Porous silicon compositions and devices and methods thereof

Patent metadata

Field	Value
Publication number	US-10629900-B2
Application number	US-201615350343-A
Country	US
Kind code	B2
Filing date	Nov 14, 2016
Priority date	May 4, 2011
Publication date	Apr 21, 2020
Grant date	Apr 21, 2020

Abstract

A porous silicon composition, a porous alloy composition, or a porous silicon containing cermet composition, as defined herein. A method of making: the porous silicon composition; the porous alloy composition, or the porous silicon containing cermet composition, as defined herein. Also disclosed is an electrode, and an energy storage device incorporating the electrode and at least one of the disclosed compositions, as defined herein.

First claim

What is claimed is:

1. A method of making a porous silicon composition comprising a porous particle, the method comprising:
compressing a mixture to a compressed form having a thickness of from 5 to 20 mm having a Mg:silica molar percent ratio from 1:1.5 to 1:1.99,
wherein the mixture comprises magnesium powder having a particle size of from 10 nm to 100 microns, and a silica source powder having a particle size of from 10 nm to 100 microns;

heating the compressed form at from 600 to 900° C. to form a fired form;
milling the fired form to an intermediate product powder;
leaching the intermediate product powder with an acid solution to produce a leached product; and
washing the leached product to form the porous particle.

2. The method of claim 1 further comprising coating the porous silicon composition with at least one of a conductive material, a strength enhancing material, or a combination thereof, to form a coated composition.

3. An energy storage device comprising an electrode, wherein the electrode comprises:
a conductive substrate coated with a mixture comprising the coated composition of claim 2 , a conductive carbon, and a binder.

4. The device of claim 3 wherein the device has:
an electrochemical gravimetric capacity of 1000 to 3400 mAh/g;
an initial coulombic efficiency of from 38 to 96%;
a second coulombic efficiency of from 60 to 97%; or
a combination thereof.

5. The method of claim 1 , wherein the heating has a heating rate less than about 10° C./min.

6. The method of claim 1 , wherein the porous silicon composition comprises:
a crystalline phase in from 50 to 99 atom % Si determined by NMR, comprising crystalline Si in from 95 to 100 wt % determined by XRD, crystalline forsterite in from 0.1 to 5 wt % determined by XRD, and crystalline quartz in from 0.1 to 1 wt % determined by XRD;
an amorphous phase comprising at least one of amorphous silica, amorphous silicate, or a mixture thereof, in from 1 to 50 atom % Si determined by NMR, based on the total amount of Si;
a total Si content in from 20 to 99 wt % determined by ICP;
a total elemental oxygen content of from 0.001 to 1 wt % determined by difference, based on a 100 wt % total; and
a form factor comprising the porous particle.

7. The method of claim 6 , wherein the porous particle has:
a porous particulate powder form having a d50 particle size of from 3 to 14 microns;
a percent porosity of from 60 to 80%;
an open pore structure having a pore size diameter from 1 to 1,000 nm, where the total pore volume is greater than 70% for pore diameters greater than 10 nm, and the total pore volume is greater than 40% for pore diameters greater than 40 nm to 1000 nm; and/or
a BET surface area of from 20 to 75 m 2 /g; or
a combination thereof.

8. The method of claim 6 , wherein the porous silicon composition has a 29 Si MAS NMR spectrum having a major single peak at a chemical shift of −81 ppm with a FWHM of less than 1 ppm and a diffuse minor signal region at from −95 to −120 ppm.

9. A method of making a porous alloy composition comprising a porous particle, the method comprising:
compressing a mixture to form a compressed form having a thickness of from 5 to 20 mm having a Mg:silica molar percent ratio from 1:1.5 to 1:1.99,
wherein the mixture comprises a magnesium powder having a particle size of from 10 nm to 100 microns, and at least one of a source of metal silicide, a silica source powder, a silicate glass, a mixture of a silica source powder and a metal oxide, or a mixture thereof, having a particle size of from 10 nm to 100 microns;

heating the compressed form at from 600 to 900° C. to form a compressed and heated form;
milling the compressed and heated form to form an intermediate product powder;
leaching the intermediate product powder with an acid solution to form a leached product; and
washing the leached product to form the porous particle.

10. The method of claim 9 further comprising coating the porous alloy composition with at least one of a conductive material, a strength enhancing material, or a combination thereof, to form a coated porous alloy composition.

11. An energy storage device comprising an electrode, wherein the electrode comprises:
a conductive substrate coated with a mixture of the coated porous alloy composition of claim 10 , a conductive carbon, and a binder.

12. The device of claim 11 wherein the device has:
an electrochemical gravimetric capacity of from 1000 to 2000 mAh/g;
an initial coulombic efficiency of from 38 to 96%;
a second coulombic efficiency of from 60 to 94%; or
a combination thereof.

13. The method of claim 9 , wherein the at least one of a source of metal silicide, a silica source powder, a silicate glass, a mixture of a silica source powder and a metal oxide, or a mixture thereof, is selected from a magnesium silicate mineral, a silicate mineral, a titanium oxide, or a mixture thereof.

14. The method of claim 9 , wherein the heating has a heating rate less than about 10° C./min.

15. The method of claim 9 , wherein the porous alloy composition comprises:
a crystalline phase in from 70 to 90 atom % Si determined by NMR, comprising crystalline Si in from 20 to 80 wt % determined by XRD, crystalline forsterite in from 0.1 to 5 wt % determined by XRD, crystalline quartz in from 0.1 to 1 wt % determined by XRD, and at least one crystalline metal silicide in from 1 to 80 wt % determined by XRD;
an amorphous phase in from 10 to 30 atom % Si determined by NMR comprising at least one of amorphous silica, amorphous silicate, or a mixture thereof;
a total Si content in from 20 to 99 wt % determined by ICP;
a total elemental oxygen content of from 0.001 to 1 wt % determined by difference, based on a 100 wt % total; and
a form factor comprising the porous particle.

16. The method of claim 15 , wherein the porous particle has:
a percent porosity (% P) in from 60 to 80 vol %;
a BET surface area of from 20 to 75 m 2 /g;
an open pore structure having a pore size diameter from 1 to 1,000 nm, wherein the porous particle has a total pore volume greater than 85% for pore diameters greater than 10 nm and a total pore volume greater than 50% for pore diameters greater than 40 nm to 1,000 nm; or
a combination thereof.

17. The method of claim 15 , wherein the porous alloy composition has a 29 Si MAS NMR spectrum having a major single peak at a chemical shift of −81 ppm, a first diffuse minor signal region from at from −95 to −135 ppm or at from −95 to −120 ppm, and a second diffuse minor signal region at from −50 to −70 ppm.

18. A method of making a cermet composition comprising a porous silicon composition, wherein the porous silicon composition comprises a porous particle, the method comprising:
compressing a mixture to a compressed form having a thickness of from 5 to 20 mm and having a Mg:silica molar percent ratio from 1:1.5 to 1:1.99,
wherein the mixture comprises magnesium powder having a particle size of from 10 nm to 100 microns, a metal oxide having a particle size of from 10 nm to 100 microns, and a silica source powder having a particle size of from 10 nm to 100 microns;

heating the compressed form at from 600 to 900° C. to form a heated form;
milling the heated form to form an intermediate product powder;
leaching the intermediate product powder with an acid solution to form a leached product; and
washing the leached product to form a porous particle.

19. The method of claim 18 further comprising coating the porous silicon containing cermet composition with at l

Assignees

• Corning Inc

Inventors

• Dutta Indrajit
• Kent Brian Alan
• Tepesch Patrick David
• O'Malley Shawn Michael
• Youngman Randall Eugene

Classifications

• C03C10/0009

  containing silica as main constituent · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• C03C11/005

  obtained by leaching after a phase separation step · CPC title

• H01M4/386 Primary

  Silicon or alloys based on silicon · CPC title