Electrode materials and processes for their preparation

Patent metadata

Field	Value
Publication number	US-12230801-B2
Application number	US-201917265053-A
Country	US
Kind code	B2
Filing date	Aug 15, 2019
Priority date	Aug 15, 2018
Publication date	Feb 18, 2025
Grant date	Feb 18, 2025

Abstract

Here is described an electrode material comprising an electrochemically active metallic film and an organic compound, e.g. an indigoid compound (indigo blue or a derivative or precursor thereof). Processes for the preparation of the electrode material and electrodes containing the material, as well as to the electrochemical cells and their use are also contemplated.

First claim

The invention claimed is:

1. An electrode material comprising a film of a metallic material as electrochemically active material, and a compound of any one of Formulae I to IV:

wherein,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from a hydrogen atom, a group selected from halogen, optionally halogenated alkyl, cycloalkyl, or aryl, CN, —NO 2 , —SO 2 OM 2 , —OP(O)(OM 2 ) 2 , —P(O)(OM 2 ) 2 , or —C(O)OM 2 , wherein M 2 is a cation of an alkali or alkaline earth metal, or a —OC(O)alkyl, —SO 2 NH 2 , —SO 2 NHalkyl, or —SO 2 N(alkyl) 2 group;
R 10 is a hydrogen atom or a carbohydrate, wherein the carbohydrate is a natural or synthetic mono or disaccharide, oligo or polysaccharides;
X 1 is, independently in each occurrence, selected from O, S, NH, NR 9 , and PH, wherein R 9 is selected from natural or synthetic carbohydrate and an amine protective group; and
i. a, c and e are single bonds, b and d are double bonds, X 2 is O, and M 1 is H or a cation of an alkali or alkaline earth metal ion forming a salt with X 2 wherein the ratio of cation to the rest of the compound of Formula I, II, or III provides electroneutrality; or
ii. a, c and e are double bonds, b and d are single bonds, X 2 is O or NOH(oxime), and M 1 is absent;

a geometric isomer of a compound of Formula I, II or III, or a tautomer, oxidized form or salt of a compound of Formula IV;
or a carbohydrate complex or conjugate thereof; and
wherein the metallic material is selected from an alkali or alkaline earth metal, and alloys thereof where the alkali or alkaline earth metal is the major component.

2. The electrode material of claim 1 , wherein X 1 is O, S or NH.

3. The electrode material of claim 2 , wherein X 1 is NH.

4. The electrode material of claim 1 , wherein the compound is of Formula I, Formula II, or Formula III.

5. The electrode material of claim 4 , wherein R 2 and R 6 are the same and selected from halogen, optionally halogenated alkyl, —CN, and —SO 2 OM 2 ; and/or R 3 and R 7 are the same and selected from halogen, optionally halogenated alkyl, —CN, and —SO 2 OM 2 .

6. The electrode material of claim 4 , wherein each of R 1 to R 8 are each a hydrogen atom.

7. The electrode material of claim 4 , wherein a, c and e are single bonds, b and d are double bonds, X 2 is O, and M 1 is H or a cation of an alkali or alkaline earth metal ion forming a salt with X 2 .

8. The electrode material of claim 7 , wherein M 1 is a cation of the same metal as the metal of the film of metallic material.

9. The electrode material of claim 4 , wherein a, c and e are double bonds, b and d are single bonds, X 2 is O, and M 1 is absent.

10. The electrode material of claim 1 , wherein the compound is of Formula IV, wherein R 2 is selected from halogen, optionally halogenated alkyl, —CN, and —SO 2 OM 2 , or wherein each of R 1 to R 4 are each a hydrogen atom.

11. The electrode material of claim 10 , wherein R 10 is a hydrogen atom.

12. The electrode material of claim 10 , wherein R 10 is β-D-glucose or cellulose.

13. The electrode material of claim 1 , wherein the compound is selected from:

14. The electrode material of claim 1 , wherein the compound is selected from indigo blue, indigo carmine, isoindigo, indigopurpurin, indolinedione, and leuco-indigo, or a M 1 salt thereof.

15. The electrode material of claim 1 , wherein the metallic film is a film of an alkali or alkaline earth metal.

16. The electrode material of claim 1 , wherein the metallic film is a film of lithium or a lithium alloy comprising at least 75% of lithium by weight.

17. The electrode material of claim 1 , wherein the metallic film has a thickness between 5 μm and 200 μm.

18. The electrode material of claim 1 , wherein said compound is at a concentration of 2 wt % or less relative to the electrode material.

19. A process for producing an electrode material as defined in claim 1 , comprising the steps of:
a) mixing the compound in a solvent to obtain a mixture, the solvent being an organic aprotic inert solvent;
b) applying the mixture obtained in step (a) on the metallic film to form a treated film; and
c) removing the solvent to afford a film of the electrode material.

20. The process of claim 19 , wherein the organic aprotic inert solvent is an alkane solvent, an ether solvent, an aromatic solvent, or a combination thereof.

21. The process of claim 19 , further comprising a step (d) of washing the film of the electrode material of step (c) with a washing solvent.

22. The process of claim 19 , wherein step (b) is performed by drop-casting, mold casting, dip coating, spin coating, spray coating, printing, slot die coating, doctor blade coating, chemical vapor deposition, or physical vapor deposition.

23. A process for producing an electrode material as defined in claim 1 , comprising the steps of:
a) mixing the compound in a lubricating agent to obtain a lubricating composition;
b) applying the lubricating composition obtained in step (a) on a metallic foil of the metallic material to form a treated foil; and
c) extruding between at least two rolls the treated foil obtained in step (b).

24. The process of claim 23 , wherein steps (b) and (c) are carried out simultaneously.

25. The process of claim 23 , wherein the lubricating agent comprises a polymer.

26. The process of claim 23 , wherein the lubricating agent comprises a solvent, the solvent being an organic aprotic inert solvent.

27. The process of claim 26 , further comprising a step (d) of removing the solvent.

28. The process of claim 23 , wherein the compound is at a concentration of between 0.001 wt % and 2 wt % in the lubricating composition.

29. A process for producing an electrode material as defined in claim 1 , comprising the steps of:
a) melting an alkali metal or an alloy thereof to obtain a molten metal;
b) mixing the compound with the molten metal, casting and allowing to solidify to form an ingot, wherein said mixing and casting may be carried out in any order; and
c) extruding between at least two rolls the ingot obtained in (b) into a film to be used as electrode material.

30. An electrode comprising an electrode material as defined in claim 1 on a current collector.

31. An electrochemical cell comprising an electrode containing an electrode material as defined in claim 1 , an electrolyte and a counter-electrode.

32. A battery comprising at least one electrochemical cell as defined in claim 31 .

Assignees

• Hydro Quebec
• Murata Manufacturing Co

Inventors

• Mallet Charlotte
• Verreault Serge
• Pronovost Josée
• Rochon Sylviane
• Daigle Jean-Christophe
• Amouzegar Kamyab
• Zaghib Karim

Classifications

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M10/0565

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

• H01M10/0525

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

• H01M4/661

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title