# US 11,028,496 B2 · Fabrication of solid-state battery cells and solid-state batteries

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- Number: US 11,028,496 B2
- Document ID: US11028496B2
- Status: Granted
- Kind: B2
- Application number: 16/631,657
- Filed: 2018-07-13
- Published: 2020-06-18
- Granted: 2021-06-08
- Earliest claimed: 2017-07-18
- Assignees: Imec Vzw
- Applicants: Imec Vzw; Katholieke Universiteit Leuven, KU LEUVEN R & D
- Inventors: Stanislaw Piotr Zankowski; Philippe M. Vereecken
- Web page: https://patentgrep.com/patent/US11028496B2

## CPC

- C25D 11/045: {for forming AAO templates}
- C23F 1/00: Etching metallic material by chemical means (manufacture of printing surfaces B41C; manufacture of printed circuits H05K)
- C23F 1/20: for etching aluminium or alloys thereof
- C23F 1/28: for etching iron group metals
- C25D 1/006: {Nanostructures, e.g. using aluminium anodic oxidation templates [AAO]}
- C25D 1/08: Perforated or foraminous objects, e.g. sieves (C25D1/10 takes precedence)
- C25D 3/12: of nickel or cobalt
- C25D 9/02: with organic materials
- C25D 9/06: by anodic processes
- C25D 11/022: {Anodisation on selected surface areas}
- C25D 11/024: {Anodisation under pulsed or modulated current or potential}
- C25D 11/10: containing organic acids
- C25D 11/12: Anodising more than once, e.g. in different baths
- C25D 11/18: After-treatment, e.g. pore-sealing
- C25D 11/24: Chemical after-treatment
- C25D 11/34: of metals or alloys not provided for in groups C25D11/04 - C25D11/32
- H01B 1/02: mainly consisting of metals or alloys
- H01B 5/002: {Auxiliary arrangements}
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/0407: {by coating on an electrolyte layer}
- H01M 4/0442: {Anodisation, Oxidation (electrolytic coating by anodisation C25D9/00)}
- H01M 4/045: {Electrochemical coating; Electrochemical impregnation}
- H01M 4/0452: {from solutions}
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 4/72: Grids
- H01M 4/80: Porous plates, e.g. sintered carriers
- H01M 8/0232: Metals or alloys
- H01M 8/0247: characterised by the form (characterised by a channel configuration H01M8/0258)
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C23C 2222/20: Use of solutions containing silanes
- H01M 4/86: Inert electrodes with catalytic activity, e.g. for fuel cells
- Y02E 60/10: Energy storage using batteries
- Y02E 60/50: Fuel cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C23F: NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE (working metal by laser beams B23K26/00; desurfacing by applying flames B23K7/00; working of metal by electro-erosion B23H; producing decorative effects by removing surface material, e.g. by engraving, by etching, B44C1/22; electrolytic etching or polishing C25F); INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

At least one embodiment relates to a method fabricating a solid-state battery cell. The method includes forming a plurality of spaced electrically conductive structures on a substrate. Forming the plurality of spaced electrically conductive structures on the substrate includes transforming at least part of a valve metal layer into a template that includes a plurality of spaced channels aligned longitudinally along a first direction. Transforming at least part of the valve metal layer into the template includes a first anodization step, a second anodization step, an etching step in an etching solution, and a deposition step. The method also includes forming a first layer of active electrode material on the plurality of spaced electrically conductive structures, depositing an electrolyte layer over the first layer of active electrode material, and forming a second layer of active electrode material over the electrolyte later.

## Claims

### Claim 1

A method for fabricating a solid-state battery cell, the method comprising:
forming a plurality of spaced electrically conductive structures on a substrate, wherein forming the plurality of spaced electrically conductive structures on the substrate comprises transforming at least part of a valve metal layer into a template comprising a plurality of spaced channels aligned longitudinally along a first direction, and wherein transforming at least part of the valve metal layer into the template comprises:
a first anodization step, which anodizes at least part of the valve metal layer in a thickness direction to form a porous layer of valve metal oxide comprising a plurality of channels, wherein each channel comprises channel walls aligned longitudinally along the first direction and a channel bottom, wherein the channel bottom is coated with a first insulating metal oxide barrier layer as a result of the first anodization step;
a protective treatment that induces hydrophobic surfaces to the channel walls and channel bottoms;
a second anodization step after the protective treatment, which substantially removes the first insulating metal oxide barrier layer from the channel bottoms to induce anodization only at the bottoms of the plurality of channels and create a second insulating metal oxide barrier layer at the channel bottoms; and
an etching step in an etching solution, wherein the etching step removes the second insulating metal oxide barrier layer from the channel bottoms, the method further comprising:
depositing a solid functional material within the channels of the template to form the plurality of spaced structures inside the plurality of channels, wherein the plurality of spaced structures are aligned longitudinally along the first direction;
forming a first layer of active electrode material on the plurality of spaced electrically conductive structures, wherein the first layer of active electrode material conformally coats surfaces of the plurality of spaced electrically conductive structures;
depositing an electrolyte layer over the first layer of active electrode material; and
forming a second layer of active electrode material over the electrolyte layer, wherein:
the first layer of active electrode material forms a cathode layer of the solid-state battery cell and the second layer of active electrode material forms an anode layer of the solid-state battery cell; or
the second layer of active electrode material forms the cathode layer of the solid-state battery cell and the first layer of active electrode material forms the anode layer of the solid-state battery cell.

### Claim 2 (depends on 1)

The method for according to claim 1, wherein the valve metal layer comprises a layer of aluminum, an aluminum alloy, titanium, a titanium alloy, tantalum, or a tantalum alloy.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the protective treatment comprises annealing at a temperature between 300° C. and 550° C.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the protective treatment comprises depositing a protective layer on the channel walls and on the channel bottoms, and wherein the second anodization step further comprises removing the protective layer only from the channel bottoms.

### Claim 5 (depends on 4)

The method according to claim 4, wherein the protective layer comprises hydrophobic silane or a polymer that is resistant to the etching solution.

### Claim 6 (depends on 4)

The method according to claim 4, wherein the protective layer comprises polystyrene, poly(methyl 2-methylpropanoate), or poly(dimethylsiloxane).

### Claim 7 (depends on 1)

The method according to claim 1, wherein the etching solution is an aqueous etching solution comprising phosphoric acid, sulfuric acid, oxalic acid, chromic acid, ammonia, hydrogen peroxide, or potassium hydroxide.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the etching solution comprises a surface tension adjusting agent.

### Claim 9 (depends on 1)

The method according to claim 1, further comprising providing ultrasonic waves during the second anodization step.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the first anodization step anodizes only a part of the valve metal layer in the thickness direction, to thereby form the template and a substrate supporting the template, and wherein the substrate comprises a remaining, non-anodized part of the valve metal layer.

### Claim 11 (depends on 1)

The method according to claim 1, wherein depositing the solid functional material comprises depositing an electrically conductive material, a semiconductor material, or an electrically insulating material.

### Claim 12 (depends on 1)

The method according to claim 1, wherein forming the first layer of active electrode material comprises:
depositing an interlayer on the substrate, wherein the interlayer comprises a transition metal oxide, a noble metal, or a noble-metal oxide, and wherein the interlayer has a thickness between 0.5 nm and 30 nm;
depositing a functional material precursor layer on the interlayer; and
activating the functional material precursor layer by annealing in order to form the layer of functional material.

### Claim 13 (depends on 1)

The method of claim 1, wherein the protective treatment is performed after the first anodization step.

### Claim 14

A method for fabricating a solid-state battery cell, the method comprising:
forming a plurality of spaced electrically conductive structures on a substrate;
forming a first layer of active electrode material on the plurality of spaced electrically conductive structures, wherein forming the first layer of active electrode material on the plurality of spaced electrically conductive structures comprises:
depositing an interlayer on the substrate, wherein the interlayer comprises a transition metal oxide, a noble metal, or a noble-metal oxide, and wherein the interlayer has a thickness in the range between 0.5 nm and 30 nm;
depositing a functional material precursor layer on the interlayer; and
activating the functional material precursor layer by annealing in order to form the layer of functional material, wherein the first layer of active electrode material conformally coats surfaces of the plurality of spaced electrically conductive structures;
depositing an electrolyte layer over the first layer of active electrode material; and
forming a second layer of active electrode material over the electrolyte layer, wherein:
the first layer of active electrode material forms a cathode layer of the solid-state battery cell and the second layer of active electrode material forms an anode layer of the solid-state battery cell; or
the second layer of active electrode material forms the cathode layer of the solid-state battery cell and the first layer of active electrode material forms the anode layer of the solid-state battery cell.

### Claim 15 (depends on 14)

The method according to claim 14, wherein depositing the functional material precursor layer comprises depositing an electrode material precursor layer, and wherein activating the functional material precursor layer comprises annealing with an ion containing precursor present, thereby forming a layer of active electrode material.

### Claim 16 (depends on 14)

The method according to claim 14, wherein depositing the functional material precursor layer comprises anodic electrodeposition.

### Claim 17 (depends on 14)

The method according to claim 14, wherein the electrically conductive substrate is a transition metal substrate.

### Claim 18 (depends on 14)

The method according to claim 14, wherein the electrically conductive substrate is a three-dimensional substrate comprising a plurality of electrically conductive structures being aligned longitudinally along a first direction.

### Claim 19 (depends on 18)

The method according to claim 18, wherein the electrically conductive substrate further comprises a plurality of electrically conductive interconnecting structures oriented along a second direction different from the first direction.

### Claim 20 (depends on 14)

The method according to claim 14, wherein the interlayer comprises a transition metal oxide and wherein depositing the interlayer comprises electrodeposition in a solution having a pH between 7 and 12.