WO2025076169A1 - Fabrication rouleau à rouleau de film nanostructuré - Google Patents

Fabrication rouleau à rouleau de film nanostructuré Download PDF

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Publication number
WO2025076169A1
WO2025076169A1 PCT/US2024/049718 US2024049718W WO2025076169A1 WO 2025076169 A1 WO2025076169 A1 WO 2025076169A1 US 2024049718 W US2024049718 W US 2024049718W WO 2025076169 A1 WO2025076169 A1 WO 2025076169A1
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WO
WIPO (PCT)
Prior art keywords
substrate
porous
ion
conductive
template
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/049718
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English (en)
Inventor
Rui CHENG
Sheng SHEN
Qixian WANG
Zexiao WANG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Carnegie Mellon University
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Carnegie Mellon University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Carnegie Mellon University filed Critical Carnegie Mellon University
Publication of WO2025076169A1 publication Critical patent/WO2025076169A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/006—Nanostructures, e.g. using aluminium anodic oxidation templates [AAO]
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/08—Perforated or foraminous objects, e.g. sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • Nanostructures have shown great promise in a variety of applications in energy transport, conversion, and storage, opto-electronics, nano-electronics, photonics, sensing, biotechnology, and medicine.
  • a series of fabrication methods based on lithography, physical vapor deposition, chemical vapor deposition, chemical synthesis, electrochemical deposition, etc. have been developed to control the shape, size distribution, and surface chemistry of nanostructures.
  • most of the methods are either costly or non-scalable.
  • Roll-to-roll fabrication is a film-based scalable fabrication method that is a highly favorable approach for industry, while so far, the roll-to-roll technology for nanostructure fabrication is mainly based on nanoimprinting and lithography.
  • One aspect of the present application is to provide a method for fabricating a nanostructured film, comprising: preparing a first ion-conductive layer formed of a first porous scaffold or polymer gel containing first electrolytes, creating a stacked structure comprising a conductive substrate, a first porous template disposed on the substrate, the first ion-conductive layer disposed on the template, and a first metal anode disposed on the first ion-conductive layer; providing a first plurality of rollers on the first metal anode; applying pressure to the stacked structure via the first plurality of rollers so that the first porous template conforms and stays attached to the substrate; applying a first galvanic potential between the first metal anode and the conductive substrate; growing a first nanostructure from the substrate into the first porous template by first electrochemical deposition so that the substate and the first porous template are bonded together; and removing the first porous template by chemical dissolution or chemical etching to obtain the nanostructured film.
  • the nanostructure deposition may be conducted on both sides of the substrate.
  • the method may further comprise preparing a second ion-conductive layer formed of a second porous scaffold or polymer gel containing second electrolytes.
  • the stacked structure may further comprise, in sequence, a second porous template disposed beneath the substrate, the second ion- conductive layer disposed underneath the second porous template, and a second metal anode.
  • the nanostructure deposition may be conducted on both sides of the substrate.
  • the method may further comprise: preparing a second plurality of ion-conductive tube rollers, with each of the second plurality of ion-conductive tube rollers comprising, in sequence, radially from outside to inside, a second porous tube, second electrolytes, and a second anode; placing the second plurality of ion-conductive tube rollers underneath the stacked structure, applying pressure to the stacked structure via the second plurality of ion- conductive tube rollers so that the second porous template conforms and stays attached to the substrate; growing a second nanostructure from the substrate into the second porous template by second electrochemical deposition so that the substrate and the second porous template are bonded together; applying a second galvanic potential between the second anode and the substrate; and removing the second porous template to obtain the nanostructured film by chemical dissolution or chemical etching.
  • Y et another aspect of the present application is a multi-layer product comprising: a conductive substrate; a first porous template disposed on the substrate; and a first plurality of ion-conductive tube rollers on the first porous template, wherein each of the first plurality of ion-conductive tuber rollers comprises, in sequence, radially from outside to inside, a first porous tube containing first electrolytes, and a first anode.
  • the mult-layer product may further comprise a conveyor belt beneath the substrate.
  • the multi-layer product may further comprise: a second porous template disposed underneath the conductive substrate; a second plurality’ of ion-conductive tube rollers underneath the second porous template, with each of the second plurality' of ion-conductive tube rollers comprising, in sequence, radially from outside to inside, a second porous tube, second electrolytes, and a second anode.
  • FIG 3 schematically shows the template layer (301) and conductive substrate (302) transported (moved or delivered) between the roller assembly and the conveyor belt (305) based on yet another embodiment of this application.
  • the roller assembly consists of the anode (303) and the ion-conductive tube roller containing electrolyte (304).
  • the term “about’’ when immediately preceding a numerical value means a range of plus or minus 10% of that value, for example, “about 50” means 45 to 55, “about 25,000” means 22,500 to 27.500, etc., unless the context of the disclosure indicates otherwise, or is inconsistent with such an interpretation.
  • the electrodeposited nanostructures on the substrate can be grown to a desired size solely through the above-described process, or through a two-step growing process.
  • the template and substrate may be bonded through the above-described process and then separated from the stacking and delivered to an electrochemical bath, with a metal anode disposed in parallel with the bonded template and substrate to continue growing the nanostructure to a desired size.
  • the ion-conductive layer may be a porous scaffold containing electrolyte, for example, membrane, filter film, porous polymer films, foam, fabric, paper, sponge, etc., where the electrolyte is filled/infiltrated/contained inside the porous and the scaffold layer plus electrolyte is conductive to ions.
  • the ion-conductive layer may also be formed of hydrogels or other polymer gels capable of containing the electrolyte and conductive to ions.
  • the gel used for the ion-conductive layer may be a network of polymer chains capable of absorbing and retaining a sufficient amount of aqueous or organic solvents while maintaining their structure.
  • the anode is preferably Ni
  • the electrolyte is preferably nickel sulfate, nickel chloride, nickel sulfamate, nickel ammonium sulfate, etc.
  • the substrate is either conductive or coated with a conductive top layer.
  • the conductive layer or coating may be formed of an electrically conductive metal, including, but not limited to, Ag, Au, Pt, Cu, Al, Fe, Zn, Ni, Co, Ru, bronze, brass, Pb, stainless steel, etc., or a conductive polymer, including, but not limited to, PEDOT:PSS, PH1000, and Poly(3-hexylthiophene) (P3HT), or a semiconductor with acceptable resistivity, including but not limited to Si, doped-Si, silicon nitride, indium doped tin oxide, and fluorine-dope tin oxide, and other conductive material, such as graphene, carbon nanotube, and carbon fiber.
  • an electrically conductive metal including, but not limited to, Ag, Au, Pt, Cu, Al, Fe, Zn, Ni, Co, Ru, bronze, brass, Pb, stainless steel, etc.
  • a conductive polymer including, but not limited
  • a stiff ion-conductive tube containing electrolyte serves as both the roller and the ion-conductive layer between the anode and template (see Figure 3).
  • a cylindrical rod serves as the anode.
  • the inner and outer surfaces of the tube may further be covered by a soft ion-conductive layer mentioned in the 1 st approach to achieve a soft contact between the tube roller and the anode rod. and between the tube roller and the template layer (see Figure 4).
  • the stacked layer passing through the rollers is simplified to contain a porous template and the substrate film.
  • a template-substrate-template stack may also be used to pass through groups of rollers (preferably 2-100 pairs of rollers, more preferably 5-20 pairs of rollers) to concurrently achieve the nanostructure deposition on both sides of the substrate (see Figure 5).
  • the overall fabrication speed has been greatly increased, and the deposition areahas largely improved (e.g., longitudinally from 7mm to 66mm).
  • the benefit comes not just from the roller-compressed area but also from the areas between the rollers. After the compression from the roller area, the layers are tightly attached to each other, and nanowires may keep growing into the template.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un procédé de dépôt guidé par gabarit rouleau à rouleau à faible coût et hautement contrôlable pour fabriquer un film nanostructuré comprenant : la création d'une structure empilée comprenant un substrat conducteur, un gabarit poreux disposé sur le substrat, une couche conductrice d'ions formée d'un échafaudage poreux ou d'un gel polymère contenant des électrolytes disposée sur le gabarit, et une anode disposée sur la couche conductrice d'ions ; la fourniture de rouleaux sur l'anode ; l'application d'une pression à la structure empilée par l'intermédiaire des rouleaux de sorte que le premier gabarit poreux se conforme et reste fixé au substrat ; l'application d'un potentiel galvanique entre l'anode métallique et le substrat conducteur pour faire croître une nanostructure à partir du substrat dans le gabarit poreux par dépôt électrochimique ; et le retrait du gabarit poreux par dissolution chimique ou gravure chimique pour obtenir le film nanostructuré. Des rouleaux tubulaires comprenant, radialement, des tubes, des électrolytes et des anodes peuvent remplacer les rouleaux, les électrolytes et les anodes. Le film nanostructuré peut également être amené à croître des deux côtés du substrat.
PCT/US2024/049718 2023-10-04 2024-10-03 Fabrication rouleau à rouleau de film nanostructuré Pending WO2025076169A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363542430P 2023-10-04 2023-10-04
US63/542,430 2023-10-04

Publications (1)

Publication Number Publication Date
WO2025076169A1 true WO2025076169A1 (fr) 2025-04-10

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/049718 Pending WO2025076169A1 (fr) 2023-10-04 2024-10-03 Fabrication rouleau à rouleau de film nanostructuré

Country Status (2)

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TW (1) TW202532703A (fr)
WO (1) WO2025076169A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090176159A1 (en) * 2008-01-09 2009-07-09 Aruna Zhamu Mixed nano-filament electrode materials for lithium ion batteries
US20090266418A1 (en) * 2008-02-18 2009-10-29 Board Of Regents, The University Of Texas System Photovoltaic devices based on nanostructured polymer films molded from porous template
US20180183052A1 (en) * 2016-12-27 2018-06-28 Nanotek Instruments, Inc. Process for Flexible and Shape-Conformal Cable-Shape Alkali Metal-Sulfur Batteries
US20200052318A1 (en) * 2018-08-10 2020-02-13 Ess Tech, Inc. Methods and system for manufacturing a redfox flow battery system by roll-to-roll processing
US20200243834A1 (en) * 2018-11-13 2020-07-30 Alliance For Sustainable Energy, Llc Solid-state energy storage devices and methods of making the same
US20230006185A1 (en) * 2021-07-02 2023-01-05 Sion Power Corporation Systems and methods for roll to roll deposition of electrochemical cell components and other articles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090176159A1 (en) * 2008-01-09 2009-07-09 Aruna Zhamu Mixed nano-filament electrode materials for lithium ion batteries
US20090266418A1 (en) * 2008-02-18 2009-10-29 Board Of Regents, The University Of Texas System Photovoltaic devices based on nanostructured polymer films molded from porous template
US20180183052A1 (en) * 2016-12-27 2018-06-28 Nanotek Instruments, Inc. Process for Flexible and Shape-Conformal Cable-Shape Alkali Metal-Sulfur Batteries
US20200052318A1 (en) * 2018-08-10 2020-02-13 Ess Tech, Inc. Methods and system for manufacturing a redfox flow battery system by roll-to-roll processing
US20200243834A1 (en) * 2018-11-13 2020-07-30 Alliance For Sustainable Energy, Llc Solid-state energy storage devices and methods of making the same
US20230006185A1 (en) * 2021-07-02 2023-01-05 Sion Power Corporation Systems and methods for roll to roll deposition of electrochemical cell components and other articles

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TW202532703A (zh) 2025-08-16

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