WO2012105901A1 - Batterie au lithium-ion comportant des nanofils - Google Patents

Batterie au lithium-ion comportant des nanofils Download PDF

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Publication number
WO2012105901A1
WO2012105901A1 PCT/SE2012/050099 SE2012050099W WO2012105901A1 WO 2012105901 A1 WO2012105901 A1 WO 2012105901A1 SE 2012050099 W SE2012050099 W SE 2012050099W WO 2012105901 A1 WO2012105901 A1 WO 2012105901A1
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Prior art keywords
nanowires
lithium
ion battery
film
electrolyte
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English (en)
Inventor
Lars Samuelson
Jonas Ohlsson
Martin Magnusson
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QuNano AB
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QuNano AB
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/36—Carbides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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

  • the present invention relates to a lithium-ion battery comprising nanowires.
  • a lithium-ion battery (sometimes Li-ion battery or LIB) is a family of
  • cathode throughout the text to mean the negative pole during recharging, i.e., the electrode where the lithium ions are stored in a charged battery.
  • electrochemical cells use an intercalated lithium compound as the electrode material instead of metallic lithium.
  • Lithium-ion batteries are common in consumer electronics. They are one of the most popular types of rechargeable battery for portable electronics, with one of the best energy densities, no memory effect, and a slow loss of charge when not in use. Beyond consumer electronics, LIBs are also growing in popularity for military, electric vehicle, and aerospace applications. Research is yielding a stream of improvements to traditional LIB technology, focusing on energy density, durability, cost, and intrinsic safety.
  • the liquid organic electrolyte is usually a solution of an ion-forming inorganic lithium compound in a mixture of a high-permittivity solvent (eg. propylene carbonate) and a low- viscosity solvent (eg. dimethoxye thane) .
  • Lithium ion batteries commonly use a carbon cathode (graphite), to collect lithium ions.
  • the theoretical capacity of graphite cathodes is 372 mA ⁇ h / g.
  • the theoretical capacity of silicon is 4212 mA ⁇ h / g.
  • silicon will swell up to 420% from its normal volume at full lithium insertion.
  • the characteristic impedance of silicon nanowires varies widely with the amount of lithium: low impedance for both low and high concentrations of lithium, but high for intermediate concentrations.
  • an objective of the present invention is to improve the performance of lithium batteries comprising silicon-based nanowires.
  • a first aspect of the present invention provides a lithium-ion battery comprising two electrodes (a cathode and an anode) and an electrolyte disposed between said two electrodes, wherein at least one elastic film makes up outermost layer of one of said electrodes such that said film abuts against the electrolyte.
  • Said battery further comprises a plurality of gas-phase synthesized nanowires comprising silicon that are partially immersed in said film and extend from said film into the electrolyte, wherein said plurality of nanowires is elastically deformable at least in the radial direction of the nanowires.
  • a second aspect of the present invention provides a method of manufacturing a lithium-ion battery, said method comprising the steps of providing a first electrode, providing catalytic seed particles suspended in a gas, providing gaseous precursors comprising constituents of nanowires to be formed, forming, in a gas-phase synthesis, the nanowires from the gaseous precursors and catalytic seed particles, while the catalytic seed particles are suspended in the gas, immersing, at or near room temperature, the nanowires into an elastic film that makes up outermost layer of said electrode, providing an electrolyte so positioned that the nanowires extend into said electrolyte, and providing a second electrode.
  • the above arrangement enables the lithium battery to accommodate large strain without deterioration of its performance, i.e. breaking of the nanowires, indirectly caused by their volume change upon insertion and extraction of lithium ions into the nanowire material, is avoided. More specifically, when nanowires, during a charging cycle, swell up, in radial but also longitudinal direction, due to intercalation of lithium ions, the elastic film into which these are immersed and, consequently, are connected with is, thanks to its inherent properties, elastically deformed. Analogously, during a discharge cycle, i.e. when lithium ions leave the nanowires, resulting in their girth and length reduction, the elastic film, once again, undergoes an elastic deformation. This deformation is of substantially equal magnitude as the deformation during the charging cycle. The ability of the elastic film to deform itself elastically as required by the expansion / contraction of the nanowires renders possible effective
  • the elastic properties of the nanowires and the film jointly contribute to greatly reduce material fatigue.
  • the number of cracks in the nanowires and in the film is
  • the manufacturing method of the nanowires i.e. gas phase synthesis
  • the battery itself may be assembled at or near room temperature.
  • This offers significant advantages when it comes to choice of material for the film.
  • a chosen material is elastic, a plethora of different materials may be used.
  • the gas phase synthesis also renders possible continuous production of nanowires, preferably in a roll-to-roll process. Consequently, mass production of the components of a lithium ion battery is hereby greatly facilitated.
  • Fig. 1 schematically illustrates a battery electrode incorporating the nanowire structure according to the invention
  • Fig. 2 schematically illustrates a lithium ion battery according to the invention.
  • Fig. 3 shows an embodiment wherein the nanowires are partly embedded in the elastic film;
  • Fig. 4 shows nanowires having dendrites.
  • a battery electrode 102 according to the invention is schematically illustrated.
  • Said electrode 102 is a part of a "double-layer structure" 101 also comprising protruding nanowires 103.
  • the electrode comprises a film (not shown in Fig. 1) on which nanowires have been deposited.
  • the electrode may further comprise a suitable substrate (not shown in Fig. 1). In such a case, said substrate is positioned on the face of the film facing away from the nanowires.
  • the nanowires of the present invention are synthesized in gas-phase by means of a process denominated aerotaxy. Said process is disclosed in applicant's published International patent application PCT/SE201 1/ 050599, incorporated herein in its entirety by reference.
  • the method comprises following basic steps (the materials mentioned by way of example in the description below are the more commonly used ones, but should not be regarded as an exhaustive list):
  • An aerosol of nanoparticles is produced, consisting of gold particles in the size range from 5 to 500 nm in diameter (typically 80 nm) , suspended in a nitrogen carrier gas at a pressure in the range from 10 mbar to 10 bar (typically 1 bar)
  • the aerosol is mixed with precursor molecules, typically SiH4, at a partial pressure sufficient to grow the desired amount of silicon nanowire material
  • the aerosol is led through a reaction furnace in a continuous flow, where the precursor molecules crack on the catalytic Au particles, growing into nanowires
  • the resulting Au / Si nanowire aerosol is collected by any of the following means:
  • a flat filter substrate e.g. , a track-etched membrane Collection in a filter for subsequent transfer to a liquid (colloidal) solution
  • any other known method for extracting particles from a gas stream We here distinguish between two main cases, namely where the nano wires are deposited on the elastic film directly from the gas phase, and where the wires come from a liquid (offline, using liquid batches of nanowire colloids).
  • the wires When depositing directly from the gas phase, either by means of electric fields or onto filter material, the wires may be co-deposited with polymers using chemical vapor deposition (CVD) type transport (or simply cold wall condensation) .
  • CVD chemical vapor deposition
  • electric field alignment may be combined with a filter type deposition.
  • the filter e.g. a nucleopore, needs to be flat on the scale of the nanowires.
  • the layer closest to the film may be made with a dense conducting polymer, ensuring good electrical contact.
  • a dense conducting polymer On this layer, in a second phase of deposition, another layer is deposited.
  • a layer of nanowires, , dense enough to form an electrically interconnected network is deposited.
  • the (co)deposited polymer is frequently a porous polymer matrix, allowing an electrolyte to flow/ diffuse into the pores.
  • a solid electrolyte may be co-evaporated in the second phase of the deposition.
  • the second layer may be omitted.
  • An electric field may be employed to align the nanowires more or less vertically, which increases the packing density of wires.
  • the resulting structure is then a porous network of interconnected nanowires, where lowermost non-immersed portion of the nanowire is firmly embedded in a conducting polymer, and the thereto adjacent part of the nanowire is held in place by a material allowing transport of (lithium) ions such as a porous polymer matrix.
  • the composite material achieved in this way is elastic, which is beneficial both for the nanowire expansion as they absorb lithium ions, and for producing a battery in a volume-efficient manner.
  • electric field alignment will yield vertical wires also in the liquid case, and filter-based deposition is well known.
  • CVD or cold-wall methods will not work in a liquid.
  • the wires may be deposited and/ or aligned in a continuous process, such as the above-mentioned roll-to- roll process.
  • the deposition and/ or alignment can be assisted by an electric field applied over the electrode and further by charging the wires, and optionally also the film and the substrate, if present.
  • nanowires can be deposited in predetermined positions on the film.
  • the present invention provides a continuous, high through-put, process for manufacturing aligned wires, optionally with "real-time" feed-back control to obtain high quality wires.
  • wires produced by this method can be utilised to realise wire based semiconductor devices such as solar cells, field effect transistors, light emitting diodes, thermoelectric elements, etc which in many cases outperform
  • the nanowires are aligned on the film onto which they are deposited.
  • a method for aligning nanowires is disclosed in applicant's published International Patent Application PCT/SE2010/051461 , the content of which is incorporated herein in its entirety by reference.
  • Such alignment is achieved in general by a method of aligning nanowires on a film during manufacture of a nanowire structure, comprising the steps of: providing a population of nanowires, and applying an electric field (E) over the population of nanowires (1), whereby an electric dipole in the nanowires makes them align along the electric field (E) .
  • E electric field
  • the positively charged end of each wire is forced in the direction of the electric field (E).
  • the electrical field induces an electrical dipole in the nanowires by separation of positive and negative charge carriers towards opposite ends of the nanowires, which contributes to the electrical dipole moment being formed along the nanowires.
  • the immersed nanowires are randomly distributed and randomly oriented. Consequently, the catalytic particles associated with said nanowires (a catalytic particle is positioned at one end of each nanowire) are also substantially randomly distributed.
  • a randomly oriented plurality of wires exhibits, if the density is sufficient, a very high degree of interconnectivity whereas perfectly vertically oriented nanowires may exhibit a lower degree of electrical interconnectivity, since perfect alignment requires all wires to touch the conducting part of the electrode.
  • a certain degree of orientation may exhibit acceptable interconnectivity, while providing a lower electrical resistance due to a more direct path from top to bottom.
  • the nanowires are preferably made of silicon or silicon carbide, or silicon nanowires are combined with combination with carbon nanotubes, i.e. the carbon nanotubes are provided as a conductive core with a layer of silicon nanowires for the lithium absorption.
  • Other semiconductor materials such as GaAs can also be used.
  • the nanowires are typically doped.
  • B or P p-type or n-type are used as dopants, i.e. they are incorporated into the bulk in order to increase conductivity.
  • the conductivity of the wires should be such that the electric resistance of the cathode as a whole meets the requirements of a functional battery structure.
  • Fig. 1 an electrode 102 is shown, wherein the nanowires 103 are indicated as being single straight structures, but it is also possible to generate dendrite structures, i.e. structures having a branched character.
  • dendrite structures i.e. structures having a branched character.
  • An example of such branched structures is shown in Fig. 4, taken from applicant's own WO
  • the elastic film is made of polymer material.
  • the polymer is sticky such that the nanowires when deposited become "immersed" into the polymer surface.
  • said polymer material must be stable in the electrochemical environment inside a battery structure.
  • the polymer is elastic in order to accommodate the swelling that may occur during the intercalation process where lithium is intercalated into the nanowire material.
  • the elastic film is made of metal having sufficient elasticity to withstand a permanent deformation.
  • a metal exhibiting this property is gold.
  • the nanowires 103 and the electrode 102 with the elastic film (not shown in Fig. 1) form a composite structure 101 , which for structural stiffness may need a backing (not shown in Fig. 1) that also serves for current collection.
  • this nanowire structure is usable as a cathode in a lithium ion battery, replacing the standard manganese dioxide or carbon cathode (graphite) cathode.
  • Fig. 2 schematically illustrates a battery 200 comprising a nanowire structure 203 according to the invention.
  • This battery comprises an anode 202, typically made of lithium or a lithium containing compound or alloy.
  • anode 202 typically made of lithium or a lithium containing compound or alloy.
  • Several possible compositions are known in the art such as lithium cobalt oxide, polyanions, such as lithium iron phosphate, spinel, such as lithium manganese oxide, LiCo02, LiMn204 , LiNi02, LiFeP04, Li2FeP04F, LiCo l/3Nil /3Mnl/302, Li(LiaNixMnyCoz)02.
  • the invention is not particularly restricted to the choice of anode material as long as it is a functioning lithium containing anode.
  • the electrode structure shown in Fig. 1 can be used, suitably having some backing 206 for structural stiffness.
  • said backing 206 is a layer made of metal such as copper, aluminium or steel, or a solid, conductive substrate and is, in a non-limiting embodiment, positioned on the face of the elastic film facing away from the electrolyte.
  • the electrolyte 204 suitably comprises a lithium salt in an organic solvent.
  • the electrolyte 204 may furthermore be dissolved in a matrix material (not shown in Fig. 2), such as porous plastic or cellulose.
  • a matrix material such as porous plastic or cellulose.
  • electrolytes are possible as long as they contain lithium ions and meet the requirements imposed by the material choices for the other components.
  • the invention is not particularly restricted as regards electrolyte material and/ or state.
  • An elastic film 205 that makes up outermost layer of said electrode is arranged such that it abuts against the electrolyte.
  • said elastic film 205 is conductive.
  • said elastic film 205 is non- conductive and is therefore complemented by a further, thereto adjacent conductive film (not shown in Fig. 2).
  • a plurality of gas-phase synthesized nano wires comprising silicon is partially immersed in said film 205 and extends from said film into the electrolyte 204.
  • the nanowires comprise silicon for its excellent ability to absorb lithium ions.
  • nanowires are made of pure silicon, whereas, in an alternative embodiment, they are made in silicon carbide. In this context, other material compositions and shapes are also possible. It is equally conceivable that nanowires with different structural properties are immersed in the same elastic film. These nanowires are, thanks to their intrinsic properties, elastically deformable in their radial as well as longitudinal direction.
  • the process for making the nanowires i.e. the fact that they are separately made and deposited allows to position wires on thin films with small heat budget, e.g. on a thin polymer film that optionally is conductive. There is no intrinsic limit to film thickness. If substrate is part of the electrode, the film should ideally be thicker than the substrate.
  • a film with nanowires deposited on / into the film has better elastic resistance than if nanowires are grown, epitaxially or in any other way, on or to a film. Moreover, grown nanowires frequently break after only a few charge / discharge cycles. This stands in sharp contrast with the durability of gas-phase
  • synthesized nanowires of the present invention are synthesized nanowires of the present invention. Furthermore, in order to achieve large contact area it is possible to fabricate dendrite nanostructures. This improves fast charging/ discharging of the battery due to large interface area between the electrode and the electrolyte. For high capacity, large
  • the central core may be of other material than the protruding nanowires, which reduces potential impedance problems with longer nanowires (example multi walled carbon nanotubes (MWCNT) based core and silicon nanowires).
  • MWCNT multi walled carbon nanotubes
  • a porous electrolyte-confining matrix material (e.g. paper) where one side is saturated with nanowires gives a high lithium ion absorption volume.
  • the nanowires may be applied in the form of a colloidal suspension, as a gel or powder, or be deposited directly from the gas phase.
  • use of aerotaxy nanowires allows deposition of large amounts of wires, including the possibility to mix different kinds of wires to optimize both conductivity and ion capacity.
  • the wires 103 are first deposited on and immersed in the elastic film 205, whereupon the wires may be embedded into a conducting polymer (not shown in Fig. 3) in order to achieve good electrical contact. Subsequent nanowire deposition will then be tailored to maximize ion absorption.
  • the electrode structure according to the invention i.e. silicon-based nanowires immersed in and protruding from the elastic film, can also be used in fuel cells, which is also an aspect of the invention and is encompassed in the inventive scope.

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Abstract

L'invention concerne une batterie au lithium-ion qui comporte deux électrodes et un électrolyte disposé entre lesdites deux électrodes, l'une desdites électrodes comportant au moins un film élastique qui constitue une couche située le plus à l'extérieur de ladite électrode, de sorte que ledit film bute contre l'électrolyte. Une pluralité de nanofils synthétisés en phase gazeuse comportant du silicium sont partiellement immergés dans ledit film et s'étendent à partir dudit film dans l'électrolyte. Ladite pluralité de nanofils sont élastiquement déformables au moins dans la direction radiale des nanofils. L'invention concerne également un procédé de fabrication d'une batterie au lithium-ion.
PCT/SE2012/050099 2011-02-01 2012-02-01 Batterie au lithium-ion comportant des nanofils Ceased WO2012105901A1 (fr)

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SE1150069-1 2011-02-01
SE1150069 2011-02-01

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013201307A1 (de) * 2013-01-28 2014-07-31 Namlab Ggmbh Galvanische Zelle
WO2015038735A1 (fr) * 2013-09-11 2015-03-19 Candace Chan Électrolytes solides à base de nanofils et batteries au lithium-ion comprenant ceux-ci
WO2015119843A1 (fr) * 2014-02-04 2015-08-13 The Regents Of The University Of Michigan Électrodes de batterie au lithium haute performance formées par un processus d'auto-assemblage
US10381651B2 (en) 2014-02-21 2019-08-13 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Device and method of manufacturing high-aspect ratio structures
EP3855530A1 (fr) * 2020-01-24 2021-07-28 Epinovatech AB Batterie à semi-conducteurs
US11469300B2 (en) 2018-04-22 2022-10-11 Epinovatech Ab Reinforced thin-film semiconductor device and methods of making same
US11634824B2 (en) 2021-06-09 2023-04-25 Epinovatech Ab Device for performing electrolysis of water, and a system thereof
US11652454B2 (en) 2020-02-14 2023-05-16 Epinovatech Ab Monolithic microwave integrated circuit front-end module
US11695066B2 (en) 2019-12-11 2023-07-04 Epinovatech Ab Semiconductor layer structure
US11955972B2 (en) 2020-03-13 2024-04-09 Epinovatech Ab Field-programmable gate array device
US12027989B2 (en) 2019-10-25 2024-07-02 Epinovatech Ab AC-DC converter circuit
US12395027B2 (en) 2020-05-07 2025-08-19 Epinovatech Ab Induction machine
US12557325B2 (en) 2020-05-29 2026-02-17 Epinovatech Ab Vertical HEMT and a method to produce a vertical HEMT
US12563670B2 (en) 2021-05-10 2026-02-24 Epinovatech Ab Power converter device and a system comprising the same

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DE102013201307A1 (de) * 2013-01-28 2014-07-31 Namlab Ggmbh Galvanische Zelle
DE102013201307B4 (de) * 2013-01-28 2017-11-02 Namlab Ggmbh Galvanische Zelle
WO2015038735A1 (fr) * 2013-09-11 2015-03-19 Candace Chan Électrolytes solides à base de nanofils et batteries au lithium-ion comprenant ceux-ci
US9853324B2 (en) 2013-09-11 2017-12-26 Arizona Board Of Regents On Behalf Of Arizona State University Nanowire-based solid electrolytes and lithium-ion batteries including the same
WO2015119843A1 (fr) * 2014-02-04 2015-08-13 The Regents Of The University Of Michigan Électrodes de batterie au lithium haute performance formées par un processus d'auto-assemblage
US9882198B2 (en) 2014-02-04 2018-01-30 The Regents Of The University Of Michigan High performance lithium battery electrodes by self-assembly processing
US10381651B2 (en) 2014-02-21 2019-08-13 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Device and method of manufacturing high-aspect ratio structures
US12382656B2 (en) 2018-04-22 2025-08-05 Epinovatech Ab Reinforced thin-film device
US11469300B2 (en) 2018-04-22 2022-10-11 Epinovatech Ab Reinforced thin-film semiconductor device and methods of making same
US12009431B2 (en) 2018-04-22 2024-06-11 Epinovatech Ab Reinforced thin-film device
US12027989B2 (en) 2019-10-25 2024-07-02 Epinovatech Ab AC-DC converter circuit
US11695066B2 (en) 2019-12-11 2023-07-04 Epinovatech Ab Semiconductor layer structure
US12148821B2 (en) 2019-12-11 2024-11-19 Epinovatech Ab Semiconductor layer structure
EP3855530A1 (fr) * 2020-01-24 2021-07-28 Epinovatech AB Batterie à semi-conducteurs
CN115066763B (zh) * 2020-01-24 2025-01-21 艾普诺瓦泰克公司 固态电池层结构及其生产方法
US12456734B2 (en) 2020-01-24 2025-10-28 Epinovatech Ab Solid-state battery layer structure and method for producing the same
WO2021148587A1 (fr) * 2020-01-24 2021-07-29 Epinovatech Ab Structure de couche de batterie à semi-conducteur et son procédé de production
CN115066763A (zh) * 2020-01-24 2022-09-16 艾普诺瓦泰克公司 固态电池层结构及其生产方法
EP4521491A3 (fr) * 2020-01-24 2025-03-26 Epinovatech AB Structure de couche de batterie à semi-conducteurs et son procédé de production
US11316165B2 (en) 2020-01-24 2022-04-26 Epinovatech Ab Solid-state battery layer structure and method for producing the same
US11652454B2 (en) 2020-02-14 2023-05-16 Epinovatech Ab Monolithic microwave integrated circuit front-end module
US12068726B2 (en) 2020-02-14 2024-08-20 Epinovatech Ab Monolithic microwave integrated circuit front-end module
US12355442B2 (en) 2020-03-13 2025-07-08 Epinovatech Ab Field-programmable gate array device
US11955972B2 (en) 2020-03-13 2024-04-09 Epinovatech Ab Field-programmable gate array device
US12395027B2 (en) 2020-05-07 2025-08-19 Epinovatech Ab Induction machine
US12557325B2 (en) 2020-05-29 2026-02-17 Epinovatech Ab Vertical HEMT and a method to produce a vertical HEMT
US12563670B2 (en) 2021-05-10 2026-02-24 Epinovatech Ab Power converter device and a system comprising the same
US11634824B2 (en) 2021-06-09 2023-04-25 Epinovatech Ab Device for performing electrolysis of water, and a system thereof

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