EP0890192A1

EP0890192A1 - Electrolytic composition with polymer base for electrochemical generator

Info

Publication number: EP0890192A1
Application number: EP98900830A
Authority: EP
Inventors: Alain Vallee; Michel Armand; Yves Choquette; André Belanger; Michel Gauthier; Michel Perrier; Karim Zaghib; Estelle Potvin; Simon Besner
Original assignee: Hydro Quebec
Current assignee: Bathium Canada Inc
Priority date: 1997-01-17
Filing date: 1998-01-19
Publication date: 1999-01-13
Also published as: US6280882B1; JP4831588B2; US6806002B2; JP2000507387A; WO1998032183A1; US20010041295A1

Abstract

The invention concerns an aprotic electrolytic composition located in the separator and in at least one composite electrode containing a powder of an active electrode material, and if necessary an electronic conduction additive of an electrochemical generator. The electrolytic composition comprises a first polymer matrix consisting of a polyether and at least a second polymer matrix, macroscopically separated, and also at least an alkaline salt as well as a polar aprotic solvent: The polymer matrices are capable of being swollen by at least one of the polar aprotic solvents. The solvent or mixture of solvents is unevenly distributed between the polymer matrices. The invention also concerns an electrochemical generator comprising a negative electrode and positive electrode reversible to alkaline ions and a separator with polymer electrolyte, the electrolytic component of which is the composition described above. The invention further concerns the manufacture in two or three steps of a subassembly of an electrochemical generator by coating an electrode support with a composite electrode containing the second matrix, followed by a surface coating on the electrode resulting from the preceding step with a solution containing the first polymer matrix so as to form the separator wholly or partly.

Description

Polymer-based Electrolytic Composition for Generator

ELECTROCHEMICAL TECHNICAL AREA

The present invention relates to electrolytic compositions based on polymers for electrochemical generators. More specifically, the invention relates to aprotic electrolytic compositions characterized in that they consist of at least one alkaline salt and of a polymer matrix consisting of a polyether and at least one other polymer matrix, separated macroscopically, swollen with at least one polar aprotic organic solvent, the said solvent or mixture of solvents being distributed unevenly between the matrices. PRIOR ART

Over the past ten years, primary and rechargeable lithium batteries have been the subject of considerable research and development. The objective is to develop a safe, inexpensive battery with high energy content and good electrochemical performance. With this in mind, many battery configurations have been developed to meet different applications such as microelectronics, telecommunications, portable computers and the electric vehicle to name a few.

Electroclimatic batteries or generators, whether rechargeable or not, all consist of an anode which may consist of a metal such as lithium or a reversible insertion compound of lithium such as carbon, a cathode which it consists of a reversible insertion compound with hthium such as cobalt oxide, a mechanical separator placed between the electrodes and an electrolytic component. The term “electrolytic component” means any material included in the generator used for ion transport, with the exception of electrode materials in which the Li ions can move, both at the level of the separator and in at least one composite electrode. During the discharge or the charge of the generator, the electrolytic component ensures the transport of the ionic species through the whole generator either from one electrode to the other and inside the composite electrodes. In lithium batteries the electrolytic component usually takes the form of a liquid that we call liquid electrolyte or a dry or gelled polymer matrix which can also play the role of mechanical separator.

When the electrolytic component is in a liquid form, it consists of an alkaline salt dissolved in an aprotic solvent. In the case of a lithium generator, the most common salts are LiPFό, L1BF4 and LiN (Sθ2CF3) 2 and the polar aprotic solvents can be chosen from propylene carbonate, ethylene carbonate, γ-butyrolactone and 1,3-dioxolane or their analogs to name a few. At the separator, the liquid electrolyte is generally impregnated in a porous polymer matrix inert to the aprotic solvent used or in a glass fiber paper. The use of a liquid electrolyte impregnated in an inert polymer matrix makes it possible to maintain sufficient ionic mobility to reach a level of conductivity of the order of 10 -3 Scm ^" 1 at 25 ° C. At the level of the composite electrodes when the latter consist of an insertion material linked by a polymer matrix which is inert to aprotic solvents or which has little interaction with the latter, the liquid electrolyte fills the porosity of the electrode. batteries using a liquid electrolytic component are found in US Patents 5,422,203, US No. 5,626,985 and US No. 5,630,993.

When the electrolytic component is in the form of a dry polymer matrix, it consists of a homo or copolymer of high molecular weight crosslinkable or not comprising a heteroatom in its repeating unit such as oxygen or nitrogen for example, in which an alkaline salt such as LiN (SO2CF3) 2, LiSθ3CF3 and LiClθ4 is dissolved. Polyoxyethylene is a good example of a polymer matrix capable of solvating different alkaline salts. Armand, in US Patent No. 4,303,748 describes families of polymers which can be used as an electrolytic component in lithium batteries. More elaborate families of polymers (copolymers and terpolymers crosslinkable or not) are described in US Pat. Nos. 4,578,326, US No. 4,357,401, US No. 4,579,793, US No. 4,758,483 and in Canadian patent No. 1,269,702. The use of a high molecular weight polymer makes it possible to shape electrolytes in the form of thin films (of the order of 10 to 100 μm) which have sufficiently good mechanical properties to serve as a complete separator between the anode and the cathode while ensuring ionic transport between the electrodes. In the composite, the solid electrolyte serves as a binder for the electrode materials and provides ion transport through the composite. The use of a crosslinkable polymer allows the use of a polymer of lower molar mass, which facilitates the implementation both for the separator and for the composite and also makes it possible to increase the mechanical properties of the separator and by the very fact of increasing its resistance to the growth of dendrites when using a metal hthium anode. Unlike the liquid electrolyte, the solid polymer electrolyte cannot leak or evaporate from the generator. Their drawback lies in the lower ion mobility obtained in these solid electrolytes which constrains their use at temperatures between 60 and 100 ° C.

The gel electrolytic component generally consists of a polymer matrix solvating or not for the hthium salts in which is impregnated an aprotic solvent and an alkaline salt. The most common salts are LiPFό, LiBF4 and LiN (S02CF3) 2 and the polar aprotic solvents can be chosen from propylene carbonate, ethylene carbonate, bu yrolactones and 1,3-dioxoalane to name a few those there. The gels can be obtained from homo or copolymer of high crosslinkable molecular weight or not and from homo or copolymer of low crosslinkable molar mass. In the latter case the dimensional stability of the gel is maintained following the crosslinking of the polymer matrix. Polyethers comprising crosslinkable functions such as allyls, acrylates or methacrylates are good examples of polymers which can be used in the formulation of a gel electrolyte, as described in US Pat. No. 4,830,939. This is explained by their capacity to solvate lithium salts and their compatibility with polar aprotic solvents as well as their low cost and their ease of implementation and crosslinking. The gel electrolyte has the advantage of being handled as a solid and of not leaking or leaking from the generator as is the case for generators with liquid electrolyte. The efficiency of ion transport is related to the proportion of aprotic solvent incorporated in the polymer matrix. Depending on the nature of the polymer matrix, the salt, the plasticizer and its proportion in the matrix, a gel can reach a conductivity of the order of 10 Scm at 25 ° C. while remaining solid macroscopically. As in the case of the dry electrolyte, the gel electrolyte can serve as a separator between the anode and the cathode while ensuring ionic transport between the electrodes.

In the composite electrode (s) of the generator, the gel electrolyte serves as a binder for the electrode materials and provides ion transport through the composite electrode (s). However, the loss of mechanical property resulting from the addition of the liquid phase (aprotic solvent) must generally be compensated for by the addition of solid fillers, by the crosslinking of the polymer matrix when possible or in certain cases when the proportion of liquid is too high by the use of a porous mechanical separator impregnated with gel serving as an electrolytic component in the separator. Examples of a generator using a gel electrolyte component are described in U.S. Patent Nos. 5,443,927 and U.S. Patent 4,830,939. Takeda et al. US. Pat. No. 5,658,687 claims a battery and the method of manufacturing said battery which comprises an electrolytic component consisting of a very specific, crosslinkable polyether of high molar mass. This high molecular weight polyether is obtained from an esterification reaction of a polyoxyethylene glycol in the presence of acrylic acid or methacrylic acid, sulfonic acid or para-toluenesulfonic acid and a solvent. organic. The authors specify that the addition of an organic solvent such as a cyclic carbonic ester for example, which amounts to forming a gel electrolyte, makes it possible to considerably increase the conductivity of the electrolyte. The electrolytes thus obtained from said polyether serve both as a separator and in composites, as an electrolytic material and as a binder for the electrode material. In the composite electrodes, a second polymer can be added in small proportion to the polyether serving as electrolyte. Generally this second polymer is added in order to considerably increase the mechanical properties of the composite.

The poor resistance of polyethers to oxidation is, however, an important problem linked to the use of solid electrolytes and gels based on polyether as electrolytic material in a cathode. composite whose recharge voltage can reach and exceed 3.5 to 3.7V. This results in a significant loss of generator capacity resulting from more or less massive degradation of the polyether matrix during successive discharge / charge cycles. The present invention relates to a new concept of electrolytic component comprising more than one swellable polymer matrix, with a liquid electrolyte consisting of at least one aprotic solvent and at least one alkaline salt, at different solvent levels and macroscopically separated at inside the generator. The differential swelling rate making it possible to locally optimize the conductivity properties, in particular in composite electrodes and the mechanical properties of the polymer membrane acting as a mechanical separator. PRESENTATION OF THE INVENTION The present invention relates to an electrolytic component for an electochemical generator consisting of at least two polymer matrices containing at least one alkaline salt and at least one polar aprotic organic solvent. Said electrolytic component being defined as the electrolytic material which forms the separator and the electrolytic material of at least one composite electrode. The polymer matrices are macroscopically separated there and one of them must necessarily be a polyether localized in whole or in part in the separator of the generator. By macroscopic separation is meant that the polymer matrices are not interpenetrated in the form of microscopic mixtures, such as in an interpenetrating network. The polymer matrices are chosen so as to locally optimize the level of aprotic solvent, so that the latter is distributed unevenly between the polymer matrices. By swellable polymer matrix is meant a polymer matrix capable of incorporating a level of aprotic organic solvent so as to form a gel.

It is shown in the present invention that the use of a separator based on gelled polyether does not limit the power, that is to say the discharge or load capacity of the generator in comparison with an equivalent generator whose separator consists of an ubre liquid solvent included in the pores of an inert porous separator. This comparison obtained by using a crosslinked separator so as to limit the solvent level despite the use of a polyether matrix which is very compatible with the solvent, makes it possible to optimize the mechanical strength of the polymer matrix and to optimize its thinness. On the other hand, and this is one of the advantages of the invention, it is also shown that it is possible and desirable to control the solvent content of the polymer matrix (s) in the composite electrodes preferentially at a higher solvent level so to increase the ease of diffusion of the ions of the alkaline salt generally more limiting in the composite electrodes because of the tortuosity due to the solid charges. SUMMARY DESCRIPTION OF THE DRAWINGS

Figure 1 schematically shows generators with double composite electrodes (not limiting) in four embodiments of the invention:

A) Identical polymer matrix throughout the separator. B) Polymer matrix containing more solvent (more swollen) in each composite electrode. Example: any polyether with control of the crosslinking rate or of the comonomers.

C) Different polymer matrix between the composite electrodes and the separator. Example: to anticipate solvent variations during discharge / charge cycles.

Example: Polyethers crosslinked at different rates or polymers of different natures

D) Polymer matrix of the separator in two layers so as to count a polyether separator with a composite electrode at 4V.

Figure 2 shows the generator cycling results of Example 1.

Figure 3 shows the cycling results of the generator of Example 12. Figure 1 illustrates schematically embodiments of the invention which take this teaching into account.

It will be noted that the high swelling rate of the polymer matrix of the composite electrodes can be obtained by using, in the case of an all-polyether system, a non-crosslinkable or slightly crosslinked polyether. An alternative way of obtaining a high level of solvent in the composite electrodes consists, inter alia, of using a slightly swollen polymer matrix and of filling the porosity of the composite with a free liquid phase. This embodiment will be preferred for implementing high voltage cathodes> 4V or even for giving a greater power capacity to a cathode of 3V or more such as LiFePθ4 or its analogous polyanions.

Purely as a non-limiting indication, these forms of optimization of generators comprising gels can be interpreted by considering that: the number of canonical transport of electrolytes containing lithium salts in polar aprotic medium is not 1 but less. This phenomenon results in gradients in salt concentration which it is sometimes difficult to absorb in the composite electrodes during rapid discharges or charges. The present invention tends to reduce the effect of this phenomenon; the transport of alkaline cations is accompanied by the movement of its solvating sphere when using a liquid solvent or a polymer of low molar mass. There is therefore the possibility of depletion or enrichment of the rate of liquid solvent in the composite electrodes. The present invention tends to reduce the effect of this phenomenon and optimize the performance of the generator.

The alkaline salt (s) may be sodium, potassium or other hthium salts such as, for example, the salts based on hthium trifluorosulfonimide described in US Pat. No. 4,505,997, the hthium salts derived from bisperhaloacyl or sulfonylimide crosslinkable or not described in US Patent 4,818,644 and in PCT WO92 / 02966, LiPFό, L1BF4, LiS03CF3, LiC104, LiSCN, NaSCN, NaC104, KSCN and KCIO4, etc. The nature of the salt is not a limitation of the present invention.

The polar aprotic solvent (s) may be chosen, for example, from propylene carbonates, ethylene carbonate, ethyl methyl carbonate, dimethyl ethyl carbonate, tetiahydrofuran, 2-methyltetiahydrofuran, 1,3- dioxolane, 4,4-dimethyl-1,3-dioxolane, γ-butyrolactone, butylene carbonate, sulfolane, 3-methylsulfolane, ter-butyl ether, 1,2- dimetoxyethane, 1,2-diethoxyethane, bis (methoxyethyl) ether, 1,2-ethoxymethoxyethane, terbutylmethylether, glymes and sulfonamides of formula: R1R2N-SO2-NR3R4, in which Ri, R2, R3 and R4 are alkyls comprising between 1 and 6 carbons or / and oxyalkyls comprising between 1 and 6 carbon atoms. The nature of the solvent is not a limitation of the present invention.

The active material of the cathode can be chosen from cobalt oxide, nickel oxide, nickel cobalt oxide, nickel oxide cobalt aluminum, manganese oxide (LiMn2θ4) or their analogs for so-called 4V cathodes or among cathodes of less than 4V such as phosphates or other polyanions of transition metals such as LiFePθ4, Nasicons structures also including V2O5, L1V3O8 and Mnθ2. The nature of the active material is not a limitation of the present invention. The active material of the anode can be chosen from lithium metal or a metal alloy based on hthium such as hthium-aluminum or hthium-tin or a carbon or other low-voltage insertion compound capable of inserting hthium . The nature of the active material is not a limitation of the present invention. Also included among the conductive gels of the invention are gels formed from polymers with little solvation of lithium salts or little intrinsic conductivity in the presence of salts but comprising heteroatoms such as fluorine or polar groups such as nitriles, sulfonates, fluoro methanes, which make them miscible with one or more polar aprotic organic solvents. The latter then give the gel solvating properties of the hthium salts so as to give them a role of electrolytic component. The main poorly solvating polymers can be, by way of nonlimiting example, PVDFs or their copolymers, polyacrylonitriles and polyelectrolytes comprising sulfonate or fluorosulfonate groups or their equivalents. WAYS TO IMPLEMENT THE INVENTION

Realization 1 In a first realization, the electrolytic component consists of two polymer matrices of different chemical nature swollen at different rates by at least one polar aprotic solvent containing at least one alkaline salt.

The first polymer matrix which mainly forms the separator consists of a polyether (polymer # 1) in the form of homo or copolymer of high molar mass, crosslinkable or not or else of a homo or copolymer of lower crosslinkable molar mass. The matrix can contain at least one crosslinking additive to increase the dimensional stability of the separator formed and above all to help limit the rate of swelling. The crosslinking additive is chosen from trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, glycerol triacrylate, glycerol trimethacrylate, pentaerythiol tetraacrylate, glycerol propoxylate triacrylate / glycol propoxylate triacrylate) and di (trimethylolpropane) tetraacrylate. The matrix may also contain a crosslinking initiator. The crosslinking of the matrix is carried out thermally, by UV irradiation or electron beam (EB). The level of aprotic solvent contained in the matrix is determined by the chemical nature of the polyether, its compatibility with the aprotic solvent and its degree of crosslinking. For the separator, a more limited rate of aprotic solvent will be sought, knowing that the diffusion is less limiting there than in the composite electrodes and knowing that the mechanical properties decrease with the increase in the rate of aprotic solvent.

The second polymer matrix is used mainly in the composite electrode (s) and in certain cases in the part adjacent to the electrodes, in particular near the composite cathode. The macroscopic separation of the two polymer matrices is generally located at the interface between the composite electrode (s) and the separator. The second polymer matrix consists of a homo or copolymer of high molecular weight crosslinkable or not (polymer # 2) which is not necessarily a polyether and which can be chosen for its resistance to oxidation when included in a cathode said to 4V, such as: L1C0O2, LiMnθ2 and LiMn2θ4. The level of aprotic solvent contained in the matrix is determined by the chemical nature of the polymer # 2, its degree of crosslinking and the chemical nature of the aprotic solvent used. The polymer # 2 is preferably included in a proportion mass between 5 and 20% of the composite electrode. Polymer # 2 serves both as a binder for the active material of the electrode and to isolate the active material from the rest of the electrolytic component. It must also be electiochemically stable against the electrode material in which it is included, the use of a polyether matrix being reserved for electrode materials whose voltage at recharge does not exceed 3.5 to 3.7V. The composite can be obtained by way of example by coating in a solvent phase on a current collector a solution in which the electrode material is dispersed and the polymer # 2 is dissolved. The electrode can also be obtained from other shaping methods such as extrusion, screen printing, etc. In a nonlimiting embodiment, the introduction of the aprotic solvent and the alkaline salt into the composite electrode is carried out just before it is assembled with the separator or after it has been assembled with the separator or in the form of a half-stack or in the form of a complete generator.

This procedure for introducing the aprotic solvent and the alkaline salt into the electrode during a step subsequent to that of production of the composite electrode has two advantages. The electrode can be prepared and stored under conditions which do not require particular control of the atmosphere and the humidity rate, provided that a drying step is carried out just before their use. An intimate and optimum contact is also ensured between the electrode material and the polymer # 2 so as to maximize the coating of the electrode material. The coating of the electrode material minimizes direct contact of the latter with the polyether at the interface between the separator and the composite electrode. .

The chemical nature of polymer # 2 is chosen so as to form a gel with the polar aprotic solvent. The swelling rate should not be too great in order to maintain electrical percolation in the composite electrode or should be fixed during spreading when possible. Mixtures of aprotic solvents ethyl methyl carbonate plus ethyl carbonate LiPF6 1 molar with the vinyldiene-co-hexafluoropropene copolymer (PVDF-HFP) and mixture of solvents tettamethylesulfonamide plus ethyl carbonate LiPF6 1 molar with the ethylene propylene diene copolymer (EPDM) are two examples of aprotic solvent polymer pairs as described above. At low swelling rates, the remaining porosity in the composite electrode is subsequently filled with the aprotic organic solvent in which the alkaline salt (s) is dissolved. Realization 2

The second embodiment of the electrolytic component is different from embodiment # 1 only by the composition of the matrix forming the separator, in that the polymer matrix of the latter can be formed of an interpenetrating network by the addition of a third crosslinkable polymer, solvating or not, or thus forming a semi-interpenetrating network by the addition of the third polymer. The third polymer is not necessarily a polyether and is found in a volume proportion lower than that of polymer # 1.

In the present invention, the use of polyether in the major part of the generator will be preferred because of its electiochemical and technological advantages as a conductive binder and as a crosslinkable separator. Gels formed from non-solvating polymer will mainly be used mainly in composites and especially in the cathode where the resistance to oxidation becomes critical and little limit the use of polyethers alone when the cathodes operate at recharge voltages above 3.5. at 3.7V.

Realization 3 In a third realization the electrolytic component is identical to that of realization # 1 except that the remaining porosity in the composite electrode (s) is filled by a polyether matrix swollen with at least one aprotic solvent containing at least one alkaline salt. In this case, the proportion of aprotic solvent is lower in the polyether of the separator than in the polyether contained in the composite so as to optimize the diffusion of the ions in the composite while minimizing the contact surface between the polyether and the active material of the cathode, in particular for 4V cathodes.

Realization 4 In a fourth realization the electrolytic component consists of two matrices based on polyether swollen at rates different by at least one polar aprotic solvent containing at least one alkaline salt.

In cases where cathodes operating at recharging voltages lower than 3.5 - 3.7V are used, all polyether generators will be favored while playing on the crosslinking rates so as to control the rates of aprotic solvent contained in the polyether of the separator and the polyether contained in the composite electrodes. A higher level of aprotic solvent will be sought in the composite electrodes so as to maximize the diffusion of the ions during charging or rapid discharge.

The first polymer matrix (matrix # 1) which forms the separator consists of a polyether in the form of homo or crosslinkable copolymer. The matrix may contain at least one crosslinking additive to increase the dimensional stability of the separator formed and to control its rate of swelling. The crosslinking additive may be chosen from trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, glycerol triacrylate, glycerol trimethacrylate, pentaerythiol tetraacrylate, glycerol propoxylate / propiolate trioxylate hexaacrylate and di (trimethyιolpropane) tetraacrylate. The matrix may also contain a crosslinking initiator. The crosslinking of the matrix is carried out thermally, by UV irradiation or electron beam (EB). The level of aprotic solvent contained in the matrix is determined by the chemical nature of the polyether, its degree of crosslinking and the chemical nature of the aprotic solvent used.

The second polymer matrix (matrix # 2) is included in the composite electrode (s). The macroscopic separation of the two polymer matrices is located at the interface between the composite electrode (s) and the separator or near the interface of the cathode which is then chosen from among the cathodes whose voltage at recharge is below 3.5 to 3.7V such as that based on LiFePθ4 by way of nonlimiting example. The second polymer matrix consists of a polyether in homo or copolymer form of high crosslinkable molar mass or not or else of a homo or copolymer of lower crosslinkable molar mass. The polyether matrix serves both as a binder for the active material of the electrode and of electrolytic component to ensure ionic transport in the composite electrode (s). The matrix can contain at least one crosslinking additive to increase the dimensional stability of the separator formed and to control its crosslinking rate. The crosslinking additive is chosen from trimethylolpropane triacrylate, trimethylolpropane trimethacrylate polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, glycerol triacrylate, glycerol trimethacrylate, pentaerythiol tetraacrylaate, glycerol propaylate) / glycerol propoxylate) and α (trimethylolpropane) tetraacrylate. The matrix may also contain a crosslinking initiator. The crosslinking of the matrix is carried out thermally or by electron beam irradiation (EB). However in the composite electrode the rate of aprotic solvent contained in the matrix is in this case higher than in the matrix of the separator so as to favor the diffusion of the ions in the composite electrodes. The level of aprotic solvent contained in the matrix is then fixed by the chemical nature of the polyether, its degree of crosslinking and by the chemical compatibility of the aprotic solvent used with the polyether matrix. Realization 5

This embodiment relates to the shaping of the swelling polyether-based matrix which forms the separator. The mixture of the polyether with at least one aprotic organic solvent and at least one alkaline salt is formed in the form of a thin film on a peelable support or directly on one of the electrodes of the generator by a conventional coating method by solvent route. by using, if necessary, a volatile, solvent which is chemically compatible with the components of the generator or by extrusion. For mixtures of a polyether of lower molecular weight with one or more aprotic organic solvents, which are in liquid form at the spreading temperature, the coating can then be carried out in the absence of coating solvent. During this shaping step, the polyether-based mixture may contain at least one crosslinking additive, at least one alkaline salt and a crosslinking initiator. The crosslinking of the matrix is carried out thermally, by UV irradiation or electron beam (EB). The separator is thus obtained in the swollen state with at least one aprotic organic solvent containing or not containing an alkaline salt and is ready to be used in the assembly of a generator.

Realization 6 This realization concerns the shaping of the polyether-based matrix which forms the separator. The polyether is shaped into a thin film on a peelable support by a conventional coating method by solvent or by extrusion. For polyethers of lower molar mass which are in the form of water at 25 ° C. the coating can be carried out in the absence of coating solvent. During this shaping step, the polyether can contain at least one crosslinking additive, at least one alkaline salt and a crosslinking initiator. The crosslinking of the matrix is carried out thermally, by UV irradiation or electron beam (EB). The separator thus obtained is swollen with at least one aprotic organic solvent containing or not containing an alkaline salt, just before being used in the assembly of a generator. A variant of this embodiment being that the aprotic organic solvent of the separator is introduced after assembly by transfer of solvent from one or more composite electrodes.

Embodiment 7 This embodiment relates to a two-step manufacturing process for a sub-assembly of an electrochemical generator from an electrolytic component of the present invention.

The first step consists of coating in air at least one porous composite electrode comprising a low-swelling polymer matrix acting as a hant. This swollen electrode is then easy to dry and not very hygroscopic so as to simplify this step of assembling the generator.

The second step consists in spreading under anhydrous condition on the porous composite electrode previously dried, a liquid aprotic solution comprising, a crosslinkable or non-crosslinkable polyether, swellable with one or more aprotic organic solvents containing at least one alkaline salt. If necessary, a volatile organic solvent is added to facilitate implementation. At least one crosslinking additive chosen from trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, glycerol triacrylate, glycerol trimethacrylate, pentaerythiol tetraacrylate, glycerol propoxylate (1PO / OH) triacrylate, dipentaerythiol penta / hexaacrylate and di (trimethylolpropane) tetraacrylate can also be added. The aprotic solution thus fills the porosity in whole or in part of the composite electrode and constitutes on the surface of the latter the separator in whole or in part.

The polyether-based matrix of the subassembly thus obtained can be crosslinked thermally, by UV irradiation or electron beam (EB). Realization 8

This embodiment relates to a method of assembling a generator, incorporating an electrolytic component of the present invention, by joining together by rolling or pressing two subassemblies as described in embodiment 7, ie a subassembly anodic and a cathodic. In the case where the porosity of one or of the two sub-assemblies is only partially filled, said porosity is filled after said joining by impregnating with a liquid electrolyte.

Embodiment 9 This embodiment is identical to that of embodiment 8 except that the cathode is a porous electrode or a cathode as described in embodiment 1.

Realization 10

This embodiment is identical to that of embodiment 7 with the exception that an electrolytic separator based on polyether less than 10 μm thick containing a solid reinforcing charge is inserted between the two sub-assemblies at the time of said joining .

EXAMPLES

All the examples included in this patent were carried out in the laboratory. The laboratory means which are used are only to illustrate the present invention and are in no way limiting to the present invention. By way of example, the use of a separator obtained initially in a dry form and then swollen by soaking in a salt solution of the aprotic solvent during the assembly of the generator, only constitutes a simplified process for the needs. laboratory and is not necessarily an interesting technological process. Example 1: We show in the first example that the use of a separator based on gelled polyether does not limit the power, that is to say the discharge or load capacity of the generator in comparison with a generator. equivalent, the separator of which consists of an hbre liquid solvent included in the pores of an inert porous separator. This comparison obtained by using a crosslinked separator so as to limit the rate of solvent despite the use of a polyether matrix very compatible with the solvent, makes it possible to optimize the mechanical strength of the polymer matrix and to optimize its thinness.

The present example relates to an electio-chemical generator comprising an electrolytic component as described in embodiment 1 with the exception that the separator is shaped as described in embodiment 6 to facilitate carrying out the example in the laboratory.

All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. A solution A is obtained by dissolving hthium hexafluorophosphate in glycerol tri [poly (oxyethylene) (oxypropylene)] triacrylate whose molar mass is 8000 so as to give an oxygen to lithium molar ratio (O / Li) from 30/1. A solution B is obtained by dissolving lithium hexafluorophosphate in commercial polyoxyethylene glycol dimethacrylate whose molecular mass is 200 (available from Polyscience, USA) so as to give an oxygen to lithium molar ratio (O / Li) from 30/1. A solution C is obtained by mixing a proportion of each of solutions A and B. The proportion of solution A and B is adjusted so as to obtain in solution C a volume proportion of polymer of solution A of 70% and 30% solution B polymer. 1% by weight (weight of polymers) of Irgacure-651 photoinitiator (Ciba Geigy) is added.

Solution C is spread in the form of a film 15 μ thick and crosslinked by UV irradiation.

An electro-chemical generator is manufactured using a negative electrode which contains graphite in a mass fraction of 90% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 10%. The so-called negative electrode has a capacity of 3.56 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on a copper current collector 16 μm thick so as to give a film 56 μm thick. The separator consists of a polymer membrane as described in the previous paragraph (polymer membrane with a thickness of 15 μm containing hthium hexafluorophosphate in a molar ratio O / Li = 30). The positive electrode contains a mixture of cobalt oxide (LiCoθ2) in a mass fraction of 91.6%, Shawinigan carbon black in a mass fraction of 2.7% and a polymer, vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 5.7%. Said positive electrode has a

2 capacity of 4.08 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on an aluminum current collector 8 μm thick so as to give a film 49 μm thick. At the time of assembly of the electio-chemical generator, the separator is immersed for 30 minutes in the mixture of ethyl methyl carbonate solvent plus ethylene carbonate (in a 1: 1 molar ratio) containing hthium hexafluorophosphate at a concentration of 1 molar (available from Tomyama) then the cathode and the anode are immersed for 10 minutes in a solution of the mixture of ethyl methyl carbonate solvent plus ethylene carbonate (in a 1: 1 molar ratio) containing lithium hexafluorophosphate at concentration of 1 molar (available from Tomyama). The vinyldiene fluoride co-hexafluoro propene copolymer has a much lower affinity for the aprotic solvent than that of polyether for this same aprotic solvent. The solvent is therefore distributed unevenly between the polyether matrix and the vinyldiene fluoride co-hexafluoro propene matrix. However in the composite electrodes the aprotic solvent also comes to fill the porosity of the electrodes in addition to gelling the copolymer of vinyldiene fluoride co-hexafluoro propene. So after immersion the solvent occupies 42% of the volume of the separator, 51% of the volume of the cathode and 45% of the volume of the anode. The electiochemical generator is then quickly assembled by light pressing at 25 ° C of the negative electrode of the separator and the positive electrode and put in a sealed bag. The cycling results at 25 ° C, shown in Figure 2, show normal cycling of the generator in terms of capacity and efficiency (defined as the ratio of a discharge to the subsequent charge) over more than 130 deep discharge cycles obtained at a constant discharge current Id of

0.14 mA / cm 2 and a charging current of 0.11 mA / cm 2, between voltage limits of 4.1 V and 2.7 V which corresponds to a discharge in C / 6 and a charge in C / 8. After 130 cycles of deep discharge the loss of capacity is 14% which is comparable to a Sony battery

Lithium-Ion. After cycle # 2 and cycle # 90 the discharge current was increased for three consecutive cycles, corresponding to discharge rates in C / 3, C / 2 and C / l, the results are presented below:

% of capacity obtained

Discharge rate after 2 cycles after 90 cycles

C / 3 97% 99%

C / 2 95% 95% C / l 82% 75%

These results clearly demonstrate that the use of a gel electrolyte containing a low level of aprotic solvent, close to

40% by volume, is not limiting to ion transport in the generator. These results are similar to those obtained from an equivalent generator (similar composite electrodes) using a liquid electrolyte impregnated in a porous separator of the Celgard type containing a volume proportion of solvent of 40%.

Example 2:

The present example relates to an electiochemical generator comprising an electrolytic component as described in embodiment 3 with the exception that the separator is shaped as described in embodiment 6. to facilitate carrying out the example in the laboratory.

All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. A solution A is obtained by dissolving lithium hexafluorophosphate in glycerol tri (poly (oxyethylene) (oxypropylene)) triacrylate whose molar mass is 8000 so as to give a molar oxygen to hthium ratio

(O / Li) from 30/1. A solution B is obtained by dissolving hthium hexafluorophosphate in commercial polyoxyethylene glycol diacrylate whose molecular mass is 200 (available from Polyscience, USA) so as to give an oxygen / lithium (O / Li) molar ratio of 30/1. A solution C is obtained by mixing a proportion of each of solutions A and B. The proportion of solutions A and B is adjusted so as to obtain in solution C a volume proportion of polymer of solution A of 70% and 30% solution B polymer.

Solution C is spread in the form of a film 15 μm thick and crosslinked by irradiation with an electron beam, EB, with a dose of 5 Mrad. An electiochemical generator is manufactured using a negative electrode which contains graphite in a mass fraction of 89% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 11%. Said positive electrode has a capacity of 1.90 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on a copper current collector 16 μm thick so as to give a film 30 μm thick. The separator consists of a polymer membrane as described in the previous paragraph (polymer membrane with a thickness of 15 μm containing hthium hexafluorophosphate in a molar ratio O / Li = 30). The positive electrode contains a mixture of iron phosphate (LiFePO4) in a mass fraction of 86.1%, Shawinigan carbon black in a mass fraction of 5.8% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 8.1%. Said positive electrode has a

2 capacity of 2.18 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on an aluminum current collector 8 μm thick so as to give a film 42 μm thick. When the electiochemical generator is assembled, the separator is immersed for 30 minutes in the mixture of ethyl methyl carbonate solvent plus ethylene carbonate (in a 1: 1 molar ratio) containing lithium hexafluorophosphate at a concentration of 1 molar (available from Tomyama). Following immersion, the solvent occupies 42% of the volume of the separator. A solution D containing in a volume fraction of 50% the mixture of ethyl methyl carbonate solvent plus ethylene carbonate (in a molar ratio 1: 1) and hthium hexafluorophosphate at a concentration of 1 molar (available from Tomyama) and in a volume fraction of 50% the glycerol-tri polymer [poly (oxyethylene) (oxypropylene)] triacrylate, is spread over the anode and the cathode so as to fill the porosity of these two electrodes without leaving excess on the surface of the electrodes. After being soaked by over-spreading, the negative electrode and the positive electrode are irradiated by electron beam, EB, at a dose of 5 Mrad so as to crosslink the glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate polymer. . The copolymer of vinyldiene fluoride co-hexafluoro propene has a much lower affinity for the aprotic solvent than that of polyethers for this same aprotic solvent. The solvent is therefore distributed unevenly between the polyether matrices and the vinyldiene fluoride co-hexafluoro propene matrix. In addition, the polyether matrix used to fill the porosity of the composite electrodes contains more aprotic solvent than the polyether matrix used as a separator. The electiochemical generator is then quickly assembled by light pressing at 25 ° C of the negative electrode of the separator and the positive electrode and put in a sealed bag.

After forty seven deep discharge cycles obtained at a current

2 of constant discharge Id of 0.09 mA / cm and a charging current of 0.08 2 mA / cm, between voltage limits of 4.1 V and 2.7 V we always obtain more than 70% of the capacity.

Example 3:

The present example relates to an electiochemical generator comprising an electrolytic component as described in embodiment 4 with the exception that the separator is shaped as described in embodiment 6. to facilitate carrying out the example in the laboratory.

All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. A solution A is obtained by dissolving bis (trifluoromethanesulfonimide) of hthium in glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate whose molar mass is 8000 so as to give a molar ratio oxygen to hthium (O / Li) of 30/1. A solution B is obtained by adding trimethylolpropane triacrylate (available from Polyscience, USA) to solution A so as to obtain a volume proportion of 85% solution A polymer and 15% trimethylolpropane triacrylates.

Solution B is spread in the form of a film 15 μm thick and crosslinked by irradiation with an electron beam, EB, with a dose of 5 Mrad.

An electiochemical generator is made using a negative electrode which contains graphite in a mass fraction of 90%, a polymer glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate in a mass fraction of 10% and a mixture of solvent ethyl methyl carbonate plus ethylene carbonate (in a 1: 1 molar ratio) containing bis (1rifluoromethanesulfonimide) of hthium at a concentration of 1 molar (available from Tomyama) in a volume fraction of 20% of the electrode. The so-called negative electrode

2 has a capacity of 3.48 Coulomb / cm. The electrode is obtained by coating in solvent phase (methoxyethane) on a copper current collector 16 μm thick so as to give a film 55 μm thick. The separator consists of a polymer membrane as described in the previous paragraph (polymer membrane with a thickness of 15 μm containing bis (tiifluoromethanesulfonimide) of hthium in a molar ratio O / Li = 30). The positive electrode contains a mixture of iron phosphate (LiFePθ4) in a mass fraction of 80.6%, Shawinigan carbon black in a mass fraction of 5.4% and a polymer glycerol tri [poly (oxyethylene) (oxypropylene )] triacrylate in a mass fraction of 15% and a mixture of ethyl methyl carbonate solvent plus ethylene carbonate (in a 1: 1 molar ratio) containing lithium bis (trifluoromethanesulfonimide) at a concentration of 1 molar (available from Tomyama ) in a volume fraction of 20% of the electrode. Said positive electrode has a capacity of 3.98 Coulomb / cm. The electrode is obtained by coating in solvent phase (methoxyethane) on an aluminum current collector 8 μm thick so as to give a film 49 μm thick. At the time of assembly of the electiochemical generator, the separator is immersed for 30 minutes in the mixture of solvent ethyl methyl carbonate plus ethylene carbonate (in a molar ratio 1: 1) containing the bis (trMuoromethanesulfonimide) of hthium at a concentration of 1 molar (available from Tomyama). Following immersion, the solvent occupies 42% of the volume of the separator. Depending on the different crosslinking rates between the polyether matrix of the separator and the polyether matrices in the composite electrodes, the aprotic solvent is distributed unevenly between the polyether matrices. The electiochemical generator is then quickly assembled by light pressing at 25 ° C of the negative electrode, the separator and the positive electrode and put in a sealed bag. After thirty three deep discharge cycles obtained at a constant discharge current Id of 0.15 mA / cm 2 and a charge current of 0.12 mA / cm 2, between voltage limits of 4.1 V and 2.7 V we always obtain more than 80 % of capacity.

Example 4:

This example concerns the evaluation of the mechanical properties of the gels used as a separator. The mechanical property measurement is reahsed by an evaluation of the degree of penetration of a hemispherical point in the separator. The measurement is carried out using a hemispherical point 7 mm in diameter and a load of 240 g at

25 or 60 ° C on dry and gelled membranes of 60 ± 3 μm. All the membranes are crosslinked by UV.

Membrane # 1) glycerol-tri [poly (oxyethylene) (oxypropylene)] dry triacrylate (8000):

- 25 ° C

- 0% solvent - 13% penetration

Membrane # 2) glycerol-tri [poly (oxyethylene) (oxypropylene)] dry triacrylate (8000):

- 60 ° C

- 0% solvent - 24% penetration

- 25 ° C

- 63% by volume of tetiaethyl sulfonamide - 37% of penetration Membrane # 4) glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate (8000) + polyoxyethylene glycol dimethacrylate in a volume fraction of 70% and 30% respectively: - 25 ° C

- 42% by volume of tetraethyl sulfonamide

- 25% penetration

Membrane # 5) glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate (8000) + trimethylolpropane triacrylate in a volume fraction of 70% and 30% respectively: - 25 ° C

- 39% by volume of tetraethyl sulfonamide

- 23% penetration This example clearly demonstrates that gel membranes containing a volume proportion of aprotic solvent around 40% have mechanical properties at 25 ° C which are comparable to those of a membrane without solvent used at 60 ° C in a generator with a dry electrolytic component. Example 5:

The present example relates to an electiochemical generator comprising an electrolytic component such as described in reahsation 3 with the exception that the separator is shaped as described in reahsation 6 to facilitate the reahsation of the example in the laboratory.

All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. A solution A is obtained by dissolving hthium hexafluorophosphate in glycerol tri [poly (oxyethylene) (oxypropylene)] triacrylate whose molar mass is 8000 so as to give a molar ratio oxygen to hthium (O / Li) from 30/1. A solution B is obtained by the addition in solution A of trimethylolpropane triacrylate (available from Polyscience, USA) so as to obtain a volume proportion of polymer of solution A of 85% and of trimethylolpropane triacrylate of 15%. Solution B is spread in the form of a film 15 μm thick and crosslinked by irradiation with an electron beam, EB, with a dose of 5 Mrad.

An electro-chemical generator is manufactured using a negative electrode which contains graphite in a mass fraction of 90% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 10%. Said positive electrode has a capacity of 3.54 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on a copper current collector 16 μm thick so as to give a film 56 μm thick. The separator consists of a polymer membrane as described in the previous paragraph (polymer membrane with a thickness of 15 μm containing lithium hexafluorophosphate in a molar ratio O / Li = 30). The positive electrode contains a mixture of cobalt oxide, (LiCoθ2) in a mass fraction of 91.6%, Shawinigan carbon black in a mass fraction of 2.7% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 5.7%. Said positive electrode has a

2 capacity of 4.06 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on an aluminum current collector 8 μm thick so as to give a film 49 μm thick. When the electiochemical generator is assembled, the separator is immersed for 30 minutes in the mixture of ethyl methyl carbonate plus ethylene carbonate solvent (in a 1: 1 molar ratio) containing hthium hexafluorophosphate at a concentration of 1 molar (available from Tomyama). Following immersion, the solvent occupies 41% of the volume of the separator. The cathode and the anode are soaked, so as to fill their porosity, with a solution C, said solution C containing in a volume fraction of 50% the mixture of solvent ethyl methyl carbonate plus ethylene carbonate (in a molar ratio 1: 1) and lithium hexafluorophosphate at a concentration of 1 molar (available from Tomyama) and in a volume fraction of 50% the glycerol-tri polymer [poly (oxyethylene) (oxypropylene)] triacrylate. After being soaked, the negative electrode and the positive electrode are irradiated by electron beam, EB, at a dose of 5 Mrad so as to crosslink the glycerol polymer. tii [poly (oxyethylene) (oxypropylene)] triacrylate. The copolymer of vinyldiene fluoride co-hexafluoro propene has a much lower affinity for the aprotic solvent than that of polyethers for this same aprotic solvent. The solvent is therefore distributed unevenly between the polyether matrices and the vinyldiene fluoride co-hexafluoro propene matrix. In addition, the polyether matrix used to fill the porosity of the composite electrodes contains more aprotic solvent than the polyether matrix used as a separator. The electio-climatic generator is then quickly assembled by light pressing at 25 ° C of the negative electrode of the separator and the positive electrode and put in a sealed bag.

After twenty eight deep discharge cycles obtained at a constant discharge current Id of 0.15 mA / cm and a charge current of 0.12

2 mA / cm, between voltage limits of 4.1 V and 2.7 V we always obtain more than 80% of the capacity.

Example 6: The present example relates to an electiochemical generator comprising an electrolytic component as described in embodiment 3 using a manufacturing process as described in embodiment 7 with the exception that the composite electrodes are prepared under an inert atmosphere.

All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. Solution A is obtained by mixing ethyl methyl carbonate solvent plus ethylene carbonate (in a 1: 1 molar ratio) plus hthium hexafluorophosphate at a concentration of 1 molar (solvent available from Tomyama) in a volume fraction of 50 %. with the glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate polymer in a volume fraction of 50%. An electiochemical generator is manufactured using a negative electrode which contains graphite in a mass fraction of 89% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 11%. The so-called negative electrode

2 has a capacity of 1.90 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on a copper current collector 16 μm thick so as to give a film of 30 μm. thick. The positive electrode contains a mixture of iron phosphate (LiFePθ4) in a mass fraction of 86.1%, Shawinigan carbon black in a mass fraction of 5.8% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 8.1%. Said positive electrode has a capacity of

2 2.12 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on an aluminum current collector 8 μm thick so as to give a film 42 μm thick. Said solution A is spread over the anode and on the cathode so as to fill the porosity of these two electrodes and to leave in excess between 5 and 10 μm of solution A on the surface of the electrodes so as to form a portion of the separator . Immediately after the over-spreading, the negative electrode and the positive electrode are irradiated by electron beam, EB, at a dose of 5 Mrad so as to crosslink the glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate polymer. The aprotic solvent is distributed unevenly between the polyether matrix and the vinyldiene fluoride co-hexafluoro propene matrix. The electiochemical generator is then quickly assembled by light pressing at 25 ° C of the negative electrode and the positive electrode and put in a sealed bag. After thirty eight deep discharge cycles obtained at a constant discharge current Id of 0.09 mA / cm and a current of

2 load of 0.08 mA / cm, between voltage limits of 4.1 V and 2.7 V we always obtain more than 70% of the capacity.

Example 7: The present example relates to an electiochemical generator comprising an electrolytic component as described in preferred embodiments 1 and 4 with the exception that the separator is shaped in the manner described in reahsation 6 to facilitate the realization of the example in the laboratory. All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. A solution A is obtained by dissolving hthium hexafluorophosphate in glycerol tri [poly (oxyethylene) (oxypropylene)] triacrylate whose molar mass is 8000 so as to give a molar ratio oxygen to hthium (O / Li) from 30/1. A solution B is obtained by the addition in solution A of trimethylolpropane triacrylate (available from Polyscience, USA) of so as to obtain a volume proportion of polymer of solution A of 85% and of trimethylolpropane triacrylates of 15%.

An electiochemical generator is made using a negative electrode which contains graphite in a mass fraction of 90%, a polymer glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate in a mass fraction of 10% and a mixture of solvent ethyl methyl carbonate plus ethylene carbonate (in a 1: 1 molar ratio) containing hthium hexafluorophosphate at a concentration of 1 molar (available from Tomyama) in a volume fraction of 20% of the electrode. The so-called negative electrode

2 has a capacity of 3.48 Coulomb / cm. The electrode is obtained by coating in solvent phase (methoxyethane) on a copper current collector 16 μm thick so as to give a film 55 μm thick. The separator consists of a polymer membrane as described in the previous paragraph (polymer membrane with a thickness of 15 μm containing hthium hexafluorophosphate in a molar ratio O / Li = 30). The positive electrode contains a mixture of cobalt oxide, (LiCoθ2) in a mass fraction of 91.6%, Shawinigan carbon black in a mass fraction of 2.7% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 5.7%. Said positive electrode has a capacity of 4.05 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on an aluminum current collector 8 μm thick so as to give a film 48 μm thick. At the time of assembly of the electiochemical generator, the separator is immersed for 30 minutes in the mixture of ethyl methyl carbonate solvent plus ethylene carbonate (in a molar ratio 1: 1) containing hthium hexafluorophosphate at a concentration of 1 molar (available from Tomyama) and the cathode is immersed for 10 minutes in a solution of the mixture of ethyl methyl carbonate solvent plus ethylene carbonate (in a 1: 1 molar ratio) containing lithium hexafluorophosphate at a concentration of 1 molar (available at Tomyama). Following immersion, the solvent occupies 44% of the volume of the separator and 51% of the volume of the cathode. The copolymer of vinyldiene fluoride co-hexafluoro propene has a much lower affinity for the aprotic solvent than that of polyethers for this same aprotic solvent. The solvent is distributed unevenly between the polyether matrix in the anode, the polyether matrix of the separator and the vinyldiene fluoride matrix co-hexafluoro propene. The electiochemical generator is then quickly assembled by light pressing at 25 ° C of the negative electrode of the separator and the positive electrode and put in a sealed bag. After forty three deep discharge cycles obtained at a current

2 of constant discharge Id of 0.15 mA / cm and a charging current of 0.12

Example 8: The present example relates to an electio-climatic generator comprising an electrolytic component as described in reahsation 3 using a manufacturing process as described in reahsation 10 except that the composite electrodes are prepared under an inert atmosphere. All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. A solution A is obtained by dissolving hthium hexafluorophosphate in glycerol tri [poly (oxyethylene) (oxypropylene)] triacrylate whose molar mass is 8000 so as to give a molar ratio oxygen to hthium (O / Li) from 30/1. A solution B is obtained by adding to solution A, hthium aluminate in a volume fraction of 10% versus the glycerol-tri polymer [poly (oxyethylene) (oxypropylene)] triacrylate plus a diluent dimethoxyetane in a fraction 50% volume.

Solution B is spread in the form of a film 8 μm thick and, after evaporation of the diluent, crosslinked by irradiation with electron beam, EB, with a dose of 5 Mrad so as to obtain a charged separator.

Solution C is obtained by mixing ethyl methyl carbonate solvent plus ethylene carbonate (in a 1: 1 molar ratio) plus lithium hexafluorophosphate at a concentration of 1 molar (solvent available from Tomyama) in a fraction volume of 50% with the glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate polymer in a volume fraction of 50%.

An electro-chemical generator is manufactured using a negative electrode which contains graphite in a mass fraction of 90% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 10%. The so-called positive electrode

2 has a capacity of 3.52 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on a copper current collector 16 μm thick so as to give a film 56 μm thick. The positive electrode contains a mixture of cobalt oxide,

(L1C0O2) in a mass fraction of 91.6%, carbon black of

Shawinigan in a mass fraction of 2.7% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 5.7%. Said positive electrode has a capacity of

2 4.11 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on an aluminum current collector 8 μm thick so as to give a film 49 μm thick. Said solution C is spread on the anode and on the cathode so as to fill the porosity of these two electrodes and to leave in excess between 2 and 5 μm of solution C on the surface of the electrodes so as to form a portion of the separator . Immediately after over-spreading the negative electrode and the positive electrode are irradiated with an electron beam, EB, at a dose of 5 Mrad so as to crosslink the glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate polymer. The aprotic solvent is distributed unevenly between the polyether matrices in the composite electrodes, the polyether matrix loaded with hthium uminate forming a portion of the separator and the vinyldiene fluoride co-hexafluoro propene matrix. The electiochemical generator is then quickly assembled by light pressing at 25 ° C of the negative electrode, the charged separator as described above and the positive electrode and put in a sealed bag. After fifty two deep discharge cycles obtained at a constant discharge current

Id of 0.15 mA / cm 2 and a load current of 0.12 mA / cm 2, with voltage limits of 4.1 V and 2.7 V we always obtain more than 80% of the capacity. Example 9:

The present example relates to an electiochemical generator comprising an electrolytic component as described in embodiment 1 with the exception that the separator is shaped as described in embodiment 6 to facilitate the rehsation of the example in the laboratory.

All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. Solution A is obtained by adding 4.4 g of hthium terafluoroborate to 21.2 g of glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate whose molar mass is 8000 so as to give a molar ratio of oxygen to hthium (O / Li) from 30/1. A solution B is obtained by adding 11.3 g of lithium tetrafluoroborate in 52.1 g of commercial polyoxyethylene glycol dimethacrylate whose molecular mass is 200 (available from Polyscience) so as to give a molar ratio of oxygen to hthium ( O / Li) of 30/1. A solution C is obtained by mixing a proportion of each of solutions A and B. The proportion of solutions A and B is adjusted so as to obtain in solution C a volume proportion of polymer of solution A of 70% and 30% solution B polymer. 1% by weight is added

(polymer weights) of photoinitiator Irgacure-651 (Ciba Geigy).

Solution C is spread in the form of a film 20 μm thick and crosslinked by UV irradiation for 2 min. to one

2 power of 14.6 mW / cm (UVA). An electiochemical generator is manufactured using a negative metallic μhthium electrode 30 μm thick, laminated on an 8 μm nickel current collector. The separator consists of a polymer membrane as described in the previous paragraph (polymer membrane with a thickness of 20 μm containing lithium tetrafluoroborate in a molar ratio O / Li = 30).

The positive electrode contains a mixture of cobalt oxide (LiCoθ2) in a mass fraction of 91.6%, carbon black of

2 4.07 Coulomb / cm. The electrode is obtained by phase coating solvent (acetone) on an aluminum current collector 8 μm thick so as to give a film 49 μm thick. When the electiochemical generator is assembled, the separator is immersed for 30 minutes in the mixture of solvent propylene carbonate plus ethylene carbonate (in volume proportions of 60% and 40% respectively) and the cathode is immersed in 10 minutes a solution of the mixture of solvents propylene carbonate plus ethylene carbonate (in volume proportions of 60% and 40% respectively) containing hthium tetrafluoroborate at a concentration of 0.31 mol / Kg. The vinyldiene fluoride co-hexafluoro propene copolymer has a much lower affinity for the aprotic solvent than that of polyether for this same aprotic solvent. The solvent is therefore distributed unevenly between the polyether matrix and the vinyldiene fluoride co-hexafluoro propene matrix. However in the composite electrode the aprotic solvent also comes to fill the porosity of the electrode in addition to gelling the copolymer of vinyldiene fluoride co-hexafluoro propene. So after immersion the solvent occupies 41% of the volume of the separator and 61% of the volume of the cathode. The electiochemical generator is then quickly assembled by light pressing at 25 ° C of the negative electrode of the separator and the positive electrode and put in a sealed bag. After fifty deep discharge cycles obtained at a constant discharge current Id of 0.13 mA / cm and a charge current of 0.13 mA / cm, between voltage limits of 4.2 V and 2.5 V we always obtain more than 50% of the capacity.

Example 10: The present example relates to an electiochemical generator comprising an electrolytic component as described in reahsation 1 except that the separator is shaped as described in reahsation 6 to facilitate the reahsation of the example in laboratory.

All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. Solution A is obtained by adding 4.4 g of hthium tetrafluoroborate to 21.2 g of glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate whose molar mass is 8000 so as to give a molar ratio of oxygen to hthium (O / Li) from 30/1. A solution B is obtained by adding 11.3 g of hthium tetrafluoroborate in 52.1 g of commercial polyoxyethylene glycol dimethacrylate whose molecular mass is 200 (available from Polyscience, USA) so as to give an oxygen to lithium molar ratio ( O / Li) of 30/1. A solution C is obtained by mixing a proportion of each of solutions A and B. The proportions of solutions A and B are adjusted so as to obtain in solution C a volume proportion of polymer of solution A of 70% and 30% solution B polymer. 1% by weight (polymer weight) of Irgacure-651 (S) photoinitiator (Ciba Geigy) is added.

Solution C is spread in the form of a film 20 μm thick and crosslinked by UV irradiation for 2 min, at a

2 power of 14.6 mW / cm (UVA).

An electiochemical generator is manufactured using a negative metal μhium electrode 30 μm thick, laminated on an 8 μm nickel current collector. The separator consists of a polymer membrane as described in the previous paragraph

(20 μm thick polymer membrane containing hthium tetrafluoroborate in a O / Li molar ratio = 30). The positive electrode contains a mixture of cobalt oxide, (LiCoθ2), in a mass fraction of 91.6%, of carbon black of

Shawinigan in a mass fraction of 2.7% and a polymer vinyldiene-co-hexafluoropropene fluoride, in a mass fraction of 5.7%. Said positive electrode has a capacity of 2 4.07 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on an aluminum current collector 8 μm thick so as to give a film 49 μm thick. When assembling the electiochemical generator the separator is immersed

30 minutes in the tetraethyl sulfonamide solvent and the cathode is immersed for 10 minutes in a tetraethyl sulfonamide solution containing hthium tetrafluoroborate at a concentration of 0.31 mol / Kg. The vinyldiene fluoride co-hexafluoro propene copolymer has a much lower affinity for the aprotic solvent than that of polyether for this same aprotic solvent. The solvent is therefore distributed unevenly between the polyether matrix and the vinyldiene fluoride co-hexafluoro propene matrix. However in the composite electrode the aprotic solvent also comes to fill the porosity of the electrode in addition to gelling the copolymer of vinyldiene fluoride co-hexafluoro propene. So following immersion, tetraethyl sulfonamide occupies 36% of the volume of the separator and 61% of the volume of the cathode. The electiochemical generator is then quickly assembled by light pressing at 25 ° C of the negative electrode of the separator and the positive electrode and put in a sealed bag.

After eleven deep discharge cycles obtained at a current of

2 constant discharge Id of 13 μA / cm and a charging current of 13 μ 2 A / cm, between voltage limits of 4.2 V and 2.5 V we always obtain more than 61% of the capacity.

Example 11:

The present example relates to an electrochemical generator comprising an electrolytic component as described in reahsation 1 with the exception that the separator is shaped as described in reahsation 6 to facilitate carrying out the example in the laboratory.

All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. A solution A is obtained by dissolving lithium tetrafluoroborate in glycerol tri [poly (oxyethylene) (oxypropylene)] triacrylate whose molar mass is 8000 so as to give a molar oxygen to hthium ratio (O / Li) of 30/1. A solution B is obtained by the addition in the solution A of trimethylolpropane triacrylate (available from Polyscience, USA) so as to obtain a volume proportion of polymer of solution A of 85% and of trimethylolpropane triacrylates of 15%.

Solution B is spread in the form of a film 15 μm thick and crosslinked by irradiation with an electron beam, EB, with a dose of 5 Mrad. An electiochemical generator is made using a negative metallic hthium electrode 27 μm thick, laminated on an 8 μ nickel current collector. The separator consists of a polymer membrane as described in the previous paragraph (polymer membrane with a thickness of 15 μm containing hthium tetrafluoroborate in a molar ratio O / Li = 30). The positive electrode contains a mixture of manganese oxide, (Mnθ2) in a mass fraction of 89.1%, carbon black of

Shawinigan in a mass fraction of 2.6% and a polymer vinyldiene fluoride co-hexafluoro propene, in a mass fraction of 8.3%. Said positive electrode has a capacity of 2 4.10 Coulomb / cm. The electrode is obtained by coating in solvent phase (acetone) on an aluminum current collector 8 μm thick so as to give a film 54 μm thick. When assembling the electiochemical generator, the separator is immersed for 30 minutes in the mixture of γ-butyrolactone plus carbonate solvents (in a 1: 1 molar ratio) containing hthium tetrafluoroborate at a concentration of 1 molar. The vinyldiene fluoride co-hexafluoro propene copolymer has a much lower affinity for the aprotic solvent than that of polyether for this same aprotic solvent. The solvent is therefore distributed unevenly between the polyether matrix and the vinyldiene fluoride co-hexafluoro propene matrix. However in the composite electrode the aprotic solvent also comes to fill the porosity of the electrode in addition to gelling the copolymer of vinyldiene fluoride co-hexafluoro propene. After immersion, the solvent occupies 45% of the volume of the separator. The cathode is soaked, so as to fill its porosity, with a solution C, said solution C containing in a volume fraction of 50% the mixture of solvents γ-butyrolactone plus carbonate (in a molar ratio 1: 1) containing lithium tetrafluoroborate at a concentration of 1 molar and in a volume fraction of 50% the glycerol-tri polymer [poly (oxyethylene) (oxypropylene)] triacrylate. After having been soaked the positive electrode is irradiated by electron beam, EB, at a dose of 5 Mrad so as to crosslink the glycerol-tri polymer [poly (oxyethylene) (oxypropylene)] triacrylate. The electiochemical generator is then quickly assembled by light pressing to

25 ° C of the negative electrode of the separator and the positive electrode and put in a waterproof bag. The generator suffers a single discharge

2 deep at a discharge current, Id, of 0.19 mA / cm ent voltage limits from 3.2 V to 2.0 V. Example 12: The present example relates to an electiochemical generator comprising an electrolytic component as described in reahsation 1 except that the separator is shaped in the manner described in reahsation 6 to facilitate the reahsation of the example in the laboratory.

All the manipulations were carried out in a glove box under an inert and anhydrous atmosphere. 367 g of a terpolymer based on ethylene oxide, methyl glycidyl ether and allyl glycidyl ether and 82 g of bis (trifluoromehanesulfonimide) of lithium are added to 1638 ml of acetonitrile. The concentration of salt and terpolymer is adjusted so as to give a molar oxygen to hthium ratio (O / Li) of 30/1.

To 20.0 ml of this mother solution is added 0.90 ml of a solution obtained by dissolving 4.5 g of bis (trffluoromethanesulfonimide) of hthium in 20.9 g of glycerol-tri [poly (oxyethylene) (oxypropylene)] triacrylate whose mass molar is 8000. The mixture of these two solutions is then stirred at ambient temperature for approximately 12 hours. 2% by weight of benzoyl peroxide is added relative to the weight of polymers and the solution is further stirred for 90 minutes. After having spread it in the form of a 20 μm thick film, the material is heated under an inert atmosphere to 85 ° C. for 24 hours.

An electiochemical generator is manufactured using a negative metallic μhthium electrode 30 μm thick, laminated on an 8 μm nickel current collector. The separator consists of a polymer membrane as described in the previous paragraph (polymer membrane with a thickness of 20 μm containing bis (trifluoromethanesulfonimide) of hthium in a molar ratio O / Li = 30). The positive electrode contains a mixture of titanium sulfide, (TiS2) in a mass fraction of 90.0%, Shawinigan carbon black in a mass fraction of 3.6% and a terpolymer poly (ethylene propylene diene), (EPDM) in a mass fraction of 6.4%. Said positive electrode has a capacity of 1 Coulomb / cm. The electrode is obtained by coating in solvent phase (cyclohexane) on an aluminum current collector 8 μm thick so as to give a film 15 μm thick. When assembling the electiochemical generator, add in the electrolyte of tetraethyl sulfonamide in a tetraethyl sulfonamide / bis (trifluoromethanesulfonimide) molar ratio of 1

(tetraethyl sulfonamide / Li = 1). The electrochemical generator is then quickly assembled by pressing the negative electrode of the separator and the positive electrode at 25 ° C under vacuum. The cycling results at 25 ° C, shown in Figure 3, show normal generator cycling in terms of capacity and efficiency (defined as the ratio of a discharge to subsequent charge) over 500

2 cycles, 100% corresponding to the capacity of 1 Coulomb / cm of the positive. Deep discharge cycles were obtained at a current

2 of constant discharge Id of 23 μA / cm and a charging current of 18 μ A / cm, with voltage limits of 2.7 V and 1.7 V.

Claims

1. Aprotic electrolytic composition for an electiochemical generator, said generator comprising a separator and at least one composite electrode, said composite electrode containing a powder of an active electrode material, and if necessary an electronic conduction additive, said aprotic electrolytic composition being located in the separator and in at least one said composite electrode, characterized in that it comprises a first polymer matrix consisting of a polyether and at least a second polymer matrix, macroscopically separated, and that it also comprises at least one salt alkaline, as well as at least one polar aprotic solvent, said matrices being swellable with at least one said polar aprotic solvent, said solvent or mixture of solvents being distributed unevenly between the matrices.

2. An electrolytic composition according to claim 1 characterized in that the macroscopic separation of the polymer matrices is localized at the interface between the composite electrode and the separator.

3. Electrolytic composition according to claim 1 characterized in that the macroscopic separation of the polymer matrices is localized inside the composite electrode.

4. An electrolytic composition according to claim 1 characterized in that the macroscopic separation of the polymer matrices is located inside the separator.

5. An electrolytic composition according to claim 1 characterized in that the first polymer matrix is included in the separator.

6. An electrolytic composition according to claim 1 characterized in that the distribution of the aprotic solvent throughout the polymer matrices is obtained by controlling the crosslinking rate of each of the matrices.

7. An electrolytic composition according to claim 1 characterized in that the distribution of the aprotic solvent between the polymer matrices is obtained by the introduction of a solid charge in at least one of the polymer matrices.

8. An electrolytic composition according to claim 1 characterized in that the distribution of the aprotic solvent between the polymer matrices is obtained by the choice of the solvent and of its different affinity for the different polymer matrices.

9. An electrolytic composition according to claim 1 characterized in that the distribution of the aprotic solvent between the polymer matrices is obtained by the choice of polymers.

10. An electrolytic composition according to claim 1 characterized in that at least one of the matrices is only slightly swollen by the aprotic solvent.

11. An electrolytic composition according to claim 1 characterized in that the polyether matrix in the separator has a lower swelling rate than that of the polymer matrix included in at least one composite electrode.

12. An electrolytic composition according to claim 1 characterized in that one of the polymer matrices included in at least one composite electrode is only slightly swollen, the porosity of said composite electrode being filled with said polar aprotic solvent.

13. An electrolytic composition according to claim 1 characterized in that the first polyether matrix consists of the mixture of a crosslinkable polyether and at least one other polyether or polyether-based oligomer comprising polyfunctional crosslinkable climatic groups making it possible to obtain a interpenetrating network.

14. An electrolytic composition according to claim 1 characterized in that the first matrix consists of the mixture of a non-crosslinkable polyether and at least one other polyether or ohgomer based on polyether comprising polyfunctional crosslinkable cliimic groups making it possible to obtain a semi-interpenetrating network.

15. An electrolytic composition according to claim 1 characterized in that the first polymer matrix consists of the mixture of a crosslinkable polyether and at least one crosslinking additive.

16. An electrolytic composition according to claim 15 characterized in that the crosslinking additive is chosen from trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, glycerol triacrylate, glycerol trimethacrylate, pentaerythiol tetraacrylate, glycerol propoxylate (1PO / OH) triacrylate, dipentaerythiol penta / hexaacrylate and di (watrimethylacrylate)

17. An electrolytic composition according to claim 1 characterized in that it is obtained by the crosslinking of one of the two polymer matrices in the presence of the other polymer matrix.

18. An electrolytic composition according to claim 1 characterized in that the quality of the interface and the complete adhesion of the polymer matrices is maintained or / and improved by the addition of at least one polymer, ohgomer or monomer comprising chemical groups multidimensional crosslinkable to obtain an interpenetrating network in physical contact with the two matrices.

19. An electrolytic composition according to claim 1 characterized in that the quality of the interface and the adhesion between the polymer matrices is maintained or / and improved by the addition of at least one non-crosslinkable polymer or ohgomer in physical contact with the two matrices and capable of interacting by polar groups with each of the polymer matrices of the electrolytic composition.

20. An electrolytic composition according to claim 1 characterized in that at least a fraction of the anionic groups of an alkaline salt are fixed on at least one of the polymer matrices.

21. An electrolytic composition according to claim 1 characterized in that the first polymer matrix consists of a non-crosslinkable and swellable polyether.

22. An electrolytic composition according to claim 1 characterized in that the first polyether matrix consists of a crosslinkable polyether which serves to limit the rate of swelling.

23. An electrolytic composition according to claim 1 characterized in that the second polymer matrix is chosen from vinyldiene-co-hexafluoropropene fluoride, vinyldiene fluoride, (PVDF), polyacrylonitiile, (PAN), polymethyl methacrylate, ( PMMA), poly (ethylene propylene diene), (EPDM), and a polyether, the latter being chosen so as to absorb a rate of aprotic solvent different from that of the first polymer matrix.

24. An electrolytic composition according to claim 1 characterized in that the polar aprotic solvent (s) are chosen from propylene carbonates, ethylene carbonate, tetrahydrofuran, 2-methyltetiahydrofuran, 1,3-dioxolane, 4, 4-dimethyl-1,3-dioxolane, γ-butyrolactone, butylene carbonate, sulfolane, 3-methylsulfolane, ter-butyl ether, 1,2-dimetoxyethane, 1,2-diethoxyethane, bis (methoxyethyl) ether, 1,2-ethoxymethoxyethane, terbutylmethylether, glymes and sulfonamides of formula: R1R2N-SO2-NR3R4, in which Ri, R2, R3 and R4 are alkyls comprising between 1 and 6 carbons or / and oxyalkyls comprising between 1 and 6 carbon atoms.

25. An electrolytic composition according to claim 1 characterized in that at least one of the polymer matrices serves to coat all or part of the material of the positive electrode.

26. An electrolytic composition according to claim 1 characterized in that at least one of the polymer matrices is used to coat all or part of the negative electrode material.

27. An electiochemical generator comprising a negative electrode and a positive electrode reversible to alkaline ions as well as a polymer electrolyte separator, characterized in that the electrolytic component of the generator is a composition according to one of claims 1 to 26.

28. An electiochemical generator according to claim 27 characterized in that the polymer matrix in contact with the positive electrode material is electiochemically stable in the presence of said positive electrode material.

29. An electio-chemical generator according to claim 27 characterized in that the polymer matrix in contact with the negative electrode is electiochemically compatible with the negative electrode material.

30. An electiochemical generator according to claim 27, the electrolytic component of which comprises at least one lithium salt.

31. An electiochemical generator according to claim 27, the negative electrode of which consists of metallic hthium.

32. An electromagnetic generator according to claim 27, the two electrodes of which are composite electrodes using reversible insertion materials with hthium.

33. An electrochemical generator according to claim 27, the negative electrode of which is a carbon composite.

34. An electro-climatic generator according to claim 27, the negative electrode of which is a carbon composite, the binder of which is a polymer matrix based on polyether.

35. A method of manufacturing in two stages a sub-assembly of an electrochemical generator according to claim 27, comprising a porous composite electrode, and a separator in whole or in part: the first stage consisting in coating in air d '' an electrode support with a mixture containing an electrode material, a polymer and a coating solvent, if necessary, said polymer forming the second polymer matrix of the electrolytic composition as defined in one of claims 1 to 26, said second polymer matrix being little swellable by one or more polar aprotic solvents, and acting as a binder for the electrode material, thus obtaining a porous composite electrode; the second step consisting of spreading under anhydrous condition on the porous composite electrode obtained in the first step, previously dried, a liquid aprotic solution comprising, a polyether-based polymer or prepolymer forming the first polymer matrix of the electrolytic composition as defined in one of claims 1 to 26, crosslinkable thermally, by UV irradiation or electron beam (EB) and chemically swellable with a polar aprotic solvent and, if necessary, one. volatile organic diluent, said liquid aprotic solution comprising at least one alkaline salt, so as to fill the porosity in whole or in part of said electrode with said solution and to form a coating on the surface of said electrode so as to form the separator in whole or in part.

36. A method of manufacturing in two stages a sub-assembly of an electiochemical generator according to claim 35 wherein the polymer forming the second polymer matrix of said electrolytic composition is little swellable by one or more polar aprotic solvents and acts as a hant, and is chosen from fluoride vinyldiene-co-hexafluoropropene, vinyldiene fluoride, (PVDF), polyacrylonitrile, (PAN), polymethyl methacrylate, (PMMA), poly (ethylene propylene diene), (EPDM).

37. A method of manufacturing in three stages a subassembly of an electro-climatic generator according to claim 27, comprising a porous composite electrode, and a separator in whole or in part: the first stage consisting of coating in air with a mixture containing an electrode material, a polymer and a coating solvent, if necessary, said polymer forming the second polymer matrix of the electrolytic composition as defined in one of claims 1 to 26, said second polymer matrix being not very swellable with one or more polar aprotic solvents, and acting as a hant of the electrode material, thus obtaining a porous composite electrode; the second step consisting in spreading, under anhydrous condition, on the porous composite electrode previously dried, a liquid aprotic solution comprising, a polyether-based polymer or prepolymer forming a third polymer matrix of the electrolytic composition as defined in one of the claims 1 to 26, said third matrix being crosslinkable thermally, by UV irradiation or election beam (EB) and chemically swellable with a polar aprotic solvent and if necessary a volatile organic diluent as well as at least one alkaline salt, so as to fill the porosity of said electrode with said solution; the third step consisting in spreading under anhydrous condition on the composite electrode obtained in the second step a liquid aprotic solution comprising, a polyether-based polymer or prepolymer forming the first matrix of the electrolytic composition as defined in one of the claims 1 to 26, said first matrix being crosslinkable thermally, by UV irradiation or electron beam (EB) and chemically swellable with a polar aprotic solvent but whose swelling rate is lower than that of the polyether used to fill the porosity of the composite obtained in the second step, and if necessary a volatile organic diluent as well as at least one alkaline salt, so as to constitute on the surface of said electrode a coating so as to form the separator in whole or in part.

38. A method of manufacturing in three stages a sub-assembly of an electiochemical generator according to claim 37 wherein the polymer forming the second polymer matrix of the electrolytic composition is little swellable by one or more polar aprotic solvents and acts as a hant, and is chosen from vinyldiene-co-hexafluoropropene fluoride, vinyldiene fluoride, (PVDF), polyacrylonitrile, (PAN), polymethyl methacrylate, (PMMA), poly (ethylene propylene diene), (EPDM).

39. A method of manufacturing in two stages a sub-assembly, an electiochemical generator according to claim 27, comprising a composite electrode and a separator in whole or in part: the first stage consisting of coating in anhydrous condition d '' an electrode support with a mixture containing an electrode material, a polyether-based polymer or prepolymer, at least one polar aprotic solvent, at least one alkaline salt, and a coating solvent if necessary, said polymer polyether base forming the second polymer matrix of the electrolytic composition as defined in one of claims 1 to 26, said second matrix being crosslinkable thermally, by UV irradiation or electron beam (EB) and thermally swellable by a polar aprotic solvent; the second step consisting in spreading under anhydrous condition on the composite electrode obtained in the first step a liquid aprotic solution comprising, a polyether-based polymer or prepolymer forming the first polymer matrix of the electrolytic composition as defined in one of the Claims 1 to 26, said first matrix being crosslinkable thermally, by UV irradiation or electron beam (EB) and chemically swellable with a polar aprotic solvent but whose swelling rate is lower than that of the second polyether matrix used in the composite electrode, and if necessary a volatile organic diluent as well as at least one alkaline salt, so as to form a coating on the surface of said electrode so as to form the separator in whole or in part.

40. A method of manufacturing in two stages an anode subset, an electiochemical generator according to claim 39 characterized in that the composite electrode is a carbon anode.

41. A method of manufacturing in two stages a cathode subset, an electiochemical generator according to claim 37 characterized in that the composite electrode is a composite cathode whose electrode material is a transition metal phosphate operating at 3.5 -3.7V.

42. A method of manufacturing in two stages a sub-assembly of an electiochemical generator according to claim 27, comprising a porous composite electrode and a separator in whole or in part: the first stage consisting of coating in air d '' an electrode support with a mixture containing an electrode material, a polymer and a coating solvent, if necessary, said polymer forming the second polymer matrix of the electrolytic composition as defined in one of claims 1 to 26, said second polymer matrix being little swellable by one or more polar aprotic solvents, and acting as a hant of the electrode material, thus obtaining a porous composite electrode; the second step consisting in spreading under anhydrous condition on the porous electrode obtained in the first step, previously dried, a liquid aprotic solution comprising, a polyether chemically swellable with one or more polar aprotic solvents, and a prepolymer, oligomer or monomer crosslinkable thermal, by UV irradiation or electron beam (EB), the polyether, and the prepolymer, ohgomer or monomer forming the first polymer matrix of the electrolytic composition such. as defined in one of claims 1 to 26, and if necessary a volatile organic diluent as well as at least one alkaline salt, so as to fill the porosity in whole or in part of said electrode with said solution and to constitute on the surface of said electrode a coating so as to form the separator in whole or in part.

43. A method of manufacturing in two stages a subassembly according to claim 42 characterized in that the polyether used in said solution is crosslinkable thermally, by UV irradiation or electron beam (EB).

44. A method of assembling an electiochemical generator according to claim 27, by the joining carried out by rolling or pressing, of two subassemblies, an anode and a cathode, manufactured according to claims 35, 36, 39 and 42 .

45. A method of assembling an electiochemical generator according to claim 27, by joining carried out by rolling or pressing, two sub-assemblies, an anode and a cathode, manufactured according to claims 35, 36, and 42, the porosity of one of the subassemblies being only partially filled, said porosity being filled after said joining by impregnating a liquid electrolyte.

46. A method of assembling an electiochemical generator according to claim 27, by joining carried out by rolling or pressing, a porous cathode electrode and an anode subset manufactured according to claims 35, 36, 39 , 40 and 42.

47. A method of assembling an electiochemical generator according to claim 27, by the joining carried out by rolling or pressing, of two subassemblies, an anode and a cathode, manufactured according to claims 35, 36, 39 and 42 between which is inserted at the time of said joining an electiolytic separator based on polyether less than 10 μm thick containing a solid filler.