Protection interfaces for Li-ion battery anodes

Patent metadata

Field	Value
Publication number	US-12051810-B2
Application number	US-202217863106-A
Country	US
Kind code	B2
Filing date	Jul 12, 2022
Priority date	Jun 16, 2019
Publication date	Jul 30, 2024
Grant date	Jul 30, 2024

Abstract

Interfacial films, which are both electronic conducting and ion conducting, for anode films are provided. The one or more protective films described herein may be mixed conduction materials, which are both electronic conducting and ion-conducting. The one or more protective films described herein may include materials selected from lithium transition metal dichalcogenides, Li 9 Ti 5 O 12 , or a combination thereof. The lithium transition metal dichalcogenide includes a transition metal dichalcogenide having the formula MX 2 , wherein M is selected from Ti, Mo, or W and X is selected from S, Se, or Te. The transition metal dichalcogenide may be selected from TiS 2 , MoS 2 , WS 2 , or a combination thereof. The lithium transition metal dichalcogenide may be selected from lithium-titanium-disulfide (e.g., LiTiS 2 ), lithium-tungsten-disulfide (e.g., LiWS 2 ), lithium-molybdenum-disulfide (e.g., LiMoS 2 ), or a combination thereof.

First claim

The invention claimed is:

1. A method, comprising:
forming a lithium metal film on a current collector, wherein the current collector comprises copper and/or stainless steel;
forming a protective film stack on the lithium metal film, comprising:
forming a first protective film on the lithium metal film, wherein the first protective film comprises a Li 9 Ti 5 O 12 film, and wherein forming the first protective film on the lithium metal film further comprises:
depositing a Li 4 Ti 5 O 12 film on the lithium metal film via a physical vapor deposition (PVD) process; and
exposing the Li 4 Ti 5 O 12 film to a lithiation process to form the Li 9 Ti 5 O 12 film; and

forming a second protective film on the first protective film, the second protective film comprising a lithium transition metal dichalcogenide, and wherein forming the lithium transition metal dichalcogenide comprises:
depositing a TiS 2 film on the Li 4 Ti 5 O 12 film or the Li 9 Ti 5 O 12 film via a chemical vapor deposition process; and
exposing the TiS 2 film to the lithiation process to form a LiTiS 2 film on the Li 9 Ti 5 O 12 film or the Li 9 Ti 5 O 12 film.

2. The method of claim 1 , wherein depositing the TiS 2 film on the Li 4 Ti 5 O 12 film or the Li 9 Ti 5 O 12 film comprises:
(a) flowing TiCl 4 into a processing region;
(b) purging the processing region;
(c) flowing H 2 S into the processing region to form the TiS 2 film;
(d) purging the processing region; and
(e) repeating (a)-(d) until the TiS 2 film achieves a targeted thickness.

3. The method of claim 2 , wherein the first protective film has a thickness of 100 nanometers or less, and wherein the second protective film has a thickness of 100 nanometers or less.

4. A method, comprising:
forming a lithium metal film on a current collector comprising one or more metals;
forming a protective film stack on the lithium metal film, comprising:
forming a first protective film on the lithium metal film, wherein the first protective film comprises a Li 9 Ti 5 O 12 film, and wherein forming the first protective film on the lithium metal film further comprises:
depositing a Li 4 Ti 5 O 12 film on the lithium metal film via a physical vapor deposition (PVD) process; and
exposing the Li 4 Ti 5 O 12 film to a lithiation process to form the Li 9 Ti 5 O 12 film; and

forming a second protective film on the first protective film, the second protective film comprising a lithium transition metal dichalcogenide, and wherein forming the lithium transition metal dichalcogenide comprises:
depositing a TiS 2 film on the Li 4 Ti 5 O 12 film or the Li 9 Ti 5 O 12 film via a chemical vapor deposition process; and
exposing the TiS 2 film to the lithiation process to form a LiTiS 2 film on the Li 4 Ti 5 O 12 film or the Li 9 Ti 5 O 12 film.

5. The method of claim 4 , wherein the one or more metals comprise aluminum, copper, zinc, nickel, cobalt, manganese, chromium, stainless steel, clad materials, alloys thereof, or any combination thereof.

6. A method, comprising:
forming a lithium metal film on a current collector, wherein the current collector comprises copper and/or stainless steel; and
forming a protective film stack on the lithium metal film, comprising:
forming a first protective film on the lithium metal film, wherein the first protective film comprises a Li 9 Ti 5 O 12 film, and wherein forming the first protective film on the lithium metal film further comprises:
depositing a Li 4 Ti 5 O 12 film on the lithium metal film via a physical vapor deposition (PVD) process; and
reducing the Li 4 Ti 5 O 12 film to form the Li 9 Ti 5 O 12 film; and

forming a second protective film on the first protective film, the second protective film comprising a lithium transition metal dichalcogenide, and wherein forming the lithium transition metal dichalcogenide comprises:
depositing a TiS 2 film on the Li 4 Ti 5 O 12 film or the Li 9 Ti 5 O 12 film via a chemical vapor deposition process; and
exposing the TiS 2 film to the lithiation process to form a LiTiS 2 film on the Li 4 Ti 5 O 12 film or the Li 9 Ti 5 O 12 film.

Assignees

• Applied Materials Inc

Inventors

• Rangasamy Ezhiylmurugan
• Herle Subramanya P

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M10/0525

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

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• H01M4/1395

  of electrodes based on metals, Si or alloys · CPC title