Interconnected hollow nanostructures containing high capacity active materials for use in rechargeable batteries

• US 10,461,359 B2
• Filed: 11/25/2015
• Issued: 10/29/2019
• Est. Priority Date: 05/27/2009
• Status: Active Grant

• Current Assignee: Amprius Technologies Incorporated (Amprius, Inc.)
• Original Assignee: Amprius, Inc.
• Inventors: Cui, Yi, Han, Song, Loveness, Ghyrn E.
• Primary Examiner(s): Crepeau, Jonathan
• Application Number:
  US14/952,744
• Publication Number:
  US 20160190600A1
• Time in Patent Office: 1,434 Days
• Field of Search: None
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/022 Electrodes made of one single microscopic fiber
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0402 Methods of deposition of the material
• CPC Class Codes: H01M 4/043 involving compressing or compaction
• CPC Class Codes: H01M 4/0438 by electrochemical processing electroless electrochemical plating C23C18/54
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/049 Manufacturing of an active layer by chemical means
• CPC Class Codes: H01M 4/0492 Chemical attack of the support material
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/387 Tin or alloys based on tin
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Provided are electrode layers for use in rechargeable batteries, such as lithium ion batteries, and related fabrication techniques. These electrode layers have interconnected hollow nanostructures that contain high capacity electrochemically active materials, such as silicon, tin, and germanium. In certain embodiments, a fabrication technique involves forming a nanoscale coating around multiple template structures and at least partially removing and/or shrinking these structures to form hollow cavities. These cavities provide space for the active materials of the nanostructures to swell into during battery cycling. This design helps to reduce the risk of pulverization and to maintain electrical contacts among the nanostructures. It also provides a very high surface area available ionic communication with the electrolyte. The nanostructures have nanoscale shells but may be substantially larger in other dimensions. Nanostructures can be interconnected during forming the nanoscale coating, when the coating formed around two nearby template structures overlap.

Claims

1. An electrode layer for use in a rechargeable battery, the electrode layer comprising:

a plurality of interconnected hollow tubular nanostructures having shells around internal cavities, wherein the shells comprise high capacity electrochemically active material, wherein the high capacity electrochemically active material comprises one or more materials selected from the group consisting of silicon, tin, and germanium, wherein all of the interconnected hollow tubular nanostructures in the electrode layer are interconnected by the high capacity electrochemically active material, and

wherein the internal cavities provide free space for the high capacity electrochemically active material to swell into during cycling of the rechargeable battery and wherein the hollow tubular nanostructures are characterized by one or more of the following characteristics;

     1) an aspect ratio of at least about four and a length of at least about 5 micrometers and

     2) a largest inner cross-sectional dimension between about 5 nanometers and 500 nanometers.

2. The electrode layer of claim 1, wherein the internal cavities are substantially inaccessible to an electrolyte of the rechargeable battery.

3. The electrode layer of claim 1, wherein the electrode layer is configured to provide a stable energy capacity of at least about 2000 mAh/g after at least 100 cycles based on the weight of the high capacity electrochemically active material.

4. The electrode layer of claim 1, further comprising an outer layer substantially covering an outer surface of the interconnected hollow tubular nanostructures, wherein the outer layer comprising one or more materials selected from the group consisting of carbon, titanium, silicon, aluminum, and copper.

5. The electrode layer of claim 1, wherein the electrode layer has a porosity of between about 20% and 80%.

6. The electrode layer of claim 1, wherein the rechargeable battery is a lithium ion battery and the high capacity electrochemically active material is a negative active material.

14. The electrode layer of claim 1, further comprising an outer layer substantially covering an outer surface of the interconnected hollow nanostructures, wherein the outer layer comprises one or more materials selected from the group consisting of carbon, a metal, a metal oxide, a metal nitride, and a metal carbide.

15. The electrode layer of claim 1, wherein the hollow nanostructures have an aspect ratio of at least about four and a length of at least about 5 micrometers.

16. The electrode layer of claim 1, wherein the hollow tubular nanostructures have a largest inner cross-sectional dimension between about 5 nanometers and 500 nanometers.

17. The electrode layer of claim 1, wherein the shells have a thickness between about 5 and 1000 nm.

18. The electrode layer of claim 1, wherein the silicon, tin, or germanium of the high capacity electrochemically active material of the shells directly contacts the internal cavities.

7. A rechargeable lithium ion battery comprising:

an electrode layer comprising;

a plurality of interconnected hollow tubular nanostructures having shells around internal cavities, wherein the shells comprise high capacity electrochemically active material, wherein all of the interconnected hollow tubular nanostructures in the electrode layer are interconnected by the high capacity electrochemically active material, wherein the high capacity electrochemically active material comprises one or more materials selected from the group consisting of silicon, tin, and germanium, and

wherein the internal cavities provide free space for the high capacity electrochemically active material to swell into during cycling of the rechargeable battery and wherein the hollow tubular nanostructures are characterized by one or more of the following characteristics;

     1) an aspect ratio of at least about four and a length of at least about 5 micrometers and

     2) a largest inner cross-sectional dimension between about 5 nanometers and 500 nanometers.

8. An electrode layer for use in a rechargeable battery, the electrode layer comprising:

interconnected hollow nanostructures having shells around internal cavities, wherein the shells comprise a high capacity electrochemically active material; and

a substrate underlying the interconnected hollow nanostructures,

wherein all of the interconnected hollow nanostructures in the electrode layer are interconnected at points above the substrate by first structures, the first structures including one or more of metals and the high capacity electrochemically active material, wherein the high capacity electrochemically active material comprises one or more materials selected from the group consisting of silicon, tin, and germanium, and wherein the internal cavities provide free space for the high capacity electrochemically active material to swell into during cycling of the rechargeable battery and wherein the hollow nanostructures are characterized by one or more of the following characteristics;

     1) an aspect ratio of at least about four and a length of at least about 5 micrometers and

     2) a largest inner cross-sectional dimension between about 5 nanometers and 500 nanometers.

9. The electrode layer of claim 8, wherein the internal cavities are substantially inaccessible to an electrolyte of the rechargeable battery.

10. The electrode layer of claim 8, wherein the electrode layer is configured to provide a stable energy capacity of at least about 2000 mAh/g after at least 100 cycles based on the weight of the high capacity electrochemically active material.

11. The electrode layer of claim 8, further comprising an outer layer substantially covering an outer surface of the interconnected hollow nanostructures, wherein the outer layer comprising one or more material selected from the group consisting of carbon, titanium, silicon, aluminum, and copper.

12. The electrode layer of claim 8, wherein the electrode layer has a porosity of between about 20% and 80%.

13. The electrode layer of claim 8, wherein the rechargeable battery is a lithium ion battery and the high capacity electrochemically active material is a negative active material.