IP Library Granted Patent US 12,119,482
Granted Patent B2
US 12,119,482 · App. 17/322,181 · Granted Oct 15, 2024

Graphene-containing metalized silicon oxide composite materials

Inventors: Cary Michael Hayner (Chicago, IL); Aaron Yost (Evanston, IL); Kathryn Hicks (Chicago, IL); Seonbaek Ha (Chicago, IL); Pitawat Mahawattanangul (Chicago, IL); Joshua J. Lau (Chicago, IL)
Assignee: NANOGRAF CORPORATION
H01M4/366H01M4/133H01M4/134H01M4/136H01M4/382H01M4/386H01M4/483H01M4/5825H01M4/587H01M4/622H01M10/0525H01M2004/027
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Quick Facts
Patent No.
US 12,119,482
App. No.
17/322,181
Granted
Oct 15, 2024
Kind
B2
Abstract

Active material composite particles, an electrode including the composite particles, a lithium ion secondary battery including the electrode, and method of forming the same, in which the composite particles each include a core particle including an alkali metal or an alkali earth metal silicate, and a coating disposed on the surface of the core particle. The coating includes turbostratic carbon having a Raman spectrum having: a D band having a peak intensity (I D ) at wave number between 1330 cm −1 and 1360 cm −1 ; a G band having a peak intensity (I G ) at wave number between 1580 cm −1 and 1600 cm −1 ; and a 2D band having a peak intensity (I 2D ) at wave number between 2650 cm −1 and 2750 cm −1 , wherein a ratio of I D /I G ranges from greater than zero to about 1.1, and a ratio of I 2D /I G ranges from about 0.4 to about 2.

Claims (43)

1. Active material composite particles for a lithium ion secondary battery, the composite particles each comprising:

a core particle comprising an alkali metal or an alkali earth metal silicate; and

a coating disposed on the surface of the core particle, the coating comprising turbostratic carbon having a Raman spectrum having:

a D band having a peak intensity (I D ) at wave number between 1330 cm −1 and 1360 cm −1 ;

a G band having a peak intensity (I G ) at wave number between 1580 cm −1 and 1600 cm −1 ; and

a 2D band having a peak intensity (I 2D ) at wave number between 2650 cm −1 and 2750 cm −1 ,

wherein:

a ratio of I D /I G ranges from 0.3 to 0.7; and

a ratio of I 2D /I G ranges from about 0.4 to about 2,

wherein at least some of the core particles composite particles are completely encapsulated by the corresponding coating.

2. The composite particles of claim 1 , wherein the core particle represents from about 80 wt % to about 99.5 wt % of the total weight of the composite particles.

3. The composite particles of claim 2 , wherein the coating represents from about 0.5 wt % to about 20 wt % of the total weight of the composite particles.

4. The composite particles of claim 3 , wherein the turbostratic carbon represents from about 1 wt % to about 10 wt % of the total weight of the particles.

5. The composite particles of claim 1 , wherein from about 90 wt % to about 100 wt % of the turbostratic carbon is in the form of platelets comprising from 1 to 10 sheets of graphene.

6. The composite particles of claim 5 , wherein the coating further comprises from about 0.1 wt % to about 1 wt % carbon nanotubes (CNTs), based on the total weight of the composite particles.

7. The composite particles of claim 1 , wherein at least some additional ones of the core particles are only partially encapsulated by the corresponding coatings.

8. The composite particles of claim 1 , wherein the composite particles have an average particle size ranging from about 3 μm to about 10 μm.

9. The composite particles of claim 1 , wherein the core particle comprises:

a primary phase comprising Li 2 Si 2 O 5 , Li 2 SiO 3 , Li 4 SiO 4 , or any combination thereof, and

crystalline silicon domains dispersed within the primary phase.

10. The composite particles of claim 9 , wherein the core particle further comprises SiOx domains dispersed within the primary phase, where x ranges from 0.8 to 1.2.

11. The composite particles of claim 9 , wherein:

the primary phase comprises Li 2 Si 2 O 5 ; and

the crystalline silicon domains have an average particles size less than 100 nm.

12. The composite particles of claim 1 , wherein the core particle comprises:

a primary phase comprising MgSiO 3 , Mg 2 SiO 4 , or combination thereof; and

crystalline silicon domains dispersed within the primary phase.

13. The composite particles of claim 1 , wherein:

the ratio of I 2D /I G ranges from 0.8 to 1.2;

I D is at wave number of about 1340 cm −1 ;

I G is at wave number of about 1584 cm −1 ; and

I 2D is at a wave number of about 2700 cm −1 .

14. An electrode comprising:

the composite particles of claim 1 ; and

a binder.

15. The electrode of claim 14 , wherein the binder comprises polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), poly(acrylic) acid, polyethylenetetrafluoroethylene (ETFE), polyamides, and polyimides, polyethylene (UHMW), carboxy methyl cellulose (CMC), styrene butadiene rubber (SBR), polyacrylic acid (PAA), lithium polyacrylic acid (LiPAA), or mixtures thereof.

16. The electrode of claim 14 , further comprising a conductive additive selected from the group consisting of carbon black, carbon nanotubes, an electrically conductive polymer, graphite, a metallic powder, nickel, aluminum, titanium, stainless steel, and any combination thereof.

17. A lithium secondary battery comprising:

an anode comprising the electrode of claim 14 ;

a cathode;

a casing housing the anode and cathode; and

an electrolyte disposed between the anode and cathode.

18. The battery of claim 17 , wherein the battery has a 50 th cycle capacity retention of at least 72% and a first cycle efficiency of at least 87%.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 23, 2026
From: NANOGRAF CORPORATION
To: M2INNOVATIONS, LLC
Reel/Frame 075051/0065 →
RELEASE OF SECURITY INTEREST Recorded May 5, 2026
From: VOLTA ENERGY STORAGE FUND I, L.P.
To: NANOGRAF CORPORATION
Reel/Frame 074567/0370 →
SECURITY INTEREST Recorded Aug 23, 2022
From: NANOGRAF CORPORATION
To: VOLTA ENERGY STORAGE FUND I, L.P.
Reel/Frame 060865/0247 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 21, 2021
From: HAYNER, CARY MICHAEL; YOST, AARON; HICKS, KATHRYN; HA, SEONBAEK; MAHAWATTANANGUL, PITAWAT; LAU, JOSHUA J
To: NANOGRAF CORPORATION
Reel/Frame 056937/0001 →
Continuity (3)
Provisional Application 63041388 · Jun 19, 2020
Provisional Application 63026434 · May 18, 2020
Related Publication 20210359295A1 · Nov 18, 2021