Sulfur-containing compounds and polymers and the use thereof in electrochemical cells

Patent metadata

Field	Value
Publication number	US-2020287218-A1
Application number	US-201816644714-A
Country	US
Kind code	A1
Filing date	Oct 2, 2018
Priority date	Oct 2, 2017
Publication date	Sep 10, 2020
Grant date	—

Abstract

The present technology relates to a sulfur-containing polymer or organic compound for use in a positive electrode material, especially in lithium batteries. More specifically, the use of this sulfur-containing polymer or compound as an active electrode material makes it possible to combine sulfur and an active organic cathode material. The present technology also relates to the use of the sulfur-containing polymer or organic compound as defined herein as a solid polymer electrolyte (SPE) or as an additive for electrolyte, especially in lithium batteries.

First claim

1 . Polymer of Formula I:

wherein:
A is selected from unsaturated groups allowing the delocalization of electrons, for example, substituted or unsubstituted aryl and heteroaryl groups, and their fused or unfused polycyclic equivalents;
R is a substituted or unsubstituted organic linking group selected from linear or branched C 2-6 alkylene, linear or branched C 2-6 alkyleneoxy, linear or branched C 2-6 alkyleneglycol, linear or branched C 2-6 alkyleneoxyC 2-6 alkylene, linear or branched poly(C 2-6 alkyleneglycol), C 6-12 arylene, C 3-12 cycloalkylene, C 5-12 heteroarylene, and C 3-12 heterocycloalkylene;
m represents the average number of sulfur atoms inserted into the disulfide bond of the polymer links and cannot be zero, i.e. m>0, for example, 0<m≤8, or 1≤m≤6, or 1≤m≤4; and
n represents the average number of units in the polymer, for example, n may be in the range of 2 to 500, or of 5 to 300.

2 . Polymer according to claim 1 , wherein A is selected from benzene, naphthalene, perylene, and biphenyl groups.

3 . Polymer according to claim 1 or 2 , the polymer being of Formula I(a):

wherein R, m and n are as defined in claim 1 .

4 . Polymer according to any one of claims 1 to 3 , wherein R is selected from the groups benzene, ethylene, propylene, poly(ethylene glycol), poly(propylene glycol), and copolymers of ethylene glycol and propylene glycol.

5 . Polymer according to claim 4 , the polymer being of Formula I(b):

wherein m and n are as defined in claim 1 .

6 . Compound of Formula II:

wherein A and R are as defined in any one of claims 1 , 2 and 4 ; and m represents the number of sulfur atoms inserted into the disulfide bond of the compound, for example, m>0, for example, 0<m≤8, or 1≤m≤6, or 1≤m≤4.

7 . Compound according to claim 6 , the compound being of Formula II(a):

wherein R and m are as defined in claim 6 .

8 . Compound according to claim 6 , the compound being of Formula II(b):

wherein m is as defined in claim 6 .

9 . Electrode material comprising a polymer as defined in any one of claims 1 to 5 or a compound as defined in any one of claims 6 to 8 .

10 . Electrode material according to claim 9 , further comprising elemental sulfur.

11 . Electrode material according to claim 9 or 10 , further comprising a conductive material, a binder, or a combination of both.

12 . Electrode material according to claim 11 , wherein the conductive material is selected from carbon black, Ketjen™ carbon, Shawinigan carbon, acetylene black, graphite, graphene, carbon fibers (such as carbon nanofibers (for example, VGCF formed in the gas phase)), and carbon nanotubes, or a combination of at least two thereof.

13 . Electrode material according to claim 11 or 12 , wherein the binder is a polymeric binder of polyether type, a fluorinated polymer, or a water-soluble binder.

14 . Electrode material according to claim 13 , wherein the polymeric binder of polyether type is linear, branched and/or crosslinked and is based on poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), or a mixture of the two (or an EO/PO co-polymer), and optionally comprises crosslinkable units.

15 . Electrode material according to claim 13 , wherein the fluorinated polymer binder is PVDF (polyvinylidene fluoride) or PTFE (polytetrafluoroethylene).

16 . Electrode material according to claim 13 , wherein the water-soluble binder is SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), or ACM (acrylate rubber), optionally comprising CMC (carboxymethyl cellulose).

17 . Positive electrode comprising an electrode material according to any one of claims 9 to 16 applied on a current collector.

18 . Electrolyte comprising a polymer as defined in any one of claims 1 to 5 or a compound as defined in any one of claims 6 to 8 .

19 . Electrolyte according to claim 18 , the electrolyte being a liquid electrolyte comprising a salt in a solvent.

20 . Electrolyte according to claim 18 , the electrolyte being a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

21 . Electrolyte according to claim 19 or 20 , the solvent being a polar aprotic solvent selected from ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), γ-butyrolactone (γ-BL), vinylene carbonate (VC), methyl butyrate (MB), γ-valerolactone (γ-VL), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), 2-methyltetrahydrofuran, dimethylsulfoxide, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethylmonoglyme, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, propylene carbonate derivatives, tetrahydrofuran, and mixtures thereof.

22 . Electrolyte according to claim 18 , the electrolyte being a solid polymer electrolyte (SPE) comprising a salt in a solvating polymer.

23 . Electrolyte according to any one of claims 18 to 22 , the polymer or the compound being an additive.

24 . Electrolyte according to claim 22 , the solvating polymer being the polymer as defined in any one of claims 1 to 5 or the compound as defined in any one of claims 6 to 8 .

25 . Electrolyte according to any one of claims 18 to 24 , the electrolyte further comprising elemental sulfur.

26 . Electrolyte according to any one of claims 19 to 25 , the salt being a lithium salt.

27 . Electrolyte according to claim 26 , the salt being selected from lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO 3 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiSO 3 CF 3 ) (LiTf), lithium fluoroalkylphosphate Li[PF 3 (CF 2 CF 3 ) 3 ] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF 3 ) 4 ] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O′)borate Li[B(C 6 O 2 ) 2 ] (LBBB) and a combinations thereof.

28 . Electrolyte according to any one of claims 18 to 27 , the electrolyte further comprising an electrolyte binder.

29 . Electrolyte according to claim 28 , wherein the electrolyte binder is a polymeric binder of polyether type, a fluorinated polymer, or a water-soluble binder.

Assignees

• Hydro Quebec

Inventors

• Lévesque-Bélanger Rachel
• Paolella Andrea
• Daigle Jean-Christophe
• Commarieu Basile
• Armand Michel
• Zaghib Karim

Classifications

• C08G73/1064

  containing sulfur · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M10/0565

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/602 Primary

  Polymers · CPC title