Use of thianthrene-containing polymers as a charge store

Patent metadata

Field	Value
Publication number	US-10608255-B2
Application number	US-201716306614-A
Country	US
Kind code	B2
Filing date	Aug 4, 2017
Priority date	Aug 5, 2016
Publication date	Mar 31, 2020
Grant date	Mar 31, 2020

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.

First claim

The invention claimed is:

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)

wherein n is an integer ≥4,
wherein m is an integer ≥0,
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 an adjacent repeat unit,
wherein R A , R B , R C , R D , R E , R F , R G , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 radicals are each independently selected from the group consisting of hydrogen, —NO 2 , —CN, -halogen, —COOR 8 , —C(═O)NHR 9 , —NR 10 R 11 , —OR 12 , —SR 13 , —OP(═O)(O − (M z+ ) 1/z ) 2 , —OP(═O)(OR 14 )O − (M z+ ) 1/z , —OP(═O)(OR 15 )(OR 16 ), —S(O) 2 O − (M z+ ) 1/z , —S(O) 2 OR 17 , substituted or unsubstituted (hetero)aromatic radical, and substituted or unsubstituted aliphatic radical optionally comprising at least one group selected from the group consisting of ether, thioether, amino ether, carbonyl, carboxylic ester, sulphonic ester, and phosphoric ester,
wherein R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted (hetero)aromatic radical, and substituted or unsubstituted aliphatic radical optionally comprising at least one group selected from the group consisting of ether, thioether, amino ether, carbonyl, carboxylic ester, sulphonic ester, and phosphoric ester,
wherein M z+ is selected from the group consisting of metallic cation, and organic cation,
wherein z indicates the number of positive charges of M z+ ,
wherein at least two radicals in ortho positions to one another among the R 1 , R 2 , R 3 radicals and/or at least two radicals in ortho positions to one another among the R 4 , R 5 , R 6 , R 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 optionally comprising at least one group selected from the group consisting of ether, thioether, amino ether, carbonyl, carboxylic ester, sulphonic ester, and phosphoric ester,
wherein X is selected from the group consisting of &-(X 1 )p1-[C═Y 1 ]q1-(X 2 )p2-B -(X 3 )p3-[C═Y 2 ]q2-(X 4 )p4-&&, &-(X 5 )p5-(C═Y 3 )q3-(X 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 1 , Y 2 , Y 3 are each independently selected from O, and S,
X 1 , X 2 , X 3 , X 4 , X 5 , X 6 are each independently selected from —O—, —S—, —NH—, and —Nalkyl-,
B is a divalent substituted or unsubstituted (hetero)aromatic radical or a divalent substituted or unsubstituted aliphatic radical optionally comprising at least one group selected from the group consisting of ether, thioether, amino ether, carbonyl, carboxylic ester, sulphonic ester, and phosphoric ester,
“&” denotes the bond to the carbon atom joined to R A , and
“&&” denotes the bond to a thianthrene ring.

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

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

Assignees

• Evonik Operations Gmbh

Inventors

• Wild Andreas
• Schubert Ulrich
• Häupler Bernhard

Classifications

• H01M4/604

  containing aliphatic main chain polymers · CPC title

• H01M4/137

  Electrodes based on electro-active polymers · CPC title

• C09D125/18

  Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen · CPC title

• H01M4/0402

  Methods of deposition of the material · CPC title

• C08F12/30 Primary

  Sulfur · CPC title