# US 12,119,482 B2 · Graphene-containing metalized silicon oxide composite materials

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- Number: US 12,119,482 B2
- Document ID: US12119482B2
- Status: Granted
- Kind: B2
- Application number: 17/322,181
- Filed: 2021-05-17
- Published: 2021-11-18
- Granted: 2024-10-15
- Earliest claimed: 2020-05-18
- Assignees: Nanograf Corporation
- Applicants: Nanograf Corporation
- Inventors: Cary Michael Hayner; Aaron Yost; Kathryn Hicks; Seonbaek Ha; Pitawat Mahawattanangul; Joshua J. Lau
- Web page: https://patentgrep.com/patent/US12119482B2

## CPC

- H01M 4/366: {as layered products}
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/386: {Silicon or alloys based on silicon}
- H01M 4/483: {for non-aqueous cells (H01M4/485 takes precedence)}
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/622: {being polymers}
- H01M 4/625: {Carbon or graphite}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 2004/027: {Negative electrodes}
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## 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 (ID) at wave number between 1330 cm−1 and 1360 cm−1; a G band having a peak intensity (IG) at wave number between 1580 cm−1 and 1600 cm−1; and a 2D band having a peak intensity (I2D) at wave number between 2650 cm−1 and 2750 cm−1, wherein a ratio of ID/IG ranges from greater than zero to about 1.1, and a ratio of I2D/IG ranges from about 0.4 to about 2.

## Claims

### Claim 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 (ID) at wave number between 1330 cm−1 and 1360 cm−1;
a G band having a peak intensity (IG) at wave number between 1580 cm−1 and 1600 cm−1; and
a 2D band having a peak intensity (I2D) at wave number between 2650 cm−1 and 2750 cm−1,
wherein:
a ratio of ID/IG ranges from 0.3 to 0.7; and
a ratio of I2D/IG 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.

### Claim 2 (depends on 1)

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.

### Claim 3 (depends on 2)

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.

### Claim 4 (depends on 3)

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.

### Claim 5 (depends on 1)

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.

### Claim 6 (depends on 5)

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.

### Claim 7 (depends on 1)

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

### Claim 8 (depends on 1)

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

### Claim 9 (depends on 1)

The composite particles of claim 1, wherein the core particle comprises:
a primary phase comprising Li2Si2O5, Li2SiO3, Li4SiO4, or any combination thereof, and
crystalline silicon domains dispersed within the primary phase.

### Claim 10 (depends on 9)

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.

### Claim 11 (depends on 9)

The composite particles of claim 9, wherein:
the primary phase comprises Li2Si2O5; and
the crystalline silicon domains have an average particles size less than 100 nm.

### Claim 12 (depends on 1)

The composite particles of claim 1, wherein the core particle comprises:
a primary phase comprising MgSiO3, Mg2SiO4, or combination thereof; and
crystalline silicon domains dispersed within the primary phase.

### Claim 13 (depends on 1)

The composite particles of claim 1, wherein:
the ratio of I2D/IG ranges from 0.8 to 1.2;
ID is at wave number of about 1340 cm−1;
IG is at wave number of about 1584 cm−1; and
I2D is at a wave number of about 2700 cm−1.

### Claim 14 (depends on 1)

An electrode comprising:
the composite particles of claim 1; and
a binder.

### Claim 15 (depends on 14)

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.

### Claim 16 (depends on 14)

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.

### Claim 17 (depends on 14)

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.

### Claim 18 (depends on 17)

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