Material for an electrode of an organic battery comprising benzene-bis(dithioic) acid derivatives

Patent metadata

Field	Value
Publication number	US-2016254531-A1
Application number	US-201415033658-A
Country	US
Kind code	A1
Filing date	Oct 29, 2014
Priority date	Oct 30, 2013
Publication date	Sep 1, 2016
Grant date	—

Abstract

The present invention concerns the use, as an active electrode material, of compounds comprising at least one entity of formula (I): in which the phenyl group is substituted with one to four identical or different substituent(s) R, chosen from a hydrogen atom, a halogen atom chosen from fluorine, chlorine, bromine or iodine, a —C(═S)—S—C+ group, an —O—C+ group, an —S—C+ group, C+ being an alkali cation chosen from Li+, Na+ and K+, a (C1-C 12) alkyl radical, a (C2-C12) alkenyl radical, a (C6-C14) aryl or heteroaryl radical; or two vicinal substituents R that can, if appropriate, be linked to each other to together form a 3- to 7-membered ring optionally including another heteroatom chosen from N, O or S; in the base or salt form; and the tautomeric forms of same. It also concerns an electrode material, an electrode and a lithium, sodium or potassium secondary battery, obtained from these compounds.

First claim

1 . An electrode active material comprising a compound comprising at least one entity selected from the group consisting of formula (I):

in which the phenyl group is substituted by one to four substituent(s) R, which are identical or different, selected from the group consisting of a hydrogen atom, a halogen atom chosen from fluorine, chlorine, bromine or iodine, a —C(═S)—S − C + group, an —O − C + group, an —S − C + group, with C + being an alkali metal cation chosen from Li + , Na + and K + , (C 1 -C 12 )alkyl radical, a (C 2 -C 12 )alkenyl radical or a (C 6 -C 14 ) aryl or -heteroaryl radical or it being possible for two vicinal substituents R, if appropriate, to be bonded to one another in order to together form a 3- to 7-membered ring optionally including another heteroatom chosen from N, O or S;
bases or salts thereof; and
tautomeric forms thereof.

2 . The electrode active material as claimed in claim 1 , wherein said compound is represented by formula (II):

in which:
C + is an alkali metal cation chosen from Li + , Na + and K + ; and
at least one of the substituents R 1 , R 2 , R 3 , R 4 or R 5 represents a —C(═S)—S − C + group, C + being as defined above, the others, which are identical or different, representing a substituent R as defined above;
or bases, salts, or tautomeric forms thereof.

3 . The electrode active material as claimed in claim 2 , wherein R 3 represents a —C(═S)—S − C + group, and R 1 , R 2 , R 4 and R 5 , which are identical or different, represent a substituent R as defined in above.

4 . The electrode active material as claimed in claim 1 , wherein R represents a hydrogen atom, a —C(═S)—S − C + group, an —SC + group or an S − C + group, C + being a cation chosen from Li + , Na + and K + .

5 . The electrode active material as claimed in claim 1 , wherein R represents a hydrogen atom.

6 . The electrode active material as claimed in claim 1 , wherein the compound is bislithium 1,4-benzenebisdithioate of formula:

or its tautomeric form.

7 . A compound of formula (IIa):

in which:
at least one of the substituents R 1 , R 2 , R 3 , R 4 or R 5 represents a —C(═S)—SLi group, the others, which are identical or different, representing a substituent R selected from the group consisting of a hydrogen atom, a halogen atom chosen from chlorine, bromine or iodine, a —C(═S)—SLi group, an —OLi group, an —SLi group, a (C 1 -C 12 )alkyl radical, a (C 2 -C 12 )alkenyl radical or a (C 6 -C 14 ) aryl or heteroaryl radical or it being possible for two vicinal substituents R, if appropriate, to be bonded to one another in order to together form a 3- to 7-membered ring optionally including another heteroatom chosen from N, O or S;
or base, salt, or tautomeric forms thereof.

8 . An electrode active material comprising at least one compound as defined in claim 7 .

9 . The material as claimed in claim 8 , which is provided in the form of a dispersed powder or in solution in said conducting additive or binder.

10 . An electrode formed in all or part of an active material comprising at least one electrode active material according to claim 1 and at least one electron-conducting additive.

11 . The electrode as claimed in claim 10 , said electron-conducting additive(s) being selected from the group consisting of carbon fibers, carbon black, carbon nanotubes, graphene and their analogues.

12 . The electrode as claimed in claim 10 , additionally comprising at least one binder.

13 . The electrode as claimed in claim 12 , said binder(s) being selected from the group consisting of fluorinated binders, polymers derived from carboxymethyl cellulose, polysaccharides and latexes.

14 . A process for the preparation of an electrode as defined according to claim 10 , comprising at least the stages of:
(i) having available a mixture formed:
of at least one of said electrode active material,
of a liquid phase
of one or more electron-conducting additive(s), and
optionally of one or more binder(s); and
(ii) depositing said mixture from stage (i) by coating or by a printing technique on a base substrate or by extrusion or by corolling.

15 . The process as claimed in claim 14 , said base substrate being a polymeric film of polyethylene or polypropylene type, said process comprising a subsequent stage (iii) of detaching said polymeric film, in order to form a self-supported electrode.

16 . A process for the preparation of an electrode formed in all or part of an active material comprising at least one electrode active material according to claim 1 , comprising the formation of a polymer by in situ electropolymerization on a current collector of monomers functionalized by entities of formula (I).

17 . The process as claimed in claim 16 , comprising at least the stages of:
(i) introducing said monomers functionalized by entities of the formula (I) in the powder form into the electrolyte of a lithium, sodium or potassium electrochemical cell or dissolving said functionalized monomers in the electrolyte of a lithium, sodium or potassium electrochemical cell; and (ii) carrying out at least one charging cycle of the cell in order to form a positive electrode or at least one discharging cycle of the cell in order to form a negative electrode.

18 . A lithium, sodium or potassium storage battery, comprising an electrode formed in all or part of an active material comprising at least one electrode active material according to claim 1 .

19 . The battery as claimed in claim being a lithium storage battery.

Assignees

• Commissariat Energie Atomique
• Commissariat à l'Energie Atomique et aux Energies Alternatives

Inventors

• Gutel Thibaut
• Dubois Lionel
• Iordache Adriana

Classifications

• H01M4/623

  fluorinated polymers · CPC title

• H01M4/1399

  of electrodes based on electro-active polymers · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/602

  Polymers · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title