# US 12,119,484 B2 · Lithium-containing coatings for cathode materials

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- Number: US 12,119,484 B2
- Document ID: US12119484B2
- Status: Granted
- Kind: B2
- Application number: 17/548,031
- Filed: 2021-12-10
- Published: 2023-06-15
- Granted: 2024-10-15
- Earliest claimed: 2021-12-10
- Assignees: GM Global Technology Operations LLC
- Applicants: GM Global Technology Operations LLC
- Inventors: Biqiong Wang; Meinan He; Anne M. Dailly; Matthew Beckner; Mei Cai
- Web page: https://patentgrep.com/patent/US12119484B2

## CPC

- H01M 4/366: {as layered products}
- H01M 4/0428: {Chemical vapour deposition}
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 4/628: {Inhibitors, e.g. gassing inhibitors, corrosion inhibitors}
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0567: characterised by the additives
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/028: {Positive 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

A positive electrode including a plurality of electroactive particles defining an electroactive layer is provided. A first lithium-containing coating is disposed on one or more surfaces of the electroactive layer. The first lithium-containing coating covers between about 30% and about 50% of a total exposed surface area of the electroactive layer. A second lithium-containing coating encompasses at least one electroactive particle of the plurality of electroactive particles. The second lithium-containing coating covers between about 95% and about 100% of the at least one electroactive particle. The first and second lithium-containing coatings each have a thickness between about 0.2 nm and about 5 nm. The positive electrode further includes an electrolyte additive that aids in the formation of a first passivation layer on exposed surfaces of the first lithium-containing coating, and a second passivation layer on exposed surfaces of the second lithium-containing coating.

## Claims

### Claim 1

A positive electrode comprising:
a positive electroactive material comprising a plurality of positive electroactive material particles and defining an electroactive material layer;
a first lithium-containing coating disposed on one or more surfaces of the electroactive material layer, the first lithium-containing coating consisting essentially of a single continuous layer coating, the first lithium-containing coating having a thickness greater than or equal to about 0.2 nanometers to less than or equal to about 5 nanometers and an ionic conductivity greater than or equal to about 10−7 S/cm to less than or equal to about 10−3 S/cm, the first lithium-containing coating covering greater than or equal to about 30% to less than or equal to about 50% of a total surface area of the electroactive material layer; and
a second lithium-containing coating surrounding at least one positive electroactive material particle of the plurality of positive electroactive material particles, the second lithium-containing coating having a thickness greater than or equal to about 0.2 nanometers to less than or equal to about 5 nanometers and covering greater than or equal to about 95% to less than or equal to about 100% of a total exposed surface area of the at least one positive electroactive material particle.

### Claim 2 (depends on 1)

The positive electrode of claim 1, wherein the positive electroactive material is selected from the group consisting of: NCM 111, NCM 532, NCM 622, NCM 712, NCM 811, NCMA, NCA, LNMO, and combinations thereof, and
the first and second lithium-containing coatings each comprise a lithium-containing material independently selected from the group consisting of: lithium phosphates, lithium alumina, lithium niobates, lithium silicates, lithium alumina fluoride, lithium fluoride, lithium phosphorus oxynitride (LiPON), and combinations thereof.

### Claim 3 (depends on 1)

The positive electrode of claim 1, further comprising:
greater than 0 wt. % to less than or equal to about 1 wt. % of an electrolyte additive, wherein the electrolyte additive is represented by Li[B((OCH2)xCF3)4], where 1≤x≤6.

### Claim 4 (depends on 1)

The positive electrode of claim 1, further comprising an electrolyte additive, wherein the electrolyte additive comprises:
and combinations thereof.

### Claim 5 (depends on 3)

The positive electrode of claim 3, further comprising:
a passivation layer defined by the electrolyte additive disposed on one or more exposed surfaces of the first lithium-containing coating, the passivation layer having a thickness greater than or equal to about 0.2 nanometers to less than or equal to about 5 nanometers and covering greater than or equal to about 0.1% to less than or equal to about 50% of a total exposed surface area of the first lithium-containing coating.

### Claim 6 (depends on 1)

The positive electrode of claim 1, wherein the first lithium-containing coating is prepared using one of an atomic layer deposition (ALD) process or a plasma enhanced atomic layer deposition (PEALD) process, wherein a coating precursor comprises one or more binary or ternary compounds, one or more lithium-source precursors, and one or more oxidizers.

### Claim 7 (depends on 6)

The positive electrode of claim 6, wherein the one or more binary or ternary compounds are selected from the group consisting of:
lithium phosphates, lithium alumina, lithium niobates, lithium silicates, lithium alumina fluoride, lithium fluoride, lithium phosphorus oxynitride (LiPON), and combinations thereof;
the one or more lithium-source precursors are selected from the group consisting of: lithium tert-butoxide (LiOtBu), lithium bis(trimethylsilyl)amid e (LiHMDS), lithium 2,2,6,6-tetramethyl-3,5-heptanedionate (Lithd), lithium amides, and combinations thereof; and
the one or more oxidizers are selected from the group consisting of: trimethyl phosphate ((MeO)3PO) (TMPO), H2O, TiF4, NH4F, O3, O2, and combinations thereof.

### Claim 8 (depends on 7)

The positive electrode of claim 7, wherein the atomic layer deposition (ALD) process or the plasma enhanced atomic layer deposition (PEALD) process has a deposition temperature of greater than or equal to about 100° C. to less than or equal to about 250° C.

### Claim 9 (depends on 6)

The positive electrode of claim 6, wherein the second lithium-containing coating is prepared using one of an atomic layer deposition (ALD) process and a plasma enhanced atomic layer deposition (PEALD) process, wherein a coating precursor comprises one or more binary or ternary compounds, one or more lithium-source precursors, and one or more oxidizers.

### Claim 10

A positive electrode comprising:
a plurality of positive electroactive material particles defining an electroactive material layer;
a first lithium-containing coating surrounding at least one positive electroactive material particle of the plurality of positive electroactive material particles, the at least one lithium-containing coating having a thickness greater than or equal to about 0.2 nanometers to less than or equal to about 5 nanometers and an ionic conductivity greater than or equal to about 10−7 S/cm to less than or equal to about 10−3 S/cm; and
a second lithium-containing coating disposed on the electroactive material layer, the second lithium-containing coating consisting essentially of a single continuous layer coating, the second lithium-containing coating having a thickness greater than or equal to about 0.2 nanometers to less than or equal to about 5 nanometers and covering greater than or equal to about 30% to less than or equal to about 50% of a total exposed surface area of the electroactive material layer.

### Claim 11 (depends on 10)

The positive electrode of claim 10, wherein the positive electroactive material is selected from the group consisting of: NCM 111, NCM 532, NCM 622, NCM 712, NCM 811, NCMA, NCA, LNMO, and combinations thereof, and
wherein the first and second lithium-containing coatings each comprise a lithium-containing material independently selected from the group consisting of: lithium phosphates, lithium alumina, lithium niobates, lithium silicates, lithium alumina fluoride, lithium fluoride, lithium phosphorus oxynitride (LiPON), and combinations thereof.

### Claim 12 (depends on 10)

The positive electrode of claim 10, wherein the first lithium-containing coating covers greater than or equal to about 95% to less than or equal to about 100% of a total exposed surface area of the at least one positive electroactive material particle.

### Claim 13 (depends on 10)

The positive electrode of claim 10, further comprising: greater than 0 wt. % to less than or equal to about 1 wt. % of an electrolyte additive, wherein the electrolyte additive is represented by Li[B((OCH2)xCF3)4], where 1≤x≤6.

### Claim 14 (depends on 13)

The positive electrode of claim 13, further comprising:
a passivation layer defined by the electrolyte additive disposed on one or more exposed surfaces of the first lithium-containing coating, the passivation layer having a thickness greater than or equal to about 0.2 nanometers to less than or equal to about 5 nanometers and covering greater than or equal to about 30% to less than or equal to about 50% of a total exposed surface area of the first lithium-containing coating.

### Claim 15 (depends on 10)

The positive electrode of claim 10, wherein the first lithium-containing coating is prepared using one of an atomic layer deposition (ALD) process and a plasma enhanced atomic layer deposition (PEALD) process, wherein a coating precursor comprises:
one or more binary or ternary compounds selected from the group consisting of: lithium phosphates, lithium alumina, lithium niobates, lithium silicates, lithium alumina fluoride, lithium fluoride, lithium phosphorus oxynitride (LiPON), and combinations thereof;
one or more lithium-source precursors selected from the group consisting of: lithium tert-butoxide (LiOtBu), lithium bis(trimethylsilyl)amid e (LiHMDS), lithium 2,2,6,6-tetramethyl-3,5-heptanedionate (Lithd), lithium amides, and combinations thereof; and
one or more oxidizers selected from the group consisting of: trimethyl phosphate ((MeO)3PO) (TMPO), H2O, TiF4, NH4F, O3, O2, and combinations thereof.

### Claim 16 (depends on 15)

The positive electrode of claim 15, wherein the atomic layer deposition (ALD) process or the plasma enhanced atomic layer deposition (PEALD) process has a deposition temperature of greater than or equal to about 100° C. to less than or equal to about 250° C.

### Claim 17

A positive electrode comprising:
a plurality of positive electroactive material particles defining an electroactive material layer;
at least one first lithium-containing coating surrounding at least one positive electroactive material particle of the plurality of positive electroactive material particles, the at least one first lithium-containing coating covering greater than or equal to about 95% to less than or equal to about 100% of a total exposed surface area of the at least one positive electroactive material particle; and
a second lithium-containing coating disposed on one or more surfaces of the electroactive material layer, the second lithium-containing coating consisting essentially of a single continuous layer coating, the second lithium-containing coating covering greater than or equal to about 30% to less than or equal to about 50% of a total exposed surface area of the electroactive material layer,
the at least one first lithium-containing coating and the second lithium-containing coating each comprising a lithium-containing material independently selected from the group consisting of: lithium phosphates, lithium alumina, lithium niobates, lithium silicates, lithium alumina fluoride, lithium fluoride, lithium phosphorus oxynitride (LiPON), and combinations thereof.