Sprayed formation of batteries

Patent metadata

Field	Value
Publication number	US-11870052-B2
Application number	US-202016783657-A
Country	US
Kind code	B2
Filing date	Feb 6, 2020
Priority date	Nov 17, 2016
Publication date	Jan 9, 2024
Grant date	Jan 9, 2024

Abstract

A rechargeable lithium-ion (Li-ion) battery employs a low temperature approach to battery manufacturing that forms charge material from kinetic energy of high velocity particles impelled into an aggregation such that bombardment of the particles against other particles in the aggregation forms a charge conveying structure. High velocity bombardment from a carrier gas nozzle accumulates an active charge material in a layered arrangement for the finished battery. Preparation of the particles, such as by ball milling or spraydrying, arranges particle agglomerations. The particle agglomerations, when impelled against other agglomerations or a current collector, forms a layer of cathodic, anodic or electrolytic battery material. The metallic binder conveys charge for mitigating or eliminating a need for a planar current collector underlying the sprayed layer. The resulting layers are suitable for battery operation, and are manufactured in an absence of any solvent drying or disposal.

First claim

What is claimed is:

1. A method of forming a solid-state battery, comprising:
cooling a granular form of a lithium-ion transport medium below a glass transition temperature T_g of a conductive polymer included in the lithium-ion transport medium for imparting a brittle granular texture to the cooled, granular form of the lithium-ion transport medium;
forming agglomerates including a conductive medium, the lithium-ion transport medium and an active charge material, the agglomerates including particles of evenly dispersed powders of the conductive medium and the active charge material bonded by the lithium-ion transport medium;
propelling the agglomerates at a predetermined temperature and a predetermined pressure to form sprayed agglomerates, the predetermined temperature based on the glass transition temperature of the conductive polymer included in the lithium-ion transport medium, and the predetermined pressure based on deformation of the sprayed agglomerates upon impact at the predetermined temperature; and
accumulating the sprayed agglomerates for deforming the sprayed agglomerates responsive to an impact against a collection surface and forming a layered structure for an active charge material layer of a battery based on multiple spraying iterations of the sprayed agglomerates for propelled deformation.

2. The method of claim 1 wherein the conductive medium, the lithium-ion transport medium and the active charge material define a granular texture and the layered structure of the deformed, sprayed agglomerates defines a distributed network of distinct granular particles, the network having a regular distribution of a distance from a particle of one distinct granular particle to a proximal distinct granular particle of a same type.

3. The method of claim 1 further comprising forming the agglomerates by:
pulverizing a powder form of the active charge material, the conductive medium and an electrolyte material into an agglomeration mixture;
cryogenically cooling the agglomeration mixture below a glass transition temperature of the electrolyte material while pulverizing, the temperature of the cooled agglomeration mixture based on a size of the formed agglomerations; and
warming the agglomerations above the glass transition temperature of the agglomerations for bonding the active charge material, the conductive medium and the electrolyte material into the agglomerates.

4. The method of claim 3 further comprising adding liquid nitrogen to the agglomeration mixture for reducing the temperature during pulverizing.

5. The method of claim 1 wherein the active charge material is an cathode material and the conductive medium is a carbon powder.

6. The method of claim 1 wherein the active charge material is an anode material and the conductive medium include carbon powder and graphite.

7. The method of claim 3 wherein the layered structure exhibits an absence of distinct boundaries between the deformed agglomerates.

8. The method of claim 3 wherein the agglomerates are clusters of particulate forms of the conductive medium and the active charge material, bonded by a polymer defining the lithium-ion transport medium; and
the agglomerates remain intact during propulsion by a carrier gas and deform upon impact on a current collector or others of the sprayed agglomerates,
the deformation of a plurality of the sprayed agglomerates resulting in an electrode layer of a battery.

9. The method of claim 1 further comprising forming the agglomerates by encapsulating an electrolyte core as the lithium-ion transport medium agglomerated with the active charge material and the conductive medium.

10. The method of claim 1 wherein forming the agglomerates further comprises:
ball milling the conductive medium, the lithium-ion transport medium and the active charge material as powder particles in a ball mill, including between 30%-95% by weight of the active charge material using milling balls of a size between 5-15 mm for 6-12 hours.

11. The method of claim 1 further comprising:
forming the agglomerates from a slurry including a solvent with an agglomeration mixture including the conductive medium, the lithium-ion transport medium and the active charge material.

12. The method of claim 11 wherein the slurry includes 90% by weight of the solvent with 10% of the agglomeration mixture, further comprising propelling via a carrier gas through a nozzle, the carrier gas heating an inlet of the nozzle to at least 100° C. and an outlet of the nozzle remaining between a predetermined temperature range based on the solvent; and
accumulating the sprayed agglomerates exiting the outlet of the nozzle atomized for forming the sprayed agglomerates resulting from solvent evaporation in the nozzle.

13. The method of claim 1 wherein the collection surface is a current collector receiving a first layer of the sprayed agglomerates, and successive layers of sprayed agglomerates accumulating and layering on previously sprayed agglomerates.

14. The method of claim 13 wherein propelling further includes injecting a pressurized, heated gas through a nozzle, the nozzle having an exit at a standoff distance between 0.15-0.75 in. distal from the collection surface, and feeding the agglomerates through the nozzle at a feed rate based on a thickness of a layer formed by the sprayed agglomerates on the collection surface.

15. The method of claim 1 wherein the conductive particles include materials or alloys selected from the group consisting of Al, Cu, Sn, Ta, Co, Ni, Si, V, Ga, Li and C.

16. The method of claim 1 wherein the active material includes cathode material selected from the group consisting of LiNiCoAlO 2 (NCA), LiNiMnCoO 2 (NMC), LiNi 5 Co 3 Mn 2 O 2 (Hi-NMC), LiFePO 4 (LFP), LiCoO 2 (LCO), LiMn 2 O 4 (LMO) and Li 4 Ti 5 O 12 (LTO).

17. The method of claim 1 wherein the active material includes anode material selected from the group consisting of Graphite, Silicon, Li-Sulfur, Lithium metal and tin.

18. The method of claim 1 wherein the layered structure includes one or more of a cathode layer, an anode layer and a separator layer, further comprising:
forming a cathode layer from the sprayed agglomerates employing cathodic charge material as the active charge material;
forming an anode layer from the sprayed agglomerates employing anode charge material as the active charge material,
wherein the anode layer and cathode layer are electrically isolated by consolidating a solid-electrolyte separator layer composed of one or more solid-polymer, oxide, or sulfide-based electrolytes capable of conducting ions and nonconductive to electrons.

19. The method of claim 18 further comprising calendaring one or more of the cathode, anode, and separator layers for smoothing and densifying the layered structure.

20. The method of claim 18 further comprising:
iteratively consolidating the cathode layer, separator layer and anode layer, the cathode layer, separator layer and anode layer defining a solid-state lithium-ion battery unit cell; and
encasing the solid-state lithium-ion battery unit cell by further spraying a protective layer for isolating the solid-state lithium-ion battery unit cell from ionic or conductive contact.

21. The method of claim 20 wherein further comprising spraying multiple layers in a sequence to form a multi-layer lithium ion battery that defines a Li-ion battery cell.

Assignees

• Worcester Polytech Inst

Inventors

• Birt Aaron M
• Apelian Diran
• Heelan Joseph
• Mocadlo Ryan
• Valamanesh Ali

Classifications

• H01M4/0419 Primary

  involving spraying · CPC title

• H01M4/1393

  of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M4/1395

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

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title