EP3692586A1 - Électrode comprenant du lithium élémentaire et son procédé de fabrication - Google Patents

Électrode comprenant du lithium élémentaire et son procédé de fabrication

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Publication number
EP3692586A1
EP3692586A1 EP18780035.4A EP18780035A EP3692586A1 EP 3692586 A1 EP3692586 A1 EP 3692586A1 EP 18780035 A EP18780035 A EP 18780035A EP 3692586 A1 EP3692586 A1 EP 3692586A1
Authority
EP
European Patent Office
Prior art keywords
active material
lithium
electrode
binder
material composition
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.)
Withdrawn
Application number
EP18780035.4A
Other languages
German (de)
English (en)
Inventor
Heiko Graebe
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.)
Robert Bosch GmbH
Original Assignee
Robert Bosch 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 Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of EP3692586A1 publication Critical patent/EP3692586A1/fr
Withdrawn legal-status Critical Current

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative 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

  • Electrode comprising elemental lithium and manufacturing process
  • the invention relates to an electrode for an electrochemical cell, in particular a solid-state cell, which in addition to an active material elemental lithium and was prepared without the addition of solvents.
  • the subject matter is also the manufacturing process and the use of the electrode in a solid state cell.
  • Lithium-ion batteries often use graphite as an anode active material, which is characterized by good Coloumb efficiency and low
  • Charge loss in the first charge cycle is characterized. During operation of such an electrochemical cell is formed on the surface of the
  • SEI solid-electrolyte interphase
  • Impurities such as traces of water
  • by-products e.g., LiOH
  • the invention relates to an electrode for an electrochemical cell, comprising at least one current collector and at least one
  • An active material composition wherein the active material composition comprises at least one active material, elemental lithium and at least one
  • Binder comprises and was prepared without the use of solvents.
  • the current collector consists of an electrically conductive material. Suitable materials from which the current collector may be formed are, for example, aluminum, copper, nickel or even alloys of these metals. Particularly preferred are aluminum and / or copper.
  • the layer thickness of the current collector is not particularly limited and ranges for example from 1 to 500 ⁇ , in particular from 5 to 200 ⁇ . Preferably, the current collector is designed flat.
  • the active material composition comprises at least one active material, elemental lithium and at least one binder and is arranged on at least one surface of the at least one current collector and electrically conductively connected thereto.
  • any active material which is suitable as the active material of an electrode of an electrochemical cell and optionally undergoes an irreversible reaction with the lithium contained in the cell to form a solid electrolyte interphase (SEI) and the lithium may be used as the active material so that
  • SEI solid electrolyte interphase
  • the active material comprises a carbon-based active material.
  • the active material comprises graphite or consists of graphite.
  • Graphite is particularly suitable as an active material for negative electrodes (anodes) of electrochemical cells and is characterized by a good Coloumb efficiency and low charge loss in the first charge cycle. During the first charge cycles, however, irreversible reactions with lithium lead to SEI formation on the surface of the graphite. This is a loss of lithium, which is available for energy storage in the electrochemical cell connected.
  • the graphite is used in the form of particles. These preferably have an average particle size of> 0.1 nm and ⁇ 100 ⁇ m, more preferably in a range of> 1 nm and ⁇ 1 ⁇ m, in particular in a range of> 10 nm and ⁇ 100 nm.
  • the active material composition additionally comprises elemental (metallic) lithium.
  • the lithium may in principle be in any form within the active material composition, e.g. in the form of particles, foils, strips, wires and / or pieces.
  • the lithium is distributed as homogeneously as possible in the active material composition, so that in a particularly preferred embodiment the lithium is in the form of particles in the active material composition.
  • Particles in the sense of this invention are particles of a uniform chemical composition which can be delimited from the environment by a surface and have an average particle diameter of less than 1 mm.
  • the smallest particle in the sense of this definition consists of at least two identical atoms or molecules, eg two lithium atoms.
  • the lithium particles according to the present invention have an average particle diameter of> 0.1 nm to ⁇ 100 ⁇ , more preferably from> 1 nm to ⁇ 1 ⁇ , in particular from> 10 nm to ⁇ 100 nm.
  • Films in the sense of this invention are planar structures of a uniform chemical composition, which is defined by a surface of the
  • Surrounding neighborhood and their greatest extent in two of the three spatial directions at least ten times, preferably at least one hundred times, especially at least one thousand times the extent to the third
  • lithium foils have a thickness (i.e., an extension in the third spatial direction) of> 0.1 nm to ⁇ 100 ⁇ m, more preferably from> 1 nm to ⁇ 1 ⁇ m, in particular from> 10 nm to ⁇ 100 nm.
  • Strips in the sense of this invention are flat structures of a uniform chemical composition which can be obtained by or from the surface of the
  • Surround boundaries and their largest extension in one of the three spatial directions at least ten times, preferably at least one hundred times, especially at least one thousand times the extent to the second
  • Lithium strips have, for example, a thickness (ie an extension in the second spatial direction) of> 0.1 nm to ⁇ 100 ⁇ m, more preferably from> 1 nm to ⁇ 1 ⁇ m, in particular from> 10 nm to ⁇ 100 nm and can be achieved, for example the cutting of films are obtained.
  • wires are three-dimensional structures of a uniform chemical composition that can be delimited from the environment by a surface and whose greatest extent is essentially equal in two of the three spatial directions and whose expansion in the third spatial direction is at least ten times, preferably at least
  • Lithium wires are preferred an extent in two of the three spatial directions of the second spatial direction of> 0.1 nm to ⁇ 1 mm, more preferably of> 1 ⁇ to ⁇ 1 mm,
  • Pieces in the sense of this invention are particles of a uniform chemical composition which can be delimited from the environment by a surface and have an average particle diameter of> 100 ⁇ m.
  • lithium pieces according to the present invention have an average particle diameter of> 0.5 mm to ⁇ 1 cm, more preferably from> 1 mm to ⁇ 10 mm, in particular from> 1 mm to ⁇ 5 mm.
  • the lithium is used in an amount sufficient to compensate for the loss of lithium through the formation of the SEI. This amount depends on the active material and the operating conditions of the
  • the lithium is used in an amount of 0.1 to 5 wt .-%, preferably 0.1 to 1 wt .-%, based on the total weight of the active material of the electrode.
  • the elemental (metallic) lithium preferably has a purity of at least 95%, more preferably at least 98%, and
  • the active material composition comprises at least one
  • the at least one binder comprises at least one polymer selected from polyethylene oxide (PEO), a
  • Polyoxalic acid esters in particular polyethylene oxide (PEO) and / or a copolymer of polyethylene oxide.
  • Polyethylene oxide (also polyethylene glycol) is a polymer which is composed of the repeating unit (-CH 2 -CH 2 -O-) and preferably comprises 10 to 1000, in particular 20 to 500 repeating units per molecule.
  • Copolymers of the polyethylene oxide include, in particular, block copolymers of at least one polyethylene oxide block and at least one block of an ionically or radically polymerizable monomer, in particular styrene or a styrene derivative (eg ⁇ -methylstyrene).
  • a particularly preferred copolymer is a polyethylene oxide / b7 polystyrene block copolymer.
  • Polymalonic acid esters include repeat units of the general formula
  • R 1 , R 2 H or F
  • R 3 organic radical, in particular alkyl radical of the formula - (Chbjm-, where m is an integer from 1 to 10, preferably 2 to 8, and
  • n 2 to 1000, in particular 10 to 500.
  • Polyoxalic acid esters include repeat units of the general formula
  • R 4 organic radical, in particular alkyl radical of the formula - (CH 2) q -, where q is an integer from 1 to 10, preferably 2 to 8; and
  • p 2 to 1000, in particular 10 to 500.
  • the active material composition may also contain conductive additives such as carbon black, carbon nanotubes (CNT) and / or carbon fibers
  • VGCF vapor-grown carbon fibers
  • ionic compounds in particular lithium salts.
  • Suitable lithium salts are in particular those which are also present in
  • Active material composition produced substantially without the use of solvents. That is, no solvents are added during the preparation of the active material composition and the active material composition is substantially free of solvents, i.
  • Solvents in this case are liquid compounds at room temperature which are capable of at least partially dissolving the at least one binder.
  • Active material composition is preferably done with the production method of the invention as more fully explained herein. This allows the substantially solvent-free production of a
  • Active material composition in particular in the form of a freestanding active material composition film, which is subsequently applied to the
  • the invention also relates to the use of an electrode according to the invention in an electrochemical solid-state cell, in particular as a negative electrode in a solid-state electrochemical cell.
  • Electrode furthermore at least one solid electrolyte and at least one positive electrode.
  • the solid electrolyte is characterized in that it comprises or consists of a material which is substantially solid at room temperature and at least at operating temperature has sufficient ionic conductivity to ensure the transport of ions, in particular lithium ions, between the electrodes.
  • the solid electrolyte is not electrically conductive. As a solid electrolyte can in principle all the
  • the solid-state electrochemical cell comprises at least one polymer electrolyte.
  • This preferably comprises at least one polymer and at least one conducting salt.
  • Suitable polymers include polyalkylene oxides such as polyethylene oxide (PEO) and polypropylene oxide (PPO) and copolymers thereof.
  • the polymer comprises a polyethylene oxide (PEO) and / or a copolymer of polyethylene oxide.
  • the polymer of the polymer electrolyte is identical to the at least one binder of the negative electrode of the electrochemical solid-state cell according to the invention.
  • Suitable conductive salts are in particular lithium salts.
  • the conductive salt may for example be selected from the group consisting of lithium perchlorate (L1CIO4),
  • LiPFe Lithium tetrafluoroborate
  • LiPFe lithium hexafluorophosphate
  • Lithium hexafluoroarsenate LiAsFe
  • Litrifluoromethanesulfonate Li1SO3CF3
  • LiN S02CF 3 lithium bis (trifluormethylsulphonyl) imide
  • Lithium bis (pentafluoroethylsulphonyl) imide LiN (SO 2 C 2 F 5 ) 2
  • Lithium bis (oxalato) borate LiBOB, LiB (C2C> 4) 2), lithium difluoro (oxalato) borate (LiBF 2 (C 2 C> 4)), lithium tris (pentafluoroethyl) trifluorophosphate (LiPF 3 (C 2 F 5 ) 3) and combinations thereof.
  • LiBOB LiB (C2C> 4)
  • LiBF 2 (C 2 C> 4) lithium tris (pentafluoroethyl) trifluorophosphate
  • LiPF 3 C 2 F 5
  • Conducting salt a proportion of 1 to 5 wt .-%, in particular 2 to 3 wt .-% of the total weight of the polymer electrolyte.
  • Electrodes are used, which are used as positive electrodes in
  • Electrochemical solid-state cells especially in lithium-containing
  • electrochemical solid-state cells can be used. These usually comprise at least one current collector, as well as at least one
  • the active material composition disposed on and electrically connected to at least one surface of the at least one current collector.
  • the current collector is made of an electrically conductive material and may otherwise be formed like the current collector of the negative electrode according to the invention.
  • the active material composition comprises at least one active material and usually at least one
  • the positive active material usually includes compounds, which are able to reversibly take up and release lithium ions.
  • Typical positive active materials are mixed oxides which comprise lithium and at least one metal selected from the group consisting of nickel, cobalt, manganese (so-called NCM mixed oxides). Examples include: L1C0O2, lithium-nickel-cobalt-aluminum oxides (eg LiNio.eCoo.isAlo.osCh;
  • Tavorite compounds eg LiVP0 4 F
  • Ü2Mn03 Li1.17Nio.17Coo.1Mno.56O2
  • Ü3V2 (P0 4 ) 3 are highlighted as suitable positive active materials.
  • Common positive electrode binders include styrene-butadiene copolymer (SBR), polyvinylidene fluoride (PVDF), polytetrafluoroethene (PTFE),
  • Carboxymethylcellulose CMC
  • PAA polyacrylic acid
  • PVA polyvinyl alcohol
  • EPDM ethylene-propylene-diene terpolymer
  • Active material composition preferably still conductive additives, e.g. Conductive carbon black.
  • the solid-state electrochemical cell may optionally comprise at least one separator which is between the negative and the positive
  • Electrode is arranged.
  • the purpose of the separator is to protect the electrodes from direct contact with each other, thus preventing a short circuit.
  • the separator must ensure the transfer of ions from one electrode to another. It is therefore important that the separator is electrically non-conductive, but has the highest possible ion conductivity, in particular with respect to lithium ions.
  • Suitable materials are in particular polymers, such as polyolefins, polyesters and fluorinated polymers. Particularly preferred polymers are polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polytetrafluoroethene (PTFE) and Polyvinylidene fluoride (PVDF).
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PVDF Polyvinylidene fluoride
  • the solid electrolyte takes over the role of the separator, so that it is not necessary.
  • the invention also provides a process for solvent-free
  • PEO polyethylene oxide
  • steps (i) to (vi) use a solvent.
  • process steps (i), (ii) and (iii) can be carried out separately or simultaneously. Likewise, the process steps (iv) and (v) can be carried out separately or at the same time.
  • the elemental lithium is in a preferred embodiment of the
  • the at least one binder preferably comprises PEO and / or a copolymer of PEO.
  • the at least one binder is preferably used in the form of particles, in particular in the form of particles having an average particle diameter of> 0.1 nm and ⁇ 100 ⁇ , more preferably in a range of> 1 nm and ⁇ 1 ⁇ , in particular in a range of> 10 nm and ⁇ 100 nm.
  • a homogeneous mixture of the at least one active material, the elemental lithium and the at least one binder is prepared. This can be done by any mixing method known to those skilled in the art, provided that this mixing method is suitable for the preparation of homogeneous mixtures of particles of said particle sizes. Suitable mixing devices are: mixer with movable
  • Mixing tools e.g., screw mixers, paddle mixers,
  • Plowshare mixers Plowshare mixers
  • moving vessel mixers e.g., drum mixers, cone mixers
  • pneumatic mixers e.g., fluidized bed mixers
  • process step (v) kinetic and / or thermal energy is introduced into the homogeneous mixture obtained in process step (iv).
  • adhesive bonds are formed between the at least one active material, the elemental (metallic) lithium and the at least one binder.
  • the at least one binder comprises at least one polymer selected from polyethylene oxide (PEO), a copolymer of
  • Polyoxalklareester These polymers are characterized by being at Room temperature are comparatively soft, and have a low glass transition temperature and a low melting temperature. Binders are preferably used which have a glass transition temperature T g of ⁇ 20 ° C, in particular ⁇ 10 ° C and / or a melting temperature T m of ⁇ 150 ° C, in particular ⁇ 100 ° C. Particles of these binders can by the introduction of kinetic and / or thermal energy a
  • this adhesive bond is formed by subjecting the homogeneous mixture at least temporarily, i. for a period of at least 1 minute, preferably at least 5 minutes, to one
  • Temperature is heated, which is greater than or equal to the melting temperature of the at least one binder, while the homogeneous mixture is further, preferably continuously, mixed.
  • a mixing device for this purpose, one of the aforementioned mixing devices can be used.
  • the resulting active material composition is then cooled, preferably without further mixing. After cooling, a shapable, pasty, homogeneous active material composition is obtained.
  • the adhesive bond is formed by a kinetic energy is at least briefly entered into the homogeneous mixture, which allows at least partial plasticization of the binder. This can be done, for example, by accelerating and selectively colliding the particulate constituents of the homogeneous mixture from process step (iv).
  • the process step (v) is carried out in a jet mill or a ball mill. Particularly preferred is the use of a jet mill. This allows a speedy at least partially
  • a homogeneous mixture of active material and elemental lithium is first prepared in step (iv), wherein the elemental lithium is optionally comminuted by appropriate (kinetic) energy input in step (iv) into particles into the mixture if necessary. Only then is the binder added and by further energy input in the form of kinetic and / or thermal energy, the formation of
  • the method steps (iv) and (v) are carried out in the same mixing device, in particular in a jet mill. This allows a reduction in the number of process steps.
  • mixing of the components at low energy input i. be carried out at low power of the jet mill.
  • Jet mill instead, which allows at least a partial plasticization of at least one binder.
  • the at least one active material and the lithium can first be mixed alone in a jet mill and, if necessary, comminuted. Subsequently, the binder is added and the formation of the adhesive bonds takes place.
  • the moldable, pasty, homogeneous active material composition is then in a further process step (vi) to a
  • substrate surface applied.
  • the substrate surface in the sense of this invention, in particular the surface of a tool, the surface of a
  • Support material e.g., a plastic film
  • surface of a plastic film e.g., a plastic film
  • the substrate surface is the surface of a tool, eg, the surface of a treadmill. This is preferably made of plastic.
  • Active material composition can in this case at the end of the
  • Production process can be removed as a free-standing active material composition film. This may then be detached from the substrate surface and applied to a current collector, e.g. at a temperature above the
  • the substrate surface is the surface of a current collector. In this case, no free-standing active material film is produced, but an electrode is obtained.
  • the method steps (v) and (vi) are carried out together in a calender.
  • the homogeneous mixture of active material and elemental lithium prepared in step (iv) is added to the calender, processed by additions of thermal and kinetic energy to a homogeneous, preferably moldable (pasty) mass and applied to a substrate surface. This can be done by a pressing process, a calendering process or a combination thereof. This gives a freestanding active material composition.
  • the active material layer preferably at a temperature above the glass transition temperature T g of the at least one
  • Binder is compacted by a press, a punch or a roller.
  • the densification step may additionally be carried out under the action of heat in order to prevent the binder from adhering to the surface of the substrate
  • Support current collector and cause a permanent consolidation. If the substrate surface is not the current collector, preferably no heat is supplied.
  • Inertgasatmospreheat such as dried argon or nitrogen atmosphere.
  • the invention also provides the use of the method according to the invention for producing an active material composition film for an electrode according to the invention.
  • the electrode according to the invention and the electrochemical solid-state cell according to the invention find advantageous use in an electric vehicle (EV), in a hybrid vehicle (HEV), in a plug-in hybrid vehicle (PHEV), in a tool or in a consumer electronics product. Under tools are in particular home tools and garden tools to understand. Consumer electronics products are in particular mobile phones, tablet PCs or notebooks.
  • the electrode according to the invention makes it possible to introduce additional elemental lithium into an electrochemical cell, which can compensate for the loss of lithium in the electrochemical cell which occurs as a result of the formation of a solid electrolyte interphase.
  • the production process also makes it possible to minimize the occurrence of side reactions of the lithium with the solvent and any impurities contained therein and the associated loss of elemental lithium in the active material composition of the electrode.
  • Figure 1 is a schematic representation of an inventive
  • FIG. 1 the structure of a solid-state electrochemical cell 1 is shown schematically.
  • a negative electrode 21 comprising a current collector 31 and an active material composition 41 is connected to the negative terminal 11 via the current collector 31.
  • a positive electrode 22 which also comprises an active material composition 42 and a current collector 32, via which the positive electrode 22 is connected to the positive terminal 12 for discharge.
  • the negative electrode 21 and the positive electrode 22 are disposed in a cell case 2.
  • the solid electrolyte 15 mechanically separates the negative electrode 21 and the positive electrode 22 from each other and simultaneously makes an ion conductive bond between the negative electrode 21 and the positive electrode 22.
  • the solid electrolyte 15 thus also assumes the role of the separator.
  • the active material composition 41 of the negative electrode 21 includes, for example, graphite as the active material, elemental lithium, and
  • Polyethylene oxide as a binder Preferably, the polyethylene oxide additionally comprises a conductive additive, for example Li (CF 3 ) SO 2 NSO 2 (CF 3 ) (LiTFSI).
  • the current collector 31 is preferably made of a metal, for example of copper.
  • the active material composition 42 of the positive electrode 22 includes, for example, an N-CM mixed oxide as an active material and further at least one binder such as a binder. Carboxymethylcellulose (CMC), as well as a conductive additive, e.g. Conductive carbon black.
  • the current collector 32 is preferably made of a metal, e.g. made of aluminium.
  • a polymer electrolyte for example, a mixture of polyethylene oxide and Li (CF 3 ) SO 2 NSO 2 (CF 3 ) (LiTFSI) is used.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une électrode pour une cellule électrochimique, comprenant au moins un collecteur de courant et au moins une composition de matériau actif, la composition de matériau actif comprenant au moins un matériau actif, du lithium élémentaire et au moins un liant et étant fabriquée sans utilisation de solvants.
EP18780035.4A 2017-10-05 2018-09-19 Électrode comprenant du lithium élémentaire et son procédé de fabrication Withdrawn EP3692586A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017217656.3A DE102017217656A1 (de) 2017-10-05 2017-10-05 Elektrode umfassend elementares Lithium und Herstellungsverfahren
PCT/EP2018/075316 WO2019068463A1 (fr) 2017-10-05 2018-09-19 Électrode comprenant du lithium élémentaire et son procédé de fabrication

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EP3692586A1 true EP3692586A1 (fr) 2020-08-12

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EP (1) EP3692586A1 (fr)
DE (1) DE102017217656A1 (fr)
WO (1) WO2019068463A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019128445A1 (de) * 2019-10-22 2021-04-22 Bayerische Motoren Werke Aktiengesellschaft Verfahren zum Herstellen einer Elektrode für eine Speichereinrichtung zum Speichern von elektrischer Energie, Verwendung einer solchen Elektrode sowie Elektrode

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012203019A1 (de) * 2012-02-28 2013-08-29 Technische Universität Dresden Kathode für Lithium-haltige Batterien und lösungsmittelfreies Verfahren zu deren Herstellung
DE102013219602A1 (de) * 2013-09-27 2015-04-16 Robert Bosch Gmbh Herstellungsverfahren für Lithium-Zellen-Funktionsschicht
DE102015224335A1 (de) * 2015-12-04 2017-06-08 Robert Bosch Gmbh Feststoffelektrode mit elektrolytgetränkten Aktivmaterialpartikeln
DE102016215666A1 (de) * 2016-08-22 2018-02-22 Bayerische Motoren Werke Aktiengesellschaft Elektrodenanordnung für Lithium-basierte galvanische Zellen und Verfahren zu deren Herstellung
DE102016217386A1 (de) * 2016-09-13 2018-03-15 Robert Bosch Gmbh Verfahren zur lösungsmittelfreien Herstellung einer Aktivmaterialzusammensetzung
DE102017201233A1 (de) * 2017-01-26 2018-07-26 Robert Bosch Gmbh Verfahren zur Herstellung eines Elektrodenlaminats für eine Festkörperbatterie

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DE102017217656A1 (de) 2019-04-11
WO2019068463A1 (fr) 2019-04-11

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