Methods for preparing anodes from anode active material particles with lithium borates and phosphates coatings

• US 10,454,104 B2
• Filed: 01/09/2019
• Issued: 10/22/2019
• Est. Priority Date: 04/07/2016
• Status: Active Grant

• Current Assignee: StoreDot Ltd.
• Original Assignee: StoreDot Ltd.
• Inventors: Burshtain, Doron, Kedem, Nir, Aronov, Daniel
• Primary Examiner(s): Rhee, Jane J
• Application Number:
  US16/243,193
• Publication Number:
  US 20190148722A1
• Time in Patent Office: 286 Days
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/387 Tin or alloys based on tin
• CPC Class Codes: H01M 4/624 Electric conductive fillers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Improved anodes and cells are provided, which enable fast charging rates with enhanced safety due to much reduced probability of metallization of lithium on the anode, preventing dendrite growth and related risks of fire or explosion. Anodes and/or electrolytes have buffering zones for partly reducing and gradually introducing lithium ions into the anode for lithiation, to prevent lithium ion accumulation at the anode electrolyte interface and consequent metallization and dendrite growth. Various anode active materials and combinations, modifications through nanoparticles and a range of coatings which implement the improved anodes are provided.

Claims

1. A method for preparing a lithium ion cell, comprising:

replacing a native oxide on a surface of anode active material particles that comprise at least one of Si, Ge, Sn and Al, by a layer of B₂O₃,

coating the anode active material particles by at least one coating that comprises at least one of a boron oxide, a phosphorus oxide, a borate, a phosphate and/or salts thereof,

preparing an anode from the anode active material particles, and

preparing a lithium ion cell using the prepared anode.

2. The method of claim 1, wherein the layer of B₂O₃ is part of and/or is derived from the at least one coating.

3. The method of claim 1, wherein the at least one coating comprises crystals of borate salt and/or phosphate.

4. The method of claim 1, further comprising configuring the at least one coating to provide a buffering zone that receives lithium ions from an interface of the anode active material particles with an electrolyte, wherein the buffering zone partially reduces the received lithium ions, and enables the partially reduced lithium ions to move into an inner zone of the anode active material particles for lithiation therein.

5. The method of claim 1, wherein the coating is carried out by milling and the anode preparation is carried out by mixing the milled coated particles with at least one conductive filler and at least one binder.

6. The method of claim 1, wherein the anode active material particles are 20-500 nm in diameter and the at least one coating is 2-200 nm thick.

7. The method of claim 1, wherein the at least one coating further comprises a layer of at least one of:

an amorphous carbon, graphene, graphite, a transition metal and a lithiated polymer.

8. A method of making an anode for a lithium-ion energy storage device, comprising milling anode active material particles selected from Si, Ge, Sn, Al, mixtures thereof, and/or alloys thereof—

in a non-oxidizing atmosphere with at least one boron oxide compound and/or phosphorus oxide compound to form milled particles having a coating on the particles selected from the group consisting of a boron oxide, a phosphorus oxide, a borate and/or a phosphate, having a thickness in a range of 2 nm to 200 nm.

9. The method of claim 8, wherein said at least one boron oxide compound or phosphorous oxide compound contains lithium.

10. The method of claim 9, further comprising bonding a hydrophobic polymer layer to said anode active material particles by ball milling the hydrophobic polymer with the anode active material particles.

11. The method of claim 8, further comprising mixing the milled particles with at least one conductive filler and at least one binder to prepare an anode for a lithium-ion energy storage device.

12. The method of claim 8, further comprising coating the anode active material particles with a layer of lithiated conductive polymer.

13. The method of claim 8, further comprising coating the anode active material particles with a layer of carbon or transition metal oxide having a thickness of 1-10 nm.

14. The method of claim 8, wherein the coating further comprises a layer of at least one of:

an amorphous carbon, graphene, graphite, a transition metal and a lithiated polymer.

15. A method for making a lithium ion cell comprising:

coating anode active material particles that comprise at least one of Si, Ge, Sn and Al—

by at least one coating that comprises at least one of a boron oxide, a phosphorus oxide, a borate, a phosphate and/or salts thereof, at least one lithiated conductive polymer, and/or a hydrophobic conductive polymer which has conjugated aromatic groups and is ionic conductive,

preparing an anode from the coated anode active material particles, and

preparing a lithium ion cell using the prepared anode.

16. The method of claim 15, further comprising configuring the at least one coating to provide a buffering zone that receives lithium ions from an interface of the anode active material particles with an electrolyte, wherein the buffering zone partially reduces the received lithium ions, and enables the partially reduced lithium ions to move into an inner zone of the anode active material particles for lithiation therein.

17. The method of claim 15, wherein the anode active material particles are 20-500 nm in diameter and the at least one coating is 2-200 nm thick.

18. The method of claim 15, wherein the at least one coating further comprises a layer of at least one of:

an amorphous carbon, graphene, graphite, a transition metal and a lithiated polymer.

19. The method of claim 15, further comprising carrying out the anode preparation by forming a slurry with the active material particles, a solvent, and at least one additive selected from the group consisting of conductive particles, binder and plasticizer;

and removing the solvent and consolidating the slurry to form the anode.