Coated pre-lithiated anode material particles and cross-linked polymer coatings

• US 10,290,864 B2
• Filed: 04/06/2017
• Issued: 05/14/2019
• Est. Priority Date: 04/07/2016
• Status: Active Grant

• Current Assignee: StoreDot Ltd.
• Original Assignee: StoreDot Ltd.
• Inventors: Burshtain, Doron, Kedem, Nir, Sella, Eran, Aronov, Daniel, Farran, Hani, Shapiro, Leora
• Primary Examiner(s): Walls, Cynthia K
• Application Number:
  US15/480,919
• Publication Number:
  US 20170294648A1
• Time in Patent Office: 768 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 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/134 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 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/608 containing heterocyclic rings
• CPC Class Codes: H01M 4/624 Electric conductive fillers
• CPC Class Codes: H01M 4/625 Carbon or graphite
• 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. An anode comprising anode active material particles which are coated by at least one coating, wherein the anode active material particles comprise at least one of Si, Ge, Sn and Al and the at least one coating is at least partly polymeric,

wherein the anode active material particles are attached to the polymeric coating provided that the attachment consists of a physical attachment;

wherein the anode active material particles are coated with the polymeric coating prior to the anode formation;

wherein the polymeric coating forms a polymerized matrix in which the anode active material particles are dispersed uniformly; and

wherein the anode active material particles are pre-lithiated and the at least one coating comprises a hydrophobic conductive polymer.

2. The anode of claim 1, wherein the hydrophobic conductive polymer is lithiated.

3. The anode of claim 2, wherein the lithiated hydrophobic conductive polymer comprises a buffering zone configured to receive lithium ions from an interface of the anode active material particles with an electrolyte, partially reduce the received lithium ions, and enable the partially reduced lithium ions to move into an inner zone of the anode active material particles for lithiation therein.

4. The anode of claim 1, wherein the hydrophobic conductive polymer comprises polyaniline which is polymerized prior to the anode formation.

5. The anode of claim 1, wherein the hydrophobic conductive polymer comprises conjugated aromatic groups and is ionic conductive.

6. The anode of claim 1, wherein the hydrophobic conductive polymer comprises polypyrrole and/or polyaniline.

7. The anode of claim 1, wherein the at least one coating comprises at least one lithiated polymer.

8. The anode of claim 7, wherein the at least one lithiated polymer comprises at least one of lithium polyphosphate, lithium poly(acrylic acid), lithium carboxyl methyl cellulose and lithium alginate.

9. The anode 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.

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

11. A lithium ion cell comprising the anode of claim 1.

12. An anode comprising anode active material particles which are coated by at least one coating, wherein the anode active material particles comprise at least one of Si, Ge, Sn and Al and the at least one coating is at least partly polymeric,

wherein the anode active material particles are attached to the polymeric coating provided that the attachment consists of a physical attachment;

wherein the anode active material particles are coated with the polymeric coating prior to the anode formation;

wherein the polymeric coating forms a polymerized matrix in which the anode active material particles are dispersed uniformly;

wherein the anode further comprises linker molecules configured to cross-link the polymerized matrix and the anode active material particles physically attached thereto, by binding at least some of anode material particles to the polymerized matrix; and

wherein the polymerized matrix comprises polyaniline and the linker molecules have carboxylic groups which chemically bind to oxides of the active material particles and to lone electron pairs on a nitrogen of the aniline monomers in the polyaniline matrix.

13. The anode of claim 12, wherein the linker molecules have sulfonate groups which chemically bind to oxides of the active material particles.

14. The anode of claim 12, wherein the linker molecules consist of at least one of:

5-sulfoisophthalic acid or its derivatives, succinic acid or other dicarboxylic acids.