Method and material for lithium ion battery anodes

Patent metadata

Field	Value
Publication number	US-10439206-B2
Application number	US-201515302646-A
Country	US
Kind code	B2
Filing date	Apr 9, 2015
Priority date	Apr 9, 2014
Publication date	Oct 8, 2019
Grant date	Oct 8, 2019

Abstract

Silicon-silica hybrid materials made by metallothermal reduction from silica and methods of producing such compositions are provided. The compositions have novel properties and provide significant improvements in Coulombic efficiency, dilithiation capacity, and cycle life when used as anode materials in lithium battery cells.

First claim

We claim:

1. A hybrid material comprising:
a. from about 5 wt% to about 50 wt % M x SiO 2+x , wherein M is a metal, x is 0 or a positive integer;
b. from greater than 20 wt % to about 94 wt % crystalline silicon;
wherein:
the ratio of crystalline silicon: M x SiO 2+x is from about 1:1 to about 100:1;
the hybrid material is in the form of particles having:
a surface area of from about 10 m 2 /g to about 250 m 2 /g; and
an average pore size of from about 50 Å to about 250 Å; and

the particles are present in a bimodal distribution comprising a first distribution and a second distribution.

2. The hybrid material of claim 1 , wherein the particles have open porosity from about 75% to about 98% or the hybrid material has a tap density of greater than 0.07 g/mL.

3. The hybrid material of claim 1 , wherein the particles are from about 0.01 μm to less than 45 μm in diameter along their longest axis.

4. The hybrid material of claim 1 , wherein the first distribution comprises particles from about 1 μm to less than 45 μm in diameter along their longest axis and the second distribution comprises particles having a diameter of from about 10 nm to about 500 nm along their longest axis, and wherein the second distribution comprises less than 20% of the total particles.

5. The hybrid material of claim 1 , further comprising from greater than 0 wt % to about 65 wt % MgO.

6. The hybrid material of claim 5 , wherein the material comprises from greater than 0 wt % to about 10 wt % MgO.

7. The hybrid material of claim 1 , wherein the material further comprises from greater than 0 wt % to about 20 wt % at least one of carbon, manganese, molybdenum, niobium, tungsten, tantalum, iron, copper, titanium, vanadium, chromium, nickel, cobalt, zirconium, tin, silver, indium copper, lithium or zinc.

8. A hybrid material comprising:
a. M x SiO 2+x , wherein M is a metal, x is 0 or a positive integer, from about 5 wt % to about 50 wt %; and
b. crystalline silicon from greater than 20 wt % to about 94 wt %; wherein:
the ratio of crystalline silicon: M x SiO 2+x is from about 1:1 to about 100:1;
the hybrid material is in the form of particles; and
the particles are present in a bimodal distribution comprising a first distribution and a second distribution, wherein the first distribution comprises particles from about 1 μm to less than 45 μm in diameter along their longest axis and the second distribution comprises particles having a diameter of from about 10 nm to about 500 nm along their longest axis, and wherein the second distribution comprises less than 20% of the total particles.

9. An anode comprising the material of claim 1 , wherein the anode has a specific capacity of about 50% of the initial value or greater after 100 cycles at 0.1 C discharge rate.

10. An anode comprising the material of claim 1 , wherein the anode has a gravimetric capacity of 400 mAh/g or greater after 100 cycles at 0.1 C discharge rate and the anode has a first cycle coulombic efficiency of 50% of the initial value or greater.

11. The anode of claim 9 , wherein the anode further comprises from greater than 0 wt % to about 70 wt % carbon.

12. The hybrid material of claim 8 , wherein the hybrid material has a tap density of greater than 0.07 g/mL;
wherein the hybrid material further comprises one or more of:
a. from greater than 0 wt % to about 65 wt % MgO; or
b. from greater than 0 wt % to about 70 wt % at least one of carbon, manganese, molybdenum, niobium, tungsten, tantalum, iron, copper, titanium, vanadium, chromium, nickel, cobalt, zirconium, tin, silver, indium copper, lithium or zinc; and

wherein the particles have one or more of:
a. a surface area of from about 10 m 2 /g to about 250m 2 /g;
b. an average pore size of from about 50 Å to about 250 Å; or
c. an open porosity in a range from about 75% to about 98%.

Assignees

• Corning Inc

Inventors

• Behan Francis Martin
• Dutta Indrajit
• Kent Brian Alan
• O'Malley Shawn Michael
• Schneider Vitor Marino
• Youngman Randall Eugene

Classifications

• H01M10/0525

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

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M4/364 Primary

  as mixtures · CPC title

• H01M4/134 Primary

  Electrodes based on metals, Si or alloys · CPC title

• H01M4/386

  Silicon or alloys based on silicon · CPC title