -O- or -OP (O) (OR3) -0-; (c) (A) g comprises polymerized units of a monomer with functionality that is capable of forming complexes with the conductive metal salts, preferably conductive lithium salts; (d) (B) r comprises polymerized units of a monomer, these polymerized units are not capable of complexing with the conductive metal salts , ie, these polymerized units are not capable of forming complexes with the conductive metal salts, (e) Z is H or R ^ -X-; (f) - [(A) g- (B) r] -, when r is not 9, they define either a block co-oligomer or a random co-oligomer, (9) (< 3 + r) = 1 to 25, q is 1 to 25, and r is 0 to 24. A conductive metal / oligomer salt mixture, preferably non-crystalline, has also been discovered of: (a) from 80 to 95 weight percent of an oligomer of the formula: R1-X - [(A) q- (Br)] - Z, in which: (1) R! is C 1 -C 2 alkyl, C 1 -C 12 alkoxyalkyl or C 5 -C 7 alkaryl, or - (CH 2) m-COOR 3, where m is 1 or 2, and R 3 is C 1 -C 2 alkyl; (2) -X- is -O-, -S-, -S (0) -, -S (0) 2-, -, - NH- -NR3-, NH-C (0) -NH-, - NR3-C (0) -NR3-, -NH-C (0) -0-, -NR3-C (0) -0-, (>) R3CC (0) OR3, (>) HC-C (O) 0R3, (> C) - (C (0) OR3, (>) C- (C (0) 0R3) 2, (>) R3C-C (0) R3, (>) HC-C (0) R3, (>) C- (CO (0) R3) 2, -PH-, PR3-, -P (OH) -0-, -P (OR3) -0-, -P (0) (0H) -0-, -P (O) (0R3) -0-, - 0-P (0H) -0--0-P (0R3) -0-, -OP (O) (0H) -0-, or -OP (O) (0R3) -O-; (3) (A ) g comprises polymerized units of a monomer with functionality which is capable of forming complexes with the conductive metal salts, preferably conductive lithium salts; (4) (B) r comprises polymerized units of a monomer, these polymerized units are not capable of forming complexes with the conductive metal salts; (5) - [(A) g- (B) r] -, where r is not 0, defines either a block co-oligomer or a random co-oligomer; (6) Z is H or Ri-X-, (7) (q + r) = 1 to 25, q is from 1 to 25, and r is from 0 to 24. and (b) from 5 to 20 weight percent of a or more conductive metal salts, preferably a conductive lithium salt.A preferred composition of the oligomer is n oligomer of polymerization degree of the constituent (meth) acrylate monomers, from 1 to 25, comprising: (a) from 5 to 50 weight percent end group units of at least one mercaptan residue, R ^ -S-, where R ^ is C 1 -C 2 alkyl, C 1 -C 2 alkoxyalkyl aryl or C 6 -C 7 alkaryl, or - (CH 2) m -COOR 3, where m is 1 or 2, and R 3 is C] -C? 2 alkyl; (b) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH 2 = CH-COO-CH 2 -CHR-R 2, where R is H or CH 3, and where R 2 is H, C 1 -C 2 alkyl or aryl, alkaryl or C 6 -C 20 aralkyl; (c) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-C00- (CH2-CHR-0) n-R2 where n is 1 to 12. A preferred conductive salt / oligomer mixture composition, ie a mixture of a conductive salt with an oligomer, this mixture also being conductive, which consists of: (a) from 80 to 95 weight percent of an oligomer of a degree of polymerization of the constituent (meth) acrylate monomers from 1 to 25, comprising: (1) from 5 to 50 weight percent end group units of at least one mercaptan residue, R ^ -S-, where RL is alkyl C ^ -C ^, alkoxyalkyl C? -C? aryl or alkaryl Cß-Cj, or - (CH 2) m-COOR, where m is 1 or 2, and R 3 is C 1 -C 1 alkyl; (2) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH2 = CH-COO-CH2-CHR-R2, where R is H or CH3, and where R2 is H, C1-C20 alkyl or aryl, alkaryl or C-C20 aralkyl; (3) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-COO- (CH2-CHR-0) n-R2 where n is 1 to 12; and (b) from 5 to 20 weight percent of one or more conductive metal salts, preferably a lithium conductive salt.

For the purposes of defining the present invention, the term "oligomer" refers to a polymer of low molecular weight, preferably non-crystalline, of polymerization degree below 25 and further containing a chain end group which is not hydrogen, but an alkyl, alkoxyalkyl, aryl or alkaryl group or an alkyl group further bearing an alkyl ester group, in which the alkyl group has 1 to 12 carbon atoms, preferably 4 to 8 carbon atoms. A degree of polymerization of the poly (ethyl acrylate) of 25 is a molecular weight of 2500; a degree of polymerization of poly (2-ethoxyethoxyethyl acrylate) of 25 is a molecular weight of 4700; a degree of polymerization of poly (methyl polyethylene glycol methacrylate (350)) of 25 is a molecular weight of 11,350. For a further definition, a polymerized unit of a monomer can be an internal group or an end group of the oligomer or polymer. Thus, the polymerized unit of the ethylene oxide can be a CH2-CH2-0- unit or a CH-CH2-0-Z unit, and a polymerized unit of CH2 = CR-C00-CH2-CH3, which can be a unit of -CH2-C (-) R-COO-CH2-CH3 or a unit of -CH2-CRZ-COO-CH2-CH3, where Z is H or R ^ X. The formula - [(A) g- (B) r] -, where r is not 0, defines or a block co-oligomer, ie where there is a series of -AAA- units connected to a series of BBB units , »Or a random co-oligomer, where the units of -A- and -B- are interdispersed in a random order. This use of "random" also includes those cases where the structure is not a block co-oligomer, but where the distribution of the units is ordered, for example, by reactivity ratios, such as an approach alternation. All percentages are by weight, unless indicated otherwise. An ester of (meth) acrylate is either an acrylic acid or a methacrylic acid. In the above conductive salt / oligomer mixtures, it is preferred to select the lithium salt, where it is used as the conductive metal salt, of the group consisting of LiCl04, LiPF6, LiBF4, LiC (CF3S02) 3, Li (CF3S03) and LiN (CF3S0) 2 and more preferably lithium trifluoromethansulfonimide (LiN (CF3S02) 2) • Other lithium salts soluble in the polymer, with large counterions, can also be employed, such as LiAsFg, Li [B (CgH402 ) 2], and the like. Articles, useful as battery components can be prepared, comprising the above conductive / oligomer salt mixtures, together with a membrane, such as a polyfluorocarbon or an interlaced polyacrylate, which allows sorption and permeation of the conductive salt / oligomer mixture . The membrane may have a non-woven structure, with a porosity of the order of 0.1 to 25 microns.

A compound of: (a) (1) from 5 to 60 weight percent of the oligomer described above was also found, ie an oligomer of the formula: R? -X - [(A) q- (Br)] - Z, wherein: (a) Ri is C? _C? 2 alkyl, C ^ -C ^ alkoxyalkyl, C6-C7 aryl or alkaryl, or - (CH2) m-COOR3, where m is 1 or 2, and R3 is C? -C? 2 alkyl; (b) -X- is -O-, -S-, -S (O) -, -S (0) 2-, -, -NH- -NR3-, NH-C (0) -NH-, - NR3-C (O) -NR3-, -NH-C (0) -0-, -NR3-C (0) -0-, (>) R3CC (0) OR3, (>) HC-C ( O) OR3, (> C) - (C (0) 0R3, (>) C- (C (0) OR3) 2, (>) R3C-C (0) R3 / (>) HC- C (0) R3, (>) C- (CO (0) R3) 2, -PH-, PR3-, -P (OH) -0-, -P (0R3) -0-, -P (O ) (OH) -O-, -P (0) (OR3) -0-, -0-P (0H) -0, -0-P (0R3) -0-, -OP (O) (0H) - 0-, or -0-P (0) (0R3) -0-; (c) (A) g comprises polymerized units of a monomer with functionality that is capable of forming complexes with the conductive metal salts; B) r comprises polymerized units of a monomer, these polymerized units are not capable of forming complexes with the conductive metal salts; (e) Z is H or R? ~ X; (f) - [(A) g- (B) r] -, where r is not 0, defines any of a block copolymer or a random copolymer; (9) (<? + R) = 1 to 25, q is from 1 to 25, and r is from 0 to 24; (2) from 5 to 20 weight percent of one or more conductive metal salts, preferably a lithium conductive salt; and (b) from 20 to 90 weight percent of a matrix composition comprising: (1) from 10 to 100 weight percent of a first homopolymer or copolymer having a glass transition temperature, Tg, below -35SC and a weight average molecular weight of at least 20,000, from 0 to 90 weight percent of polymerized units of an alkyl or alkylthioalkyl ester of an acrylic or methacrylic acid, and from 10 to 100 weight percent of units polymerized from a poly (alkyleneoxy) (meth) acrylate comonomer of the formula: CH2 = CR-C00- (CH2-CHR-0) p-R2, where p is from 1 to 1000; (2) from 10 to 90 weight percent of a second copolymer of a weight-average molecular weight of at least 30,000, of polymerized units of at least one alkyl ester of acrylic or methacrylic acid, in which the first homopolymer or copolymer and the second copolymer of the matrix composition are miscible, and wherein the mixture of the conductive metal salt / oligomer is miscible with the matrix composition; and (3) from 0 to 5 parts by weight of a conductive lithium salt, dissolved in the first homopolymer or copolymer of the matrix composition. This salt is in addition to the amount (5 to 20 weight percent) of the salt of the conductive metal in the compound, which may be added in a blending operation, or as a premix with the oligomer. A preferred class of compounds is that of a compound of (a) from 5 to 80 weight percent of a conductive salt / oligomer mixture of: (1) from 80 to 95 weight percent of an oligomer of one degree of polymerization of the constituent (meth) acrylate monomers from 1 to 25, comprising: (i) from 5 to 50 weight percent end group units of at least one mercaptan residue, R ^ -S-, where R ^ is alkyl C ± -Ci 2 'alkoxyalkyl cl ~ c12 aryl or C6-C7 alkaryl, or - (CH2) m-C00R3, where m is 1 or 2, and R3 is alkyl C] _ C] _2 / (ii ) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH 2 = CH-COO-CH 2 -CHR-R 2, where R is H or CH 3, and where R 2 is H , C 1 -C 2 alkyl or aryl, alkaryl or C 5 -C 20 aralkyl; (iii) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-COO- (CH2-CHR-0) n-R2 where n is 1 to 12; and (2) from 5 to 20 weight percent of one or more conductive metal salts, preferably a lithium conductive salt. (b) from 20 to 95 weight percent of a matrix composition, this matrix composition comprises: (1) from 10 to 100 weight percent of a first homopolymer or copolymer having a glass transition temperature, Tg , below -35 ° C and a weight average molecular weight of at least 20,000, from 0 to 90 weight percent of polymerized units of an alkyl or alkylthioalkyl ester of an acrylic or methacrylic acid, and from 10 to 100 percent by weight Weight of polymerized units of a poly (alkyleneoxy) (meth) acrylate comonomer of the formula: CH2 = CR-COO- (CH2-CHR-0) p-R2, where p is from 1 to 1000; (2) from 10 to 90 weight percent of a second copolymer of a weight-average molecular weight of at least 30,000, of polymerized units of at least one alkyl ester of acrylic or methacrylic acid, in which the first homopolymer or copolymer and the second copolymer of the matrix composition are miscible, and wherein the mixture of the conductive metal salt / oligomer is miscible with the matrix composition; and (3) from 0 to 5 parts by weight of a conductive lithium salt, dissolved in the first homopolymer or copolymer of the matrix composition. The following definitions are used here: compatible polymers means that they exhibit physical properties consistent with at least an average of the properties of the two components, and when the polymers are miscible means that no detected domain of size above 50 nm, in the mixture, and with a single glass transition temperature (Tg), preferably measured by the differential scanning calorimetry of the mixture. It is preferable that all the components of the compound are not crystalline (treating the oligomer / salt mixture as a component) at all temperatures of use, to avoid loss of mobility of the ionic components and thus a decrease in conductivity. The compounds taught in the preceding paragraphs may have at least one of the first or second polymers of the matrix composition in an interlaced form, preferably achieved after the thermal processing of the mixture. In these compounds, the compound can be a combination of the mixture of the conductive salt / oligomer and the matrix composition, depending on the miscibility of the components for the transport of ions in the electrolytic process. In another variant, the conductive salt / oligomer mixture may be encapsulated within the matrix composition. In another preferred variant, the conductive salt / oligomer mixture may be of layers of a film or sheet, formed from the matrix composition, this film or sheet may be physically perforated with small holes, preferably of the order of 0.1 to 2 microns. diameter (100 to 2000 nm) and with a porosity preferably 70 to 80% of the surface area of the film or sheet, to improve the transport of ions in the electrolytic process, while restricting any movement of particles or other electrode material, such as electrode granules.

A process, preferably continuous, has also been discovered for the preparation of a conductive salt / oligomer mixture of: (a) from 80 to 95 weight percent of an oligomer of a degree of polymerization of the monomers of (meth) acrylate constituents from 1 to 25, comprising: (1) from 5 to 50 weight percent end group units of at least one mercaptan residue, ^^ - S-, where R- is alkyl Ci -C ^ / alkoxyalkyl c? Ci2 aryl or C5-C7 alkaryl, or - (CH2) m-COOR3, where m is 1 or 2, and R3 is C? -C? 2 alkyl; (2) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH2 = CH-COO-CH2-CHR-R2, where R is H or CH3, and where R2 is H, C? -C2u alkyl or aryl, alkaryl or Cg-C2o aralkyl; (3) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-C00- (CH2-CHR-0) n-R2 where n is 1 to 12; and (b) from 5 to 20 weight percent of one or more conductive metal salts, preferably a lithium conductive salt, this process comprises: (1). drying the conductive metal salt, preferably a lithium salt, to remove the water; (2) passing at least one (meth) -crylate ester monomer of the formula CH2 = CR-COO- (CH2-CHR-0) n, where n is from 2 to 12, and optionally, but preferably also at minus an acrylate ester monomer of the formula: CH2 = CH-COO-CH2-CHR-R2, where R is H or CH3, and where R2 is H, CI-C2Q alkyl, aryl, alkaryl or aralkyl Cg-C2o , through at least one column of activated alumina or molecular sieves; (3) mixing the conductive metal salt, the at least one acrylate ester monomer and the at least one (meth) acrylate ester monomer, with an alkyl mercaptan, R ^ -S-, where R ^ is alkyl C? -C? 2, C ^ -C12 alkoxyalkyl aryl or C6-C7 alkaryl, or - (CH2) m -COOR3, where m is 1 or 2, and R3 is C ^ -C ^ alkyl]; (4) subjecting the mixture to a free radical polymerization process; and (5) removing any volatile residue by vacuum devolatilization. Other resources to remove waste, such as extraction, absorption and the like, can be used, but require additional stages of the process.

This process can be carried out as a continuous process for the polymerization and devolatilization reaction. An electrolytic cell has also been discovered, such as a rechargeable battery, comprising an anode, a cathode and a conductive electrolyte, which includes a conductive salt / oligomer mixture of: (a) from 80 to 95 percent in weight of an oligomer of the formula: R -X-1; (A) q- (Br)] -Z, wherein: (1) Ri is C1_C_2alkyl, C1_6 alkoxyalkyl or C6_7 alkaryl, or - (CH2) m -COOR3, where m is 1 or 2, and R 3 is C 1 -C 2 alkyl; (2) -X- is -0-, -S-, -S (0) -, -S (0) 2-, -, - NH- -NR3-, NH-C (0) -NH-, - NR3-C (O) -NR3-, -NH-C (0) -0-, -NR3-C (0) -0-, (>) R3CC (0) OR3, (>) HC-C ( O) 0R3, (> C) - (C (0) OR3f (>) C- (C (0) OR3) 2, (>) R3C-C (0) R3, (>) HC-C (0) R3, (>) C- (CO (0) R3) 2, -PH-, PR3-, -P (0H) -0-, -P (0R3) -0-, -P (0) (0H) -0-, -P (0) (OR3) -0-, -0-P (OH) -0--0-P (0R3) -0-, -0-P (0) (0H) -0-, OR -0-P (0) (0R3) -0-; (3) (A) g comprises polymerized units of a monomer with a functionality that is capable of forming complexes with the conductive metal salts, preferably salts lithium conductive; (4) (B) r comprises polymerized units of a monomer, these polymerized units are not capable of complexing with the conductive metal salts; (5) Z is H or Ri-X-; (6) - [(A) g- (B) r] -, where r is not 0, defines either a block copolymer or a random copolymer; (6) Z is H or Ri-X-; (7) (q + r) = 1 to 25, q is from 1 to 25, and r is from 0 to 24; and (b) from 5 to 20 weight percent of one or more conductive metal salts. One type of such electrolytic cell comprises an anode, a cathode and a conductive electrolyte that includes an oligomer of polymerization degree of the constituent (meth) acrylate monomers, from 1 to 25, comprising: (a) from 5 to 50 weight percent end group units of at least one mercaptan residue, R ^ -S-, where R ^ is C? -C? 2 alkyl, C? -C? 2 alkoxyalkyl aryl or C6-C7 alkaryl, or - (CH2) m-COOR3, where m is 1 or 2, and R3 is C1-C12 alkyl; (b) from 0 to 50 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH2 = CH-COO-CH2-CHR-R2, where R is H or CH3, and where R2 is H, C1-C20 alkyl or aryl, alkaryl or aralkyl c6"c20 / '(c) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR -COO- (CH2-CHR-0) n-R2 where n is from 1 to 12. Likewise, an electrolytic cell has been discovered with utility, for example, as a rechargeable battery, comprising an anode, a cathode and a conductive electrolyte , which includes from 5 to 15 weight percent of (a) a conductive salt / oligomer mixture of: (1) from 80 to 95 weight percent of an oligomer of a degree of polymerization of the (meth) monomers constituting acrylate from 1 to 25, comprising: (i) from 5 to 50 weight percent end group units of at least one mercaptan residue, R ^ -S-, where R ^ is C ^ -C alkyl ^ t alkoxy I rent C1-C1 aryl or C6-C7 alkaryl, or - (CH2) m-COOR3, where m is 1 or 2, and R3 is C1-C12 alkyl; (ii) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH 2 = CH-COO-CH 2 -CHR-R 2, where R is H or CH 3, and where R 2 is H, C1-C20 alkyl or aryl, alkaryl or Cg-C2o aralkyl; (iii) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-COO- (CH2-CHR-0) n-R2 where n is 1 to 12; and (2) from 5 to 20 weight percent of one or more conductive metal salts, preferably a lithium conductive salt and (b) from 20 to 95 weight percent of a matrix composition, this matrix composition comprises : (1) from 10 to 100 weight percent of a first homopolymer or copolymer having a glass transition temperature, Tg, below -35 ° C and a weight average molecular weight of at least 20,000, from 0 to 90 percent by weight of polymerized units of an alkyl or alkylthioalkyl ester of an acrylic or methacrylic acid, and from 10 to 100 weight percent of polymerized units of a poly (alkylenoxy) (meth) acrylate comonomer, of the formula: CH2 = CR-COO- (CH2-CHR-0) p-R2, where p is from 1 to 1000; (2) from 5 to 80 weight percent of a second copolymer of a weight average molecular weight of at least 30,000, of polymerized units of at least one alkyl ester of acrylic or methacrylic acid, wherein the first hourly copolymer or copolymer and the second copolymer of the matrix composition are miscible, and wherein the mixture of the conductive metal salt / oligomer is miscible with the matrix composition; and (3) from 0 to 5 parts by weight of a conductive lithium salt, dissolved in the first homopolymer or copolymer of the matrix composition. A process for preparing the compound and the electrolytic cell, described in the preceding paragraph, was also invented, which comprises: (a) the polymerization of the monomers, preferably free of water and impurities of alcohol and of the inhibitor, as possible, which forms the first homopolymer or matrix copolymer, in a constant flow stirred reactor, in the presence of an appropriate free radical initiator at a conversion of at least 65%; (b) transferring the first homopolymer or matrix copolymer to a stirred reactor, preferably directly, without exposure to air or water; (c) mixing with the monomers forming the second matrix copolymer, again preferably free of water and alcohol impurities and of the inhibitor, as possible, optionally with the addition of a photosensitizing initiator and a polyfunctional polymerizable monomer; (d) polymerizing the monomers forming the second matrix copolymer at a conversion of at least 65%, preferably under conditions that do not cause the polyfunctional polymerizable monomer to interlace; (e) transferring the mixture of the first and second copolymers to an extruder, which may contain devolatilization resources; (f) extruding the mixture in the form of a sheet or film, optionally with entanglement of the extruded film by irradiation with light, such as ultraviolet light, sufficient to activate the photosensitizing initiator and crosslink the second polymer in the matrix mixture; (g) applying the conductive salt / oligomer mixture to at least one surface of the extruded sheet or film, preferably under conditions where there is uniform application of the mixture and limited exposure to air or water; (h) after extrusion, but before, or concurrently with, or following, the application of the conductive salt / oligomer, perforate the film with holes of 0.1 to 25 microns, preferably 0.1 to 2 microns, to allow the controlled access of the conductive salt / oligomer on both sides of the sheet or film; (i) bringing the film coated with the oligomer between the anode and the cathode of a battery, preferably in an inert atmosphere, free of water. In the present invention, a novel thermoprocessible, non-interlaced, oligomeric, preferably non-crystalline, electrolyte was found, which can be thermally reprocessed, exhibiting a combination of stiffness and flexibility, which allows it to be used in batteries, especially those that are small or of unusual configuration, and the like, without the need for solvents, with improved water resistance when compared to poly (ethylene oxide) and with the capacity of ion transport, especially at or below room temperature when compares favorably with those of thousands of systems based on poly (ethylene oxide), which do not exhibit the other desirable physical properties of the present mixtures. The two-component matrix mixture containing the metal salt, formed of polymers of higher molecular weight absent from the oligomeric electrolyte, have suitable conductivity for certain uses, as taught in the patent application concurrently filed by the same inventor with this application , but the addition of the oligomeric electrolyte, defined herein, gives an improved conductivity, especially at room temperature or below it, without significant loss in the other physical characteristics of the two-component mixture. The following paragraphs are presented as a possible explanation of the effectiveness of the oligomers that the inventor discovered, but remain only as a hypothesis .. To achieve the desired properties, which include low viscosity, high lithium ion transfer number, solubility of the lithium salt, stability under recycling conditions and good conductivity at or below ambient temperatures, the oligomer (or conductive polymer) must comprise a "block" structure, in which a block contains a hydrocarbon portion aliphatic, which is electrically stable, but not conductive, and which acts as a chain external to the complex of lithium oxide and polyalkylene, which is in a complex-forming ligand structure. Thus, the aliphatic section tends to protect against electrical interruptions at the interface of the electrode / conductive polymer, forming a monolayer at this interface and protecting against the "impulse" of the conductive portion, when the electric field is applied. The block portion needs to be large enough to present a non-polar hydrocarbon chain, of low dielectric constant, at the electrode interface, and still with a sufficient degree of miscibility with the conductive portion of the oligomer molecule to maintain homogeneity to this oligomer during the formation. This first block can be formed, for example, by the use of a large amount of a suitable aliphatic mercaptan or other chain transfer agent in the free radical polymerization of the monomers supplying the complex structure of the ligand, or by the use of an appropriate aliphatic isocyanate, to "top off" the end of a poly (1,2-alkylene oxide) or poly-lal-lalacetone chain, or by the use of an appropriate polymerization initiator in an amount large enough for all the oligomeric chains to be initiated by a radical or ion that leaves a functionality of R ^ X- at the end of the oligomeric chain. The oligomer may be finished in H, R ^ or R ^^ X. The first block, since it is not complex with the metal ions, is free to internally plasticize the oligomer and lower its glass transition temperature (important for low temperature mobility), even though the second part of the block structure Form complex with a metal ion. The second part of the "block" or "solid" structure is the structure of the ligand formed by the formation of the metal ion complex with the units - (0-CH2-CH2) - (or other complex units), such as -CH2-Ch2-NH- (less convenient, due to the possibility of reaction between the active H and the metal of Li), -CH2-CH2-NR2, -C (= 0) -0-CH2-CH2-, - S- (CH2) 5-, -CH2-C (= 0) -0-R1) - or = P (alkyl) -N-. The composition is governed by the molecular weight of the polymerized portion of the oligomer, and the length of the side chains of the complex, both affect the viscosity of the oligomer. The length of the side chain can also affect when the crystallization of the side chain occurs. It is necessary to avoid crystallization of the side chain or main chain in the second part of the block copolymer structure, to allow sufficient flexibility of the chain for good conductivity at or below room temperature. Similarly, a vitreous block must be avoided to allow maximum mobility of the oligomer / salt complex. This second part of the block structure comprises polymerized units of a monomer with functionality that is capable of forming complexes with the conductive lithium salts. As noted in the preceding paragraph, a number of complex functionalities exist; these can be incorporated into the monomer as side chains, such as the (meth) acrylic esters of polyalkylene oxides, pentamethylene sulfide chains having a site to which a group of (meth) acryloyl can be attached and similar chains to which a carbon-carbon double bond can be bound for the subsequent radical or ionic polymerization.

In another mode, such functionality can be incorporated into the oligomer by copolymerization of monomers with complex forming groups, such as vinylene carbonate. In yet another mode, the functional monomer may be formed in situ by the appropriate ring opening or other polymerizations. Such examples would be the ring opening of ethylene oxide or propylene with an appropriate ^ -X group. Another example would be the appropriate oligomerization of beta-propiolactone, to form blocks of R1-X- (CH2-CH2-C (= 0) 0-) not the appropriate oligomerization of gamma-butyrolactone, to form R1-X- ( CH2-CH2-CH2-C (= 0) 0-) not the oligomerization of ethyl acrylate, to form blocks of R -X- (CH2-CH-C (= 0) 0-CH2CH3) n and the like. As the 1,2-ethyleneoxy bond is preferred by those skilled in the art to form complexes with lithium ions, one may consider other structures useful as the second part of the block structure, such as -0-CH2-CH CH -CH2-0-, Y where - - is - (CH2) 3-, - (CH2) 2-, -CH2-0-CH2- and Y is -O-, S-, -C (= 0) - or NR! -.

The prior art, such as Gray, discusses the selection of appropriate conductive salts and poly (ethylene oxides) and certain alternative structures, but does not teach, suggest or reveal the specific oligomers taught herein. Within the block structure, R? ~ X - [(A) q- (B) r] -Z, structure B may represent polymerized units of such monomers without functionality capable of complexing with the conductive lithium salts, such as those monomers illustrated by (a) vinyl monomers, such as styrene, an olefin such as isobutylene or ethylene, an allyl vinyl ether, and the like; (b) addition monomers, such as hexamethylene glycol, terephthalic acid, hexamethylene diamine, adipic acid and the like. Oligomers of the present invention absent any functionality of -0-CH2-CH2-0-, are generally considered necessary to form complexes with the conductive metal salts, but which carry the functionality of acrylic ester, can form, surprisingly, mixtures conductive However, it is preferred to have at least some of a known, appropriate, complex forming functionality -0-CH2 ~ CH2-0-, in combination with a metal salt of lithium or other metal, to be effective in forming conductive materials, such as a highly soluble and with a highly bulky anion, such as LiN (CF S0) 2, otherwise known as lithium bis (trifluoromethanesulfonyl) imide. Oligomers of the present invention absent from the additional lithium salt, added in their preparation or after mixing, may still be effective when employed with an appropriate cathodic / anodic system based on lithium, as the oligomers can form complexes with ions of lithium from the cathode and / or the anode to transport ionic charges between the electrodes. In this condition, the electrodes are partially dissolved by solution or complex formation in the electrolyte of the oligomer, and the system will not be effective as a previously formed lithium salt / oligomer complex, until the lithium concentration in complex reaches approximately 5 parts by weight per 95 parts of the oligomer. The lithium or other salt may be mixed with the oligomer by any conventional means, such as by mixing the melt, dissolving the salt in an appropriate volatile, non-aqueous solvent, and evaporation, and the like. However, it is easier to prepare the well-made mixture by adding the salt to the monomers and other reagents, before the oligomerization reaction, optionally with drying the mixture before polymerization. Preferred oligomer electrolytes, described in this invention, can be prepared by a volumetric free radical polymerization process in situ of a mixture of the appropriate transfer agent, such as alky1-mercaptan or a mercapto ester, an alkoxyalkyl compound with a transferable alpha-hydrogen, a disulfide, and the like, with at least one vinyl monomer, such as an acrylate or methacrylate ester containing groups that complex with the lithium or other metal salt. Suitable examples are 2 (2-ethoxyethoxy) ethyl acrylate (M # 2 in the Examples), and monomers of monomethoxy poly (ethylene glycol monomethacrylate (Mw = 350) (MMPEG (350) MMA) (# 3 in the Examples) and the like, which can be copolymerized with the alkyl acrylate, such as ethyl acrylate and the like, However, other polymerization methods, suitably adapted, such as solution and suspension polymerization techniques, can also serve to preparing the oligomer electrolytes A continuous feed stirred tank reactor (CFSTR) is an advantageous process in the preparation of such oligomers.The poly (alkylenoxy) (meth) acrylate comonomer of the first homopolymer or copolymer, which forms a complex With lithium salts or other metals, as well as helping to reduce the glass transition temperature of the polymer, it has the general formula: CH2 = CR-C02 - (-CH2CHR10) n-R2 It is preferred that R2 be any of H or CH3 c When n is an integer between 3 and 50. When n is less than 3, R2 should preferably be a C3-C20 alkyl group, C6-C20 aryl or C7-C3 alkylaryl- The methacrylate esters, ie R = CH3, are they prefer because of their photochemical stability. The alkyl or alkylthioalkyl ester of the acrylic or methacrylic acid component of the first homopolymer or copolymer can be a methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, secondary butyl acrylate, acrylate. of isobutyl, t-butyl acrylate, hexyl acrylate, heptyl acrylate, 2-heptyl acrylate, 2-ethylbutyl acrylate, dodecyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate , n-decyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, ethylthioethyl methacrylate, ethylthioethyl acrylate, and the like. The alkyl ester of the acrylic or methacrylic acid component of the second polymer, wherein the alkyl here also includes the cyclic structures, can be a methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, secondary butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, heptyl acrylate, 2-heptyl acrylate, 2-ethylbutyl acrylate, dodecyl acrylate, n-hexyl methacrylate, n-octyl methacrylate , 2-ethylhexyl methacrylate, n-decyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, hexadecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate , isopropyl methacrylate, n-butyl methacrylate, secondary butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, cyclohexium methacrylate, methacrylate of isobornyl, 3,3,5-trimethylcyclohexyl methacrylate, and the like. Other comonomers may be present in either or both of the polymer components of the composition, as long as the mutual miscibility of the polymers is maintained. The polymerization mixture may contain the mercaptan or some other chain transfer agent to control the molecular weight, and the second polymer formed may contain a multifunctional monomer at a low level to decrease entrainment in the mixture formed. A preferred matrix composition comprises the following molecularly miscible copolymers: (a) from 5 to 95 weight percent of a first copolymer, wherein the first copolymer comprises primarily 10 weight percent of the monomethoxy poly (ethylene glycol monomethacrylate) (Mw = 400) (MMPEG (400) MM), and 90 weight percent of ethyl acrylate; (b) 95 to 5 weight percent of a second copolymer, wherein this second copolymer comprises primarily 40 weight percent ethyl acrylate and 60 weight percent methyl methacrylate. Certain of the matrix compositions described in this invention are prepared by a volume polymerization or in situ emulsion process of methyl methacrylate, ethyl acrylate and ethylene glycol monomethoxy-polyimonomethacrylate (Mw = 400)). However, other polymerization methods suitably adapted, such as solution and suspension polymerization techniques, can be used to obtain the copolymers. The copolymer of the first stage can be prepared by the use of a stirred, continuous feed reactor (CFSTR). Unpolymerized monomers are removed from the effluent of the second stage copolymer in a separation agent, such as a static mixer equipped with a vacuum pump. The upper fraction of the separation column comprising the non-polymerized monomers can be transferred to the recovery system or, preferably, recycled to the second stage of the polymerization process. The miscible polymer can also be separated from the monomers, by passing it through a melt pump, equipped with a vacuum gate. The residence time in the polymerization reaction vessel (CFSTR), the charge rate of monomers, the initiator and the chain transfer concentration and the polymerization temperature are arranged in order to ensure that the conversion of the monomer varies from the 80 to 90 percent by weight. The weight average molecular weight of the first homopolymer or copolymer of the matrix composition can vary from 20,000 to about 150,000 or more. A preferred range of molecular weight is from 30,000 to 100,000. The weight average molecular weight of the second polymer can vary from 30,000 to 500,000 or more. A preferred molecular weight range of 30,000 to 200,000 is adequate to facilitate the process, and the thermal and rheological stability of the mixed compositions. In the course of the thermal process, small amounts of additives can be added to the oligomer or matrix polymers for the purpose of improving the physical properties of the final commercial article. Examples of additives may include one or more of the following classes of compounds: antioxidants, ultraviolet light absorbers, non-volatile plasticizers, such as dioctyl sebacate, low molecular weight polyesters, and the like; antistatic agents, glidants, coloring agents, fillers and other compounds. However, it is preferred to employ as few of these materials as possible to avoid side reactions that could affect the conductivity of the compound or the recyclability of the final battery. The components of the final battery, used in conjunction with the electrolytes taught herein, are known in the art. Preferably, they are based on lithium technology for the anode, in which one component is a film of the lithium metal, a lithium alloy, such as lithium / tin, or lithium combined in a suitable substrate, such as black of coal. The second cathodic component can be any of many known in the art, such as a combination of lithium / cobalt oxide, lithium / titanium sulfide, lithium / manganese oxide combinations, such as LiMn204 or LiMn02, LixMV04, (where x is from about 5 to about 9 and V is Co, Ni, Cd or Zn), vanadium pentoxide, copper oxide or chromium oxide (s), and the like. The conductive compositions and mixtures taught herein may also be useful in electrochromic applications, optical applications, where conductivity may be combined, and the like. The heterogeneous structure taught here for the oligomer / membrane combination, or the use of the oligomer on the membrane surface, accomplishes several necessary functions. The insoluble polymer film keeps the electrodes separated from each other, even if they are granular in shape. In addition, they allow easy diffusion of the oligomer / metal salt mixture. Another advantage of the oligomers of the present invention, in their free form or as a composite with a flexible matrix polymer support, is that they can be used as very thin layers or films (such as less than 25 microns thick), and still robust. Such improved conductivity allows the use of non-linear containers and helps ensure good contact between the electrolyte and the electrode on all surfaces. The oligomers are not volatile at the operating temperature of solid state devices, such as batteries. For the application and formation of the final electrolyte, the oligomers can be combined with a volatile solvent for rotary or roller coating applications. The oligomers can also be mixed with a polar polar melting point, such as ethylene carbonate. The following examples will illustrate the properties of the family of the single copolymers. All compositions mentioned in the examples are in percent by weight, unless otherwise specified.

The mechanical properties for the optically clear two-step copolymer compounds were evaluated with the aid of parts that were prepared by compression molding on a Carver press. About 10 grams of resin were placed on a piece of flat glass with dimensions of 152.4 mm x 152.4 mm x 1.59 mm), which was previously heated to 662C. A spacer 305 microns thick was placed on the glass surface covering the resinous material. Another piece of flat glass, of comparable size, was mounted on the resin to form a sandwich. The glass-polymer-vidiro composite was then slowly compressed until a maximum load of 5,512 mPa was obtained. The compound was then kept at this pressure and temperature for five minutes. At the end of five minutes, the sample was removed from the press, sectioned into 63.5 mm x 38.1 mm plates for analysis by the dart drop test, of ASTM D3029. The following abbreviations were used in the tables and examples: MMA = methyl methacrylate; EA = ethyl acrylate; Monometi1-ether / poly (ethylene glycol (400) monomethacrylate = M # l; 2 (ethoxy-ethoxy) -ethyl acrylate = M # 2; monomethacrylate monomethyl ether poly (ethylene glycol (350)) = M # 3; Poly (propylene glycol (400)) monomethacrylate = # 4.

EXAMPLE A - CFSTR Polymerization of Acrylic Olisomers The following is illustrative of a method for preparing the acrylic oligomers of the present invention. Oligomers, comprising 5 to 10 weight percent of M # 3, 95 to 90 weight percent of M # 2 and one, molar concentration of the lithium salt, (LiN (CF3S02) 2, were prepared by the volumetric polymerization technique as follows: Unei monomer mixture of 59.97% of the 2- (2-ethoxy-ethoxy) -ethyl acrylate, 6.66% of the MMPEG (350) MMA, 0.05% of the initiator of 1, 1 • -azobis (cyclohexanecarbonitrile), 13.33% n-butyl mercaptan and 20.00% LiN (CF3S02), was fed into a glass vessel, in which the mixture was purged with an inert gas, such as nitrogen. , the monomer and salt mixture was degassed and kept under a nitrogen blanket.The mixture was then pumped at a maximum rate of 15 g / min through a series of filters in the CFSTR in which the monomers were copolymerized to Supply 86 to 95 percent by weight of monomer conversion Residual monomers can be removed by convective processes for example, vacuum devolatilization, evaporation of falling film or evaporation of the cleaned film with a wiper blade.

EXAMPLES 1 TO 12 In order to avoid the potential problems engendered by the use of solvents in the preparation of polymer electrolyte films or oligomers, the electrolytes of Table I were prepared from a mixture of net monomers and lithium salts. This technique is superior to the current state of the art in that it has the potential to supply ultra-pure polymer electrolytes, highly convenient, free of solvents. Due to the inherent difficulty experienced in removing the volatile solvents from the polymer electrolytes, experiments were designed to formulate polymer electrolytes free of solvents. Unlike polymer electrolyte formulations, previously described, which involve the use of solvents (albeit volatile) for film preparation, acrylic polymer electrolytes, free of solvents, were prepared by the following unique processes: ion, of conductive salt / oligomer of the acrylic polymer electrolyte, was synthesized from a mixture of ethyl acrylate, the M # 2 and M # monomers and the ionic salts of lithium: LiCF3S0, LiBF4, LiN (CF3S0) or LÍPF5. A high concentration of the chain transfer agent (n-butyl mercaptan) was used in order to restrict the growth of the polymer chain and consequently to minimize the molecular weight. The ionic conductivity of the monomer salt mixture was determined (at room temperature, about 25 ° C, unless otherwise stated) before and after the polymerization. This analytical characteristic makes it possible to adjust the desired final ionic conductivity of the electrolyte by the selection of the monomer and the concentration of the lithium salt. The highly ionic conductive / oligomeric salt electrolyte was combined with a clear electrolyte membrane of solid acrylic polymer, which was synthesized by in situ volumetric polymerization of two acrylic copolymers and a lithium salt with a predetermined concentration. The first copolymer was synthesized from a mixture of EA or M # 1 and M # 1 monomers and the lithium salt. The second copolymer was prepared in situ from a mixture of monomers and copolymers, comprising the first copolymer and the monomers of MMA and EA. The last monomers are preferably in a weight ratio of 3: 2, respectively. The copolymerization of the monomers MMA and EA, in the presence of the copolymer of the first step (P (EA-M # l) = 90/10) and the lithium salt provided a clear and elastic, dimensionally stable polymeric compound.

TABLE I The data listed in Table I reveal that: (a) The ionic conductivity of the monomer salt solution undergoes an order of magnitude change in value with the conversion of the monomers to the low molecular weight polymer; (b) For a given composition of copolymer and molecular weight, the concentration of salt in excess of 1 mole per liter results in an increase in Tg and a concomitant reduction in ionic conductivity; (c) The data given in Table I support the hypothesis that the viscosity of the polymer electrolyte is proportional to the molecular weight (at least in the presented range of molecular weight) and inversely proportional to the ionic conductivity; (d) the data listed in Table I also suggest that neither LiBF4 nor LiCF3S03 were highly solvated by the acrylic copolymers. The electrolyte of the polymer, designated as Example 12 in Table I, was prepared in order to test the effect of incorporating the acrylamide comonomer into the monomer mixture of EA / M # 1. Because acrylamide has a relatively greater dielectric constant than both EA and M # 1, it was postulated that the inclusion of the above monomer should increase the relative permittivity of the monomer mixture, thus promoting the dissolution of the lithium salt. However, a comparison of the electrical properties of the composition of Example 11 with that of Example 12, reveals that the ionic conductivity was relatively unaffected by the inclusion of a part of the acrylamide monomer in the EA / M # 1 monomer mixture. . The electrochemical stability of three of the electrolyte compositions listed in Table I, Examples 7, 11 and 12, was determined in the potential range between -1 and 4.5 volts (vs. Li + / Li) with the use of a voltiammeter in a platinum working electrode. A typical experiment is to sweep the potential of the cell anodically from -1 to 4.5 volts, followed by a cathodic scan of 4.5 to -1 volt, at a sweep speed of 50 mV / sec. The electrolyte of Example 7 was subjected to repeated cycles at a maximum of 4,713 cycles. The volt-ampere graphs shown do not show the oxidation of the electrolyte or the Li / dissolution processes. The results suggest that these electrolytes are stable in contact with the Li electrode. EXAMPLES 13 AND 14 As shown in Table II and discussed previously, the low molecular weight electrolyte was prepared from a mixture of M # 2 and / or ethyl acrylate and M # 3 in the presence of a 0.7 concentration. molar of the lithium salt (LiN (CF3S02) 2). The copolymer electrolyte, designated as Example 13, exhibited a Tg and molecular weight greater than those of the electrolyte of Example 14. The difference in thermal and molecular properties is reflected in the ionic conductivity of these electrolytes. (All conductivities are at room temperature, unless otherwise indicated): TABLE II EXAMPLES 15 TO 17 These examples show that the measured Tg of the low molecular weight copolymer of Example 15, which was prepared in the absence of the salt, is about -81-1 ° C. The Tg of the copolymer that was prepared in the presence of 0.7M of the lithium salt, LiN (CF3S02), Example 17, was about -80.4SC. When an equimolar amount (0.7 M) of the salt, LiN (CF3S02) 2) was added to the salt-free copolymer, the Tg increased from -81.1P-C to -67.52C. The significant change in Tg, Table III, is reflected in the lower ionic conductivity of the copolymer electrolyte with addition of the subsequent salt. TABLE III The absence of change in the Tg of the salt complex, which results from in situ polymerization, is an unusual occurrence in the solid / liquid binary solutions of the polymer and salt. The addition of salt to a polymer almost always increases the Tg of the resulting complex. This manifests itself in the form of physical entanglements, which emanate from strong dipolar interactions. The effect is substantially amplified especially in the case of electrolytes that require high concentration of salt to improve the density of the charge carriers. While the high concentration of salt is beneficial to the general ionic conductivity, the resulting physical entanglement retards the mobility of polymer segments and thus immobilizes the movement of the ions.

Table IV lists the experimental variation of the glass transition temperature (Tg) with the concentration for some of the most widely used salts. A review of the data suggests that both salts, based on the triflyl anion (CF S02) -, produce a smaller increase in the Tg with the concentration of the salt. The fact that all lithium salts produce a substantial increase in the Tg of the final polymer / salt complex, at high salt concentrations, suggests that the copolymer electrolytes derived from the in situ polymerization of the salt plus the monomer mixture It has unusual physical properties. TABLE IV EXAMPLES 18 TO 26 In these examples, the solid portion of the electrolyte was synthesized from an EA / M # 3 = 90/10 mixture, an interlayer, the poly (ethylene glycol (200) dimethacrylate) and a 0.35 molar concentration of the lithium salt, LiN (CF3S0) 2. This system forms solid solutions that vary in optical quality from translucent to clear. For a given binary copolymer compound, the formation of clear solid solutions is directly related to the concentration of the salt (LiN (CF3S02) 2) that forms the complex. As can be seen in Table V, the 0.35 molar salt complexes, Examples 24 and 25, are optically clear, while the 0.18 molar salt complex, Example 26, was opaque in appearance. The heterogeneous nature of the last complex was supported by the occurrence of two glass transition temperatures in the thermal graph of the DSC. The lower temperature (-19.42C) represents the rubber phase, while the higher temperature (+ 19.5P-C) represents the vitreous phase of the polymer / salt complex. As discussed previously, the solid portion of the polymer electrolyte does not support the transport of fast Li + ions, because the relaxation rate of the copolymer chains, at room temperature, was too low to promote the translational movement of the polymer. cation along coordination sites. The membrane designated Example 24, Table V, provides an ionic conductivity of approximately 2.5 x 10 ~ 5 S / cm. When a film sample of Example 24 is combined with the liquid electrolyte of Example 14 (conductivity of approximately 1.76 x 10 ~ 4 S / cm), a 27 fold increase in conductivity is obtained (0.7 x 10-4 S / cm) . A similar increase in conductivity also occurs in the case of the membrane of Example 25 (2.03 x 10 ~ 4 S / cm). Both membranes contain a 0.35 molar concentration of the lithium salt, LiN (CF3So2) 2. The salt content of Examples 22 and 25 differentiates these membranes from those prepared without salt, Table V. As can be seen from the data listed in Table V, the last membranes are at least an order of magnitude lower in conductivity than the membranes. membranes rich in salt. Each membrane is exposed to the liquid electrolyte at room temperature for a maximum of 10 minutes. The variation in the percentage of mass captured is directly related to the non-uniformity in the thickness of the membranes. TABLE V TABLE V (Continued) EXAMPLES 27 and 28 These examples demonstrate that the impurities in the morimers and the mercaptan used to form the oligomer can affect the final properties of the oligomer in its ability to undergo recycling in the cell (intercalation / de-interleaving of the lithium ion). The impurities can passivate the electrode components, such as lithium / graphite or the electrode surfaces of the lithiated cobalt oxide compound, by deposit, or by degradation of the electrodes by means of leaching or swelling of the binder. These impurities may include the methyl ether of hydroquinone (MEHQ, an inhibitor of premature polymerization), water, acrylic acid, alcohol, heptane and toluene. The contents of water and MEHQ can be reduced by the multiple passages of the monomers through columns of molecular sieves and alumina beads. The lithium salt must be thoroughly dried before use, such as by drying in a vacuum oven at 100 ° C, for at least 24 hours. The cyclic measurement of volt-amperes (CV) was performed in a small cabinet under argon. A potentiostat / galvanostat PAR Model 376 device, controlled with a universal programmer PAR Model 175, was used to perform the CV measurements. The working electrode was a lithium / cobalt oxide / poly (vinylidene fluoride) / carbon black compound; it was immersed in the conductive salt electrolyte of the oligomer to provide a geometric surface area of approximately 1.6 cm 2. Static-type cyclic volt-ampere graphs were made; The appearance of the electrodes also be observed. In cyclic volt-ampere graphs, a negative value greater than about 3.5 volts indicates the lithium reduction of lithium and higher positive values at voltages of approximately 4.0 - 4.2 volts indicate the deintercalation of anodic oxidation of lithium. Likewise, if the area swept by the waves increases in the repeated scan between 1 mV / sec, between 3.0 and 4.3 volts, this is indicative of a continuous irreversible reduction of some unknown species in the working electrode. Three materials were tested: Example 17 (Table V, weight average molecular weight of 5760), Example 27 (repeat of Example 17, but with purified monomers, weight average molecular weight of 1220) and a commercial liquid electrolyte without polymeric component, Lipaste from Tomiyama Chemical, which is believed to have 11.7% by weight of LiPFg in ethylene carbonate / propylene carbonate / diethyl carbonate = 41 / 24.8 / 22.5 (Example 28). For Example 27, compared to Example 17, the content of the MEHQ of the monomer / salt mixture, before polymerization, was reduced from 393 to less than 15 ppm, and the water content was reduced from 90 to 80. ppm. Example 17, although it exhibited attractive properties in its initial use, gave indications by the previous test that it is not completely acceptable for the repeated cycle of cells. In addition there is evidence of surface corrosion on both the Li metal electrodes and the compounds, while no evidence is seen on the electrodes immersed in the electrolyte of Example 27. The commercial liquid sample (Example 28) showed evidence of the CV measurements of the initial large irreversible oxidation and reduction currents, probably by the formation of a solid electrolyte interface, which was not detected optically. After repeated screening, the waveforms of Example 28 were similar to those observed initially and consistently in Example 27. It is anticipated that the oligomer of Example 27 can be further purified with the aid of a falling film or a cleaning evaporator at room temperature. empty. TABLE VI EXAMPLE 29 In this example, the preparation of the two component matrix in the form of a film is described, as a separating film on which the conductive salt / oligomer mixture is coated. (1) The copolymer of the first step was synthesized from a weight ratio of 9: 1 ethyl acrylate (EA) and the M # 1 monomers respectively. EA / M # 1 copolymer was prepared by the use of a continuous flow stirred tank reactor (CFSTR). A copolymer comprising 10 weight percent of M # 1 and the rest of EA was prepared by the volumetric polymerization technique as follows: The monomer mixture was prepared from the two monomers and the other essential ingredients. A typical mixture contains: 87.7% of EA, 9.7% of M # l, 0.07% of 1, 1 • azobis (cyclohexanecarbonitrile and 2.44% of n-dodecyl-mercaptan.) This mixture was fed into a glass container in which purged with an inert gas, such as argon.After purging, the monomer mixture was degassed and kept under an argon shell.This mixture was then pumped at a maximum rate of 15 g / min through a series of filters in the CFSTR in which the copolymer monomers bristled to provide approximately 86 percent by weight conversion.The polymerization of ethyl acrylate and M # l can be achieved at temperatures ranging from 105 to 1252C. The temperature, the operating pressure and the agitation rate were adjusted to 8.4 kg / cm2 (827 kPa) and 300 RPM, respectively.Since the polymerization reaction is highly exothermic, the temperature of the reactor was controlled with the help of a jacket of cooling. bristling was performed in the absence of a solvent. (2) The second stage copolymer was similarly synthesized from a mixture containing the following ingredients: 49.9 percent by weight of the first stage copolymer (EA / M # 1 = 90/10) plus any residual monomer, 29.9 percent by weight. weight percent MMA, 19.9 weight percent EA, 0.03% 1.1 • azobis (cyclohexanecarbonitrile, and 0.25% n-dodecyl mercaptan) The mixture was similarly purged with argon, degassed and kept low an argon shell The degassed mixture was fed through a series of filters at a maximum rate of 15 g / min in a CFSTR in which the polymerization of the first stage occurred, to supply a two-stage copolymer system, Molecularly miscible A minimum of 0.5 molar lithium salt LiN (CF S02) 2 was added to the monomer mixture from the second stage prior to polymerization The polymerization of the second stage was also carried out at temperatures vary from 120 to 1252C. The agitation regime and the pressure were the same used in the preparation of the prepolymer of the first stage. The unpolymerized MMA and EA monomers were intimately mixed with the copolymers of the second stage to form a gel that can be processed in molten form. (3) The second stage copolymer gel (95% by weight) was combined with 5 weight percent of the glycol di (meth) acrylate (200), 0.05-0.5% benzoyl peroxide (initiator) and 0.05 at 0.5% benzoin (2-ethoxy-2-phenylacetophenone, activator); all percentages based on the combined total weight of the residual monomer and interleaver. The entire mixture was fed into a continuous flow stirred tank (CDSTM), where it was homogenized before being fed into a pump or melt extruder. The gel was extruded in a thin film (50 microns) and then irradiated with ultraviolet light to form a dimensionally stable film. This thin film was subsequently embossed and perforated (pores from 0.1 to 1 miera) before being coated by spraying or by roller with the previously described oligomer electrolyte. EXAMPLE 30 The molecularly miscible, two-step copolymer system can also be prepared by the emulsion polymerization of the aforementioned monomers. The copolymers of the initial stage comprise from 5 to 95 weight percent of M # 1 and the rest of EA and were prepared by the emulsion polymerization technique as follows: A mixture of monomers was prepared, having an EA ratio: M # l of 90:10. The mixture contains 54.9% EA, 6.1% of M # l, 1.5% of n-dodecyl mercaptan, 36.7% of DI water and 0.8% of a 10% aqueous solution of sodium dodecylbenzenesulfonate. The monomer mixture was polymerized according to the following procedure. To a suitable glass vessel, equipped with agitator, heater, reflux condenser and nitrogen spray tube, 97.2% DI water and 0.03% sodium carbonate were added. The mixture was sprayed for one hour with nitrogen, while heating to 702C. The spray rate was then changed to a sweep and 2.7% of a 10% aqueous solution of sodium dodecylbenzene sulfonate was added to the mixture. The temperature of the reaction vessel was then raised to 852C. At this temperature, 18.03 ml of the initiator mixture, which consists of 0.34% sodium persulfate and 99.7% deionized water, were added to the reaction vessel. The monomer mixture was then fed into the reaction vessel at a rate of 7.56 ml / min. As the polymerization proceeds, the initiator mixture was added to the reaction vessel at a rate of 1.3 ml / min. The accumulation of solids was measured every 30 minutes. Upon completion of the addition of initiator and monomers, the mixture was maintained at 852C for one hour. Then it was cooled and stored in a polyethylene jar in preparation for the second stage and the end of the polymerization. The copolymers of the first stage comprise from 5 to 95 weight percent of monomers of MMA and the rest of EA, and from 5 to 95% of the copolymer of the first stage, P (EA-M # l = 90/10) , were prepared by the in situ emulsion polymerization technique, as follows: A monomer mixture was prepared, having an MMA: EA ratio of 60-40. The mixture contains 37.2% of MMA, 24.8% of EA, 0.3% of n-dodecyl-mercaptan, 36.5% of DI water and 1.2% of a 10% aqueous solution of sodium dodecylbenzenesulfonate. The monomer mixture was polymerized according to the following procedure. To a suitable glass vessel, equipped with agitator, heater, reflux condenser and nitrogen spray tube, were added: 67.9% of the initial stage emulsion and 32.1% of DI water. The mixture was sprayed for one hour with nitrogen, while heating to 70 ° C. The spray regime was then changed to a sweep. The temperature of the reaction vessel was then raised to 85 ° C. At this temperature, 17.63 ml of the initiator mixture, which consists of 0.22% sodium persulfate and 99.78% deionized water, were added to the reaction vessel. The monomer mixture was then fed to the reaction vessel at a rate of 4.30 ml / min. As the polymerization proceeded, the initiator mixture was added to the reaction vessel at a rate of 1.17 ml / min. The accumulation of solids was measured every 30 minutes. Upon completion of the addition of initiator and monomers, the mixture was maintained at 85 ° C for one hour. It was then cooled, filtered and the polymer isolated by freezing drying. EXAMPLE 31 The following demonstrates the electrochemical stability of the oligomer electrolyte obtained by the method of Example A, from M # 2 / M # 3 = 90/10. The molecular weight of gel permeation chromatography (against a poly (methyl methacrylate) standard) was: Mw = 411; Mw / Mn = 1.222. The oligomer formed a complex with the lithium salt, (Li (CF3 so2) 2) 1 ° 7 m / kg. The data was obtained by the cyclic voltiamperimeter at a tracking rate of 100 mV / s on an aluminum working electrode and a lithium counter and reference electrodes. The aluminum electrode showed no response between 2.0 and 5.0 volts and an unappreciable response, reaching only 5.5 microamperes / cm2 at 6 volts versus lithium. This is an unusually high limit of potential, taking into account that the limit of 4.3 V is considered as an overload potential or "abuse" for the present commercial cells and prototype of Li / LiNiCo02 or Li / LiCo0. "At or above 4.3 volts, there are problems regarding the stability of electrolytes and binders, as well as irreversible phase changes in metal oxides" (J. Electrochem. Soc, Vol. 143, No. 4, April nineteen ninety six). The PEO or PPO polymers, known in the literature, will have a window of electrochemical stability from 0 to approximately 3.7 volts versus lithium; see Electrochemistry of Novel Materials. Frontiers of Electrochemistry, edited by Jacek Lipkowski and Philip N. Ross; page 94, 1994, VCH Publishers, Inc. The higher stability of the electrolyte should make the present oligomer attractive in combination with the lithium manganese oxide cathode material (LiMn2? 4), high voltage.

Claims (22)

1. CLAIMS 1. An oligomer of the formula: R1-X- [(A) q- (r)] -Z, in which: (a) Ri is C? _C? 2 alkyl, C? -C? 2 'alkoxyalkyl aryl or alkaryl Cg-C ?, or - (CH2) m-COOR3, where m is 1 or 2, and R3 is C1-C12 alkyl; (b) -X- is -0-, -S-, -S (0) -, -S (0) 2-, -, -NH-, -NR3-, NH-C (0) -NH-, -NR3-C (0) -NR3-, -NH-C (0) -0-, -NR3-C (0) -0-, (>) R3CC (0) OR3, (>) HC-C (O) 0R3, (> C) - (C (0) 0R3, (>) HC-C (0) R3, (>) C- (CO (0) R32, -PH-, PR3-, -P (0H) -0-, -P (0R3) -0-, -P (0) (0H) -0-, -P (0) (0R3) -0-, -0-P (OH) - 0--0-P (0R3) -0-, -0-P (0) (OH) -O- or -0-P (0) (0R3) -0-; (c) (A) g comprises units polymerized from a monomer with functionality that is capable of forming complexes with the conductive metal salts; (d) (B) r comprises polymerized units of a monomer, these polymerized units are not capable of complexing with the conductive metal salts; e) Z is H or Ri-X-; (f) - [(A) g- (B) r] -, when r is not 9, define either a block copolymer or a random copolymer; (9) (cj) + r) = 1 to 25, q is from 1 to 25, and r is from 0 to 24.
2. 2. A mixture of a conductive metal salt / oligomer of: (a) from 80 to 95 weight percent of an oligomer of the formula: R1-X- [(A) q- (Br)] -Z, in which : (1) Ri is C 1 -C 2 alkyl, C 1 -C 12 alkoxyalkyl aryl C 5 -C 7 alkaryl, or - (CH 2) m-COOR 3, where m is 1 or 2, and R 3 is C 1 -C 6 alkyl C?; (2) -X- is -O-, -S-, -S (0) -, -S (0) 2-, -, -NH- -NR3-, NH-C (0) -NH-, - NR3-C (O) -NR3-, -NH-C (0) -0-, -NR3-C (0) -0-, (>) R3CC (0) OR3, (>) HC-C ( O) OR3, (> C) - (C (0) OR3, (>) C- (C (0) OR3) 2, (>) R3C-C (0) R3, (>) HC- C (0) R3, (>) C- (CO (0) R3) 2, -PH-, PR3-, -P (OH) -0-, -P (0R3) -0-, -P (0 ) (0H) -0-, -P (0) (0R3) -O-, -0-P (0H) -0--0-P (OR3) -0-, -OP (O) (OH) - O-, or -OP (O) (OR3) -0-; (3) (A) g comprises polymerized units of a monomer with functionality that is capable of forming complexes with the conductive metal salts; (4) (B) r comprises polymerized units of a monomer, these polymerized units are not capable of complexing with the conductive metal salts; (5) - [(A) g- (B) r] -, where r is not 0, defines or a block copolymer or a random copolymer; (6) Z is H or Ri-X-; (7) (q + r) = 1 to 25, q is from 1 to 25, and r is from 0 to 24 and (b) from 5 to 20 weight percent of one or more conductive metal salts.
3. 3. An oligomer of polymerization degree of the constituent (meth) acrylate monomers, from 1 to 25, this oligomer comprises: (a) from 5 to 50 weight percent end group units of at least one mercaptan residue, R ^ -S-, where R; L is C? -C? 2 alkyl, C? ~ C? 2 aryl or C6-C7 alkaryl, or - (CH2) m-COOR3, where m is 1 or 2, and R3 is C ^ -C ^ alkyl; (b) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH 2 = CH-COO-CH 2 -CHR-R 2, where R is H or CH 3, and where R 2 is H, C1-C2Q alkyl or aryl, alkaryl or Cg-C2o aralkyl; (c) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-COO- (CH2-CHR-0) n-R2 where n is 1 to 12
4. 4. A metal conductive / oligomer salt mixture of: (a) 80 to 95 weight percent of an oligomer of one degree of polymerization of the constituent (meth) acrylate monomers from 1 to 25, comprising: (2) from 5 to 50 weight percent of end group units of at least one mercaptan residue, R ^ S-, where R ^ is C1-C2alkyl, alkoxyalkyl C1-C12 aryl or C6-C7 alkaryl, or - (CH2) m-COOR3, where m is 1 or 2, and R3 is C1-C2alkyl; (2) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH2 = CH-COO-CH2-CHR-R2, where R is H or CH3, and where R2 is H, C 1 -C 20 alkyl or aryl, alkaryl or C 6 -C 2 aralkyl; (3) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-C00- (CH2-CHR-0) n-R2 where n is 1 to 12; and (b) from 5 to 20 weight percent of one or more conductive metal salts.
5. 5. The mixture of claim 2 or claim 4, wherein the conductive metal salt is a lithium salt, selected from the group consisting of: LÍCIO4, LÍPF6, L1BF4, LÍ (CF3S03) and LÍN (CF3S02) 2.
6. 6. The mixture of claim 5, wherein the lithium conductive salt is LiN (CF3S02).
7. 7. An article, comprising the mixture "of claim 2 or claim 4, and a membrane that allows sorption and permeation of the conductive salt / oligomer mixture.
8. 8. The article of claim 7, wherein the membrane has a non-woven structure.
9. 9. A compound of: (a) (1) 5 to 60 weight percent of the oligomer of claim 1; (2) 5 to 20 weight percent of one or more conductive metal salts; and (b) from 20 to 90 weight percent of a matrix composition, comprising: (1) from 10 to 100 weight percent of a first homopolymer or copolymer having a glass transition temperature, Tg, below of -35 ° -C and a weight average molecular weight of at least 20,000, from 0 to 90 weight percent of polymerized units of an alkyl or alkylthioalkyl ester of an acrylic or methacrylic acid, and from 10 to 100 percent by weight of polymerized units of a poly (alkyleneoxy) (meth) acrylate comonomer of the formula: CH2 = CR-C00- (CH2-CHR-0) p-R2, where p is from 1 to 1000; (2) from 10 to 90 weight percent of a second copolymer of a weight-average molecular weight of at least 30,000, of polymerized units of at least one alkyl ester of acrylic or methacrylic acid, in which the first homopolymer or copolymer and the second copolymer of the matrix composition are miscible, and wherein the mixture of the conductive metal salt / oligomer is miscible with the matrix composition; and (3) from 0 to 5 parts by weight of a conductive lithium salt, dissolved in the first homopolymer or copolymer of the matrix composition.
10. 10. A compound of: (a) from 5 to 80 weight percent of a conductive salt / oligomer mixture of: (2) from 80 to 95 weight percent of an oligomer of a degree of polymerization of the (metal) monomers ) acrylate constituents from 1 to 25, comprising: (i) from 5 to 50 weight percent end group units of at least one mercaptan residue, R ^ -S-, where R ^ is C? alkyl? C? 2, alkoxyalkyl cl_c12 aryl or alkaryl? -C? , or - (CH2) m-C00R3, where m is 1 or 2, and R3 is C ^ -C ^ alkyl; (ii) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH2 = CH-C00-CH2-CHR-R2, wherein R is H or CH3, and where R2 is H, CI-C2Q alkyl or aryl, alkaryl or Cg-C2o aralkyl, (iii) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-COO- (CH2-CHR-0) n-R2 where n is from 1 to 12; and (2) from 5 to 20 weight percent of one or more conductive metal salts, preferably a lithium conductive salt. (b) from 20 to 95 weight percent of a matrix composition, this matrix composition comprises: (1) from 10 to 100 weight percent of a first homopolymer or copolymer having a glass transition temperature, Tg , below -35 ° C. and a weight average molecular weight of at least 20,000, from 0 to 90 weight percent of polymerized units of an alkyl or alkylthioalkyl ester of an acrylic or methacrylic acid, and from 10 to 100 percent by weight. weight of polymerized units of a poly (alkylenoxy) (meth) acrylate comonomer of the formula: CH2 = CR-COO- (CH2-CHR-0) p-R2, where p is from 1 to 1000; (2) from 10 to 90 weight percent of a second copolymer of a weight-average molecular weight of at least 30,000, of polymerized units of at least one alkyl ester of acrylic or methacrylic acid, in which the first homopolymer or copolymer and the second copolymer of the matrix composition are miscible, and wherein the mixture of the conductive metal salt / oligomer is miscible with the matrix composition; and (3) from 0 to 5 parts by weight of a conductive lithium salt, dissolved in the first homopolymer or copolymer of the matrix composition.
11. 11. The compound of claims 9 or 10, wherein at least one of the first homopolymer or copolymer or the second copolymer of the matrix composition is entangled.
12. 12. The compound of claims 9 or 10, wherein this compound is a combination of the metal conductive / oligomer salt mixture and the matrix composition.
13. 13. An article formed of the compound of claims 9 or 10, wherein the mixture of the metal conductive / oligomeric salt is encapsulated within the matrix composition.
14. 14. An article formed of the compound of claims 9 or 10, wherein the mixture of the metal conductive / oligomeric salt is layered to a film or sheet obtained from the matrix composition.
15. 15. A process for the preparation of a conductive metal / oligomer salt mixture of: (a) 80 to 95 weight percent of an oligomer of a degree of polymerization of the constituent (meth) acrylate monomers from 1 to 25, which it comprises: (2) from 5 to 50 weight percent end group units of at least one mercaptan residue, R ^ S-, where R- is C? -C? alkyl, C? -C? alkoxyalkyl. 2 aryl or alkaryl CQ-C-, or - (CH 2) m -COOR 3, where m is 1 or 2, and R 3 is C 1 -C 1 alkyl; (2) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH 2 = CH-COO-CH 2 -CHR-R 2, where R is H or CH 3, and where R 2 is H, C?-C2o alkyl or aryl, alkaryl or Cg-C2o aralkyl; (3) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-COO- (CH2-CHR-0) n-R2 where n is 1 to 12; and (b) from 5 to 20 weight percent of a conductive metal outlet, this process comprises: (2) drying the conductive metal salt to remove the water; (2) passing at least one (meth) acrylate ester monomer of the formula: CH2 = CR-C00- (CH2-CHR-0) n-R2, where n is from 2 to 12, through a column activated alumina or molecular sieves; (3) mixing the conductive metal salt, the at least one acrylate ester monomer and the at least one (meth) acrylate ester monomer with an alkyl mercaptan, R ^ -SH, where R ^ is C ^ alkyl. -C ^, C 1 -C 6 alkoxyalkyl or Cg-C 7 alkaryl, or (CH 2) m -COOR, where m is 1 or 2 and R 3 is C 1 -C 2 alkyl; (4) subjecting the mixture to a free radical polymerization process; and (5) removing any volatile residue by vacuum devolatilization.
16. 16. The method of claim 15, wherein the polymerization process is continuous.
17. 17. An electrolytic cell, comprising an anode, a cathode and a conductive electrolyte, including a conductive salt / oligomer mixture of: (a) from 80 to 95 weight percent of an oligomer of the formula: R1-X- [ (A) q- (Br)] - Z, in which: (2) Ri is C1_C12 alkyl, C1_12 alkoxyalkyl or aryl or C, -Cy, or - (CH2) m-COOR, where m is 1 or 2, and R3 is C? -C? 2 alkyl; (2) -X- is -O-, -S-, -S (0) -, -S (0) 2-, -, - NH- -NR3-, NH-C (0) -NH-, - NR3-C (O) -NR3-, -NH-C (0) -0-, -NR3-C (0) -0-, (>) R3CC (0) OR3, (>) HC-C ( O) OR3, (> C) - (C (0) OR3, (>) C- (C (0) OR3) 2, (>) R3C-C (0) R3, (>) HC- C (0) R3, (>) C- (CO (0) R3) 2, -PH-, PR3-, -P (0H) -0-, -P (0R3) -0-, -P (0 ) (0H) -0-, -P (0) (0R3) -0-, -0-P (0H) -0--0-P (OR3) -0-, -OP (O) (OH) - O-, or -OP (O) (0R3) -0-; (3) (A) g comprises polymerized units of a monomer with functionality that is capable of complexing with the conductive metal salts; (4) (B) r comprises polymerized units of a monomer, these polymerized units are not capable of complexing with the conductive metal salts; (5) Z is H or Ri-X; (6) - [(A) g- (B) r] -, where r is not 0, defines either a block copolymer or a random copolymer; (7) (q + r) = 1 to 25, q is from 1 to 25, and r is from 0 to 24. and (b) from 5 to 20 weight percent of one or more conductive metal salts.
18. 18. An electrolytic cell comprising an anode, a cathode and a conductive electrolyte, including a degree of polymerization of the constituent (meth) acrylate monomers from 1 to 25, which contains: (a) from 5 to 50 weight percent end group units of at least one mercaptan residue, Ri-S-, where R ^ is alkyl C? ~ C? , C 1 -C 6 alkoxyalkyl or alkaryl Cg-Cy, or - (CH) m-COOR 3, where m is 1 or 2, and R 3 is C 1 -C 2 alkyl; (b) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH 2 = CH-COO-CH 2 -CHR-R 2, where R is H or CH 3, and where R 2 is H, C 1 -C 2 alkyl or aryl, alkaryl or aralkyl c 6"c 20 '* (c) from 0 to 95 weight percent of polymerized units of at least one ester monomer of (meth) acrylate of the formula: CH2 = CR-COO- (CH2-CHR-0) n-R2 where n is from 2 to 12.
19. 19. An electrolytic cell comprising an anode, a cathode and a conductive electrolyte, including a mixture of a conductive salt / oligomer of: (a) 80 to 95 weight percent of an oligomer of a degree of polymerization of the monomers of ( meth) acrylate constituents from 1 to 25, comprising: (2) from 5 to 50 weight percent end group units of at least one mercaptan residue, R ^^ - S-, where R ^ is C1 alkyl -C? 2, C1-C12 alkoxyalkyl aryl or C6-C7 alkaryl, or - (CH2) m-C00R3, where m is 1 or 2, and R3 is C ^ -C ^ alkyl]; (2) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH2 = CH-COO-CH2-CHR-R2, where R is H or CH3, and where R2 is H, C1-C20 alkyl or aryl, alkaryl or Cg-C2o aralkyl; (3) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-COO- (CH2-CHR-0) n-R2 where n is 2 to 12; and (b) from 5 to 20 weight percent of one or more conductive metal salts.
20. 20. An electrolytic cell, comprising an anode, a cathode and a conductive electrolyte including a compound of 5 to 15 weight percent of (a) a conductive salt / oligomer mixture of: (2) 80 to 95 percent by weight weight of an oligomer of a degree of polymerization of the constituent (meth) acrylate monomers from 1 to 25, comprising: (i) from 5 to 50 weight percent end group units of at least one mercaptan residue , R ^ -S-, where R ^^ is C1-C12 alkyl, alkoxyalkyl C 1 -C 12 aryl or alkaryl Cg-Cy, or - (CH 2) m-C00R 3, where m is 1 or 2, and R 3 is C 1 -C 1 alkyl; (ii) from 0 to 95 weight percent of polymerized units of at least one acrylate ester monomer of the formula: CH2 = CH-COO-CH2-CHR-R2, wherein R is H or CH3, and where R2 is H, C2-C2o alkyl or aryl, alkaryl or Cg-C2o aralkyl, * (iii) from 0 to 95 weight percent of polymerized units of at least one (meth) acrylate ester monomer of the formula: CH2 = CR-COO- (CH2-CHR-0) n-R2 where n is from 1 to 12; and (2) from 5 to 20 weight percent of one or more conductive metal salts; (b) from 20 to 95 weight percent of a matrix composition, this matrix composition comprises: (2) from 10 to 100 weight percent of a first homopolymer or copolymer having a glass transition temperature, Tg , below -35 ° C and a weight average molecular weight of at least 20,000, from 0 to 90 weight percent of polymerized units of an alkyl or alkylthioalkyl ester of an acrylic or methacrylic acid, and from 10 to 100 weight percent of polymerized units of a poly (alkylenoxy) (meth) acrylate comonomer of the formula: CH2 = CR-COO- (CH2-CHR-0) p-R2, where p is from 1 to 1000; (2) from 5 to 80 weight percent of a second copolymer of a weight average molecular weight of at least 30,000, of polymerized units of at least one alkyl ester of acrylic or methacrylic acid, in which the first homopolymer or copolymer and the second copolymer of the matrix composition are miscible, and wherein the mixture of the conductive metal salt / oligomer is miscible with the matrix composition; and (3) from 0 to 5 parts by weight of a conductive lithium salt, dissolved in the first homopolymer or copolymer of the matrix composition.
21. 21. A process for preparing the battery of claim 20, which comprises: (a) polymerizing the monomers forming the first homopolymer or copolymer, in a stirred, constant flow reactor, at least one conversion of 65%; (b) transferring the first homopolymer or copolymer to a stirred reactor; (c) mixing with the monomers forming the second copolymer; (d) the polymerization of the monomers forming the second copolymer at at least a 65% conversion; (e) transferring the mixture of the first homopolymer or copolymer and the second copolymer to an extruder; (f) extruding the mixture in the form of a sheet or film; (g) the application of the conductive salt / oligomer to at least one surface of the extruded sheet or film; (h) after extrusion, but before, simultaneously with, or following, the application of the conductive salt / oligomer, perforate the film to allow controlled access of the conductive salt / oligomer on both sides of the sheet or movie; (i) conducting the oligomer coated film between the anode and the cathode of an electrolytic cell article.
22. 22. The method of claim 21, further characterized by: (a) in step (c) of claim 1, a photosensitized initiator and a polyfunctional polymerizable monomer are added to the monomer mixture; (b) after step (f) of claim 21, the extrudate is illuminated with sufficient light to cause entanglement by the polymerization of the polyfunctional polymerizable monomer.