# US 11,909,024 B2 · Multi-layer structures prepared by layer-by-layer assembly

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- Number: US 11,909,024 B2
- Document ID: US11909024B2
- Status: Granted
- Kind: B2
- Application number: 17/100,091
- Filed: 2020-11-20
- Published: 2021-03-25
- Granted: 2024-02-20
- Earliest claimed: 2013-01-01
- Assignees: Massachusetts Institute of Technology
- Applicants: Massachusetts Institute of Technology
- Inventors: Paula T. Hammond; Sun Hwa Lee
- Web page: https://patentgrep.com/patent/US11909024B2

## CPC

- H01M 12/08: composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 50/417: Polyolefins
- H01M 50/437: Glass
- H01M 50/457: comprising three or more layers
- H01M 50/46: Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M 4/628: {Inhibitors, e.g. gassing inhibitors, corrosion inhibitors}
- H01M 50/489: Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M 50/497: Ionic conductivity
- H01M 2300/0082: Organic polymers
- H01M 2300/0094: in the form of layered products, e.g. coatings
- 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 protective layer can be deposited on a surface of an porous polymer separator placing on a Li-metal electrode to protect against adverse electrochemical activity in a battery. The protective layer can be a multilayered structure including graphene oxide.

## Claims

### Claim 1

A multi-layer structure comprising a tetralayer on a substrate, the tetralayer including an ion-conductive polymer and a barrier layer, the tetralayer on the substrate positioned between a surface of a separator and a surface of a Li-metal electrode in a battery, wherein the tetralayer includes a first polyethylene oxide layer, a graphene oxide layer adjacent to the first polyethylene oxide layer, a second polyethylene oxide layer adjacent to the graphene oxide layer and opposite the first polyethylene oxide layer, and a polyacrylic acid layer adjacent to the second polyethylene oxide layer.

### Claim 2 (depends on 1)

The structure of claim 1, wherein the substrate includes a polymer membrane.

### Claim 3 (depends on 2)

The structure of claim 2, wherein the polymer membrane includes polypropylene.

### Claim 4 (depends on 1)

The structure of claim 1, wherein the tetralayer includes graphene oxide, polyethylene oxide or polyacrylic acid.

### Claim 5 (depends on 1)

The structure of claim 1, wherein the tetralayer is on a polypropylene membrane.

### Claim 6 (depends on 2)

The structure of claim 2, wherein the surface of the tetralayer is more hydrophilic than a surface of the substrate.

### Claim 7 (depends on 1)

The structure of claim 1, wherein the thickness of the structure increases as the number of tetralayers increases.

### Claim 8 (depends on 1)

The structure of claim 1, wherein increasing the thickness of the tetralayer changes the ionic conductivities of the structure.

### Claim 9 (depends on 1)

The structure of claim 1, wherein electrolyte permeability of the tetralayer are repressed with increasing thickness of the tetralayer.

### Claim 10 (depends on 1)

The structure of claim 1, wherein the tetralayer includes graphene oxide which lowers the permeability of the tetralayer.

### Claim 11

A battery device comprising an electrode protective structure, wherein the electrode protective structure includes graphene oxide in a tetralayer on a substrate positioned between a surface of a separator and a surface of a Li-metal electrode, wherein the tetralayer includes a first polyethylene oxide layer, a graphene oxide layer adjacent to the first polyethylene oxide layer, a second polyethylene oxide layer adjacent to the graphene oxide layer and opposite the first polyethylene oxide layer, and a polyacrylic acid layer adjacent to the second Polyethylene oxide layer.

### Claim 12 (depends on 11)

The device of claim 11, wherein the electrode protective structure contacts a surface of an anode.

### Claim 13 (depends on 11)

The device of claim 11, wherein the electrode protective structure includes ion-conductive polymer, a barrier layer, polyethylene oxide, or polyacrylic acid.

### Claim 14 (depends on 11)

The device of claim 11, wherein the electrode protective structure includes a first polyethylene oxide layer, a graphene oxide layer adjacent to the first polyethylene oxide layer, a second polyethylene oxide layer adjacent to the graphene oxide layer and opposite the first polyethylene oxide layer, and a polyacrylic acid layer adjacent to the second polyethylene oxide layer.

### Claim 15 (depends on 14)

The device of claim 14, wherein the electrode protective structure includes layers formed on a polypropylene membrane.

### Claim 16 (depends on 14)

The device of claim 14, wherein the electrode protective structure includes layers that suppress dendritic growth on an electrode.

### Claim 17 (depends on 14)

The device of claim 14, wherein the electrode protective structure includes layers that suppress dendritic growth on a lithium anode.