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WO2025153367A1 - Ensemble électrode pour une cellule de stockage d'énergie - Google Patents

Ensemble électrode pour une cellule de stockage d'énergie

Info

Publication number
WO2025153367A1
WO2025153367A1 PCT/EP2025/050326 EP2025050326W WO2025153367A1 WO 2025153367 A1 WO2025153367 A1 WO 2025153367A1 EP 2025050326 W EP2025050326 W EP 2025050326W WO 2025153367 A1 WO2025153367 A1 WO 2025153367A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
nanostructures
electrode assembly
array
electrode
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/EP2025/050326
Other languages
English (en)
Inventor
Claudia LINTZ
Leon Katzenmeier
Odysseas Paschos
Peter Lamp
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.)
Scires Battery Technologies GmbH
Original Assignee
Scires Battery Technologies GmbH
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 Scires Battery Technologies GmbH filed Critical Scires Battery Technologies GmbH
Publication of WO2025153367A1 publication Critical patent/WO2025153367A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • alkali- metal-ion based batteries in particular lithium-ion batteries, are widely used.
  • the applications for such energy storage cells are for example electrical or electronic devices, such as smartphones, computers and in the field of electromobility, such as electric or hybrid vehicles and in stationary energy storage applications.
  • an electrode assembly is used where alkali-metal-ions can be stored in an active material, such as graphite as an anode, and wherein the stored alkali-metal-ions then can be used for providing an electrical current for an electrical device.
  • Lithium-ion batteries currently comprise a higher energy density compared to other batteries such as sodium- ion batteries, at least at normal operating temperatures.
  • current collector as used herein is to be understood as a component that is made from an electronically conductive material and which is applied to an electrochemically active material in which electrochemical reactions take place at the positive electrode or negative electrode in order to collect electrons from or distribute electrons to the electrochemically active material and thereby provide a low-resistance path for the flow of electric current.
  • electrochemically active material as used herein refers to a liquid or solid material through which ions, in particular sodium-ions, can move, enabling current transport between electrodes of a battery, in particular between a cathode and an anode. In contrast to the electronic conductivity (by electrons) in the electrode materials, the electrolyte must be ionically conductive, i.e.
  • the electrolyte has a high electrical resistance.
  • the electrolyte is preferably chemically stable against decomposition in a wide temperature window and electrochemically stable in the widest possible voltage window. Ideally, it is non-toxic and non-flammable and has at least a high flash point and a low heat of combustion. Liquid systems may be favoured over polymer and solid electrolytes due to their better ion conductivity.
  • separator or “separator layer” as used herein means, in particular, an electronically insulating device which separates and distances an anode from a cathode.
  • a separator layer is applied to an anode layer and/or a cathode layer.
  • the separator layer is formed as an independent body.
  • the separator or the separator layer can also at least partially contain an electrolyte, whereby the electrolyte preferably contains sodium ions.
  • the electrolyte can also be electrochemically effectively connected to neighbouring layers of an electrode stack or electrode coil.
  • a separator is thin-walled, particularly preferably in the form of a microporous film.
  • the separator layer or the separator extends at least partially over a boundary edge of at least one electrode. Particularly preferably, the separator layer or the separator extends beyond all boundary edges of neighbouring electrodes.
  • active material means in particular a material which can be electrochemically active and which is suitable for coating electrodes for battery cells and in which alkali-metal- ions, in particular sodium ions, can be stored.
  • the active material for a cathode can be a Prussian blue analogue, a sodium layered oxide, such as sodium manganese oxide, sodium iron manganese oxide, a polyanionic material, such as sodium vanadium iron phosphate, a combination of the aforementioned materials or another material.
  • alkali-metal as used herein means in particular a plurality of zerovalent atoms of the chemical elements lithium or sodium.
  • alkali-metal-ion means an ion of chemical elements lithium or sodium.
  • substantially equal as used here means in particular that two values, in particular distance values, do not deviate from each other by more than 10%, in particular not more than 5%.
  • the electrode assembly according to the first aspect can enable a higher energy density compared to electrode assemblies which comprise a second electrode, an anode, with a layer having an active material, because according to the current disclosure, the alkali- metal-ions can be stored directly in the cavities of the nanostructures as alkali-metal and not in a chemical bond as in traditional Li-ion or Na-ion electrode assemblies.
  • the lithium-ions can be stored via intercalation in a graphite structure, which means the lithium-ions are then spatially separated due to the structure of the graphite.
  • the alkali- metal-ions when stored in the nanostructures, they are deposited as metal.
  • the stored ion-density per volume can be improved by the electrode assembly according to the first aspect.
  • This can enable an energy storage cell with a higher energy density which comprises such an electrode assembly.
  • the array of nanostructures can act as separator when none of the cavities of the nanostructures is completely filled with metal-alkali. As in this case no additional separator is needed, the electrode assembly is smaller in height compared to an electrode assembly with an additional separator.
  • the metal base layer can enable an easy and efficient connection to the array of nanostructures. Thereby the metal base layer can act as a current collector.
  • the second metal is the same as the third metal and the nanostructures of the array of nanostructures comprise an oxidized metal of the third metal, in particular aluminium-oxide (AI 2 O 3 ).
  • This array of nanostructures of an oxidized metal of the metal base layer enables an efficient manufacturing process because it is based on the same metal as the metal base layer and can be achieved by an anodization process of the metal base layer. This also enables that the metal base layer and the array of nanostructures are directly mechanically connected.
  • the metal oxide of the second metal is electronically insulating.
  • the second metal is aluminium, the oxide AI 2 O 3 of which is by its nature electronically insulating.
  • the third metal is aluminium or copper, because it is cheap and corrosion resistant inside a battery.
  • the electrode assembly comprises an interface between the metal base layer and the array of nanostructures, wherein the metal base layer and the array of nanostructures are directly, meaning without intermediate layer, mechanically connected.
  • the electrode assembly comprises an interface between the metal base layer and the array of nanostructures, wherein the metal base layer and the array of nanostructures are electrically connected over at least 90%, preferably at least 95% and more preferably at least 98% of the area of the interface.
  • the electrode assembly comprises a separation layer which is arranged between the layer having an active material and the array of nanostructures, and which electronically isolates the first electrode from the second electrode.
  • This separation layer can avoid a short cut by avoiding an electrical connection between the first electrode and the second electrode.
  • the nanostructures are arranged in a hexagonal closest packing. This enables a high ratio of nanostructures per area, which enables a high number of alkali-metal-ions which can be stored in the array of nanostructures. In this way the energy density which can be provided by the electrode assembly can be increased.
  • the cavities are at least partially filled with alkali-metal, in particular before assembling an energy storage cell including the electrode assembly. This ensures a sufficient number of alkali-metal-ions at the electrode assembly when operated at the energy storage cell.
  • the nanostructures of the array of nanostructures comprise nanotubes, which are aligned to each other.
  • Such nanotubes can be grown by anodizing of a metal sheet, such as the metal foil. During such an anodization process a voltage can be applied and causing side walls of neighbouring nanotubes to repel each other, and nanotubes with aligned walls can grow.
  • the alignment of the tube shapes enables that the alkali-metal can be stored in the nanostructures and exit the nanostructures as alkali-metal-ions efficiently.
  • materials with which alkali-metal ions can chemically react at STP or in which alkali-metal ions can intercalate at STP are absent from the array of nanostructures and from the metal base layer and from any space, if present, between the metal base layer the array of nanostructures.
  • STP means standard temperature and pressure, as defined by IIIPAC.
  • each of the nanotubes of the array of nanotubes has a diameter regarding its cross-section which is between 10 and 500 nm, in particular 10 nm to 100 nm, in particular 400 nm to 500 nm.
  • a diameter regarding its cross-section which is between 10 and 500 nm, in particular 10 nm to 100 nm, in particular 400 nm to 500 nm.
  • a diameter range between 10 nm and 100nm is therefore advantageous for guiding the deposition of the alkali-metal-ions into the cavities.
  • a diameter range between 400 nm to 500 nm is advantageous as it enables a higher available energy density by the array of nanostructures.
  • a second aspect of the solution is directed to an energy storage cell comprising a housing, an electrode assembly of any of the preceding claims which is arranged in the housing and wherein the housing is at least partially filled with an electrolyte with alkali- metal-ions wherein the electrolyte at least partially encloses the electrode assembly.
  • the energy storage cell is an energy storage cell having an alkali- metal anode, in other words an energy storage cell having a metallic anode, in yet other words an energy storage cell of the type known in the technical field as lithium metal energy storage cell or sodium metal energy storage cell.
  • a third aspect of the present solution is directed to a device comprising an energy storage cell of the second aspect.
  • a fourth aspect of the solution is directed to a method for manufacturing an electrode assembly.
  • the method comprises: (i) Providing a first electrode, which comprises a current collector, in particular a metal foil, of a first metal and a layer having an active material in which alkali-metal-ions can be stored, and which is arranged at the current collector; (ii) Providing a second electrode, which comprises an array of nanostructures, in particular nanotubes, of a second metal, in particular a metal oxide, wherein the nanostructures of the array of nanostructures comprises cavities which are configured to store alkali-metal; (iii) Providing a metal base layer of a third metal which is mechanically connected to the array of nanostructures; (iv) Arranging the layer having an active material of the first electrode between the current collector and the array of nanostructures.
  • the array of nanostructures is manufactured, in particular before manufacturing the electrode assembly, comprising the steps: (i) Providing a sheet of a the second metal (ii) Anodizing the surface of the sheet to obtain a patterned metal sheet with an anodized structure of the second metal which is grown on the seeds; (iii) Removing the anodized structure for obtaining a regular pattern at the surface of the sheet; (iv) Anodizing the patterned metal sheet for growing aligned nanostructures of an anodized metal.
  • a process for removing the patterned metal sheet is applied. This enables to separate the patterned metal sheet from the nanostructures to obtain the nanostructures as a separate structure.
  • Fig. 1 schematically illustrates a cross-sectional view of an electrode assembly according to an embodiment
  • Fig. 2 schematically illustrates a cross-sectional view of an electrode assembly according to a further embodiment
  • Fig. 3 schematically illustrates a cross-sectional view of a battery cell according to an embodiment
  • Fig. 1 schematically illustrates a cross-sectional view of an electrode assembly 100 according to an embodiment of the invention.
  • the electrode assembly 100 comprises a metal foil 110, which can comprise or consist of for example aluminium or copper.
  • a layer 120 having an active material is arranged which is configured to store alkali-metal-ions such as sodium-ions, lithium-ions or potassium ions, for example, in case of lithium, lithium nickel manganese cobalt oxide or lithium iron phosphate, or, in the case of sodium, Prussian blue analogs such as Na 2 Fe[Fe(CN) 6 , sodium nickel manganese cobalt oxide, sodium vanadium phosphate or sodium iron phosphate.
  • the electrode assembly 100 further comprises nanostructures 140, in particular nanotubes, and a metal base layer 150.
  • the nanostructures 140 are, in this example but not necessarily, based on the same metal as the metal base layer 150 and can be obtained by anodizing the metal base layer 150.
  • the nanostructures 140 comprise, or are of formed from, an oxidized metal of the metal base layer 150.
  • the metal base layer can be made of aluminium or an aluminium alloy, whereas the nanostructures then have aluminium-oxide, AI 2 O 3 .
  • the nanostructures 140 can be obtained by a process as described in Fig. 4.
  • the electrode assembly 100 comprises a separation layer 130 which is electrically isolating with respect to electrons, but which can be permeated by ions, in particular by alkali-metal-ions.
  • the nanostructures can be arranged as an array of nanostructures 140 wherein each of the nanostructures comprise a cavity which is closed on one side and has an opening on an opposite side to the closed side, whereas the openings are facing the separation layer 130.
  • the nanostructures 140 are arranged in a hexagonal closest packing which can result in a packing efficiency of about 90%.
  • the density of the aluminium-oxide can be up to 4g/cm 3 .
  • the nanostructures 140, in particular nanotubes can comprise a diameter in their cross-section between 20 nm and 500 nm. With increasing diameter, the available energy density by the array of nanostructures 140 can be increased. With decreasing diameter, a guidance of the deposition of the alkali-metal-ions into the cavities of the nanostructures 140 as alkali-metal can be improved.
  • the nanostructures are straight and extend parallel to each other in a first direction, which is, in figs. 1-3 the vertical direction.
  • the array of nanostructures 140 preferably has a thickness, meaning a dimension in the direction from the metal foil 110 to the metal base layer, in other words a dimension in the first direction, of between 1 and 100 pm, and in this example circa 50 pm.
  • the cavities in the array of nanostructures 140 are, in this example, closed at their lower end.
  • the thickness of the oxide material forming the closure of the cavities is preferably between 10 and 100nm, and in this example circa 20nm.
  • the metal foil 110 and the layer 120 together form a first, positive, electrode of the electrode assembly 100, and the array of nanostructures 140 together form a second, negative electrode of the electrode assembly 100.
  • the metal foil 110 respectively the metal base layer 150, act as current collectors in the electrode assembly 100.
  • Fig. 2 schematically illustrates a cross-sectional view of an electrode assembly 200 according to a further embodiment.
  • the electrode assembly 200 according to Fig. 2 does not comprise a separation layer 130.
  • the electrode assemblies of Figs. 1 and 2 are identical.
  • Such an electrode assembly 200 without a separation layer 130 requires less space and the overall energy density of a battery cell 300 comprising an electrode assembly 200 can be improved.
  • a metal base layer 150 made of copper, with an array of nanostructures 140 made of aluminium oxide, can be used.
  • the interface between the metal base layer 150 and the array of nanostructures 140 should preferably be such that areas without electrical contact are minimised. Therefore it is preferential that the metal base layer 150 and the array of nanostructures 140 should be both mechanically and electrically connected over a large proportion of the area of their interface.
  • the array of nanostructures 140 is manufactured according to steps (a)-(d) of the method described below, as a consequence of the manufacturing method 100% of interface of the the metal base layer 150 and the array of nanostructures 140 is electrically and mechanically connected.
  • the array of nanostructures 140 is manufactured by including step (e) of the method described below, pressure needs to be applied to the metal base layer 150 and the array of nanostructures 140 to ensure good contact.
  • Fig. 3 schematically illustrates a cross-sectional view of a battery cell 300 according to an embodiment in a charged state.
  • the battery cell 300 comprises a housing 310 in which an electrode assembly 100 according to Fig. 1 is arranged. It is also possible that instead of the electrode assembly 100 an electrode assembly 200 according to Fig. 2 or another electrode assembly which relates to the current disclosure is arranged in the housing 310.
  • the battery cell 300 comprises electrical connections for receiving a voltage by an electrical device between the metal foil 110 and the metal base layer 150 of the nanostructures 140.
  • the housing is filled with an electrolyte, which is conductive to alkali-metal-ions, for example sodium-ions.
  • an electrolyte which is conductive to alkali-metal-ions, for example sodium-ions.
  • the alkali-metal is removed as alkali-metal-ions from the nanostructures 140 and an electrical current can flow between the metal base layer 150 and the metal foil 110 via the electrical connection 330 and the electrical device 320.
  • the alkali-metal- ions are then stored in the layer 120 having an active material.
  • Step (a) comprises providing a metal sheet 410, for example of aluminium.
  • the patterned metal sheet 160 relate to the metal base layer 150 according to Figs. 1 to 3.
  • Step (d) comprises anodizing the surface of the patterned metal sheet 160 for growing aligned nanostructures 140, in particular nanotubes, of an oxidized metal on the patterned metal sheet 160;
  • the patterned metal sheet 160 in combination with the aligned nanostructures relate to the metal base layer 150 and the nanostructures 140 according to Figs. 1 to 3.
  • Step (e) comprises applying a process for removing the patterned metal sheet 160 to obtain the aligned nanostructures 140 of the oxidized metal. This can be achieved by briefly applying a very high voltage. It is also possible to carry out the method without step (e). Therefore, step (e) is optional.
  • the product obtained after step (d) or step (e) is also known as anodic aluminium oxide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

L'invention concerne un ensemble électrode (100, 200) pour une cellule de stockage d'énergie (300), comprenant : une première électrode, qui comprend un collecteur de courant (110) d'un premier métal et une couche (120) ayant un matériau actif dans lequel des ions de métal alcalin peuvent être stockés, et qui est disposée au niveau du collecteur de courant (110) ; une seconde électrode, qui comprend un réseau de nanostructures (140) d'un oxyde métallique d'un deuxième métal, les nanostructures (140) du réseau de nanostructures (140) comprenant des cavités qui sont conçues pour stocker un métal alcalin ; une couche de base métallique (150) d'un troisième métal qui est raccordée mécaniquement au réseau de nanostructures (140) ; la couche (120) comprenant un matériau actif étant agencée entre le collecteur de courant (110) et le réseau de nanostructures (140).
PCT/EP2025/050326 2024-01-16 2025-01-08 Ensemble électrode pour une cellule de stockage d'énergie Pending WO2025153367A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP24152051.9 2024-01-16
EP24152051 2024-01-16

Publications (1)

Publication Number Publication Date
WO2025153367A1 true WO2025153367A1 (fr) 2025-07-24

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2025/050326 Pending WO2025153367A1 (fr) 2024-01-16 2025-01-08 Ensemble électrode pour une cellule de stockage d'énergie

Country Status (1)

Country Link
WO (1) WO2025153367A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090214942A1 (en) * 2008-02-22 2009-08-27 Alliance For Sustainable Energy, Llc. Oriented nanotube electrodes for lithium ion batteries and supercapacitors
KR20100065767A (ko) * 2008-12-08 2010-06-17 광주과학기술원 전도성 선형 구조체를 포함하는 전극 구조체, 그 제조방법 및 리튬이차전지
KR101319461B1 (ko) 2011-08-26 2013-10-29 경상대학교산학협력단 리튬 금속 산화물 나노 구조체가 형성된 전극-집전체 일체형 전극소자 및 이의 제조 방법
US20140212733A1 (en) 2011-09-29 2014-07-31 Uchicago Argonne, Llc High capacity electrode materials for batteries and process for their manufacture
US20200194773A1 (en) 2017-07-18 2020-06-18 Imec Vzw Fabrication of Solid-State Battery Cells and Solid-State Batteries

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090214942A1 (en) * 2008-02-22 2009-08-27 Alliance For Sustainable Energy, Llc. Oriented nanotube electrodes for lithium ion batteries and supercapacitors
KR20100065767A (ko) * 2008-12-08 2010-06-17 광주과학기술원 전도성 선형 구조체를 포함하는 전극 구조체, 그 제조방법 및 리튬이차전지
KR101319461B1 (ko) 2011-08-26 2013-10-29 경상대학교산학협력단 리튬 금속 산화물 나노 구조체가 형성된 전극-집전체 일체형 전극소자 및 이의 제조 방법
US20140212733A1 (en) 2011-09-29 2014-07-31 Uchicago Argonne, Llc High capacity electrode materials for batteries and process for their manufacture
US20200194773A1 (en) 2017-07-18 2020-06-18 Imec Vzw Fabrication of Solid-State Battery Cells and Solid-State Batteries

Non-Patent Citations (1)

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Title
CHEN JINGJUAN ET AL.: "Performance of through-hole anodic aluminum oxide membrane as a separator for lithium-ion battery", JOURNAL OF MEMBRANE SCIENCE, vol. 461, 1 July 2014 (2014-07-01), pages 22 - 27, XP093179533, DOI: 10.1016/j.memsci.2014.03.005

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