Electroactive materials for metal-ion batteries

Patent metadata

Field	Value
Publication number	US-11011748-B2
Application number	US-201916274182-A
Country	US
Kind code	B2
Filing date	Feb 12, 2019
Priority date	Nov 8, 2018
Publication date	May 18, 2021
Grant date	May 18, 2021

Abstract

This invention relates to particulate electroactive materials comprising a plurality of composite particles, wherein the composite particles comprise: (a) a porous carbon framework including micropores and optional mesopores having a total volume of at least 0.7 cm3/g and up to 2 cm3/g, wherein at least half of the total micropore and mesopore volume is in the form of pores having a diameter of no more than 1.5 nm; and (b) silicon located within the micropores and optional mesopores of the porous carbon framework in a defined amount relative to the total volume of the micropores and optional mesopores.

First claim

The invention claimed is:

1. A particulate material comprising a plurality of composite particles, wherein the composite particles comprise:
(a) a porous carbon framework comprising micropores and mesopores,
wherein the micropores and mesopores have a total pore volume as measured by gas adsorption of P 1 cm 3 /g, wherein P 1 has a value of at least 0.75 and up to 1.5, and
wherein the PD 50 pore diameter as measured by gas adsorption is no more than 1.5 nm; and

(b) a plurality of elemental nanoscale silicon domains located at least within the micropores of the porous carbon framework;

wherein the weight ratio of silicon to the porous carbon framework in the composite particles is in the range from [0.65×P 1 to 1.3×P 1 ]:1, and
wherein at least 90 wt % of the silicon mass in the composite particles is located within the internal pore volume of the porous carbon framework.

2. A particulate material according to claim 1 , wherein P 1 has a value of at least 0.8.

3. A particulate material according to claim 1 , wherein P 1 has a value of up to 1.3.

4. A particulate material according to claim 1 , wherein the PD 50 pore diameter of the porous carbon framework is no more than 1.4 nm.

5. A particulate material according to claim 1 , wherein the PD 60 pore diameter of the porous carbon framework is no more than 2 nm.

6. A particulate material according to claim 5 , wherein the PD 70 pore diameter of the porous carbon framework is no more than 2.5 nm.

7. A particulate material according to claim 6 , wherein the PD 80 pore diameter of the porous carbon framework is no more than 3 nm.

8. A particulate material according to claim 1 , wherein the PD 90 pore diameter of the porous carbon framework is no more than 10 nm.

9. A particulate material according to claim 8 , wherein the PD 95 pore diameter of the porous carbon framework is no more than 15 nm.

10. A particulate material according to claim 1 , wherein the porous carbon framework has a monomodal pore size distribution.

11. A particulate material according to claim 1 , wherein the porous carbon framework has a bimodal or multimodal pore size distribution.

12. A particulate material according to claim 11 , wherein the porous carbon framework has a bimodal or multimodal pore size distribution including at least one peak at less than 2 nm and at least one peak in the range from 5 to 50 nm.

13. A particulate material according to claim 1 , wherein the porous carbon framework comprises macropores having a diameter in the range from greater than 50 nm to 100 nm having a total volume P 2 cm 3 /g as measured by mercury porosimetry, wherein P 2 is no more than 0.2×P 1 .

14. A particulate material according to claim 1 , wherein the weight ratio of silicon to the porous carbon framework is in the range from [1×P 1 to 1.3×P 1 ]:1.

15. A particulate material according to claim 1 , wherein at least a portion of the micropores comprise void space that is fully enclosed by the silicon.

16. A particulate material according to claim 1 , wherein the composite particles have a D 50 particle diameter in the range of 0.5 to 50 μm.

17. A particulate material according to claim 16 , wherein the composite particles have a D 50 particle diameter of at least 1 μm.

18. A particulate material according to claim 16 , wherein the composite particles have a D 50 particle diameter of no more than 40 μm.

19. A particulate material according to claim 1 , wherein the composite particles have a D 10 particle diameter of at least 0.2 μm.

20. A particulate material according to claim 1 , wherein the composite particles have a D 90 particle diameter of no more than 80 μm.

21. A particulate material according to claim 1 , wherein the composite particles have a BET surface area of at least 0.1 m 2 /g and no more than 60 m 2 /g.

22. A particulate material according to claim 1 , wherein the volume of micropores and mesopores of the composite particles, as measured by nitrogen gas adsorption, is no more than 0.15×P 1 .

23. A particulate material according to claim 1 , having specific capacity on lithiation of 1200 to 2340 mAh/g.

24. A particulate material according to claim 1 , wherein
the PD 50 pore diameter of the porous carbon framework is no more than 1.4 nm; and
the PD 80 pore diameter of the porous carbon framework is no more than 3 nm.

25. A particulate material according to claim 24 , wherein the composite particles have a BET surface area of at least 0.1 m 2 /g and no more than 60 m 2 /g and a D 50 particle diameter in the range of 0.5 to 50 μm.

26. A particulate material according to claim 1 , wherein the sum of the amount of silicon and carbon of the composite particles is at least 85%, and the sum of the amount of silicon, carbon and oxygen is at least 95 wt %.

27. A composition comprising a particulate material as defined in claim 1 , and at least one other component selected from: (i) a binder; (ii) a conductive additive; and (iii) an additional particulate electroactive material.

28. An electrode comprising a particulate material as defined in claim 1 in electrical contact with a current collector.

29. A rechargeable metal-ion battery comprising:
(i) an anode, wherein the anode comprises an electrode as described in 28 ;
(ii) a cathode comprising a cathode active material capable of releasing and reabsorbing metal ions; and
(iii) an electrolyte between the anode and the cathode.

30. A particulate material according to claim 1 , wherein
the PD 70 pore diameter of the porous carbon framework is no more than 3 nm; and
the PD 90 pore diameter of the porous carbon framework is no more than 10 nm.

31. A particulate material according to claim 1 , wherein the volume of silicon in the composite particles is equivalent to 20% to 55% of the total micropore/mesopore volume P 1 cm 3 /g of the porous carbon framework.

32. A particulate material according to claim 1 , wherein the weight ratio of silicon to the porous carbon framework is in the range from [1×P 1 to 1.3×P 1 ]:1.

33. A particulate material according to claim 1 , wherein the weight ratio of silicon to the porous carbon framework is in the range from [1×P 1 to 1.3×P 1 ]:1, and wherein P 1 has a value of up to 1.3.

34. A particulate material according to claim 1 , wherein the composite particles are spheroidal particles having an average sphericity S av of at least 0.70.

35. A particulate material comprising a plurality of composite particles, wherein the composite particles comprise:
(a) a porous carbon framework comprising micropores and optional mesopores,
wherein the micropores and optional mesopores have a total pore volume as measured by gas adsorption of P 1 cm 3 /g, wherein P 1 has a value of at least 0.75 and up to 1.5, and
wherein the PD 50 pore diameter as measured by gas adsorption is no more than 1.5 nm; and

(b) a plurality of elemental nanoscale silicon domains located at least within the micropores of the porous carbon framework;

wherein the weight ratio of silicon to the porous carbon framework in the composite particles is in the range from [0.65×P 1 to 1.3×P 1 ]:1, and wherein at least 90 wt % of the silicon mass in the composite particles is located within the in

Assignees

• Nexeon Ltd

Inventors

• Mason Charles
• Taylor Richard
• Farrell James
• Macklin William

Classifications

• H01M4/364 Primary

  as mixtures · CPC title

• H01M10/0525

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

• H01M4/134 Primary

  Electrodes based on metals, Si or alloys · CPC title

• H01M4/133

  Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M4/13

  Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof · CPC title