USE OF THIANTHRENE-CONTAINING POLYMERS AS A CHARGE STORE

Abstract

The present invention relates to the use of a thianthrene-containing polymer as redox-active electrode material, for example as an electrode slurry, for electrical charge storage means, especially secondary batteries, It additionally also relates to the electrode material comprising the polymer, and to an electrode and an electrical charge storage means comprising the polymer,

Claims

1: A redox-active electrode material for electrical charge storage, comprising: a polymer P which comprises n mutually joined repeat units of the chemical structure (I) ##STR00023## wherein n is an integer4, wherein m is an integer0, wherein the repeat units of the chemical structure (I) within the polymer P are the same or at least partly different from one another, wherein the repeat units of the chemical structure (I) within the polymer P are joined to one another in such a way that the bond identified by * in a particular repeat unit is joined to the bond identified by ** in [[the]] an adjacent repeat unit, wherein R.sup.A, R.sup.B, R.sup.C, R.sup.D, R.sup.E, R.sup.F, R.sup.G, R.sup.H, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals are each independently selected from the group consisting of hydrogen, NO.sub.2, CN, halogen, COOR.sup.8, C(O)NHR.sup.9, NR.sup.10R.sup.11, OR.sup.12, SR.sup.13, OP(O)(O.sup.(M.sup.z+).sub.1/z).sub.2, OP(O)(OR.sup.14)O.sup.(M.sup.z+).sub.1/z, OP(O)(OR.sup.15)(OR.sup.16), S(O).sub.2O.sup.(M.sup.z+).sub.1/z, S(O).sub.2OR.sup.17, substituted or unsubstituted (hetero)aromatic radical, and substituted or unsubstituted aliphatic radical, wherein at least one group selected from the group consisting of disulphide, ether, thioether, amino ether, carbonyl, carboxylic ester, sulphonic ester, and phosphoric ester is optionally present within the substituted or unsubstituted aliphatic radical, wherein R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted (hetero)aromatic radical, and substituted or unsubstituted aliphatic radical, wherein at least one group selected from the group consisting of disulphide, ethe thioether, amino ether, carbonyl, carboxylic ester, sulphonic ester, and phosphoric ester is optionally present within the substituted or unsubstituted aliphatic radical, wherein M.sup.z+ is selected from the group consisting of metallic cation, and organic cation, wherein z indicates the number of positive charges of M.sup.z+, wherein at least two radicals in ortho positions to one another among the R.sup.1, R.sup.2, R.sup.3 radicals andlor at least two radicals in ortho positions to one another among the R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals may each also be bridged by at least one substituted or unsubstituted (hetero)aromatic ring or by a substituted or unsubstituted aliphatic ring, wherein at least one group selected from the group consisting of disulphide, ether, thioether, amino ether, carbonyl, carboxylic ester, sulphonic ester, and phosphoric ester is optionally present within the substituted or unsubstituted aliphatic ring, wherein X is selected from the group consisting of &-(X.sup.1)p1-[CY.sup.1]q1-(X.sup.2)-p2-B-(X.sup.3)p3-[CY.sup.2]q2-(X.sup.4)p4-&&, &-(X.sup.5)p5-(CY.sup.3)q3-(X.sup.6)p6-&&, and direct bond, wherein, p1, q1, p2 are each 0 or 1, with the proviso that it is not simultaneously true that p1=p2=1 and q1=0, p3, q2, p4 are each 0 or 1, with the proviso that it is not simultaneously true that p3=p4=1 and q2=0, p5, q3, p6 are each 0 or 1, with the proviso that it is not simultaneously true that p5=p6=1 and q3=0, and that, when p5 =1 and q3=0, p6=0, and that it is not true that p5=q3=p6=0, Y.sup.1, Y.sup.2, Y.sup.3 are each independently selected from O, and S, X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6 are each independently selected from O, S, NH, and Nalkyl-, B is a divalent substituted or unsubstituted (hetero)arornatic radical or a divalent substituted or unsubstituted aliphatic radical, wherein at least one group selected from the group consisting of disulphide, ether, thioether, amino ether, carbonyl, carboxylic ester, sulphonic ester, and phosphoric ester is optionally present within the substituted or unsubstituted aliphatic radical, & denotes the bond to the carbon atom joined to R.sup.A, and && denotes the bond to the thianthrene ring.

2: The redox-active electrode material for electrical charge storage according to claim 1, wherein the R.sup.A, R.sup.B, R.sup.C, R.sup.D, R.sup.E, R.sup.F, R.sup.G, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals are each independently selected from the group consisting of hydrogen, CN, -halogen, COOR.sup.8, C(O)NHR.sup.9, NR.sup.10R.sup.11, OR.sup.12, SR.sup.13, OP(O)(O.sup.(M.sup.z+).sub.1/z).sub.2, OP(O)(OR.sup.14)O.sup.(M.sup.z+).sub.1/z, OP(O)(OR.sup.15)(OR.sup.16), S(O).sub.2O.sup.(M.sup.z+).sub.1/z, S(O).sub.2OR.sup.17, substituted or unsubstituted (hetero)arotnatic radical, and substituted or unsubstituted aliphatic radical, at least one group selected from the group consisting of disulphide, ether, thioether, and sulphonic ester is optionally present within the substituted or unsubstituted aliphatic radical, wherein R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17 are each independently selected from hydrogen, substituted or unsubstituted (hetero)aromatic radical, and substituted or unsubstituted aliphatic radical, wherein at least one group selected from disulphide, ether, thioether, and sulphonic ester is optionally present within the substituted or unsubstituted aliphatic radical, wherein NV is selected from the group consisting of alkali metal cation, alkaline earth metal cation, transition metal cation, tetraalkylammoni Urrl cation, imidazolium cation, monoallimidazolium cation, and dialkylimidazolium cation, wherein at least two radicals in ortho positions to one another among the R.sup.1, R.sup.2, R.sup.3 radicals and/or at least two radicals in ortho positions to one another among the R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals may each also be bridged by at least one substituted or unsubstituted (hetero)aromatic ring or by a substituted or unsubstituted aliphatic ring, wherein at least one group selected from the group consisting of disulphide, ether, thioether, and sulphonic ester is optionally present within the substituted or unsubstituted aliphatic ring, and wherein B is a divalent substituted or unsubstituted (hetero)aromatic radical or a divalent substituted or unsubstituted aliphatic radical, wherein at least one group selected from the group consisting of disulphide, ether, thioether, and sulphonic ester is optionally present within the substituted or unsubstituted aliphatic radical.

3: The redox-active electrode material for electrical charge storage according to claim 2, wherein the R.sup.A, R.sup.B, R.sup.C, R.sup.D, R.sup.E, R.sup.F, R.sup.G radicals are each independently selected from the group consisting of hydrogen, CN, -halogen, COOR.sup.8, C(O)NHR.sup.9, NR.sup.10R.sup.11, OR.sup.12, SR.sup.13, substituted or unsubstituted phenyl radical, and substituted or unsubstituted aliphatic radical, wherein at least one group selected from the group consisting of ether, thioether, and sulphonic ester is optionally present within the substituted or unsubstituted aliphatic radical, wherein the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals are each independently selected from the group consisting of hydrogen, CN, -halogen, COOR.sup.8, OR.sup.22, SR.sup.23, OP(O)(O.sup.(M.sup.z+).sub.1/z).sub.2, OP(O)(OR.sup.24)O.sup.(M.sup.z+).sub.1/z, OP(O)(OR.sup.25)(OR.sup.26), S(O).sub.2O.sup.(M.sup.z+).sub.1/z, S(O).sub.2OR.sup.27, substituted or unsubstituted (hetero)aromatic radical, and substituted or unsubstituted aliphatic radical, wherein at least one group selected from the group consisting of disulphide, ether, thioether, and sulphonic ester is optionally present within the substituted or unsubstituted aliphatic radical, wherein R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.18, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27 are each independently selected from hydrogen, substituted or unsubstituted (hetero)aromatic radical, and substituted or unsubstituted aliphatic radical, wherein at least one group selected from the group consisting of disulphide, ether, thioether, and sulphonic ester is optionally present within the substituted or wisubstituted aliphatic radical, wherein M.sup.z+ is selected from the group consisting of Li.sup.+, Na.sup.+, Mg.sup.2+, Ca.sup.2+, Zn.sup.2+, Fe.sup.2+, Fe.sup.3+, Cd.sup.2+, Hg.sup.+, Hg.sup.2+, Ni.sup.2+, Ni.sup.3+, Ni.sup.4+, tetraalkylammonium cation, imidazolium cation, monoalkylimidazolium cation, and dial kylimidazol ium cation, wherein the alkyl groups in the tetraalkylammonium cation, monoalkylimidazolium cation, and dialkylimidazolium cation each independently have 1 to 10 carbon atoms, wherein at least two radicals in ortho positions to one another among the R.sup.1, R.sup.2, R.sup.3 radicals and/or at least two radicals in ortho positions to one another among the R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals may each also be bridged by at least one substituted or unsubstituted (hetero)aromatic ring or by a substituted or unsubstituted aliphatic ring, wherein at least one group selected from thegroup consisting of disulphide, ether, thioether, and sulphonic ester is optionally present within the substituted or unsubstituted aliphatic ring, wherein Y.sup.1, Y.sup.2, Y.sup.3 are each independently selected from O, and S, X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6 are each independently selected from O, and B is a divalent substituted or unsubstituted (hetero) aromatic radical or a divalent substituted or unsubstituted aliphatic radical, wherein at least one group selected from ether, and thioether is optionally present within the substituted or unsubstituted aliphatic radical.

4: Use The redox-active electrode material for electrical charge storage according to claim 3, wherein the R.sup.A, R.sup.B, R.sup.C, R.sup.D, R.sup.E, R.sup.F, R.sup.G radicals are each independently selected front the group consisting of hydrogen, CN, -halogen, COOR.sup.8, OR.sup.12, SR.sup.13, substituted or unsubstituted phenyl radical, and substituted or unsubstituted alkyl radical, wherein at least one group selected from ether, and thioether is optionally present within the substituted or unsubstituted alkyl radical, wherein the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals are each independently selected from the group consisting of hydrogen, -halogen, COOR.sup.18, OR.sup.22, SR.sup.23, OP(O)(O.sup.(M.sup.z+).sub.1/z).sub.2, OP(O)(OR.sup.24)O.sup.(M.sup.z+).sub.1/z, OP(O)(OR.sup.25)(OR.sup.26), S(O).sub.2O.sup.(M.sup.z+).sub.1/z, S(O).sub.2OR.sup.27, and substituted or unsubstituted alkyl radical, wherein at least one group selected from ether, thioether, and sulphonic ester is optionally present within the substituted or unsubstituted alkyl radical, wherein R.sup.8, R.sup.12, R.sup.13, R.sup.18, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27 are each independently selected from hydrogen, substituted or unsubstituted (hetero)aromatic radical, and substituted or unsubstituted alkyl radical, wherein at least one group selected from the group consisting of disulphide, ether, thioether, and sulphonic ester is optionally present within the substituted or unsubstituted alkyl radical, wherein B is selected from the group consisting of Li.sup.+, Na.sup.+, Mg.sup.2+, Ca.sup.2+, Zn.sup.2+, Fe.sup.2+, Fe.sup.3+, Cd.sup.2+, Hg.sup.+, Hg.sup.2+, Ni.sup.2+, Ni.sup.3+, Ni.sup.4+, wherein B is a divalent substituted or unsubstituted (hetero)aromatic radical or a divalent substituted or unsubstituted alkylene or alkenylene radical, wherein at least one group selected from ether, and thioether is optionally present within the substituted or unsubstituted alkylene or alkenylene radical.

5: The redox-active electrode material for electrical charge storage according to claim 4, wherein the R.sup.A, R.sup.B, R.sup.C, R.sup.D, R.sup.E, R.sup.F, R.sup.G radicals are each independently selected from the group consisting of hydrogen, CN, -halogen, COOR.sup.S, substituted or unsubstituted phenyl radical, and substituted or unsubstituted alkyl radical, wherein the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals are each independently selected from the group consisting of hydrogen, -halogen, COOR.sup.18, OR.sup.22, SR.sup.23, and substituted or unsubstituted alkyl radical, wherein R.sup.8, R.sup.18, R.sup.22, R.sup.23 are each independently selected from hydrogen, and substituted or unsubstituted alkyl radical, wherein B is selected from the group consisting of phenylene, tolylene, and divalent substituted or unsubstituted alkylene or alkenylene radical,

6: The redox-active electrode material for electrical charge storagp according to claim 5, wherein, the R.sup.A, R.sup.B, R.sup.C, R.sup.E, R.sup.F radicals are each independently selected from the group consisting of hydrogen, -halogen, and alkyl radical, the R.sup.D, R.sup.G radicals are independently selected from the group consisting of hydrogen, -halogen, alkyl radical, COOR.sup.8, and phenyl radical unsubstituted or substituted by a group selected from alkyl, alkenyl, and of CN, the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals are each independently selected from the group consisting of hydrogen, -halogen, COOR.sup.18, OR.sup.22, SR.sup.23, and alkyl radical, R.sup.8, R.sup.18, R.sup.22, R.sup.23 are each independently selected from hydrogen, and alkyl radical, wherein X is selected from the group consisting of &-(X.sup.1)p1-[CY.sup.1]q1-(X.sup.2)-p2-B-(X.sup.3)p3-[CY.sup.2]q2-(X.sup.4)p4-&&, and direct bond, wherein B is selected from the group consisting of phenylene, tolylene, alkylene radical, and alkenylene radical.

7: The redox-active electrode material for electrical charge storage according to claim 6, wherein, the R.sup.A, R.sup.B, R.sup.C, R.sup.E, R.sup.F radicals are each independently selected from the group consisting of hydrogen, F, and Cl, the R.sup.D, R.sup.G radicals are independently selected from the group consisting of hydrogen, F, Cl, phenyl, and phenyl radical substituted by at least one vinyl group, wherein the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 radicals are each independently selected from the group consisting of hydrogen, F, Cl, OR.sup.22, SR.sup.23, and alkyl radical having 1 to 6 carbon atoms, R.sup.22, R.sup.23 are each independently selected from alkyl radical having 1 to 6 carbon atoms, wherein X is selected from the group consisting of direct bond, &-OCHCH-&&, &-CHCH-O-&&, &-OCH.sub.2CHCH-&&, &-CHCHCH.sub.2O-&&, phenylene, &-CH.sub.2-phenylene-&&, &-phenylene-CH.sub.2-&&, and alkylene having 1 to 6 carbon atoms.

8: The redox-active electrode material for electrical charge storage according to claim 1, wherein n is an integer4 and 5000 and m is an integer0 and 5000.

9: The redox-active electrode material for electrical charge storage according to claim 1, further comprising a conductivity additive.

10: The redox-active electrode material for electrical charge storage according to claim 9, wherein the conductivity additive is at least one material selected from the group consisting of carbon materials, electrically conductive polymers, metals, semimetais, and (semi)metal compounds.

11: The redox-active electrode material for electrical charge storageaccording to claim 9, further comprising a binder additive.

12: The redox-active electrode material for electrical charge storage according to claim 11, wherein the binder additive is at. least one binder additive selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, polyhexaffuoropropylene, polyvinyl chloride, polycarbonate, polystyrene, polyacrylates, polymethacrylates, polysulphones, cellulose derivatives, and polyurethanes.

13: An electrode comprising the redox-active electrode material for electrical charge storage according to claim 9.

14: An electrical charge storage device, comprising the electrode according to claim 13.

15: A method of preparing a redox-active electrode, comprising: at least partially coating at least one surface layer of a substrate with the redox-active electrode material of claim 1.

16: The electrical charge storage device according to claim 14, wherein said device is a secondary battery.

Description

FIGURES

[0148] FIG. 1 (abbreviated to FIG. 1) shows a cyclic voltamrnogram of a monomer 2 (prepared according to Example 1) in CH.sub.2C12 (0.1 M TBAPFs, scan rate 100 mV s.sup.1). The x axis indicates the potential V; the y axis indicates the current I in mA.

[0149] FIG. 2 (abbreviated to FIG. 2) indicates the measured voltages V (y axis) against the capacity (x axis) of an electrode according to the invention produced with 3 after 1 or 10 or 100 or 250 charge-discharge cycle(s) (charging rate=1 C, i.e. full charge within 60 minutes). The filled boxes in the diagram correspond to the charging cycles, the empty boxes to the discharging cycles.

[0150] FIG. 3 (abbreviated to FIG. 3) indicates the measured voltages V (y axis) against the capacity (x axis) of an electrode according to the invention produced with 4 after 1 or 10 or 100 or 250 charge-discharge cycle(s) (charging rate=1 C, i.e. full charge within 60 minutes). The filled boxes in the diagram correspond to the charging cycles, the empty boxes to the discharging cycles,

[0151] The examples which follow are intended to elucidate the present invention without limiting said invention thereto.

EXAMPLES

1. General Remarks

1.1 Abbreviations

[0152] AIBNazobis(isobutyronitrile); DMAcdimethy acetamide; DMAPdimethylaminopyridine; DMFdimethylformamide; DVBdivinylbenzene; JohnPhos(2-biphenyl)di-tert-butylphosphine; NEt.sub.3triethylamine; Pd(dba)2bis(dibenzylideneacetone)palladium(O); NMPN-methyl-2-pyrrolidone; PSpolystyrene; SECsize exclusion chromatography; TBAClO.sub.4tetrabutylammonium perchlorate; TBAFtetrabutylammonium fluoride; TBAPF.sub.6tetrabutylammonium hexailuorophosphate; THFtetrahydrofuran; Tol.toluene; TVCT2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane.

[0153] The numbers in brackets given in the reaction schemes which follow relate to the respective section in which the synthesis has been described.

1.2 Test Methods

[0154] .sup.1H and .sup.13C NMR spectra were recorded with a Bruker AC 300 (300 MHz) spectrometer at 298 K. For cyclic voltammetry and galvanostatic experiments, a Biologic VMP 3 potentiostat was available. Size exclusion chromatography was conducted on an Agilent 1200 series system (degasser: PSS, pump: G1310A, autosampler: G1329A, oven: Techlab, DAD detector: G1315D, RI detector: G1362A, eluent: DMAc+0.21% LiCl, 1 ml/min, temperature: 40 C., column: PSS GRAM guard/1000/30 ).

2. Inventive Examples

[0155] 2.1I1: Synthesis and Polymerization of 2-vinylthianthrene to give poly-(2-vinylthianthrene) 3 or 4

##STR00022##

2.1.1 Synthesis of 2-vinylthianthrene 2

[0156] 2-Bromothianthrene (2.07 g, 7 mmol), bis(dibenzylideneacelone)palladium(0) (121 mg, 0.21 mmol) and (2-biphenyl)di-teat-butylphosphine (125 mg, 0.42 mmol) were freed of air and water by repeated evacuation and filling with inert gas. Subsequently, THF (14 ml), tetrabutylammonium fluoride solution (7,7 ml, 7,7 mmol, 1 M in THF) and 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (1.21 ml, 3.5 mmol) were added and the solution was heated to 75 C. On completion of conversion (monitoring by TLC), the reaction mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic phase was dried with MgSO.sub.4 and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica gel, heptane). 1.59 g (6.57 mmol, 94%) of 2 were obtained as a white solid.

[0157] A cyclic voltammogram with 2 was recorded. The cyclic voltammogram is shown in FIG. 1 (FIG. 1).

.sup.1H NMR (CDCl.sub.3, 300 MHz, ppm): 7.56-7.45 (m, 4H), 7.35-7.26 (m, 3H), 6.71 (dd, 1H). 5.81 (d, 1H), 5.33 (d, 1H).
2.1.2 Synthesis of poly(2-vinylthianthrene) 3

[0158] A 1 M solution of 2 (242 mg, 1 mmol) in dry DMF and AIBN (4.9 mg, 0.03 mmol) was inertized by 3 freeze-pump-thaw cycles. The solution was then stirred at 80 C. for 16 hours. The polymer was precipitated and washed in diethyl ether (15 ml) and then dried under reduced pressure. This gave 208 mg (0.86 mmol, 86%) of 3 as a white solid.

.sup.1H NMR (DMF, 300 MHz, ppm): 7.61-7.01 (b, 7H), 1.5-0.8 (b, 3H).
SEC (DMAc, 0.21% LiCl, PS standard): M.sub.n=35,500, PDI 4.8.
2.1.3 Synthesis of poly(2-vinylthianthrene-co-divinylbenzene) 4

[0159] A solution of 2 (727 mg, 3 mmol), divinylbenzene (3.9 mg, 0.03 mmol) and AIBN (14.8 mg, 0.09 mmol) in 3 ml of dry NMP was inertized by 3 freeze-pump-thaw cycles. The solution was then stirred at 75 C. for 24 hours. The polymer was precipitated and washed in diethyl ether/dichloromethane 1/1 (45 ml) and then dried under reduced pressure. This gave 691 mg (2.85 mmol, 95%) of 4 as a white solid,

2.1.4 Production of an Electrode with poly-(2-vinylthianthrene) 3

[0160] 3 was processed in a mortar to give a fine powder. Subsequently added to 30 mg of 3 and 10 mg of poly(vinylidene fluoride) (PVDF; Sigma Aldrich as binder additive) was 1 ml of NMP, and the mixture was stirred for 16 h. This suspension was added to 60 mg of SuperP (carbon black, carbon particles) and the mixture was mixed in a mortar for ten minutes until a homogeneous paste formed. This paste was applied to an aluminium foil (15 m, MIT Corporation), The resultant electrode was dried at 45 C. under reduced pressure for 16 hours. The proportion of the active material on the electrodes was determined on the basis of the masses of dried electrodes, The button cells (2032 type) were constructed under an argon atmosphere. Suitable electrodes were punched out with the aid of an MIT Corporation Precision Disc Cutter (diameter 15 mm). The electrode being used as cathode was positioned at the base of the button cell and separated from the lithium anode with the aid of a porous polypropylene membrane (Celgard, MIT Corporation). Subsequently positioned atop the lithium anode were a stainless steel weight (diameter: 15.5 mm, thickness: 0.3 mm, MIT Corporation) and a stainless steel spring (diameter: 14.5 mm, thickness: 5 mm). The button cell was filled with electrolyte (EC/DMC 3/7 v/v, 0.5 M LiClO.sub.4) and covered with the lid before being sealed with an electrical compression machine (MIT Corporation MSK-100D),

[0161] The battery shows a discharge plateau at 3.9 V (FIG. 2).

[0162] In the first charge/discharge cycle, the battery shows a capacity of 103 mAh/g (93% of the theoretically possible capacity); atter 250 charge/discharge cycles, the battery shows a capacity of 81 mAh/g (FIG. 2).

2.1.5 Production of an Electrode with poly-(2-vinylthianthrene-co-divinylbenzene) 4

[0163] 4 was processed in a mortar to give a fine powder. Subsequently added to 400 mg of 4 and 50 mg of poly(vinylidene fluoride) (PVDF: Sigma Aldrich as binder additive) was 10 ml of NMP, and the substances were dissolved in a dissolver at 2000 rpm at 50 C. To this solution were added 550 g of SuperP (carbon particles) and, if required, NMP, and the mixture was mixed at 8000 rpm for 30 min. The paste obtained was applied to an aluminium foil (15 m, MIT Corporation). The resultant electrode was dried at 40 C. under reduced pressure for 24 hours, The proportion of the active material on the electrodes was determined on the basis of the masses of dried electrodes. The button cells (2032 type) were constructed under an argon atmosphere. Suitable electrodes were punched out with the aid of an MIT Corporation Precision Disc Cutter (diameter 15 mm). The electrode being used as cathode was positioned at the base of the button cell and separated from the lithium anode with the aid of a porous polypropylene membrane (Celgard, MIT Corporation). Subsequently positioned atop the lithium anode were a stainless steel weight (diameter: 15.5 mm, thickness: 0.3 mm, MIT Corporation) and a stainless steel spring (diameter: 14.5 mm, thickness: 5 mm). The button cell was filled with electrolyte (EC/DMC 3/7 v/v, 1 M LiClO.sub.4) and covered with the lid before being sealed with an electrical compression machine (MIT Corporation MSK-100D).

[0164] The battery shows a discharge plateau at 3.9 V (FIG. 3).

[0165] In the first charge/discharge cycle, the battery shows a capacity of 103 mAh/g; after 250 charge/discharge cycles, the battery shows a capacity of 85 mAh/g (FIG. 3).

3. Results

[0166] The value of 81 mAh/g after 250 charge/discharge cycles observed in the case of the inventive polymer 3 (section 2.1.4) shows that the polymers according to the invention are superior to those from the prior art, namely those described by Speer et al. that are based on a norbornenyl backbone. As shown in FIG. 4 (page 15263) of Speer et al., the battery produced with the prior art polymer has a maximum specific capacity of 63 mAh/g. This value is below the value of 81 mAh/g which is still obtained with the polymer according to the invention after 250 charge/discharge cycles. This shows that the polymers according to the invention permit higher discharge voltages and higher cycling stability. This was completely surprising,