Electroactive materials for metal-ion batteries
This invention relates to particulate electroactive materials consisting of a plurality of composite particles, wherein the composite particles comprise: (a) a porous carbon framework including micropores and mesopores having a total volume of 0.5 to 1.5 cm 3 /g; and (b) silicon located at least within the micropores of the porous carbon framework in a defined amount relative to the volume of the micropores and mesopores. At least 20 wt % of the silicon is characterized as surface silicon by thermogravimetric analysis.
1. A particulate material consisting of 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 represents a natural number having a value of from 0.5 to 1.5,
wherein the PD 90 pore diameter is at least 3 nm and less than 12 nm; and
wherein the micropore volume fraction based on P 1 is from 0.43 to 0.85; and
(b) a plurality of nanoscale elemental silicon domains located within the pores of the porous carbon framework,
wherein the particulate material comprises from 25 to 65 wt % silicon, and wherein at least 20 wt % of the silicon is surface silicon as determined by thermogravimetric analysis (TGA).
2. A particulate material according to claim 1 , wherein P 1 has a value of at least 0.65.
3. A particulate material according to claim 1 , wherein P 1 has a value of no more than 1.3.
4. A particulate material according to claim 1 , wherein the PD 90 pore diameter of the porous carbon framework is no more than 10 nm.
5. A particulate material according to claim 1 , wherein the micropore volume fraction of the porous carbon framework is at least 0.5, based on the total volume of micropores and mesopores.
6. A particulate material according to claim 1 , wherein the micropore volume fraction of the porous carbon framework is no more than 0.8, based on the total volume of micropores and mesopores.
7. A particulate material according to claim 1 , wherein the total volume of micropores in the porous carbon framework is at least 0.36 cm 3 /g.
8. A particulate material according to claim 1 , wherein the fractional volume of pores having a pore size of 5 nm or less is at least 0.8.
9. A particulate material according to claim 1 , wherein the total volume of pores having a diameter in the range of from greater than 50 nm to 100 nm is defined as P 2 cm 3 /g, wherein P 2 is no more than 0.2×P 1 .
10. A particulate material according to claim 1 , wherein the porous carbon framework has a BET surface area from 1200 to 3000 m 2 /g.
11. A particulate material according to claim 1 , comprising at least 30 wt % silicon.
12. A particulate material according to claim 1 , comprising no more than 60 wt % silicon.
13. A particulate material according to claim 1 , wherein the porous carbon framework is a steam-activated porous carbon framework.
14. A particulate material according to claim 1 , wherein the porous carbon framework comprises at least 95 wt % carbon.
15. A particulate material according to claim 1 , wherein the weight ratio of silicon to the porous carbon framework is at least 0.75×P 1 .
16. A particulate material according to claim 1 , wherein the weight ratio of silicon to the porous carbon framework is no more than 1.9×P 1 .
17. A particulate material according to claim 1 , wherein at least 30 wt % of the silicon is surface silicon as determined by thermogravimetric analysis (TGA).
18. A particulate material according to claim 1 , wherein at least 40 wt % of the silicon is surface silicon as determined by thermogravimetric analysis (TGA).
19. A particulate material according to claim 1 , wherein no more than 10 wt % of the silicon is coarse bulk silicon as determined by thermogravimetric analysis (TGA).
20. A particulate material according to claim 1 , wherein no more than 5 wt % of the silicon is coarse bulk silicon as determined by thermogravimetric analysis (TGA).
21. A particulate material according to claim 1 , wherein at least a portion of the micropores and/or mesopores comprise void space that is fully enclosed by the silicon.
22. A particulate material according to claim 1 , wherein the volume of micropores and mesopores of the composite particles, in the presence of silicon, as measured by nitrogen gas adsorption, is no more than 0.15×P 1 .
23. A particulate material according to claim 1 , wherein the composite particles are obtained by chemical vapor infiltration (CVI) of a silicon-containing precursor into the pore structure of a porous carbon framework.
24. An electrode comprising a particulate material as defined in claim 1 in electrical contact with a current collector.
25. A rechargeable metal-ion battery comprising:
(i) an anode, wherein the anode comprises an electrode as described in claim 24 ;
(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.
26. A process for preparing composite particles, the process comprising the steps of:
(a) providing a plurality of porous carbon particles comprising micropores and/or mesopores, wherein:
(i) the micropores and mesopores have a total pore volume as measured by gas adsorption of P 1 cm 3 /g, wherein P 1 represents a natural number having a value of from 0.5 to 1.5;
(ii) the PD 90 pore diameter is at least 3 nm and less 12 nm; and
(iii) the micropore volume fraction based on P 1 is from 0.43 to 0.85;
(b) contacting the plurality of porous carbon particles with a gas comprising 0.5 to 20 vol % of a silicon precursor gas at a temperature from 400 to 700° C.