Method for producing an electrode material

Patent metadata

Field	Value
Publication number	US-10844145-B2
Application number	US-201716301810-A
Country	US
Kind code	B2
Filing date	May 22, 2017
Priority date	Jun 2, 2016
Publication date	Nov 24, 2020
Grant date	Nov 24, 2020

Abstract

The present invention relates to a process for polymerization, wherein the monomers are used in the form of solid particles in an aqueous phase. The polymers obtained thereby can be oxidized further to polymers which can be used as electrical charge storage means, especially secondary batteries.

First claim

The invention claimed is:

1. Process A process for polymerizing a compound of the structural formula (I)

wherein R 1 , R 2 , R 3 , R 4 , R 5 are selected from the group consisting of hydrogen, and branched or unbranched alkyl group having 1 to 4 carbon atoms,
X is selected from the group consisting of *—CH 2 —C′H—CH 2 —**, *—C′H—CH 2 —**, and *—C′═CH—**,
wherein “*” in each case denotes the bond to the carbon atom bonded to R 1 and R 2 ,
wherein “**” in each case denotes the bond to the carbon atom bonded to R 3 and R 4 ,
wherein “C” denotes a carbon atom additionally bonded to the Y radical,
wherein Y is selected from the bridging radicals (II) and (III),
wherein (II) has the structure &—(Y 1 ) p1 —[C═X 1 ] p2 —(Y 2 ) p3 —B—(Y 3 ) p6 —[C═X 2 ] p5 —(Y 4 ) p4 —&&,
and wherein (III) has the structure &—(Y 5 ) p9 -(C═X 3 ) p8 —(Y 6 ) p7 —&&,
wherein, in the bridging radicals (II) and (III),
p1, p2, p3 are each 0 or 1, with the proviso that it is not simultaneously the case that p1=p3=1 and p2=0,
p4, p5, p6 are each 0 or 1, with the proviso that it is not simultaneously the case that p4=p6=1 and p5=0,
p7, p8, p9 are each 0 or 1, with the proviso that it is not simultaneously the case that p7=p9=1 and p8=0,
X 1 , X 2 , X 3 are independently selected from the group consisting of oxygen, and sulphur,
Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 are independently selected from the group consisting of O, S, NH, and N-alkyl,
B is a divalent (hetero) aromatic radical or a divalent aliphatic radical optionally substituted by at least one group selected from the group consisting of nitro group, —NH 2 , —CN, —SH, —OH, and halogen, and optionally having at least one group selected from the group consisting of ether, thioether, amino ether, carbonyl group, carboxylic ester group, carboxamide group, sulphonic ester group, and phosphoric ester,
and wherein “&&” for Y denotes the bond via which Y is joined to X and wherein “&” for Y denotes the bond via which Y is joined to the carbon atom joined to R 5 ,
comprising the following successive steps:
(a) producing a dispersion D of solid particles of the compound of the structural formula (I) in an aqueous phase, and
(b) polymerizing the solid particles of the compound of the structural formula (I) of the dispersion D obtained in step (a), giving a polymer P 1 comprising repeat units of the structural formula (VI)

wherein the polymerization in step (b) is conducted at a temperature below the melting temperature of the compound of the structural formula (I) used.

2. The process according to claim 1 , wherein the number of repeat units (VI) in the polymer P 1 is 4 to 1 million.

3. The process according to claim 1 , wherein the compound of the structural formula (I) used is at least a compound selected from the group consisting of the structural formulae (IV), (IV)′, and (IV)″:

wherein, in the structural formulae (IV), (IV)′, (IV)″, the R 5 , R 5′ , R 5″ radicals are each independently methyl or hydrogen,
and wherein, in the structural formulae (IV), (IV)′, (IV)″, the Y, Y′, Y″ radicals are independently selected from the bridging radicals (II) and (III) with the definitions given in claim 1 .

4. The process according to claim 1 , wherein the compound of the structural formula (I) used is a compound of the structural formula (IV).

5. Process according to claim 4 , wherein the compound of the structural formula (I) is the structure (V)

wherein R 5 =H or methyl.

6. The process according to claim 1 , wherein the proportion of water in the aqueous phase is >50.0% by weight, based on the total weight of the aqueous phase.

7. The process according to claim 1 , wherein the dispersion D is produced in step (a) by dispersing a mixture of the compound of the structural formula (I) and the aqueous phase at a temperature T A1 , wherein T A1 >T SMI , wherein T AMI is the melting temperature of the compound of the structural formula (I) used, and, after the dispersion, the temperature is lowered from T A1 to T A2 , and wherein T A2 <T SMI .

8. The process according to claim 1 , wherein at least 50% of the solid particles of the compound of the structural formula (I) used in the dispersion D have a particle size of ≤800 μm, determined by the method described in DIN 66156-2, using sieves according to DIN ISO 3310.

9. The process according to claim 8 , wherein, at the same time, at least 80% of the solid particles of the compound of the structural formula (I) used in the dispersion that have a particle size of ≤800 μm have a particle size between 32 and 400 μm.

10. The process according to claim 1 , wherein the aqueous phase in the dispersion D comprises at least one constituent selected from the group consisting of crosslinkers, surfactants, and chain transfer agents.

11. The process according to claim 1 , wherein the aqueous phase in the dispersion D does not include any organic solvent.

12. The process according to claim 1 , wherein the polymerization in step (b) is conducted at a temperature 1° C. or more below the melting temperature of the compound of the structural formula (I) used.

13. The process according to claim 1 , wherein the polymerization in step (b) is a free-radical polymerization.

14. The process according to claim 1 , wherein the polymerization initiator is added to the dispersion D obtained in step (a) after the temperature of the dispersion D obtained in step (a) has dropped below the melting point of the compound of the structural formula (I) used.

15. The process according to claim 1 , wherein the temperature of the dispersion D in step (b) is below the melting temperature of the compound of the structural formula (I) used until at least 30% of the compound of the structural formula (I) used has reacted in step (a).

16. The process according to claim 1 , wherein the polymer P 1 obtained in step (b), after step (b), is subjected to a nitroxidation, giving a polymer P 2 comprising repeat units of the structural formula (VII)

17. A redox-active electrode material for electrical charge storage, comprising: the polymer P 2 according to claim 16 .

18. An electrode slurry for electrical charge storage, comprising: the polymer P 2 according to claim 16 .

Assignees

• Evonik Operations Gmbh

Inventors

• Meier Christian
• Miess Christine
• Korell Michael
• Kummer Malin
• Schmitt Günter

Classifications

• C08F4/40 Primary

  Redox systems · CPC title

• C08F2/16 Primary

  Aqueous medium · CPC title

• C08F220/34

  Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate} · CPC title

• C08F8/06

  Oxidation · CPC title

• H01M4/0466

  Electrochemical polymerisation · CPC title