WO2024041825A1 - Procédé de dépôt compact de lithium sur un substrat électroconducteur - Google Patents

Procédé de dépôt compact de lithium sur un substrat électroconducteur Download PDF

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Publication number
WO2024041825A1
WO2024041825A1 PCT/EP2023/070430 EP2023070430W WO2024041825A1 WO 2024041825 A1 WO2024041825 A1 WO 2024041825A1 EP 2023070430 W EP2023070430 W EP 2023070430W WO 2024041825 A1 WO2024041825 A1 WO 2024041825A1
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Prior art keywords
lithium
substrate
process according
ammonia
metallic
Prior art date
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PCT/EP2023/070430
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English (en)
Inventor
Ulrich Wietelmann
Dirk Dawidowski
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Albemale Gerrmany 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.)
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Application filed by Albemale Gerrmany Gmbh filed Critical Albemale Gerrmany Gmbh
Publication of WO2024041825A1 publication Critical patent/WO2024041825A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
    • 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 invention relates to processes for the production of a lithiophilic intermediate layer on an electrically conductive substrate and for the subsequent deposition of compact lithium on such an intermediate layer.
  • the invention further relates to the correspondingly manufactured substrates coated with the lithiophilic intermediate layer and the compact lithium.
  • the currently commercially available lithium batteries function according to the intercalation principle.
  • a graphitic material with a maximum capacity of 372 mAh/g (corresponding to the formula LiC 6 ) is used as the anode.
  • Higher capacities and thus energy densities can be achieved by partial or complete replacement of graphite by alloy active materials (for example silicon or tin ("alloy anode materials") or by complete replacement of graphitic materials by metallic lithium .
  • GB 642 034 A describes an electrochemical manufacturing process of alkali and alkaline earth metals.
  • lithium salts are electrolyzed in liquid ammonia, among other things, and liquid or paste-like lithium/ammonia adducts are obtained.
  • lithium metal can be obtained from this by evaporating the ammonia at low temperatures. The metal is obtained in the form of a sponge-like mass (p. 7, lines 35- 47) .
  • WO 2021/245196 A1 describes processes for the production of lithium metal and lithium alloy shaped bodies from ammoniacal lithium metal solutions.
  • the present invention aims to provide a scalable process for producing a thin, uniform and compact lithium coating on substrates with good electronic conductivity, such as metal or carbon-based films, which can also be carried out at mild temperatures. Further, such a substrate shall be provided, which is equipped with a thin, uniform and compact lithium coating .
  • the lithiophilic interlayer consists of a 1 - 5000 nm, preferably 5 - 1000 nm thick coating of the metal- or carbon- based substrates/foils with at least one metallic or metalloid element capable of forming alloys with lithium.
  • This element is selected from the group Zn, Al, B, Cd, Au, Ag, Si, Pb, Sn, Ge, Ga, In, Mg, Cr, V, Mo, W, Zr, Mn.
  • Preferred elements are Zn, Al, B, Cd, Au, Ag, Si, Pb, Sn, Ga, In and Mg.
  • the elements Zn, Al, Au, Si, Sn, Ga and are particularly preferred. These elements are present either in pure form or as a mixture of at least two of the elements mentioned.
  • the lithiophilic coating is applied to at least one of the substrate/foil sides, preferably on all sides or both sides.
  • the compact lithium-coated conductive substrate according to the invention consists of sheet-like metal or sheet-like carbon-based material having on at least one side of the substrate a 1 to 5000 nm thick lithiophilic intermediate layer containing or consisting of at least one metallic or metalloid element selected from the group consisting of Zn, Al, B, Cd, Au, Ag, Si, Pb, Sn, Ge, Ga, In, Mg, Cr, V, Mo, W, Zr, Mn.
  • the lithiophilic interlayer can be deposited by different processes, the most important ones being the following:
  • the substrate e.g. a foil
  • the electrically conductive substrate is preferably coated beforehand with a thin (1 - 50 nm thick) nickel layer, provided the substrate itself is not made of nickel.
  • the nickel layer serves as a diffusion barrier between the substrate and the gold layer.
  • electrochemical thin-film deposition (“plating”).
  • a solution of the lithium-alloyable element is electrolyzed, with the electrically conductive substrate, usually in foil form, serving as the cathode on which the lithium-alloyable element is deposited.
  • electrolyte residues Prior to the subsequent lithium coating step according to the invention, electrolyte residues must be removed by dripping, washing and, if necessary, drying.
  • substrates with good electronic conductivity flat structures consisting of copper, nickel, iron or films consisting of or containing carbon nanotubes (CNT's) or graphene are preferably used. Such substrates are typically used as current-conducting films in lithium batteries.
  • SEM Scanning Electron Microscopy
  • the measurements were made in accordance with DIN EN ISO 9220 (Metallic coatings - Measurement of coating thickness - Scanning electron microscope method).
  • Very thin coating thicknesses ( ⁇ 100 nm) can also be measured using X- ray methods, especially the X-ray reflectivity technique (XRR). This technique is described by Miho Yasaka, The Rigaku Journal, 26(2), 2010.
  • the substrate/foil coated homogeneously is next contacted with a solution of pure metallic lithium in ammonia, preferably with pure liquid lithium bronze of the composition Li(NH 3 )4 at temperatures in the range of -40 to +40°C, preferably in the range of -10 to +30°C, even more preferably +15 to +30°C, especially preferably at ambient temperatures of +20 to +30°C.
  • the electrically conductive substrate/foil equipped with the lithiophilic intermediate layer is dipped into the liquid lithium/ammonia composition. This can be done, for example, piece by piece with the aid of tweezers or continuously by a roll-to-roll process.
  • the contact times range from 0.1 to 10,000 seconds, preferably 1 to 2,000 seconds.
  • part of the ammonia is evaporated and either an alloy consisting of lithium and the alloy-forming element of the intermediate layer is formed in the contact area with the conductive lithiophilic substrate or/and the metallic lithium is deposited in pure form over the intermediate layer.
  • Lithium alloy layers are often formed with a decreasing concentration of the alloy-forming element towards the outside.
  • Lithium formation and deposition onto the electrically conductive substrates/foils equipped with a lithiophilic interlayer is then completed by quantitative removal of the ammonia.
  • This step is carried out at temperatures between -40°C and +100°C, preferably -10 and +60°C, more preferably +15 to +30°C and particularly preferably at ambient temperatures of +20 to +30°C, preferably under reduced pressure, i.e. in the pressure range of 0.001 to 700 mbar.
  • the ammonia can also be removed by passing an inert gas stream. Since the ammonia concentration is reduced by the stripping gas (the inert gas stream) and the recovery of ammonia is made more difficult, this process is generally less cost-effective than the vacuum process.
  • the elemental lithium metal remains in the form of a thin, homogeneous (cohesive), areal, compact layer on the lithiophilized deposition substrate.
  • the metallic lithium is deposited on the lithiophilic intermediate layer with a layer thickness of 0.01 to 50 ⁇ m, preferably 0.1 to 30 ⁇ m, particularly preferably 0.5 to 25 ⁇ m, as determined by SEM.
  • the compactness of the lithium can be characterized by measuring the specific surface area of the lithium coating, measured by gas adsorption using the BET (Brunauer, Emmett, Teller) method. These measurements were performed with the ASAP 2020 instrument from Micromeritics. Because of the high reactivity of metallic lithium, a noble gas such as argon/liquid argon was used as the determination gas . The measurements were carried out in accordance with ISO 9277 ("Determination of the specific surface area of solids by gas adsorption - BET").
  • the lithium layers produced by the method according to the invention have specific surface areas in the range between 500 and 20,000 cm 2 /g Li, preferably 1,000 to 10,000 cm 2 /g.
  • lithium metal or preferably lithium of purer battery or alloy grade is used as the lithium source.
  • metal grades are available, for example, from Sigma-Aldrich-Fluka (SAF).
  • SAF Sigma-Aldrich-Fluka
  • metal impurities of no more than 15,000 ppm, with sodium taking by far the highest percentage.
  • Transition metals especially Fe, Ag, Cu, Zn
  • the sum of transition metal impurities is mostly in the range of 100 ppm and below.
  • lithium is available from SAF in battery quality, i.e. a Li content (based on metallic trace elements) of 99.9 %.
  • Such particularly pure battery grade contains a maximum of 1500 ppm of foreign metal impurities, with sodium predominating in this case as well.
  • metallic lithium with a summed transition metal impurity content of not more than 200 ppm, particularly preferably not more than 100 ppm and very especially preferably not more than 50 ppm is preferably used.
  • the thermal decomposition or dissociation of the lithium ammonia solutions and compounds used, in particular of the defined lithium bronze, can take place either in the presence of an additional organic solvent (for example a hydrocarbon or ethers or amines) or without such additives.
  • an additional organic solvent for example a hydrocarbon or ethers or amines
  • saturated aliphatic hydrocarbons such as pentanes, hexanes, heptanes, octanes or common, commercially available mixtures of such compounds (technical "petroleum ethers", “white oils”, “benzines" are suitable as organic solvents.
  • Aromatic hydrocarbons can be used to a limited extent. The latter can promote undesirable decomposition with lithium amide formation.
  • etheric compounds such as diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, methyl tetrahydrofuran, tetrahydropyran, glymes and the like is also possible, but less preferred than the use of hydrocarbons .
  • the metallic lithium freshly deposited from lithium-NH 3 compositions is very reactive to air and moisture.
  • passivation of the metal surface i.e. application of a thin protective layer, is a further preferred process step.
  • Such a process step involves contacting with gaseous or liquid substances that form stable polymers and/or salts upon contact with lithium.
  • Such a process step is described, for example, in WO 2011/073324 A1.
  • elements or compounds selected from the group consisting of inorganic compounds consisting of: N 2 , CO 2 , CO, O 2 , N 2 O, NO, NO 2 , HF, F 2 , PF 3 , PF 5 , BF 3 , POF 3 , H 3 PO 4 , or liquid organic compounds/solvents/solutions (coating agents) selected from the groups: carbonic acid esters; lithium chelatoborate solutions as solutions in organic solvents; organosulfur compounds; N-containing organic compounds; organic phosphorus- containing compounds; partially fluorinated hydrocarbons; silicon-containing organic compounds.
  • the organic solvents mentioned are preferably selected from the group consisting of: oxygen-containing heterocycles, carbonic acid esters, nitriles, carboxylic acid esters or ketones; the organosulfur compounds are preferably selected from the group consisting of: sulfites, sulfones, sultones.
  • lithium chelatoborate lithium bis(oxalato)borate (LiBOB) is preferably used.
  • Example 1 Application of an ultrathin gold layer on a copper foil
  • Example 2 Deposition of a lithium metal film on a copper sheet
  • the specific surface area of the lithium layer on the top surface determined by BET was 1,800 cm 2 /g.
  • Example 3 Application of a gold layer using a sputtering process
  • a 20 ⁇ m thick copper sheet with a width of 15 mm was sputtered with gold in a high vacuum sputter coater from Leica (model EM ACE600) .
  • Argon was used as the sputtering gas, and the sputtering time was 15 minutes.
  • Example 4 Deposition of a lithium metal film on an Au- sputtered copper sheet
  • the specific surface area of the lithium layer on the top surface determined by BET was 2,100 cm 2 /g.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electrochemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un substrat conducteur revêtu de lithium compact, le substrat étant constitué de métaux de type feuille ou de matériaux à base de carbone de type feuille. Sur au moins un côté du substrat est présente une couche intermédiaire lithiophile épaisse de 1 à 5 000 nm qui contient ou est constituée d'au moins un élément métallique ou métalloïde choisi dans le groupe Zn, Al, B, Cd, Au, Ag, Si, Pb, Sn, Ge, Ga, In, Mg, Cr, V, Mo, W, Zr, Mn. L'invention concerne également des procédés de production d'un tel substrat revêtu de lithium.
PCT/EP2023/070430 2022-08-23 2023-07-24 Procédé de dépôt compact de lithium sur un substrat électroconducteur WO2024041825A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102022121255.6A DE102022121255A1 (de) 2022-08-23 2022-08-23 Verfahren zur Kompaktabscheidung von Lithium auf einem elektrisch leitfähigen Substrat
DE102022121255.6 2022-08-23

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WO2024041825A1 true WO2024041825A1 (fr) 2024-02-29

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB642034A (en) 1946-05-27 1950-08-23 G And W H Corson Inc A process of producing alkali and alkaline earth metals
WO2011073324A1 (fr) 2009-12-18 2011-06-23 Chemetall Gmbh Lithium métal passivé en surface, et procédé pour sa production
US20210257624A1 (en) * 2020-02-18 2021-08-19 Samsung Sdi Co., Ltd. Negative electrode and solid-state secondary battery including the same
WO2021245196A1 (fr) 2020-06-04 2021-12-09 Albemarle Germany Gmbh Procédé pour la préparation de pièces moulées en lithium métal et en alliage de lithium
US20220216482A1 (en) * 2019-04-17 2022-07-07 2555663 Ontario Limited Lithium metal anode assemblies and an apparatus and method of making same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB642034A (en) 1946-05-27 1950-08-23 G And W H Corson Inc A process of producing alkali and alkaline earth metals
WO2011073324A1 (fr) 2009-12-18 2011-06-23 Chemetall Gmbh Lithium métal passivé en surface, et procédé pour sa production
US20220216482A1 (en) * 2019-04-17 2022-07-07 2555663 Ontario Limited Lithium metal anode assemblies and an apparatus and method of making same
US20210257624A1 (en) * 2020-02-18 2021-08-19 Samsung Sdi Co., Ltd. Negative electrode and solid-state secondary battery including the same
WO2021245196A1 (fr) 2020-06-04 2021-12-09 Albemarle Germany Gmbh Procédé pour la préparation de pièces moulées en lithium métal et en alliage de lithium

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
H. JAFFE, Z. PHYS., vol. 93, 1935, pages 741 - 761
J. BRONN: "Liquefied ammonia as a solvent", 31 December 1905, JULIUS SPRINGER, pages: 116 - 117
M. PIS) UR, J. PHYS. CHEM., vol. 37, 1933, pages 93 - 99
MIHO YASAKA, THE RIGAKU JOURNAL, vol. 26, 2010, pages 2
R. HOFFMANN ET AL., ANGEW. CHEM. INT., vol. 48, 2009, pages 8198 - 8232

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TW202409346A (zh) 2024-03-01
DE102022121255A1 (de) 2024-02-29

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