SURFACE TREATED SILICON CONTAINING ACTIVE MATERIALS FOR ELECTROCHEMICAL CELLS
Provided are active materials for electrochemical cells. The active materials include silicon containing structures and treatment layers covering at least some surface of these structures. The treatment layers may include aminosilane, a poly(amine), or a poly(imine). These layers are used to increase adhesion of the structures to polymer binders within active material layers of the electrode. As such, when the silicon containing structures change their size during cycling, the bonds between the binder and the silicon containing structure structures or, more specifically, the bonds between the binder and the treatment layer are retained and cycling characteristics of the electrochemical cells are preserved. Also provided are electrochemical cells fabricated with such active materials and methods of fabricating these active materials and electrochemical cells.
1 . An active material for use in electrochemical cells, the active material comprising a powder formed by discrete particles, each particle in the powder comprising:
a silicon containing structure
comprising a core and an external surface;
a treatment layer covering at least a portion of the external surface of the silicon containing structure,
wherein the treatment layer comprises one or more treatment materials selected from the group consisting of an aminosilane, a poly(amine), a poly(imine), and an amine functionalized alkoxy siloxane; and
a carbon shell covering at least a portion of the treatment layer,
wherein the carbon shell comprises carbon particles having a particle size of less than 1 micrometer.
2 . The active material of claim 1 , wherein the one or more treatment materials comprise one or more aminosilanes selected from the group consisting of aminopropyltriethoxysilane, aminopropylmethoxysilane, bis-gamma-trimethoxysilypropyl amine, aminoneohexyltrimethoxysilane, and aminoneohexylmethyldimethoxysilane.
3 . The active material of claim 1 , wherein the one or more treatment materials comprise one or more materials selected from the group consisting of poly(ethyleneimine), poly(allylamine), and poly(vinylamine).
4 . (canceled)
5 . The active material of claim 1 , wherein a volume ratio of the treatment layer to the silicon containing structure is between about 0.001% and 10%.
6 . The active material of claim 1 , wherein a volume ratio of the treatment layer to the silicon containing structure is less than about 0.1%.
7 . The active material of claim 1 , wherein the treatment layer is formed by molecules of the one or more treatment materials adsorbed on the external surface of the silicon containing structure.
8 . The active material of claim 1 , wherein the treatment layer is formed by molecules of the one or more treatment materials covalently bound to the external surface of the silicon containing structure.
9 . The active material of claim 8 , wherein the one or more treatment materials comprises amine functionalized alkoxy siloxane.
10 . The active material of claim 9 , wherein the one or more treatment materials form oligomeric brushes extending away from the external surface of the silicon containing structure.
11 - 13 . (canceled)
14 . The active material of claim 1 , wherein the external surface of the silicon containing structure comprises silicon dioxide.
15 . A method of fabricating an active material comprising a powder of discrete surface treated silicon containing particles for use in electrochemical cells, the method comprising:
preparing a solution,
the solution comprising a carrier solvent and one or more treatment materials,
wherein the carrier solvent comprises a mixture of alcohol and deionized water, and
wherein the one or more treatment materials are selected from the group consisting of an aminosilane, a poly(amine), a poly(imine), and an amine functionalized alkoxy siloxane;
combining the solution with discrete silicon containing structures,
wherein each of the discrete silicon containing structures comprises a core and an external surface,
wherein the one or more treatment materials of the solution attach to the external surface of each of the discrete silicon containing structures when the solution is combined with the discrete silicon containing structures; and
removing the carrier solvent from a combination of the discrete silicon containing structures and the solution while retaining the one or more treatment materials on the external surface of each of the discrete silicon containing structures; and
after removing the carrier solvent from the combination of the discrete silicon containing structures and the solution, performing a heat treatment on the discrete silicon containing structures having the one or more treatment materials attached to the external surface,
wherein the heat treatment adoptively or covalently anchors the one or more treatment materials to the external surface of each of the discrete silicon containing structures.
16 . The method of claim 15 , wherein an acidity of the solution is maintained at between about 4.0 pH and 6.0 pH for amino-silanization.
17 . (canceled)
18 . The method of claim 15 , wherein the heat treatment is performed at a temperature of between about 80° C. and 130° C.
19 . The method of claim 15 , further comprising combining the solution with carbon containing structures, wherein the carbon containing structures form a layer over the silicon containing structures.
20 . A method of fabricating an electrode for a lithium ion cell, the method comprising:
preparing a solution,
the solution comprising a carrier solvent and one or more treatment materials,
wherein the carrier solvent comprises a mixture of alcohol and deionized water, and
wherein the one or more treatment materials are selected from the group consisting of an aminosilane, a poly(amine), a poly(imine), and an amine functionalized alkoxy siloxane;
combining the solution with discrete silicon containing structures,
wherein each of the discrete silicon containing structures comprises a core and an external surface,
wherein the one or more treatment materials of the solution attach to the external surface of each of the discrete silicon containing structures; and
removing the carrier solvent from a combination of the discrete silicon containing structures and the solution while retaining the one or more treatment materials on the external surface of each of the discrete silicon containing structures; and
after removing the carrier solvent from the combination of the discrete silicon containing structures and the solution, performing a heat treatment on the discrete silicon containing structures having the one or more treatment materials attached to the external surface,
wherein the heat treatment adoptively or covalently anchors the one or more treatment materials to the external surface of each of the discrete silicon containing structures;
forming a slurry comprising of the discrete silicon containing structures, water, and a binder,
wherein the binder is selected from the group consisting of poly acrylic acid (PAA), styrene butadiene (SBR), and an alginates;
coating the slurry onto a current collector substrate; and
drying the slurry to form the electrode.
21 . The active material of claim 1 , wherein the treatment layer comprises a poly(imine).
22 . The active material of claim 1 , wherein the silicon containing particle has a size of between about 1 and 50 microns.
23 . The method of claim 15 , wherein a volume ratio of the alcohol to water is 10:1.
24 . The method of claim 23 , wherein the alcohol is ethanol.
25 . The method of claim 15 , further comprising combining carbon containing structures having a particle size of less than 1 micron with the discrete silicon containing structures having the one or more treatment materials on the external surface, wherein combining the carbon containing structures with the discrete silicon containing structures forms a carbon shell at least partially covering the one or more treatment materials on the external surface of the discrete silicon containing structures.