Lithium metal anode comprising Langmuir-Blodgett films as an artificial solid electrolyte interface layer, lithium metal battery comprising the same, and preparation method thereof

Patent metadata

Field	Value
Publication number	US-10243197-B2
Application number	US-201715442908-A
Country	US
Kind code	B2
Filing date	Feb 27, 2017
Priority date	Oct 28, 2016
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

Provided is a lithium metal anode comprising a Langmuir-Blodgett films as an artificial solid electrolyte interface layer, a lithium metal battery comprising the same, and a preparation method thereof. Various ultra-thin film layers made of carbon and ceramic are formed on the surface of the LiM to serve as a stable artificial SEI layer and suppress formation and perforation of lithium dendrite and side reactions.

First claim

What is claimed is:

1. A preparation method of a composite layer, comprising:
(A) forming at least one Langmuir-Blodgett artificial SEI layer on a substrate by performing a process of moving a Langmuir-Blodgett artificial SEI layer dispersed on a surface of a dispersion medium onto the substrate and drying the moved thin film layer at least once, and
(B) transferring the at least one Langmuir-Blodgett artificial SEI layer formed on the substrate onto an alkali metal,
wherein the at least one Langmuir-Blodgett artificial SEI layer is made of the same material or different materials, independently selected from the group consisting of graphene nanoparticle, nitrogen-doped graphene oxide, graphene oxide, lithium-terminated sulfonated titania nanopowder, reduced graphene oxide, graphene powder, crumpled graphene oxide, crumpled reduced graphene oxide, crumpled reduced graphene oxide with titania nanoparticle, titania nanopowder, and mixtures thereof, and
wherein when two or more Langmuir-Blodgett artificial SEI layers are included, two Langmuir-Blodgett artificial SEI layers adjacent to each other are made of the same material or different materials,
wherein the step (B) is performed by pressing the alkali metal and the substrate to be closely adhered to each other so that the alkali metal and the Langmuir-Blodgett artificial SEI layer become adjacent to each other, and
wherein the pressing is performed by moving the alkali metal and the substrate, closely adhered to each other, through a rolling press in a state where protection films are placed at front and rear portions thereof.

2. A preparation method of a composite layer, comprising:
(A) forming at least one Langmuir-Blodgett artificial SEI layer on a substrate by performing a process of moving a Langmuir-Blodgett artificial SEI layer dispersed on a surface of a dispersion medium onto the substrate and drying the moved thin film layer at least once, and
(B) transferring the at least one Langmuir-Blodgett artificial SEI layer formed on the substrate onto an alkali metal,
wherein the at least one Langmuir-Blodgett artificial SEI layer is made of the same material or different materials, independently selected from the group consisting of graphene nanoparticle nitrogen-doped graphene oxide, graphene oxide, lithium-terminated sulfonated titania nanopowder, reduced graphene oxide, graphene powder, crumpled graphene oxide, crumpled reduced graphene oxide, crumpled reduced graphene oxide with titania nanoparticle, titania nanopowder, and mixtures thereof,
wherein when two or more Langmuir-Blodgett artificial SEI layers are included, two Langmuir-Blodgett artificial SEI layers adjacent to each other are made of the same material or different materials,
wherein in the step (A), the Langmuir-Blodgett artificial SEI layer is moved by lifting up the substrate immersed in the dispersion medium so that the Langmuir-Blodgett artificial SEI layer covers the substrate, and
wherein in the step (A), when the substrate is lifted up, a suspension made of the same material as the Langmuir-Blodgett artificial SEI layer is simultaneously put into the dispersion medium,
wherein the step (A) is performed when the Langmuir-Blodgett artificial SEI layer occupies 30% to 90% of the surface of the dispersion medium.

3. The preparation method of a composite layer according to claim 2 ,
wherein the suspension has a concentration of 0.5 to 5 wt %.

4. The preparation method of a composite layer according to claim 2 ,
wherein the suspension is put so that an area ratio of the surface of the dispersion medium, occupied by the Langmuir-Blodgett artificial SEI layer, is maintained to be 30% to 90% in comparison to an initial area.

5. The preparation method of a composite layer according to claim 2 ,
wherein the dispersion medium is water, and a suspension medium of the suspension is ethanol.

6. The preparation method of a composite layer according to claim 1 ,
wherein the step (B) is performed by means of roll pressing.

7. The preparation method of a composite layer according to claim 1 ,
wherein an interval of pressing cylinders of the rolling press is adjusted to be 50% to 90% of an entire thickness of layers put between press rolls, and a roll rotation speed is maintained to be 0.1 cm/sec to 1 cm/sec.

8. The preparation method of a composite layer according to claim 1 ,
wherein the step (B) further includes removing the substrate from the alkali metal to which the Langmuir-Blodgett artificial SEI layer is transferred.

9. A preparation method of a composite layer, comprising:
(A) forming at least one Langmuir-Blodgett artificial SEI layer on a substrate by performing a process of moving a Langmuir-Blodgett artificial SEI layer dispersed on a surface of a dispersion medium onto the substrate and drying the moved thin film layer at least once, and
(B) transferring the at least one Langmuir-Blodgett artificial SEI layer formed on the substrate onto an alkali metal,
wherein the at least one Langmuir-Blodgett artificial SEI layer is made of the same material or different materials, independently selected from the group consisting of graphene nanoparticle, nitrogen-doped graphene oxide, graphene oxide, lithium-terminated sulfonated titania nanopowder, reduced graphene oxide, graphene powder, crumpled graphene oxide, crumpled reduced graphene oxide, crumpled reduced graphene oxide with titania nanoparticle, titania nanopowder, and mixtures thereof, and
wherein when two or more Langmuir-Blodgett artificial SEI layers are included, two Langmuir-Blodgett artificial SEI layers adjacent to each other are made of the same material or different materials, and
wherein the step (B) is performed under a dry environment with a relative humidity of 0% to 1%.

10. The preparation method of a composite layer according to claim 5 ,
wherein the substrate is an aluminum foil, and the protection film is a polycarbonate film.

11. The preparation method of a composite layer according to claim 10 ,
wherein the alkali metal is lithium, and
wherein the composite layer is a lithium metal anode.

12. The preparation method of a composite layer according to claim 1 ,
wherein the alkali metal is lithium, and
wherein the composite layer is a lithium metal anode.

13. The preparation method of a composite layer according to claim 2 ,
wherein the alkali metal is lithium, and
wherein the composite layer is a lithium metal anode.

Assignees

• Korea Inst Sci & Tech
• Univ Cornell
• Korean Institute Of Science And Tech

Inventors

• Cho Won Il
• Kim Mun Sek
• Nah In Wook
• Kim Min Seop
• Archer Lynden A
• Choudhury Snehashis
• Tu Zhengyuan

Classifications

• H01M4/366

  as layered products · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/583

  Carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M4/0402 Primary

  Methods of deposition of the material · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title