SOLID ELECTROLYTE FOR AN ELECTROCHEMICAL GENERATOR

Abstract

A compound containing at least one species of formula (I):

##STR00001## where: A.sup.x is an anion of valency x equal to 1 or 2 chosen from sulfonate, sulfonylimide of SO.sub.2N.sup.SO.sub.2C.sub.yF.sub.2y+1 type with y being an integer between 0 and 4; borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulfide, selenate, nitrate and perchlorate anions; C.sup.x+ is a counter-cation of the anion A.sup.x, chosen from a proton H.sup.+ and alkali metal and alkaline-earth metal cations; p is an integer ranging from 1 to 10; E is an organic spacer comprising a linear sequence of at least two covalent bonds; n is an integer greater than or equal to 2; and G represents: (a) a group

##STR00002## or (b) a group

##STR00003## the anion A.sup.x being covalently bonded to the polycyclic group Ar.

Claims

1. A compound comprising at least one species of formula (I): ##STR00042## wherein: A.sup.x is an anion of valency x equal to 1 or 2 chosen from sulfonate, sulfonylimide of SO.sub.2N.sup.SO.sub.2C.sub.yF.sub.2y+1 type with y being an integer between 0 and 4; borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulfide, selenate, nitrate and perchlorate anions; C.sup.x+ is a counter-cation of the anion A.sup.x, chosen from a proton H.sup.+ and alkali metal and alkaline-earth metal cations; p is an integer ranging from 1 to 10, E is an organic spacer comprising a linear sequence of at least two covalent bonds; n is an integer greater than or equal to 2; and G represents: (a) a group ##STR00043## in which: X represents N, P or SiR, with R representing a hydrogen atom or a C.sub.1-4-alkyl group, Ar represents a polycyclic group formed from 2 to 6 rings, at least one of which is aromatic, each ring being, independently of each other, 4- to 6-membered, said polycyclic group possibly including up to 18 heteroatoms. - represents a bond with the spacer E; and - represents one or more bonds with said anions A.sup.x; or (b) a group ##STR00044## in which: X.sub.1 and X.sub.2, which may be identical or different, represent NR, O or S, with R representing a hydrogen atom or a C.sub.1-4-alkyl group; - represents a bond with the spacer E; and - represents one or more bonds with said anions A.sup.x; Ar is as defined previously; said anion(s) A.sup.x being covalently bonded to the polycyclic group Ar.

2. The compound as claimed in claim 1, said compound being a polymer comprising, or even being formed from, monomer units of formula (I) below: ##STR00045## in which G, E, A.sup.x, C.sup.x+ and p are as defined in claim 1.

3. The compound as claimed in claim 1, said compound being a polymer comprising, or even being formed from, monomer units of formula (II): ##STR00046## in which E, Ar, A.sup.x, C.sup.x+ and p are as defined in claim 1.

4. The compound as claimed in claim 1, wherein Ar has one of the following polycyclic backbones: ##STR00047##

5. The compound as claimed in claim 1, wherein Ar is an aromatic bicyclic group.

6. The compound as claimed in claim 1, wherein E is a linear or branched, saturated or unsaturated aliphatic chain, containing at least two double bonds, said chain being optionally interrupted with one or more heteroatoms, with one or more metalloids, and/or with one or more aromatic or nonaromatic, 4- to 6-membered (hetero)cycles; said chain being optionally substituted with one or more fluorine atoms and/or with one or more groups R.sub.1, R.sub.1 representing a group chosen from a hydroxyl group, optionally in protonated form O.sup.C.sup.+; an dNH.sub.2 group and an oxo group.

7. The compound as claimed in claim 1, wherein E represents a saturated linear C.sub.4 to C.sub.20 aliphatic chain, said chain being optionally interrupted with one or more heteroatoms, and/or with one or more aromatic or nonaromatic 4- to 6-membered rings, said chain being optionally substituted with one or more hydroxyl groups.

8. The compound as claimed in claim 1, wherein n is between 2 and 1500.

9. The compound as claimed in claim 1, wherein A.sup.x is a sulfonate anion or a trifluoromethylsulfonylimide anion.

10. The compound as claimed in claim 1, wherein C.sup.x+ is a proton H or the Li.sup.+ cation.

11. The compound as claimed in claim 1, said compound being a polymer comprising, or even being formed from, monomer units of formula (III): ##STR00048## in which E, A.sup.x and C.sup.x+ are as defined in claim 1.

12. (canceled)

13. A solid electrolyte comprising, one or more compounds as claimed in claim 1, in the organized state.

14. The electrolyte as claimed in calim 13, said electrolyte having an ion conductivity at 120 C. of greater than or equal to 10.sup.9 S/cm.

15. The electrolyte as claimed in claim 13, said electrolyte an ion conductivity at 200 C. of greater than or equal to 10.sup.7 S/cm.

16. A process for forming a film comprising a solid electrolyte on the surface of a substrate, comprising (a1) adding a solution comprising at least one compound as claimed in claim 1 in a polar solvent; (b1) depositing said solution from (a1) onto the surface of said substrate; and (c1) evaporating the solvent under conditions suitable for forming a film comprising the solid electrolyte formed from the compound of formula (1) in its organized state.

17. A process for forming a solid electrolyte film, which is self-supported or supported on a substrate, comprising (a2) forming a powder from a compound as claimed in claim 1; (b2) melt-extruding said powder in the form of a solid electrolyte film formed from said compound of formula (I) in its organized state; and (c2) spreading said electrolyte film optionally on the surface of a substrate.

18. The process as claimed in claim 16, wherein said film comprising the solid electrolyte has a thickness of between 5 and 50 m.

19. The process as claimed in claim 16, said process further comprising exposing said film formed to an electric or magnetic field or to ionizing radiation.

20. A composite electrode for an electrochemical system, comprising at least one solid electrolyte as claimed in claim 13.

21. An electrochemical system comprising a solid electrolyte as claimed in claim 13.

22. The electrochemical system as claimed in claim 21, comprising: a solid electrolyte film comprising the solid electrolyte, and at least one composite electrode comprising the solid electrolyte.

23. The system as claimed in claim 21, wherein the system is a battery.

24. The compound as claimed in claim 1, wherein X.sub.1 and X.sub.2 both represent NH or O.

25. The compound as claimed in claim 1, wherein Ar is an aromatic bicyclic group with a naphthalene aromatic backbone.

26. The compound as claimed in claim 1, wherein Ar is a naphthalene group.

27. The compound as claimed in claim 7, wherein said optional heteroatom is an oxygen atom.

28. The compound as claimed in claim 7, wherein said optional aromatic or nonaromatic 4- to 6-membered ring is a benzene ring.

29. The compound as claimed in claim 7, wherein said optional hydroxyl group is in a protonated form O+C+.

30. The process as claimed in claim 17, in which said film comprising the solid electrolyte has a thickness of between 5 and 50 m.

31. The process as claimed in claim 17, said process further comprising exposing said film formed to an electric or magnetic field or to ionizing radiation.

32. The system as claimed in claim 21, said system being a lithium battery.

Description

FIGURES

[0222] FIG. 1: Infrared spectrum of polymer P1 in accordance with the invention formed according to example 1;

[0223] FIG. 2: Infrared spectrum of lithiated polymer P1 in accordance with the invention formed according to example 2;

[0224] FIG. 3: TGA Thermogravimetric analysis diagram obtained for the lithiated polymer powder P1 formed according to example 2;

[0225] FIG. 4: Image obtained with a polarized light microscope of the lithiated polymer P1 in the organized (crystalline) state, prepared according to example 2 on a silicon substrate;

[0226] FIG. 5: XRD diagram obtained for the lithiated polymer P1 in the organized (crystalline) state, prepared according to example 2;

[0227] FIG. 6: Schematic representation of the TLM structure and of the total resistance characteristic as a function of the distance between the contacts;

[0228] FIG. 7: Infrared spectrum of polymer P2 in accordance with the invention formed according to example 4;

[0229] FIG. 8: TGA Thermogravimetric analysis diagram obtained for the polymer powder P2 formed according to example 4;

[0230] FIG. 9: Infrared spectrum of lithiated polymer P2 in accordance with the invention formed according to example 5;

[0231] FIG. 10: image obtained with a polarized light microscope of the lithiated polymer P2 in the organized (crystalline) state, prepared according to example 5 on a copper substrate;

[0232] FIG. 11: XRD diagram obtained for the lithiated polymer P2 in the organized (crystalline) state, prepared according to example 5;

[0233] FIG. 12: Infrared spectrum of polymer P3 in accordance with the invention formed according to example 6;

[0234] FIG. 13: TGA thermogravimetric analysis diagram obtained for the powder of polymer P3 formed according to example 6;

[0235] FIG. 14: Infrared spectrum of polymer P6 in accordance with the invention formed according to example 10;

[0236] FIG. 15: Infrared spectrum of polymer P7 in accordance with the invention formed according to example 11;

[0237] FIG. 16: TGA thermogravimetric analysis diagram obtained for the powder of polymer P7 formed according to example 11;

[0238] FIG. 17: Infrared spectrum of polymer P8 in accordance with the invention formed according to example 12;

[0239] FIG. 18: TGA thermogravimetric analysis diagram obtained for the powder of polymer P8 formed according to example 12;

[0240] FIG. 19: Conductivity of polymer P2 obtained as a function of the temperature, formed according to example 4;

[0241] FIG. 20: Infrared spectrum of Pro-ANTFSA in accordance with the invention formed according to example 13, step 3;

[0242] FIG. 21: Monitoring of the change in pH as a function of the molar amount of LiOH.H.sub.2O for example 13, step 4;

[0243] FIG. 22: Infrared spectrum of polymer P9 in accordance with the invention formed according to example 15;

[0244] FIG. 23: TGA thermogravimetric analysis diagram obtained for the powder of polymer P9 formed according to example 15;

[0245] FIG. 24: Infrared spectrum of polymer P10 in accordance with the invention formed according to example 16;

[0246] FIG. 25: TGA thermogravimetric analysis diagram obtained for the powder of polymer P10 formed according to example 16;

[0247] FIG. 26: Infrared spectrum of polymer P11 in accordance with the invention formed according to example 17;

[0248] FIG. 27: TGA thermogravimetric analysis diagram obtained for the powder of polymer Pll formed according to example 17;

[0249] FIG. 28: Ion conductivity of polymers P2, P7, P9, P10 and P11 obtained as a function of the temperature under the planes of a rheometer.

EXAMPLES

Example 1

Preparation of a Polymer P1 in Accordance with the Invention from Lithium 4-Amino-1-Naphthalenesulfonate and Butadiene Diepoxide

[0250] ##STR00022##

[0251] Synthesis of Lithium 4-amino-1-naphthalenesulfonate (LiAN)

[0252] 1.340 g of 4-amino-l-naphthalenesulfonic acid (HAN) and 0.210 g of lithium hydroxide monohydrate (LiOH.H.sub.2O) are placed in 20 mL of distilled water. The reaction medium is stirred overnight at room temperature. The excess HAN is removed by filtration. The filtrate is then concentrated by evaporating off the solvent under reduced pressure. After washing twice with ethanol, a pink powder is obtained. Monocrystals were obtained by crystallization from water.

[0253] The x-ray diffraction (XRD) analysis shows that the LiAN crystallizes in a monoclinic lattice (lattice parameters: a=12.14 , b=9.67 , c=11.94 and =90, =115.93, =90).

[0254] .sup.1H NMR (400 MHz; DMSO-d6; 300 K): ppm 7.89 (dd, 1H); 7.18 (dd, 1H); 6.83 (d, 1H); 6.52 (m, 2H); 5.68 (d, 1H); 4.96 (s, 2H).

[0255] .sup.13C NMR (400 MHz; DMSO-d6; 300 K): ppm 146.11; 132.34; 130.61; 128.10; 126.45; 125.33; 123.56; 122.94; 122.26; 105.17.

[0256] .sup.7Li NMR (400 MHz; D.sub.2O); ppm 0.157

[0257] Synthesis of the Polymer

##STR00023##

[0258] 2.96 g of LiAN (12.93 mmol) prepared previously, 0.77 mL of butadiene diepoxide BdO (12.93 mmol) and 10 mL of dimethylformamide DMF are placed in a three-necked round-bottomed flask equipped with a condenser and a magnetic bar. The reaction mixture is stirred and heated at 55 C. under an inert atmosphere (flushing with a stream of argon) overnight. The reaction mixture is then heated to 100 C. to complete the polymerization.

[0259] At the end of the reaction, the solvent is evaporated off under reduced pressure, and a stable pale yellow powder is obtained.

[0260] The infrared spectrum of the polymer obtained, denoted as P1, is shown in FIG. 1.

Example 2

Preparation of a Film of Lithiated Polymer P1 in its Organized State Lithiation of Polymer P1

[0261] ##STR00024##

[0262] At the end of the reaction during the synthesis of polymer P1 as described in example 1, 0.82 g of lithium hydride LiH (103.44 mmol), i.e. four equivalents relative to the hydroxyl functions present, are added. The mixture is maintained at 70 C. to about 4 hours. The excess lithiating agent is neutralized by gradual addition of 1 mL of ethanol. The solvent is removed under reduced pressure to give a yellow powder.

[0263] The infrared spectrum of the lithiated polymer P1 obtained is shown in FIG. 2.

[0264] The powder obtained was also characterized by thermogravimetric analysis (TGA) under argon and with a heating rate of 20 C./min. The results of the thermogravimetric analysis are shown in FIG. 3.

[0265] Preparation of a Film of Conductive Polymer in its Organized State

[0266] A solution of the lithiated polymer P1 in methanol at a concentration of 100 mg/mL is prepared.

[0267] Deposition is performed on various substrates (stainless steel, polyimide (Kapton), silicon, glass) covered with a crystallizing dish.

[0268] A film of the conductive polymer in an organized (crystalline) state is obtained overnight.

[0269] This organization is observable by polarized light microscopy.

[0270] FIG. 4 shows, for example, the image obtained by microscopy of the electrolyte film formed on the surface of silicon.

[0271] X-ray diffraction (XRD) analysis (x-ray diffractogram shown in FIG. 5) shows that the polymer in the organized state crystallized in an orthorhombic lattice (lattice parameters: a=6.49 , b=10.01 and c=4.85 ).

Example 3

Measurement of the Ion Conductivity of the Lithiated Polymer P1

[0272] The ion conductivity the lithiated polymer P1 prepared according to example 2 is evaluated by measuring the resistance of the contacts according to the TLM (transmission line method) method.

[0273] Deposits of polymer prepared according to example 2 in an organized (crystalline) state and in amorphous and semicrystalline states, are produced on the device for measuring the TLM ion conductivity.

[0274] FIG. 6 schematically shows the TLM structure and of the total resistance characteristic as a function of the distance between the contacts. The standard method consists in depositing on a rectangular sample several contacts (A, B, C and D) in the form of parallel lines. The distance between the contacts is different so as to create a resistance scale. In the case of a homogeneous material, the resistance produced varies linearly as a function of the distance between two measurement contacts, and it is then possible to extract therefrom the value at the origin which represents the sum of the resistances of the two contacts.

[0275] The ion conductivities obtained for the various deposits are presented in table 1 below, bearing in mind that the electrolyte was not anhydrous.

TABLE-US-00001 TABLE 1 Amorphous Semicrystalline Crystalline Polymer deposit (not compliant) (not compliant) (invention) Conductivity (mS/cm) 3.5 10.sup.2 7.2 10.sup.1 2.1

[0276] The polymer in its crystalline and hydrated organized state shows good ion conductivity. It may advantageously be used as a solid electrolyte in a lithium battery with an electrochemical couple chosen so that the two materials are in the electrochemical stability zone of water.

Example 4

Preparation of a Polymer P2 in Accordance with the Invention from Lithium 4-Amino-1-Naphthalenesulfonate (LiAN) and 1,4-butanediol diglycidyl ether (BDGE)

[0277] ##STR00025##

[0278] Polymer P2 is synthesized according to a protocol similar to that presented in example 1, using 2.38 mL of 1,4-butanediol diglycidyl ether (12.93 mmol) in place of BdO, 2.96 g of LiAN (12.93 mmol) and 10 mL of DMF. The temperature is set at 70 C. at the start of the reaction. An orange-yellow powder is obtained. The glass transition temperature (Tg) is 84 C.

[0279] The infrared spectrum of polymer P2 obtained is shown in FIG. 7.

[0280] The powder obtained was also characterized by thermogravimetric analysis (TGA) under argon and with a heating rate of 20 C./min. The results of the thermogravimetric analysis are shown in FIG. 8.

Example 5

Preparation of a Film of Lithiated Polymer P2 in its Organized State Lithiation of Polymer P2

[0281] ##STR00026##

[0282] The hydroxyl functions of polymer P2 prepared in example 4 are lithiated according to a protocol similar to that of example 2, by adding, at the end of the reaction during the synthesis of polymer P2, 0.82 g of lithium hydride LiH (103.44 mmol), i.e. four equivalents relative to the hydroxyl functions present. The mixture is maintained at 70 C. for about four hours. The excess LiH is neutralized by gradual addition of 1 mL of ethanol. The solvent is removed under reduced pressure to give a yellow powder.

[0283] The infrared spectrum of the lithiated polymer P2 obtained is shown in FIG. 9.

[0284] Preparation of a Film of Conductive Polymer in its Organzied State

[0285] A solution of the lithiated polymer P2 in methanol at a concentration of 100 mg/mL is prepared.

[0286] Deposition is performed on various substrates (stainless steel, polyimide (Kapton), silicon, glass) covered with a crystallizing dish.

[0287] A film of the conductive polymer in an organized (crystalline) state is obtained overnight.

[0288] This organization is observable by polarized light microscopy.

[0289] FIG. 10 shows, for example, the image obtained by microscopy of the electrolyte film formed on the surface of a copper substrate.

[0290] X-ray diffraction (XRD) analysis (x-ray diffractogram shown in FIG. 11) shows that the polymer in the organized state crystallized in an orthorhombic lattice.

Example 6

Preparation of a Polymer P3 in accordance with the Invention from Lithium 4-Amino-1-Naphthalenesulfonate (LiAN) and Resorcinol Diglcidyl Ether (RDGE)

[0291] ##STR00027##

[0292] Polymer P3 is synthesized according to a protocol similar to that presented in example 1, using 2.87 g of resorcinol diglycidyl ether (12.93 mmol) in place of BdO, 2.96 g of LiAN (12.93 mmol) and 10 mL of DMF. The temperature is set at 70 C. at the start of the reaction. An orange-yellow powder is obtained. The glass transition temperature (Tg) is 136 C.

[0293] The infrared spectrum of polymer P3 obtained is shown in FIG. 12.

[0294] The powder obtained was also characterized by thermogravimetric analysis (TGA) under argon and with a heating rate of 20 C./min. The results of the thermogravimetric analysis are shown in FIG. 13.

Example 7

Preparation of a Film of Lithiated Polymer P3 in its Organzied State Lithiation of Polymer P3

[0295] ##STR00028##

[0296] The hydroxyl functions of polymer P3 prepared in example 6 are lithiated according to a protocol similar to that of example 2, adding, at the end of the reaction during the synthesis of polymer P3, 0.82 g of lithium hydride LiH (103.44 mmol), i.e. four equivalents relative to the hydroxyl functions present. The mixture is maintained at 70 C. for about four hours. The excess LiH is neutralized by gradual addition of 1 mL of ethanol. The solvent is removed under reduced pressure to give a yellow powder.

[0297] Preparation of a Film of Conductive Polymer P3 in its Organzied State

[0298] A solution of the lithiated polymer P3 in methanol at a concentration of 100 mg/mL is prepared.

[0299] Deposition is performed on various substrates (stainless steel, polyimide (Kapton), silicon, glass) covered with a crystallizing dish.

[0300] A film of the conductive polymer in an organized (crystalline) state is obtained overnight and can be observed by polarized light microscopy.

Example 8

Preparation of a Polymer P4 in Accordance with the Invention from 4-Amino-1-Naphthalenesulfonic Acid and Butadiene Diepoxide

[0301] ##STR00029##

[0302] 2.89 g of 4-amino-l-naphthalenesulfonic acid HAN (12.93 mmol), 0.77 mL of butadiene diepoxide BdO (12.93 mmol) and 10 mL of dimethylformamide DMF are placed in a three-necked round-bottomed flask equipped with a condenser and a magnetic bar. The reaction mixture is stirred and heated at 55 C. under an inert atmosphere (flushing with a stream of argon) until a homogeneous mixture is obtained. The reaction mixture is then heated to 100 C. to complete the polymerization. At the end of the reaction, the solvent is evaporated off under reduced pressure, and a stable pale yellow powder is obtained.

[0303] Polymer P4 in its organized state may be used as a proton-conducting electrolyte, for example in a proton-exchange-membrane fuel cell (PEMFC) or a low-temperature electrolyzer.

Examle 9

Preparation of a Polymer P5 in Accordance with the Invention from 4-Amino-1-Naphthalenesulfonic Acid and 1,4-Butanediol Diglycidyl Ether (BDGE)

[0304] ##STR00030##

[0305] Polymer P5 is synthesized according to a protocol similar to that of the preceding example 8, using 2.38 mL of 1,4-butanediol diglycidyl ether BDGE (12.93 mmol) in place of BdO, 2.89 g of HAN (12.93 mmol) and 10 mL of DMF. The temperature is set at 70 C. at the start of the reaction. An orange-yellow powder is obtained.

[0306] Polymer P5 in its organized state may be used as a proton-conducting electrolyte.

Example 10

Preparation of a polymer P6 in Accordance with the Invention from 4-Amino Acid and Resorcinol Diglycidyl Ether (RDGE)

[0307] ##STR00031##

[0308] Polymer P6 is synthesized according to a protocol similar to that of the preceding example 8, using 2.87 g of resorcinol diglycidyl ether RDGE (12.93 mmol) in place of BdO, 2.89 g of HAN (12.93 mmol) and 10 mL of DIVIF. The temperature is set at 70 C. at the start of the reaction. An orange-yellow powder is obtained.

[0309] The infrared spectrum of polymer P6 obtained is shown in FIG. 14. The glass transition temperature (Tg) is 37 C.

[0310] Polymer P6 in its organized state may be used as a proton-conducting electrolyte.

Example 11

Preparation of a Polymer P7 in Accordance with the Invention from Lithium 4-Amino-1-Naphthalenesulfonate (LiAN) and poly(dimethylsiloxane) diglycidyl ether (PDMSDGE)

[0311] ##STR00032##

[0312] Polymer P7 is synthesized according to a protocol similar to that presented in example 1, using 11.59 g of poly(dimethylsiloxane) diglycidyl ether (11.83 mmol) in place of BdO, 2.71 g of LiAN (11.83 mmol) and 15 mL of DMF. The temperature is set at 70 C. at the start of the reaction. A brown powder is obtained.

[0313] The infrared spectrum of polymer P7 obtained is shown in FIG. 15.

[0314] The powder obtained was also characterized by thermogravimetric analysis (TGA) under argon and with a heating rate of 20 C./min. The results of the thermogravimetric analysis are shown in FIG. 16.

Example 12

Preparation of a polymer P8 in Accordance with the Invention from 4-Amino-1-Naphthalenesulfonic Acid and poly(dimethylsiloxane) diglycidyl ether (PDMSDGE)

[0315] ##STR00033##

[0316] Polymer P8 is synthesized according to a protocol similar to that of the preceding example 8, using 11.39 g of poly(dimethylsiloxane) diglycidyl ether PDMSDGE (11.62 mmol) in place of BdO, 2.59 g of HAN (11.62 mmol) and 10 mL of DMF. The temperature is set at 70 C. at the start of the reaction. A viscous yellow paste is obtained.

[0317] The infrared spectrum of polymer P8 obtained is shown in FIG. 17.

[0318] The polymer obtained was also characterized by thermogravimetric analysis

[0319] (TGA) under argon and with a heating rate of 20 C./min. The results of the thermogravimetric analysis are shown in FIG. 18. The glass transition temperature (Tg) is 24 C.

[0320] Polymer P8 in its organized state may be used as a proton-conducting electrolyte.

Example 13

Measurement of the Ion Conductivity of the Lithiated Polymer P2

[0321] The ion conductivity of polymer P2 is evaluated by measuring the resistance of two interdigitated gold electrodes (NOVOCONTROL) over a temperature range extending from 100 C. to 215 C.

[0322] Polymer P2 powder is deposited so as to cover the device. To ensure good impregnation, the polymer is maintained at 150 C. for 15 minutes. The images obtained with a polarized light microscope are shown in FIG. 19.

TABLE-US-00002 TABLE 2 Transition Polymer state Glassy .fwdarw. Mesophase Mesophase .fwdarw. Isotropic Transition 50 210 temperature ( C.)

[0323] The ion conductivities obtained for the various deposits are shown in FIG. 20.

[0324] The polymer in its organized state shows good ion conductivity. It may advantageously be used as a solid electrolyte in a lithium battery.

Example 14

Synthesis of lithium 4-amino-1-naphthalentrifluorosulfonamide (LiANTFSI)

[0325] Step 1: Protection of the Primary Amine (Pro-HAN)

##STR00034##

[0326] 4.77 g of 4-amino-l-naphthalenesulfonic acid HAN (20.73 mmol), 3.4 mL of phthaloyl chloride (21.25 mmol) and 30 mL of pyridine are placed in a three-necked round-bottomed flask equipped with a condenser and a magnetic bar. The reaction mixture is stirred and heated at 100 C. under an inert atmosphere (flushing with a stream of argon) for 17 hours. At the end of the reaction, the solvent is evaporated off under reduced pressure. A pale yellow precipitate is obtained after recrystallization from methanol. (Yield=42%) .sup.1H NMR (200 MHz; DMSO-d6; 300 K): ppm 8.94 (m, 3H); 8.58 (m, 1H); 7.74 (m, 12H);

[0327] Step 2: Synthesis of the Thionyl Chloride Derivative (Pro-ANSO.sub.2Cl)

##STR00035##

[0328] 2.35 g of Pro-HAN (5.43 mmol), 0.7 mL of thionyl chloride (9.68 mmol) and 11 mL of dimethylformamide (DMF) are placed in a three-necked round-bottomed flask equipped with a condenser and a magnetic bar. The reaction mixture is stirred for 3 hours at room temperature under an inert atmosphere (flushing with a stream of argon). The reaction is stopped by pouring the reaction medium into cold distilled water. After filtration and drying, a white precipitate is obtained (yield=100%).

[0329] .sup.1H NMR (400 MHz; DMSO-d6; 300 K): ppm 8.94 (dd, 1H); 8.01 (m, 5H); 7.75 (m, 1H); 7.57(m, 3H);

[0330] Step 3: Synthesis of the TFSI Derivative (Pro-ANTFSA)

##STR00036##

[0331] 403.5 mg of Pro-ANSO.sub.2Cl (1.08 mmol), 163.7 mg of trifluoromethanesulfonamide (1.08 mmol), 11.2 mg of 4-(dimethylamino)pyridine (DMAP), 0.23 g of triethylamine (TEA) and 5 mL of dichloromethane (CH.sub.2Cl.sub.2) are placed in a three-necked round-bottomed flask equipped with a condenser and a magnetic bar. The reaction mixture is stirred for 16 hours at room temperature under an inert atmosphere (flushing with a stream of argon). After extraction, 2x5 mL of 4% NaHCO.sub.3 and 15 mL of 1M HCl, the organic phase is evaporated. A yellow oil is then obtained.

[0332] The infrared spectrum of the product obtained is shown in FIG. 21.

[0333] Step 4: Synthesis of Li-ANTFSI

##STR00037##

[0334] 522.72 mg of Pro-ANTSFA (1.08 mmol), 163.7 mg of trifluoromethanesulfonamide (1.08 mmol), 1.2 mL of hydrazine monohydrate and 8.6 mL of methanol are placed in a three-necked round-bottomed flask equipped with a condenser and a magnetic bar. The reaction mixture is stirred for 17 hours at room temperature under an inert atmosphere (flushing with a stream of argon). The precipitate obtained is filtered off and washed with methanol. The filtrate is evaporated.

[0335] The product obtained is dissolved in 20 mL of distilled water and 52 mg (1.23 mmol) of lithium hydroxide hydrate. pH monitoring was performed during the lithiation and is shown in FIG. 22.

[0336] The product is obtained after evaporating off the solvent and washing several times with ethanol.

Example 15

[0337] Preparation of a Polymer P9 in Accordance with the Invention from Lithium 4-Amino-1-Naphthalenesulfonate (LiAN) and Diglycidyl Ether (DGE)

##STR00038##

[0338] Polymer P9 is synthesized according to a protocol similar to that presented in example 1, using 100 mg of diglycidyl ether (0.77 mmol) in place of DGE, 0.176 g of LiAN (0.176 mmol) and 5 mL of DMF. The temperature is set at 70 C. at the start of the reaction. A light brown powder is obtained.

[0339] The infrared spectrum of polymer P7 obtained is shown in FIG. 23.

[0340] The powder obtained was also characterized by thermogravimetric analysis (TGA) under argon and with a heating rate of 10 C./min. The results of the thermogravimetric analysis are shown in FIG. 24.

Example 16

Preparation of a polymer P10 in Accordance with the Invention from Lithium 4-Amino-1, 7-Naphthalenedisulfonate (LiDiAN) and Butanediol Diglycidyl Ether (BDGE)

[0341] Synthesis of Lithium 4-Amino-1-Naphthalenedisulfonate (LiDiAN)

##STR00039##

[0342] 0.483 g of 4-amino-1,7-naphthalenesulfonic acid (DiHAN) and 0.067 g of lithium hydroxide monohydrate (LiOH.H.sub.2O) are place in 10 mL of distilled water. The reaction medium is stirred overnight at room temperature. The excess HAN is removed by filtration. The filtrate is then concentrated by evaporating off the solvent under reduced pressure. After washing twice with ethanol, an orange powder is obtained.

[0343] Synthesis of the Polymer

[0344] Polymer P10 is synthesized according to a protocol similar to that presented in example 1, using 0.16 mL of 1,4-butanediol diglycidyl ether (0.85 mmol) in place of BdO, 0.2685 g of LiDiAN (0.85 mmol) and 5 mL of DMF. The temperature is set at 70 C. at the start of the reaction. A brown powder is obtained.

[0345] The infrared spectrum of polymer P10 obtained is shown in FIG. 25.

[0346] The powder obtained was also characterized by thermogravimetric analysis (TGA) under argon and with a heating rate of 10 C./min. The results of the thermogravimetric analysis are shown in FIG. 26.

Example 17

Preparation of a polymer P11 in Accordance with the Invention from Lithium 5-Amino-1-Naphthalenesulfonate and Butadiene Diepoxide

[0347] Synthesis of Lithium 5-Amino-1-Naphthalenesulfonate (LiAN)

##STR00040##

[0348] 24.44 g of 5-amino-1-naphthalenesulfonic acid (HAN) and 4.13 g of lithium hydroxide monohydrate (LiOH.H.sub.2O) are placed in 500 mL of distilled water. The reaction medium is stirred overnight at room temperature. The excess HAN is removed by filtration. The filtrate is then concentrated by evaporating off the solvent under reduced pressure. After washing twice with ethanol, a violet-colored powder is obtained.

[0349] .sup.1H NMR (400 MHz; pyridine-d6; 300 K): ppm 9.2 (d, 1H); 8.5 (d, 1H); 7.3 (m, 4H); 5.92 (s, 2H);

[0350] Synthesis of the Polymer

##STR00041##

[0351] Polymer P10 is synthesized according to a protocol similar to that presented in example 1, using 2.37 mL of 1,4-butanediol diglycidyl ether (12.25 mmol) in place of BdO, 2.81 g of LiAN (12.25 mmol) and 15 mL of DMF. The temperature is set at 70 C. at the start of the reaction. A dark brown powder is obtained.

[0352] The infrared spectrum of the polymer obtained, denoted as P11, is shown in FIG. 27.

[0353] The powder obtained was also characterized by thermogravimetric analysis (TGA) under argon and with a heating rate of 10 C./min. The results of the thermogravimetric analysis are shown in FIG. 28.

Example 18

Measurement of the Phase Transitions by POM of Polymer P7

[0354] Polymer P7 powder is deposited on a glass microscope plate. The sample is placed in a mounting plate and its state is observed at various temperatures. Table 3 reports the transitions observed. The images obtained with a polarized light microscope are shown in FIG. 27.

TABLE-US-00003 TABLE 3 Transition Polymer state Glassy .fwdarw. Mesophase Mesophase .fwdarw. Isotropic Transition 40 235 temperature ( C.)

Example 19

Measurement of the Ion Conductivity of the Polymers P

[0355] The ion conductivity of the polymers P was evaluated by measuring the resistance of two aluminum plates of a rheometer over a temperature range extending from 100 C. to 215 C.

[0356] The results obtained are shown in FIG. 28.