Solid electrolyte for organic batteries
A process can be used to produce a charge storage unit, especially a secondary battery, the electrodes of which contain an organic redox-active polymer, and which includes a polymeric solid electrolyte. The solid electrolyte is obtained by polymerizing from mixtures of acrylates with methacrylates in the presence of at least one ionic liquid, which imparts advantageous properties to the charge storage unit.
1. A process for producing a charge storage unit, the process comprising:
(a) polymerizing a mixture M comprising at least one compound of the formula (I), at least one compound of the formula (II):
wherein R A , R M are independently selected from the group consisting of hydrogen, an alkyl group, a (poly)ether group, an aryl group, an aralkyl group, an alkaryl group, and a haloalkyl group,
and at least one ionic liquid IL, to obtain a polymer electrolyte P ele , and
(b) disposing the polymer electrolyte P ele obtained in (a) between two electrodes E cat and E an , wherein E cat and E an each independently comprise at least one conductivity additive L and at least one organic redox-active polymer P redox selected from the group consisting of polyimides and polymers comprising m units of the general formula (III):
wherein m is an integer ≥4, W is a repeat unit, Sp is an organic spacer and R X is an organic redox-active group, wherein the bond identified by (i) in a unit of the formula (III) binds to the bond identified by (ii) in an adjacent unit of the formula (III).
2. The process according to claim 1 , wherein, in (a), a molar ratio of all compounds of formula (I) included in the mixture M to all compounds of the formula (II) included in the mixture M is in the range of 99:1 to 1:99.
3. The process according to claim 1 , wherein the ionic liquid IL has a structure Q + A − in which Q + is a cation selected from the group consisting of the structures (Q1), (Q2), (Q3), (Q4), and (Q5)
wherein R Q1 , R Q2 , R Q3 , R Q4 , R Q5 , R Q6 , R Q7 , R Q8 are each independently selected from the group consisting of an alkyl group, a haloalkyl group, and a cycloalkyl group,
wherein R Q9 , R Q10 , R Q11 , R Q12 , R Q13 , R Q14 , R Q15 , R Q16 , R Q17 , R Q18 , R Q19 , R Q20 , R Q21 , R Q22 , R Q23 , R Q24 , R Q25 , R Q26 , R Q27 , R Q28 , R Q29 , R Q30 , R Q31 , R Q32 , R Q33 , R Q34 , R Q35 are each independently selected from the group consisting of hydrogen, an alkyl group, a (poly)ether group, a haloalkyl group, and a cycloalkyl group, and
in which A − is an anion.
4. The process according to claim 1 , wherein a total molar amount of all ionic liquids IL included in the mixture M in (a), based on a total molar amount of all compounds of the formulae (I) and (II) included in the mixture M, is ≥0.1 molar equivalent.
5. The process according to claim 1 , wherein (a) is conducted on a surface of at least one of the electrodes E cat and E an .
6. The process according to claim 1 , wherein the polymer P redox is a polymer comprising m units of the general formula (III) in which R X is selected from the group consisting of compounds of the general formulae (III-A), (III-B), (III-C), and (III-D), where
and wherein, in the structures (III-A), (III-B) and (III-C), at least one aromatic carbon atom may be substituted by a group selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, and a hydroxyl group.
7. The process according to claim 1 , wherein the polymer P redox is a polyimide selected from the group consisting of the structures (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), and (IV-7):
wherein n in each case is an integer ≥4 and the bond identified by (iv) in the structures (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7) binds in each case to the bond identified by (v), and
wherein, in the structures (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), at least one aromatic carbon atom may be substituted by a group selected from the group consisting of alkyl, halogen, alkoxy, and OH.
8. The process according to claim 1 , wherein the W radical in the structure (III) is selected from the group consisting of the structures (W1), (W2), and (W3):
wherein the bond identified by (i) in a unit of the formula (W1), (W2), or (W3) binds in each case to the bond identified by (ii) in an adjacent unit of the formula (W1), (W2) or (W3),
wherein the bond identified by (iii) in each case indicates the bond to Sp, and
wherein R W1 , R W2 , R W3 , R W4 , R W5 , R W6 , R W7 are independently selected from the group consisting of hydrogen, an alkyl group, a haloalkyl group, and —COOR W8 wherein R W8 =H or alkyl, and
wherein Sp in the structure (III) is selected from the group consisting of a direct bond, (Sp1), and (Sp2):
-(O) pA1 —[C═O] pA2 —(O) pA3 —B Sp —(O) qA1 —[C═O] qA2 —(O) qA3 - , (Sp1):
-(O) qA4 —[C═O] qA5 —(O) qA6 (Sp2):
wherein pA1, pA2, pA3 in each case is 0 or 1, excluding the case that pA2=0 and pA1=pA3=1,
wherein qA1, qA2, qA3 in each case is 0 or 1, excluding the case that qA2=0 and qA1=qA3=1,
wherein qA4, qA5, qA6 in each case is 0 or 1, where at least one of qA4, qA5, qA6=1 and excluding the case that qA5=0 and qA4=qA6=1,
wherein B Sp is selected from the group consisting of
a divalent (hetero)aromatic radical, and
a divalent aliphatic radical, optionally substituted by at least one group selected from the group consisting of a nitro group, —NH 2 , —CN, —SH, —OH, and halogen; and optionally having at least one group selected from the group consisting of an ether, a thioether, an amino ether, a carbonyl group, a carboxylic ester, a carboxamide group, a sulfonic ester, and a phosphoric ester, and
where in the cases in which Sp binds to a non-carbon atom in the R X radical, the structure (Sp1) is subject to the additional condition qA3=0, qA2=1, and qA1=1; or qA3=qA2=qA1=0; or qA3=0, qA2=1, and qA1=0, and the structure (Sp2) is subject to the additional condition that qA6=0, qA5=1, and qA4=1; or qA6=0, qA5=1, and qA4=0, and
wherein denotes the bond pointing toward R X , and
wherein denotes the bond pointing toward W.
9. The process according to claim 1 , wherein the polymer P redox comprises t repeat units joined to one another, selected from the group consisting of the structures P1, P2, and P3:
wherein t is an integer ≥4, and
the bond identified by (vi) in a unit of the formula P1 binds to the bond identified by (vii) in an adjacent unit of the formula P1, and
the bond identified by (viii) in a unit of the formula P2 binds to the bond identified by (ix) in an adjacent unit of the formula P2, and
the bond identified by (x) in a unit of the formula P3 binds to the bond identified by (xi) in an adjacent unit of the formula P3.
10. The process according to claim 1 , wherein the conductivity additive L is selected from the group consisting of carbon materials, electrically conductive polymers, metals, semimetals, metal compounds, and semimetal compounds.
11. A charge storage unit obtainable by the process according to claim 1 .
12. A charge storage unit, comprising a polymer electrolyte P ele disposed between two electrodes E cat and E an , wherein E cat and E an each independently comprise at least one conductivity additive L and at least one organic redox-active polymer P redox selected from the group consisting of polyimides and polymers comprising m units of the general formula (III):
wherein m is an integer ≥4, W is a repeat unit, Sp is an organic spacer and R X is an organic redox-active group, wherein the bond identified by (i) in a unit of the formula (III) binds to the bond identified by (ii) in an adjacent unit of the formula (III),
wherein
the polymer electrolyte P ele is obtained by polymerizing a mixture M comprising at least one compound of the formula (I), at least one compound of the formula (II):
wherein R A , R M are independently selected from the group consisting of hydrogen, an alkyl group, a (poly)ether group, an aryl group, an aralkyl group, an alkaryl group, and a haloalkyl group,
and at least one ionic liquid IL.
13. The charge storage unit according to claim 12 , wherein a molar ratio of all compounds of formula (I) included in the mixture M to all compounds of the formula (II) included in the mixture M is in the range of 99:1 to 1:99.
14. The charge storage unit according to claim 12 , wherein the ionic liquid IL has a structure Q + A − in which Q + is a cation selected from the group consisting of the structures (Q1), (Q2), (Q3), (Q4), and (Q5):
wherein R Q1 , R Q2 , R Q3 , R Q4 , R Q5 , R Q6 , R Q7 , R Q8 are each independently selected from the group consisting of an alkyl group, a haloalkyl group, and a cycloalkyl group,
wherein R Q9 , R Q10 , R Q11 , R Q12 , R Q13 , R Q14 , R Q15 , R Q16 , R Q17 , R Q18 , R Q19 , R Q20 , R Q21 , R Q22 , R Q23 , R Q24 , R Q25 , R Q26 , R Q27 , R Q28 , R Q29 , R Q30 , R Q31 , R Q32 , R Q33 , R Q34 , R Q35 are each independently selected from the group consisting of hydrogen, an alkyl group, a (poly)ether group, a haloalkyl group, and a cycloalkyl group, and
in which A − is an anion.
15. The charge storage unit according to claim 12 , wherein a total molar amount of all ionic liquids IL included in the mixture M, based on a total molar amount of all compounds of the formulae (I) and (II) included in the mixture M, is ≥0.1 molar equivalents.
16. The charge storage unit according to claim 12 , wherein the polymer P redox is a polymer comprising m units of the general formula (III) in which R X is selected from the group consisting of compounds of the general formulae (III-A), (III-B), (III-C), and (III-D), where
and wherein, in the structures (III-A), (III-B) and (III-C), at least one aromatic carbon atom may be substituted by a group selected from the group consisting of alkyl, halogen, alkoxy, and OH.
17. The charge storage unit according to claim 12 , wherein the polymer P redox is a polyimide selected from the group consisting of the structures (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), and (IV-7):
wherein n in each case is an integer ≥4 and the bond identified by (iii) in the structures (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7) binds in each case to the bond identified by (iv), and
wherein, in the structures (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), at least one aromatic carbon atom may be substituted by a group selected from the group consisting of alkyl, halogen, alkoxy, and OH.
18. The charge storage unit according to claim 12 , wherein the W radical in the structure (III) is selected from the group consisting of the structures (W1), (W2), and (W3):
wherein the bond identified by (i) in a unit of the formula (W1), (W2), or (W3) binds in each case to the bond identified by (ii) in an adjacent unit of the formula (W1), (W2) or (W3),
wherein the bond identified by (iii) in each case indicates the bond to Sp, and
wherein R W1 , R W2 , R W3 , R W4 , R W5 , R W6 , R W7 are independently selected from the group consisting of hydrogen, an alkyl group, a haloalkyl group, and —COOR W8 wherein R W8 =H or alkyl, and
wherein Sp in the structure (III) is selected from the group consisting of a direct bond, (Sp1), and (Sp2):
-(O) pA1 —[C═O] pA2 —(O) pA3 —B Sp —(O) qA1 —[C═O] qA2 —(O) qA3 - , (Sp1):
-(O) qA4 —[C═O] qA5 —(O) qA6 (Sp2):
wherein pA1, pA2, pA3 in each case is 0 or 1, excluding the case that pA2=0 and pA1=pA3=1,
wherein qA1, qA2, qA3 in each case is 0 or 1, excluding the case that qA2=0 and qA1=qA3=1,
wherein qA4, qA5, qA6 in each case is 0 or 1, where at least one of qA4, qA5, qA6=1 and excluding the case that qA5=0 and qA4=qA6=1,
wherein B Sp is selected from the group consisting of
a divalent (hetero)aromatic radical, and
a divalent aliphatic radical, optionally substituted by at least one group selected from the group consisting of a nitro group, —NH 2 , —CN, —SH, —OH, and halogen; and optionally having at least one group selected from the group consisting of an ether, a thioether, an amino ether, a carbonyl group, a carboxylic ester, a carboxamide group, a sulfonic ester, and a phosphoric ester, and
where in the cases in which Sp binds to a non-carbon atom in the R X radical, the structure (Sp1) is subject to the additional condition qA3=0, qA2=1, and qA1=1; or qA3=qA2=qA1=0; or qA3=0, qA2=1, and qA1=0, and the structure (Sp2) is subject to the additional condition that qA6=0, qA5=1, and qA4=1; or qA6=0, qA5=1, and qA4=0, and
wherein denotes the bond pointing toward R X , and
wherein denotes the bond pointing toward W.
19. The charge storage unit according to claim 12 , wherein the polymer P redox comprises t repeat units joined to one another, selected from the group consisting of the structures P1, P2, and P3:
wherein t is an integer ≥4, and
the bond identified by (vi) in a unit of the formula P1 binds to the bond identified by (vii) in an adjacent unit of the formula P1, and
the bond identified by (viii) in a unit of the formula P2 binds to the bond identified by (ix) in an adjacent unit of the formula P2, and
the bond identified by (x) in a unit of the formula P3 binds to the bond identified by (xi) in an adjacent unit of the formula P3.
20. The charge storage unit according to claim 12 , wherein the conductivity additive L is selected from the group consisting of carbon materials, electrically conductive polymers, metals, semimetals, metal compounds, and semimetal compounds.