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

Patent metadata

Field	Value
Publication number	US-11469419-B2
Application number	US-201816644714-A
Country	US
Kind code	B2
Filing date	Oct 2, 2018
Priority date	Oct 2, 2017
Publication date	Oct 11, 2022
Grant date	Oct 11, 2022

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

The invention claimed is:

1. Polymer of Formula I:

wherein:
A is an unsaturated group allowing the delocalization of electrons selected from 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; and
n represents the average number of units in the polymer.

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

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

3. The polymer according to claim 1 , the polymer being of Formula I (b):

wherein m and n are as defined in claim 1 .

4. Electrode material comprising a polymer as defined in claim 1 , and optionally elemental sulfur, and/or a conductive material, and/or a binder.

5. The electrode material according to claim 4 , wherein the conductive material is carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanotubes, or a combination of at least two thereof.

6. The electrode material according to claim 4 , wherein the binder is a polymeric binder of polyether type, a fluorinated polymer, or a water-soluble binder.

7. The electrode material according to claim 6 , wherein:
the polymeric binder of polyether type is linear, branched 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;
the fluorinated polymer binder is PVDF (polyvinylidene fluoride) or PTFE (polytetrafluoroethylene); or
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).

8. Positive electrode comprising an electrode material according to claim 4 applied on a current collector.

9. Electrochemical cell comprising a cathode, an electrolyte and an anode, wherein the cathode comprises an electrode material as defined in claim 4 .

10. Lithium battery comprising an electrochemical cell as defined in claim 9 .

11. Electrolyte comprising a polymer as defined in claim 1 , and optionally elemental sulfur.

12. The electrode according to claim 11 , the electrolyte being a liquid electrolyte comprising a salt in a solvent or a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

13. The electrode according to claim 12 , the solvent of the liquid or gel electrolyte is 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.

14. The electrode according to claim 11 , the electrolyte being a solid polymer electrolyte (SPE) comprising a salt in a solvating polymer.

15. The electrode according to claim 14 , the salt being a lithium salt 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 (LiBF 4 ), 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 combinations thereof.

16. The electrode according to claim 11 , the electrolyte further comprising an electrolyte binder.

17. Electrochemical cell comprising a cathode, an anode and an electrolyte as defined in claim 11 .

18. Lithium battery comprising an electrochemical cell as defined in claim 17 .

19. Solid polymer electrolyte comprising a salt in a solvating polymer and optionally elemental sulfur, wherein the solvating polymer is as defined in claim 1 .

20. The polymer according to claim 1 , wherein A is selected from benzene, naphthalene, perylene, and biphenyl groups.

21. The polymer according to claim 1 , wherein R is selected from the groups benzene, ethylene, propylene, poly(ethylene glycol), poly(propylene glycol), and copolymers of ethylene glycol and propylene glycol.

22. The polymer according to claim 1 , wherein m is 0<m≤8.

23. The polymer according to claim 1 , wherein m is 1≤m≤6.

24. The polymer according to claim 1 , wherein m is 1≤m≤4.

25. The polymer according to claim 1 , wherein n is in the range of 5 to 300.

Assignees

• Hydro Quebec

Inventors

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

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0565

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

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M10/0567

  characterised by the additives · CPC title