# US 2022/0045352 A1 · Glass solid electrolyte layer, methods of making glass solid electrolyte layer and electrodes and battery cells thereof

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- Number: US 2022/0045352 A1
- Document ID: US20220045352A1
- Status: Published application
- Kind: A1
- Application number: 17/303,706
- Filed: 2021-06-04
- Published: 2022-02-10
- Earliest claimed: 2020-08-04
- Assignees: PolyPlus Battery Company
- Applicants: PolyPlus Battery Company
- Inventors: Steven J. Visco; Vitaliy Nimon; Valentina Loginova; Yevgeniy S. Nimon; Bruce D. Katz
- Web page: https://patentgrep.com/patent/US20220045352A1

## CPC

- C03C 15/02: for making a smooth surface
- H01M 10/0562: Solid materials
- C03C 15/00: Surface treatment of glass, not in the form of fibres or filaments, by etching (etching or surface-brightening compositions, in general C09K13/00)
- C03C 23/0025: {by a laser beam}
- H01M 4/0407: {by coating on an electrolyte layer}
- H01M 4/0409: {by a doctor blade method, slip-casting or roller coating}
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
- H01M 2300/0068: inorganic
- Y02E 60/10: Energy storage using batteries
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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

Battery component structures and manufacturing methods for solid-state battery cells include a unitary Li ion conducting sulfide glass solid electrolyte structure that serves as the basic building block around which a solid-state battery cell can be fabricated. The unitary glass structure approach can leverage precision controlled high throughput processes from the semiconductor industry that have been inventively modified as disclosed herein for processing a sulfide glass solid electrolyte substrate into a unitary Li ion conducting glass structure, for example, by using etching and lithographic photoresist formulations and methods. The glass substrate may be precision engineered to effectuate a dense glass portion and a porous glass portion that can be characterized as sublayers having predetermined thicknesses. The porous glass sublayer includes a plurality of discrete substantially vertical closed-end holes or trenches that are precision engineered into one or both major substrate surfaces using microfabrication processes.

## Claims

### Claim 1

A unitary Li ion conducting glass structure comprising: a substantially flat Li ion conducting sulfide glass substrate having first and second major opposing surfaces, the glass substrate having a first porous glass portion that is characterizable as a first porous sublayer with a certain thickness and a dense glass portion that is characterizable as a dense glass sublayer with a certain thickness, wherein the first porous sublayer comprises a first plurality of discrete closed-end substantially vertical holes and/or trenches that extend into the substrate from the substrate first major surface to a predetermined depth, the first porous sublayer defining a hole and/or trench pattern on the first major surface.

### Claim 2 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the glass substrate is characterizable as having a asymmetric architecture composed of the dense glass sublayer and the first porous glass sublayer, wherein the dense glass sublayer defines the substrate second major surface and extends therefrom into the substrate.

### Claim 3 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 further comprising a second porous portion that is characterizable as a second porous sublayer comprising a second plurality of discrete closed-end and substantially vertical holes that extend into the substrate from the substrate second major to a predetermined depth, the second porous sublayer defining a hole pattern on the second major surface; and wherein the glass substrate is characterizable as having a sandwich architecture composed of the dense glass sublayer sandwiched between the first and second porous glass sublayers.

### Claim 4 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the number density of holes in the first or second porous sublayer is >100 per mm2.

### Claim 5 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the holes are substantially circular and effectuate a substantially regular hole pattern on their respective substrate surface.

### Claim 6 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the holes are highly anisotropic with an aspect ratio >10:1.

### Claim 7 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the holes have substantially vertical sidewalls.

### Claim 8 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the holes have a concave shaped sidewall.

### Claim 9 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the hole pattern is created by lithography and etching.

### Claim 10 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the thickness of the dense glass sublayer is about 1-to-50 um.

### Claim 11 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the thickness of the first porous sublayer and second porous sublayer (when present) is about 5 to 100 um.

### Claim 12 (depends on 3)

The solid electrolyte glass substrate of claim 3 wherein the first surface hole pattern and second surface hole pattern is different.

### Claim 13 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the holes are substantially circular shaped and have a diameter value that is in a selected from the group consisting of >5 to 10 um, >1 to 5 um, and >100 nm to 1 um.

### Claim 14 (depends on 1)

The unitary Li ion conducting glass structure of claim 1 wherein the Li ion conducting sulfide glass substrate comprising lithium, sulfur, and one or more of boron, germanium, phosphorus and silicon.

### Claim 15

A method of making a unitary Li ion conducting glass structure, the method comprising:
i) providing a substantially dense and flat Li ion conducting sulfide glass substrate, the substrate having first and second opposing major surfaces;
ii) etching a hole pattern into one or both major surfaces to produce a plurality of discrete spaced-apart closed end holes and/or trenches, wherein the etching involves contacting the substrate surface with an etching media.

### Claim 16 (depends on 15)

The method of claim 15 wherein the etching step involves exposing the first substrate surface to a liquid etching solution comprising water as the etchant and a carrier solvent that is inert in direct contact with the glass substrate.

### Claim at position 17

17-19. (canceled)

### Claim 20 (depends on 15)

The method of claim 15 wherein the etching step involves exposing the first substrate surface to a liquid etching solution comprising an organic carbonic acid as the etchant and a carrier solvent that is inert in direct contact with the glass substrate.

### Claim 21

(canceled)

### Claim 22 (depends on 15)

The method of claim 15 wherein the etching media is a gaseous/vapor etching mixture comprising water as the etchant and a carrier gas that is inert in direct contact with the glass substrate.

### Claim 23 (depends on 15)

The method of claim 15 wherein the etching media is a gaseous/vapor etching mixture comprising an organic carbonic acid as the etchant and a carrier gas that is inert in direct contact with the glass substrate.

### Claim at position 22

24-33. (canceled)

### Claim 34

A battery cell comprising a solid electrolyte glass substrate, comprising a unitary Li ion conducting glass structure comprising: a substantially flat Li ion conducting sulfide glass substrate having first and second major opposing surfaces, the glass substrate having a first porous glass portion that is characterizable as a first porous sublayer with a certain thickness and a dense glass portion that is characterizable as a dense glass sublayer with a certain thickness, wherein the first porous sublayer comprises a first plurality of discrete closed-end substantially vertical holes and/or trenches that extend into the substrate from the substrate first major surface to a predetermined depth, the first porous sublayer defining a hole and/or trench pattern on the first major surface; and further comprising active cathode material disposed inside the holes.

### Claim at position 24

35-36. (canceled)