LITHIUM ELECTROCHEMICAL GENERATOR OF THE LITHIUM-OXYGEN OR LITHIUM-AIR TYPE COMPRISING A SPECIFIC NEGATIVE ELECTRODE MATERIAL

• US 20200136135A1
• Filed: 10/23/2019
• Published: 04/30/2020
• Est. Priority Date: 10/29/2018
• Status: Active Grant

• Current Assignee: Commissariat a L'Energie Atomique (French Alternative Energies and Atomic Energy Commission)
• Original Assignee: Commissariat a L'Energie Atomique (French Alternative Energies and Atomic Energy Commission)
• Inventors: Chavillon, Benoit, Invernizzi, Ronan, Mayousse, Eric
• Granted Patent: US 11,258,061 B2
• Time in Patent Office: Days
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 12/02 Details of electrodes H01M4/00; of non-active parts H01M50/00
• CPC Class Codes: H01M 12/04 composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 2004/8689 Positive electrodes
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/8668 Binders
• CPC Class Codes: H01M 4/8673 Electrically conductive fillers
• CPC Class Codes: H01M 4/9016 Oxides, hydroxides or oxygenated metallic salts
• CPC Class Codes: H01M 4/9041 Metals or alloys H01M4/92 takes precedence
• CPC Class Codes: H01M 4/9058 of noble metals or noble-metal based alloys
• CPC Class Codes: H01M 6/164 by the solvent
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A lithium-air or lithium-oxygen electrochemical generator comprising at least one electrochemical cell comprising a positive electrode, a negative electrode and an electrolyte conducting lithium ions disposed between the negative electrode and the positive electrod wherein the negative electrode comprises, as active material, a lithium and calcium alloy.

Claims

1. Lithium-air or lithium-oxygen electrochemical generator comprising at least one electrochemical cell comprising a positive electrode, a negative electrode and an electrolyte conducting lithium ions disposed between said negative electrode and said positive electrode, characterised in that the negative electrode comprises, as active material, a lithium and calcium alloy, the lithium and calcium alloy being a lithium alloy comprising calcium to the extent of 2% to 34% atomic.

2. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the negative electrode consists solely of the active material, which is the lithium and calcium alloy.

3. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the negative electrode is in the form of a sheet or plate having a thickness ranging from 5 to 200 μ

m.

4. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the lithium and calcium alloy comprises solely lithium and calcium.

5. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the lithium and calcium alloy is a lithium alloy comprising calcium to the extent of 2% to 15% atomic.

6. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the calcium in the lithium and calcium alloy is wholly or partly in the form of CaLi₂.

7. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the negative electrode is self-supporting.

8. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the positive electrode is an air or oxygen electrode.

9. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the positive electrode comprises:

at least one electron-conducting material;

optionally at least one catalyst; and

optionally at least one binder.

10. Lithium-air or lithium-oxygen electrochemical generator according to claim 9, wherein the electron conducting material is a carbon material chosen from graphite, mesocarbon beads, carbon fibres, carbon black, graphene, carbon nanotubes and mixtures thereof.

11. Lithium-air or lithium-oxygen electrochemical generator according to claim 9, wherein the catalyst is:

a catalyst consisting of a transition metal with a degree of oxidation 0, such as cobalt, and more specifically a noble metal with a degree of oxidation 0 such as platinum, gold, palladium, ruthenium or alloys thereof, such as a Pt—

Au alloy;

a catalyst comprising a simple ruthenium oxide such as RuO₂, a simple manganese oxide such as MnO₂ or Mn₂O₃, a simple iron oxide such as Fe₃O₄ or Fe₂O₃, a simple cobalt oxide such as Co₃O₄ or a simple copper oxide such as CuO;

a catalyst comprising a mixed cobalt oxide such as CoFe₂O₄, a mixed manganese oxide such as LaMnO₃ or a mixed nickel oxide such as LaNiO₃;

or

mixtures thereof.

12. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the binder is a polymeric binder.

13. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the electrolyte is an aqueous or non-aqueous liquid electrolyte, an ionic liquid, a solid electrolyte or a polymer electrolyte.

14. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the electrolyte is a non-aqueous liquid electrolyte.

15. Lithium-air or lithium-oxygen electrochemical generator according to claim 1, wherein the electrolyte is a non-aqueous liquid electrolyte, which comprises:

as solvent(s), one or more organic solvents chosen from carbonate solvents, ether solvents, sulfone solvents, sulfoxide solvents, lactone solvents, lactam solvents, nitrile solvents, fluorinated solvents and mixtures thereof;

at least one lithium salt;

optionally an additive other than a lithium salt.