Porous sintered superstructure with interstitial silicon for use in anodes for lithium batteries
Anodes for the lithium secondary batteries include a strong, electrically conductive, porous superstructure filled with a milled or melted interstitial material, such as nano-scaled silicon; the milled or melted interstitial material provides high lithiation capacity, and the superstructure provides durability and controls the anode's electromechanical expansion and contraction during the lithiation and de-lithiation cycle. Embodiments include porous superstructures comprised of silicon carbide, tungsten, and other materials, many of which offer capability of lithiating.
1. An anode for a lithium-ion secondary battery comprising:
a porous superstructure, said porous superstructure including an electrically conductive material selected from the group consisting of silicon carbide and tungsten, said porous superstructure having a porous matrix; and
an interstitial material including silicon, said interstitial material being positioned within the porous matrix.
2. The anode for a lithium-ion secondary battery of claim 1 wherein said porous superstructure includes silicon.
3. The anode for a lithium-ion secondary battery of claim 2 wherein said interstitial material including silicon further includes graphene.
4. The anode for a lithium-ion secondary battery of claim 1 wherein said porous superstructure consists essentially of silicon carbide.
5. The anode for a lithium-ion secondary battery of claim 4 wherein said interstitial material including silicon further includes graphene.
6. The anode for a lithium-ion secondary battery of claim 4 wherein said interstitial material includes milled silicon particulates having a median diameter of less than one micron, said milled silicon particulates being sintered with said silicon carbide.
7. The anode for a lithium-ion secondary battery of claim 6 wherein said milled silicon particulates have a median diameter of approximately 140 nanometers.
8. The anode for a lithium-ion secondary battery of claim 1 wherein said porous superstructure consists essentially of tungsten.
9. The anode for a lithium-ion secondary battery of claim 8 , said interstitial material formed within the porous matrix.
10. The anode for a lithium-ion secondary battery of claim 8 wherein said interstitial material including silicon further includes graphene.
11. The anode for a lithium-ion secondary battery of claim 1 wherein interstitial material including silicon further includes a dopant selected from the group consisting of boron, phosphorus, arsenic, antimony, bismuth, gallium, indium, thallium, and germanium.
12. An anode for a lithium-ion secondary battery comprising:
an electrically conductive superstructure including a porous matrix including silicon carbide; and
an interstitial material including silicon, said interstitial material being positioned within the porous matrix of the electrically conductive superstructure, where
the silicon carbide and the silicon have a graphene coating.
13. The anode of claim 12 wherein said interstitial material includes milled silicon particulates having a median diameter from 50 to 800 nanometers.
14. The anode of claim 12 wherein the interstitial material is introduced to said porous matrix during fabrication by melting silicon in contact with the electrically conductive superstructure so that capillary forces introduce silicon into said porous matrix.
15. The anode of claim 12 wherein the interstitial material including silicon further includes a dopant selected to affect the electromechanical properties of the interstitial material.
16. The anode of claim 15 wherein said dopant is selected from the group consisting of boron, phosphorus, arsenic, antimony, bismuth, gallium, indium, thallium, and germanium.
17. A process for fabricating an anode for a lithium-ion secondary battery comprising:
providing a superstructure material with a porous matrix; and
infiltrating the porous matrix with an interstitial material including silicon through capillary forces,
wherein said superstructure material with the porous matrix includes silicon or silicon carbide, and
wherein infiltrating the porous matrix with an interstitial material including silicon involves:
milling silicon in an attrition mill, thereby producing milled silicon particulates that have a median particle diameter of less than one micron and are substantially equiaxed;
pressing the milled silicon particulates into a pre-form with said superstructure material; and
sintering said milled silicon particulates and said superstructure material at a temperature less than 1,400 degrees Celsius.
18. The process of claim 17 wherein the milling silicon in the attrition mill further includes mixing graphite with the silicon in the attrition mill and milling the silicon with the graphite to form silicon particulates that include a coating of graphene.
19. The process of claim 17 wherein said superstructure material with a porous matrix further includes tungsten or molybdenum.