Graphite-carbohydrate active material particles with carbonized carbohydrates

• US 10,468,727 B2
• Filed: 01/28/2019
• Issued: 11/05/2019
• Est. Priority Date: 04/07/2016
• Status: Active Grant

• Current Assignee: StoreDot Ltd.
• Original Assignee: StoreDot Ltd.
• Inventors: Jacob, David, Remizov, Sergey, Shadmi, Nitzan, Farran, Hani, Aronov, Daniel, Brudnik, Boris
• Primary Examiner(s): Walls, Cynthia K
• Application Number:
  US16/258,728
• Publication Number:
  US 20190157727A1
• Time in Patent Office: 281 Days
• CPC Class Codes: C09D 179/02 Polyamines
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• 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 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/364 as mixtures
• 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: Y02E 60/10 Energy storage using batteries

Abstract

Methods of making anode active materials include milling graphite particles with carbohydrate particles to yield graphite-carbohydrate particles, milling the particles with anode material and carbonizing to form composite anode material particles. The anode active materials thus producted are provided with an at least partially porous carbon-graphite coating with both electronic and ionic conductivity.

Claims

1. A method for making composite anode material comprising:

milling graphite particles with carbohydrate particles to yield graphite-carbohydrate particles,

milling the graphite-carbohydrate particles with anode material particles having a native oxide layer, to form a graphite-carbohydrate layer over at least part of a surface of the anode material particles, and

carbonizing the milled anode material particles to form composite anode material particles which are de-oxidized and have at least a partial composite porous carbon-graphite coating forming an at least partial porous graphite shell over the anode material particles.

2. The method of claim 1, further comprising mixing the graphite particles and the carbohydrate particles at a weight ratio between 3:

7 and 8;

2.

3. The method of claim 2, wherein the mixing is carried out at a 1:

1 weight ratio.

4. The method of claim 1, wherein the carbohydrate particles comprise sugar crystals and the graphite-carbohydrate layer is a graphite-sugar layer.

5. The method of claim 1, further comprising carrying out the milling and the carbonizing in a dry environment and avoiding agglomeration of the anode material particles.

6. The method of claim 1, further comprising configuring the at least partial porous graphite shell to have a lower surface energy than the anode material particles, to prevent agglomeration of the composite anode material particles in a water-based slurry.

7. The method of claim 1, further comprising configuring the at least partial porous graphite shell to have a lower surface energy than the anode material particles, to prevent agglomeration of the composite anode material particles in an organic solvent.

8. The method of claim 1, further comprising carrying out the carbonizing at between at 600°

C. and 900°

C. in an inert environment.

9. The method of claim 8, wherein the inert environment comprises at least one of Ar, N, CO₂, and their mixtures.

10. The method of claim 9, further comprising fine tuning the inert environment to carry out simultaneously at least partial reduction of the native oxide layer and removal of water and gasses from graphite-carbohydrate layer, to adjust a porosity of the carbon-graphite coating.

11. The method of claim 10, comprising fine tuning the inert environment with respect to the reduction and formation of carbonization products according to reaction C_m(H₂O)_n→

mC+nH₂O, wherein m and n are integers.

12. The method of claim 1, wherein the forming of the at least partial porous graphite shell over the anode material particles is configured to retain electronic conductivity to the anode material particles through the graphite of the shell while providing ionic conductivity through pores of the porous shells.

13. The method of claim 1, wherein the forming of the at least partial porous graphite shell over the anode material particles is configured to mechanically stabilize the composite anode material particles during expansion upon lithiation thereof—

by bonding the porous graphite shell to the anode material particles during the carbonizing.

14. The method of claim 1, further comprising coating the composite anode material particles by at least one polymer coating and/or lithiated coating.

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

16. The method of claim 1, wherein the anode material particles are at least partly metalloid, comprising at least one of Si, Ge and Sn.