WO2012013286A1 - Procédé et dispositif pour fabriquer une structure d'électrode multicouche, cellule galvanique - Google Patents

Procédé et dispositif pour fabriquer une structure d'électrode multicouche, cellule galvanique Download PDF

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Publication number
WO2012013286A1
WO2012013286A1 PCT/EP2011/003308 EP2011003308W WO2012013286A1 WO 2012013286 A1 WO2012013286 A1 WO 2012013286A1 EP 2011003308 W EP2011003308 W EP 2011003308W WO 2012013286 A1 WO2012013286 A1 WO 2012013286A1
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WIPO (PCT)
Prior art keywords
carrier substrate
layer
electrode
layers
electrode structure
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PCT/EP2011/003308
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German (de)
English (en)
Inventor
Tim Schaefer
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Li-Tec Battery Gmbh
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Publication date
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Publication of WO2012013286A1 publication Critical patent/WO2012013286A1/fr

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    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0404—Machines for assembling 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • 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
    • H01M4/0419—Methods of deposition of the material involving spraying
    • 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
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • Electrode structure galvanic cell
  • the present invention relates to a process for the preparation of a
  • Electrode structure in particular for a galvanic cell, a galvanic cell with such an electrode assembly and an apparatus for
  • Connection system is laminated and wound, housed and poled etc.
  • the inventors are also known a method in which on a
  • Substrate film on both sides in each case a layer of a filler material is thermally sprayed to a film layer with certain electrical or
  • an insulator foil, an anode foil, a separator foil and a cathode foil are laminated and the laminated foil layer structure rolled up in such a dimensioned length (wound), that the entire wound length (area or volume) provides the required capacity of a galvanic cell.
  • the thus prepared coils are then contacted and housed to complete a galvanic cell, and a plurality of cells thus fabricated are interconnected and in turn housed to form a battery.
  • a step of forming at least two layers of the electrode assembly to each other by thermal spraying or deposition Under an electrode structure is in accordance with the invention, a
  • An electrode assembly may also include a part (such as a cathode structure or an anode structure or a
  • Galvanic cell is understood in the context of the invention, an electrochemical system, which is also able to convert chemical into electrical energy and / or vice versa, and in particular is also able to deliver electrical energy.
  • thermal spraying is a process for applying an injection molding material (also referred to as additive in the context of this application) in particle form, using thermal and kinetic energy.
  • the method may be implemented in preferred embodiments or developments such that the step of thermal spraying comprises at least one, preferably several, in particular all of the steps:
  • a plasma is understood to mean a gas which consists partly or completely of free charge carriers, such as electrons and ions.
  • Thermal spraying is the plasma spraying.
  • the additive is melted in or outside a spray apparatus by a plasma jet and thrown onto the workpiece surface.
  • the plasma is generated by an arc, which is concentrated in a working gas (argon, helium, nitrogen,
  • preferably water-cooled spray nozzle burns and is accelerated.
  • the process can be used in normal atmosphere, in inert atmosphere, in inert gas, in vacuum or under water.
  • the plasma breaks that
  • layer-wise drying means that in the course of application or immediately after the application of a layer, it is dried before a further layer is applied or further method steps are carried out. It does not have to (but can) all layers are specially dried.
  • preconditioning is understood to mean the setting of air to a specific dew point or dew point range. As within the meaning of the invention preferably usable dew point range, an absolute dew point of -60 to -100 has been found.
  • Training be realized so that at least one, preferably more, in particular all of the steps:
  • a carrier substrate preferably in the form of a film, in particular in band form, preferably provided on a roll;
  • a carrier substrate is understood to mean a structure which can be coated by a thermal spraying method.
  • an electrically insulating plastic such as polyimide
  • a collector material in particular a metallic material such as aluminum or copper, an electrically conductive polymer film or a carbon material, or a separator material, each preferably in sheet form, comprises or consists thereof.
  • a collector material is understood to be an electrically conductive material which, in conjunction with a galvanic cell, can be used to collect charge carriers in the active part of a galvanic cell and to exchange them with the environment.
  • Separator material is understood in the context of the invention, a material that between an anode region (negatively charged region) and a
  • Cathode area (positively charged area) of a galvanic cell can be arranged to separate them.
  • a separator material is largely impermeable to charge carriers (electrons) (electrically insulating), but at least partially permeable to ions.
  • Electrode structure each fulfill the function of an anode, a cathode, a current collector or conductor, a separator, an electrolyte or an insulator in terms of a galvanic cell, preferably at least one of the layers lithium or a lithium compound or a lithium-intercalatable material.
  • a lithium-intercalatable material is understood as meaning a material which can take up or store lithium, in particular lithium ions, without substantially changing its structure.
  • lithium intercalatable materials are, for example, but not limited to, crystals such as graphite or Si (silicon), preferably in an amorphous, nanocrystalline form, or the like for the anode side and certain heavy metal oxides for the cathode side.
  • At least one of the layers may comprise lithium or a lithium compound such as Li 4 Ti 5 O 12 (lithium titanate) for the anode side and compounds (oxides) with cobalt, nickel and other elements such as LiNi x Co x O or LiFePo 4 or LiMn 2 0 4 or Li (Co x Ni y Mn z ) 0 2 or LiNiP0 4 or LiMnP0 4 or LiCo0 2 or LiNi0 2 or the like for the cathode side.
  • the above-mentioned substances are to be understood as preferred but not exclusive examples.
  • the method is preferred, but not limited to, to fabricating an electrode assembly for lithium-ion cells, lithium-polymer cells, or other lithium-based primary or secondary cell types of any type.
  • the sprayed material at least one layer of additives, in particular from nano-Sl, magnesium oxide,
  • three-dimensional structures of the additives extend at least partially in a direction orthogonal or oblique to a plane of the carrier substrate.
  • Such additives can be used as the main constituent of a separate layer or as an admixture with other additives. If you
  • Form three-dimensional structures they are suitable as a conductivity additive, for example, to interlock different layers, in particular a conductor layer and an electrode layer with each other.
  • the method can be used in further preferred embodiments or
  • the base material is preferably coated on at least one side, in particular on both sides, with an inorganic material
  • an at least partially permeable base material preferably an organic material is used, which is preferably configured as a non-woven fabric,
  • the organic material preferably comprises a polymer, and more preferably a polyethylene terephthalate (PET),
  • PET polyethylene terephthalate
  • organic material is coated with an inorganic, preferably ion-conducting material, which is more preferably ion-conducting in a temperature range of -40 ° C to 200 ° C,
  • the inorganic material preferably comprises at least one compound from the group of oxides, phosphates, sulfates, titanates, silicates, aluminosilicates of at least one of the elements Zr, Al, Li, particularly preferably zirconium oxide,
  • the inorganic, ion-conducting material preferably has particles with a maximum diameter of less than 100 nm.
  • Carrier substrate forms.
  • sprayed layers are formed in segments, with separation regions between the segments extending in at least one direction along a surface of a carrier substrate, preferably along and / or across a feed direction of the carrier substrate, demarcated and separately controllable regions may be formed in an electrode assembly.
  • the method may be further preferred
  • Separation areas between the segments are preferably formed by one or more of the following measures:
  • the electrode assembly has at least two carrier substrates, preferably
  • a step of feeding a second carrier substrate and attaching to the outermost layer is provided, wherein preferably on the second
  • Carrier substrate further layers are formed; and or
  • first sub-electrode structure with a first carrier substrate and a second sub-electrode structure with a second carrier substrate are formed, which then in another
  • Process section are joined together on opposite flat sides, for example by means of an adhesive and / or by the action of heat and / or by the action of pressure and / or by adhesion at least one of the formed on the opposite sides
  • Partial electrode structure and the second part of the electrode structure further layers are formed.
  • the method can be used in further preferred embodiments or
  • Each carrier substrate is a collector foil material or has a collector material as a sprayed layer
  • first carrier substrate and the second carrier substrate have non-overlapping edge zones
  • edge zones are preferably formed in that the first carrier substrate and the second carrier substrate are offset in the lateral direction, or
  • first carrier substrate and the second carrier substrate in the region of one or both lateral edges notches preferably have the same distance and the same length, whereby tabs are defined between the recesses, wherein in the electrode structure tabs of the first
  • Carrier substrate have no overlap or contact with tabs of the second carrier substrate
  • Training be realized so that it has at least one of the steps:
  • Assembling the electrode structure as an active region of a galvanic cell preferably comprising a step of winding the electrode
  • Electrode structure or steps of cutting to cell size and stapeln the cut sections can be the step of winding the electrode structure onto a flat core, wherein the flat core is preferably formed from a material which conducts heat well.
  • the invention also includes a galvanic cell whose electrode assembly is made by a method as described above.
  • the invention also encompasses a device which is designed and arranged for producing a multilayer electrode structure or a galvanic cell, in particular by a method as described above, and which comprises:
  • a drying device which is designed and arranged to dry a sprayed-on layer before forming a next layer, wherein the drying device has a
  • Feed device which is designed and arranged for supplying preconditioned, in particular dried air
  • a supply and conveying device which is designed and arranged for supplying and conveying a carrier substrate or a half-finished or finished electrode assembly.
  • Fig. 1 is a schematic representation of a plant for producing a
  • Electrode strip a schematic representation of an injection unit in the system of Fig. 1;
  • Fig. 3 is a schematic representation of a sequence of several
  • Injection units in the plant of Figure 1 in a plan view. are Fign.
  • 4A to 4G are schematic cross-sectional views of a
  • Electrode structure at locations "A” to "D” in Figure 3, "E” in Figure 1 and “F” and “G” in Fig. 5. a schematic representation of a system for producing a finished strip with two electrode bands; a schematic representation of an injection unit in one
  • Embodiment a schematic representation of a spray gun in a further embodiment; a schematic representation of an injection unit in a further embodiment; a schematic representation of a system for producing a finished strip with two carrier film strips; a schematic representation of a processing line as an embodiment of the present invention; a schematic representation of a procedure for producing a film stack as an embodiment of the present invention; Fig. 12 is a schematic representation of a plant for the production
  • FIGS. 13A and 13B are schematic illustrations of one
  • FIG. 14A to 14C are schematic representations of a
  • Fig. 15 is a schematic view of an electrode tape according to an embodiment of the present invention
  • Fig. 16 is a schematic diagram of an electrode tape according to an embodiment of the present invention
  • Fig. 17 is a schematic representation of a film roll with
  • Electrode tapes according to FIG. 16 are Electrode tapes according to FIG. 16.
  • FIG. 1 is a schematic representation of a system 10 for producing an electrode tape 22 as a preferred embodiment of the present invention.
  • the system 10 has a unwind station 12, which is a continuous
  • Carrier film strip 14 provides, a Vorbearbeitungsumble 16 for pre-processing of the carrier film tape 14, a coating line 18 for coating the carrier film strip 14, a post-processing line 20 for post-processing of the coated strip, and a Aufrollstation 24 for rolling the Electrode band 22 on. Between the pre-processing section 16 and the post-processing section 20, the film strip is also referred to as semifinished product 34.
  • the unwind station 12 receives a coil 12a rotatably mounted, on which the carrier film tape 14 is rolled up.
  • the unwind station 12 may preferably include drive means for driving the coil, brake means for braking the coil, a shuttle roller for setting a predetermined belt tension, detection means for detecting state values of the carrier film belt 14 such as a running speed Slack or tension or markers on the belt, evaluation means for evaluating the condition values to detect, for example, an intact condition of the belt, a previous run length, a break or end thereof, control means for controlling the drive means and / or the braking means and or the pendulum roller, preferably within specified parameters of
  • the unwinding station 12 may also have only a few of the named elements in preferred modifications.
  • the pre-processing path 16 although not shown in detail, preferably a guide roller, one or more drive roller pairs, a detection device for detecting state values of the
  • Deflection rollers for reducing internal mechanical stresses wherein the guide rollers can be additionally tempered, one or more storage rollers for length compensation of the carrier film strip 14, and
  • the Preprocessing section 16 may also have only some of the elements mentioned in preferred modifications.
  • the coating line 18 has an input unit 26, a plurality
  • Injection units 28 (28-1, 28-n), an output unit 30 and a
  • the injection units 28 serve the - here, without limiting the generality, both sides - coating the film strip with one additive. A preferred construction of the injection units 28 will be explained in more detail later.
  • output unit 30 may preferably comprise one or more guide and / or deflection rollers, one or more drive roller pairs, one or more storage rollers for length compensation of the foil strip, and other suitable devices.
  • Input unit 26 and the output unit 30 may in preferred
  • Supply unit 32 serves to supply in particular the injection units 28 and is connected via a line network 32a with these.
  • the finishing line 20, although not shown in detail, may preferably include a guide roll, one or more drive roller pairs, a calendering arrangement for calendering the semi-finished product 34, one or more cooling rolls for cooling the electrode belt 22, one or more
  • Preprocessing section 16 may also have only some of the elements mentioned in preferred modifications.
  • the Aufrollstation 24 receives a coil 24a rotatably mounted, which is initially empty and in the course of operation of the system 10, the electrode tape 22 receives.
  • the reeling station 24 may preferably include a driving means for driving the coil, a braking means for braking the coil, a swinging roller for setting a predetermined one Tape tension, a detection device for detecting
  • Condition values of the carrier film tape 14 an evaluation device for evaluating the state values, a control device for controlling the
  • the unwinding station 2 may also have only a few of the named elements in preferred modifications.
  • Detecting devices pendulum rollers, storage rollers, drive rollers, etc. are provided. Upon detection of one end of the carrier sheet belt 14 in the unwind station 12 or a fully filled coil 24a in the
  • the semifinished product 34 in the injection unit 28 is guided via a deflection roller 36, a first wet roller 38, a first drying roller 40, a second wet roller 38, a second drying roller 40 and a further deflection roller 42.
  • an additive Z is applied in a spray mist 45 to the semifinished product 34 by means of at least one plasma spraying apparatus 44.
  • the previously applied additive layer (Z) with one of at least one air nozzle 46 discharged air jet 47 deleted deleted. In this way, the semi-finished product 34 is coated on both sides.
  • Each of the plasma sprayers 44 has a (bipolar)
  • DC power supply 48 for supplying a working voltage and a gas supply line 50 for supplying a gas (G) such as argon, helium, nitrogen, hydrogen or the like. Via a valve 52, a gas stream 54 of the gas G in the gas connection line 50 can be controlled.
  • An additive supply line 66 enters the plasma spray gun 44
  • the additive Z is stored in an additive container 68 as a supply of powdery, granulated or otherwise eligible additive particles 70 is plasticized in this form by means of a feed line 66 arranged in the extruder 72 and the
  • Plasma spray gun 44 supplied in plasticized form.
  • the air stream 78, the gas stream 54 and the cooling water stream 60 are provided by the supply unit 32 of the coating line 18 (FIG. 1).
  • the used cooling water (hot water WW) 64 is supplied to the supply unit 32 again, where it is cooled and returned to the cooling water circuit.
  • the used cooling water (hot water WW) 64 is collected and, optionally after purification and further treatment, discharged as wastewater.
  • the air L is in the
  • Supply unit 32 conditioned and dried.
  • the additives (Z) to be sprayed are stored centrally in the supply unit 32 and supplied to the injection units 28, where they are plasticized shortly before introduction into the plasma spraying apparatuses 44.
  • the promotion of additives may, for example, but not only, by bed, Rüttel thoroughlyung, with a carrier gas, a Carrier liquid, in particular an ionic liquid, or others
  • the additives can be processed in powdery, granulated or other form.
  • the above-described extruder 72 exemplifies a paste extrusion method. In preferred modifications, the
  • Additives also plasticized by other extrusion processes, made doughy by the addition of an ionic liquid and / or melted.
  • the ionic liquid may be an electrolyte that is preferably added to the electrode areas.
  • Preparing the additive may be applied directly to the spray gun 44 or may be part of a specially adapted spray gun.
  • supply lines 66 in can be understood symbolically so far.
  • the plasma spray gun 44 has an AC or DC instead of the DC jack 48
  • Multi-phase power connection as well as a power supply for rectifying
  • FIG. 3 shows a schematic plan view of an exemplary sequence of several injection units 28 in the system 10 of FIG. 1 as a preferred one
  • FIGS. 4A to 4E Embodiment of the present invention.
  • the viewing direction in Fig. 3 corresponds to an arrow "III" in Fig. 2.
  • the progress of a means of the in Figs. 1 illustrated plant or in Figs. 2 and 3, according to the present invention will also be described on the basis of selected states in FIGS. 4A to 4E.
  • Injection units 28-1, 28-2 and 28-3 provided in succession.
  • dashed lines To simplify the drawing leads are shown only schematically and without inputs or attachments; general supply elements for electricity, gas and cooling water are also omitted in the figure.
  • Dash-dotted lines "A”, “B”, “C”, “D” mark boundaries in front of and behind and between the injection units 28-1, 28-2, 28-3, respectively.
  • the in Fign. 4A to 4D illustrated process states of the film strip 14 or semi-finished product 34 correspond to cross-sections of the same at the boundary lines "A" to "D” in Fig.
  • the process state shown in Fig. 4E is that of the finished electrode tape 22 after the post-processing section 20 and corresponds to a cross-section of the electrode tape 22 at a dot-dash line "E" in Fig. 1 in
  • a plurality of plasma sprayers 44-1, 44-2, 44-3 and a plurality of air nozzles 46 are arranged in rows side by side in the injection units 28-1, 28-2, 28-3, respectively. In this way, the
  • FIG. 4A shows the uncoated state of the carrier film belt 14 before entering the first injection unit 28-1 (boundary line "A" in Fig. 3).
  • the carrier film tape 14 is a tape made of a polyimide film.
  • the carrier film tape 14 is a tape made of a polyimide film.
  • Carrier sheet material other materials, in particular, but not only, electrically insulating polymeric films may be used.
  • the carrier films used may be provided (primed) in a further preferred modification with a primer or primer.
  • the first injection unit 28-1 is used to coat the carrier film strip 14 with a conductive material which is effective in a galvanic cell as a current collector (collector) of an electrode side.
  • the collector material contains copper for the anode side or
  • Aluminum for the cathode side.
  • a different metal a conductive polymer, carbon fibers, graphite or another conductor material is used for the conductor layers.
  • the carrier film belt 14 is fed to the first injection unit 28-1 after pre-processing in the pre-processing path 16.
  • a plasticized additive mass 80-1 containing particles of a collector material (coll.) Is fed via an additive feed line 66-1 and into a spray mist 45-1 by means of four plasma spraying units 44-1 arranged side by side be applied to the carrier film tape 14.
  • the four plasma spray guns 44-1 each generate spray mist 45-1, which at the latest when impinging on the guided over the wet roller 38
  • the structure of the semifinished product 34 (1) after the first injection unit 28-1 (boundary line "B" in FIG. 3) is shown in cross section in FIG. 4B. Accordingly, a conductor layer (collector layers) 2 with copper-containing material (Cu) is arranged as a collector material in this process state on the front and back of the carrier film strip. The conductor layers 2 each extend over the entire width of the carrier film strip 14.
  • the second injection unit 28-2 serves to coat the semifinished product 34 (1) with an electrochemically active material which is effective in a galvanic cell as electrode of an electrode side.
  • the electrode material contains lithium-intercalatable graphite for the anode side or a lithium-intercalatable heavy metal oxide for the
  • the semi-finished product 34 (1) is fed to the second injection unit 28-2.
  • a plasticized additive mass 80-2 is supplied which contains particles of the electrode material (El.) And applied to the carrier film strip 14 by means of three plasma spray devices 44-2 arranged next to one another in a spray mist 45-2 ,
  • the three plasma spray guns 44-2 each generate spray mist 45-2, which unite at the latest when striking the guided over the wet roller 38 semi-finished 34- 1 and cover a delimited by aperture 82 width of the semifinished product 34 (1).
  • Six air nozzles 46 are arranged over the relevant width of the semifinished product 34-1 and each generate air jets 47, which unite at the latest when hitting the moist, coated, guided over the drying roller 40 semi-finished 34 (1) and the relevant width of the
  • Injection unit 28-2 as semifinished product 34 (2).
  • Electrochemically active electrode material arranged for the anode side.
  • the electrode layers 4 each extend over a limited width of the semifinished product 34 (FIG. 2). While the electrode layers 4 release only a little of the conductor layers 2 at one edge, they release the conductor layers 2 over a greater width at the opposite edge.
  • the third injection unit 28-3 serves to coat the semifinished product 34 (2) with a material which is effective in a galvanic cell as a separating material (separator) between the electrode sides.
  • the separator material contains an organic, in particular polymeric, material such as PET and an inorganic, in particular ceramic material such as zirconium oxide. Such a material combination corresponds to that of a film material sold under the trade name Separion.
  • the inorganic material may also be another suitable ceramic compound, in particular from the group of oxides, phosphates, sulfates, titanates, silicates, aluminosilicates of at least one of the elements Zr, Al, Li.
  • the separator material may be any lithium ion-conducting electrolyte.
  • the semi-finished product 34 (2) is fed to the third injection unit 28-3. There is three juxtaposed plasma sprayers 44-3 on a
  • Additive supply line 66-3 a plasticized additive mass 80-3 supplied containing particles of the separator material (Sep.).
  • the three Plasma spray guns 44-3 each produce spray mist 45-3, which unite at the latest when striking the guided over the wet roller 38 semi-finished 34- 2 and cover a delimited by an aperture 82 width of the semifinished product 34 (2).
  • Six air nozzles 46 are arranged over the relevant width of the semifinished product 34-2 and generate air jets 47, which unite at the latest when hitting the moist, coated, guided over the drying roller 40 semi-finished 34 (2) and the width of the concerned
  • Cover semi-finished 34-2 as a continuous air curtain The above-described process, visible in FIG. 3 for the front side of the film strip, is repeated for the backside of the strip according to the arrangement in the lower half of FIG. Thereafter, the foil strip leaves the third
  • Injection unit 28-3 as semifinished product 34 (3).
  • the covered width is slightly larger in the third injection unit 28-3 than in the second injection unit 28-2.
  • the injection width of the third injection unit 28-3 can also be limited by one or more apertures.
  • Process state on the front and back of the semifinished product 34 (2) each have a separator 6 (Sep.) arranged.
  • the separator layers 6 each extend slightly wider than the electrode layers 4, so that the latter are completely covered.
  • the smaller edge left free in FIG. 4C is completely covered by the separator layers 4;
  • the larger edge left open in FIG. 4C remains largely free, so that the collector layers 2 remain uncovered there.
  • the application of the separator material (Sep.) by the injection units 28-3 and the subsequent drying are preferably carried out such that the organic material in the separator layer 6 assumes a fleece-like structure.
  • Fig. 4E shows the structure of the finished electrode tape 22 after exiting the post-processing line 20 (boundary line "E" in Fig. 1).
  • the separator material (Sep.) by the injection units 28-3 and the subsequent drying.
  • Post-processing section 20 has inter alia a calender arrangement, in which the semi-finished product 34 (3) is calendered.
  • calendering the surface of the layer structure is made uniform and are in particular stepped transitions between the electrode layers 4 and the
  • the free edge on one side of the electrode tape 22, on which the collector layers are not covered, is also referred to as the lead-out region or contact region 84.
  • the additives contain a conductor material, an electrochemically active material or a separator material.
  • the additives of the respective layers can, if required, further additives, polymer binders, conductive salts, organic or inorganic solvents, etc.
  • 4F shows two electrode bands 22-1, 22-2, which are produced according to the method explained above, in an assembly-appropriate arrangement.
  • a first electrode band 22-1 corresponds to an electrode assembly of a cathode side of a galvanic cell with a carrier layer
  • Carrier film strip 14 Carrier film strip 14), a collector layer 2-1 on both sides with aluminum (AI), an electrode layer 4-1 arranged thereon with a Li-intercalatable heavy metal oxide (Met-Ox) and one of these in each case
  • Electrode tape 22-2 an electrode structure of an anode side of a galvanic cell with a carrier layer (carrier film tape 14), a double-sided collector layer 2-1 with copper (Cu), one on each
  • Electrode belts 22-1, 22-2 are arranged offset so that the areas covered with separator layers 6 facing each other and the respective contact areas 84-1, 84-2 protrude from opposite sides.
  • the interconnected separator layers 6 form a continuous separator layer, and the discharge regions 84-1, 84-2 protrude laterally in different directions from the layer structure.
  • the layer structure between the carrier layers 14 of the electrode strips 22-1, 22-2 thus corresponds to the construction of a galvanic cell with electrodes 4-1, 4-2, a separator 6 arranged therebetween and connected to the respective electrodes 4-1, 4-2 Collectors 2-1, 2-2 with
  • Deriving areas 84-1, 84-2 which can not come into contact with each other.
  • This layer structure will be referred to hereinafter as the characteristic cell layer 86.
  • a layer structure, as shown in Fig. 4G, is wound in subsequent steps, not shown, assembled, housed, contacted and poled, etc., to be processed into salable galvanic cells. Since the layer structure of the electrode strips 22-1, 22-2 is symmetrical and, when the layer structure is wound, the surface of the separator region 6 of the anode region located at the top in FIG. 4G comes into contact with the surface of the separator region 6 of the cathode region lying below in FIG. 4G, With each wrapping, a further layer structure is formed, which is the
  • characteristic cell stratification 86 corresponds. With n complete layers, 2n-1 characteristic cell stratifications are thus formed. The projecting on opposite end faces of such a film roll
  • Deriving regions 84-1, 84-2 form so-called discharge vanes, which can be used for contacting in the galvanic cell.
  • a release layer is applied to the surface before being wound up, which volatilizes either independently or before it, for example in the case of further processing Unwind the coil, remove it.
  • the finished strips 22 can be wound up together with a separating film which is to be removed during further processing, for example during unwinding of the coil.
  • the carrier film tapes 14 are made of, or at least comprise, the conductor material (collector material) itself such as copper, aluminum, or another metal, carbon fiber material, graphite, or conductive polymer. If such a carrier film with collector material, optionally primed, as
  • FIG. 5 is a schematic representation of a system 100 for producing a finished strip 1 10 of two electrode strips 22-1, 22-1.
  • the system 100 has a first unwind station 102-1, which supplies a first electrode belt 22-1 wound continuously on a coil 102a, a second unwind station 102-1, which supplies a second electrode belt 22-2 continuously wound on a coil 102a, two pre-processing paths 104-1, 104-2 for pre-processing the electrode bands 22-1, 22-2, a
  • Laminating line 106 for laminating the electrode strips 22-1, 22-2, a post-processing line 108 for post-processing of the laminated strip, and a Aufrollstation 112 for rolling up the finished strip 1 10 on a coil 1 12a.
  • the unwind stations 102-1, 102-2, the pre-processing lines 104-1, 104-2, the post-processing section 108 and the reeling station 112 are the same or similar to the corresponding system parts of the system 10 of FIG. 1, so that to avoid repetition of the made to that
  • the laminating section 106 has two input stations 1 14-1, 114-2
  • Pressure roller pair 118 for applying a pressure 120 to be laminated to electrode bands 22-1, 22-2, an output unit 122, a
  • the input stations 114-1, 114-2, the output unit 122 and the supply unit 124 are the same or similar to the corresponding system parts of the injection line 18 of FIG. 1, so that reference can be made to avoid repetition on the explanations made there, as far as the following description nothing different or supplementary can be found.
  • the first electrode band 22-1 is a cathode band and the second electrode band 22-2 is an anode band.
  • the cathode belt 22-1 and the anode belt 22-2 have a construction according to FIG. 4F and are guided in the installation 100 in such a way that they are in front of the lamination path 106 (see a dot-dash line "F" in FIG ) as shown schematically in Fig. 4F.
  • the cathode belt 22-1 and the anode belt 22-2 are first led via the input stations 114-1, 114-2 to the wetting units 16-16, 16-2.
  • the wetting units 1 16-1, 116-2 each have a plurality of guide rollers 1 16a, a wet roller 1 16b and one or more spraying device / s 116c.
  • the sprayer (s) 116c provide uniform widthwise wetting of the surface of one of the separator layers 6 (FIG. 4F) of the electrode belt 22-1 or 22-2 with a polymer.
  • the polymer serves to dissolve or render the separator layers 6 susceptible to adhesion.
  • the structure of the wetting unit 116-1 is shown in FIG indicated schematically;
  • the wetting unit 116-2 is, although not shown in detail, constructed mirror-inverted identical.
  • the cathode belt 22-1 and the anode belt 22-2 are then fed to the pressure roller pair 118, where the separator layers 6 are pressed against each other under pressure (arrows 120) and join together.
  • the pressure on the pressure rollers can be produced hydraulically, via electrical actuating drives or the like.
  • the connection process is through the
  • Heating device 126 is supported, which heats the connection point in the region of the pressure roller pair 118 with heat radiation (arrow 127).
  • Supply unit 124 serves to supply the various parts of the lamination path 106 with electrical current or electrical voltage, air, process gases, additives, hydraulic force, etc.
  • wetting facilities are dispensed with.
  • one or both of the pair of pressure rollers 118 are heated to assist in the bonding process.
  • Pressure roller pair 118 supplied electrode strips 22-1, 22-2 sprayed.
  • the sprayers 116c may in preferred modifications be
  • FIG. 6 shows a view corresponding to FIG. 2 of an injection unit 28 in a further preferred embodiment of the invention.
  • the semifinished product 34 is guided via a deflecting roller 36, then via two injection rollers 130 and finally via a further deflecting roller 36.
  • the running or deflection directions of the injection rollers 130 are
  • Each spray roll 130 is associated with a series of spray guns 44 flanked by two rows of air nozzles 46.
  • the series arrangements of spray guns 44 and air nozzles 46 extend over all or part of the width of the spray rolls 130, analogous to the arrangement in FIG. 3; in the illustrated view, only one spray gun 44 and two flanking air nozzles 46 are visible on each spray roller 130.
  • the spray guns 44 are each a spray mist 45, and the air nozzles 46 each emit an air jet 47, which limits the spray mist 45 and directs and optionally mixed with this.
  • a layer of an additive (Z) is applied to the front or back of the semifinished product 34, which by means of the surrounding air jets 47, the in
  • Width direction of the injection rollers 130 forming air curtains is effectively dried simultaneously with and immediately after the order.
  • Fig. 7 shows schematically a spray gun 132 after another
  • FIG. 8 shows in a view corresponding to FIG. 2 an injection unit 28 in a further preferred embodiment of the invention.
  • the semifinished product 34 via a guide roller 36, via an injection roller 130, which is a first series arrangement of
  • a deflecting roller 36 arranged away from the injection roller 130, from the latter via a further injection roller 130, which is associated with a second series arrangement of plasma sprayers 44, a deflecting roller 36 remote from the further injection roller 130, and finally via a further guide roller 36 led.
  • Deflection directions of the injection rollers 130 are in opposite directions, so that on the one (in the figure upper) spray roller 130, a first flat side (front) of the semifinished product 34 lies outside and on the other (in the figure lower) spray roller 130, a second flat side (back) of the semifinished product 34 is outside.
  • a layer of an additive (Z) is applied in each case on the front or rear side of the semifinished product 34 in the manner already described.
  • the injection unit 28 is encapsulated in a housing 140 such that
  • a fan 142 On a wall of the housing 140, a fan 142 is arranged, which presses via an air line 74 supplied air L (air stream 78) in the housing 140. On another wall of the housing 140, a further fan 144 is arranged, which dissipates used air or exhaust air AL in an exhaust duct 146 and thus from the housing 140 also (exhaust air flow 148).
  • the air line 74 is connected to a
  • the blower 142 may be part of a Air conditioner which conditions or dries and heats conventional atmospheric or room air.
  • the guided into the housing 1 0 air (L) also passes over the semifinished product 34, in particular in the area between a plasma spray gun 44 and the next guide roller 130. This is an effective drying by the plasma spray gun 44th
  • Processing state (temperature, etc.) brought.
  • the semifinished product 34 is supported between an injection roller 130 and the subsequent deflection roller 36 by suitable means.
  • the support means may preferably (but not only) be disposed on the side of the semifinished product which has not been last coated.
  • a suitable support means may preferably, but not only, be a slide plate on which the semifinished product slides, an air cushion plate over which the semifinished product floats on an air cushion, an endless conveyor belt which moves with the semifinished product 34 and on which the semifinished product 34 rests , If the support means is located above the semifinished product 34 in order to avoid contact with the last sprayed-on layer, a device may be provided which attaches the semifinished product 34, for example by negative pressure, magnetic or electrostatic attraction or the like
  • multiple injection units 28 may be housed in a common housing 140 and supplied with dry air.
  • Coiling of the electrode strips 22, are performed.
  • two installations 10 according to FIG. 1 and one installation 100 according to FIG. 5 can be combined in a single installation, wherein the reeling station 24 of the installation 10 in FIG. 1 as well as the unrolling stations 102 in FIG.
  • the post-processing section 20 of the system 10 in FIG. 1 and / or the preprocessing sections 104 in the system in FIG. 5 or individual stations can also be omitted or combined in intermediate processing lines.
  • FIG. 9 schematically shows an exemplary plant 150 for the continuous production of a finished strip 110 from two carrier film strips 14-1, 14-2 as a further embodiment variant of the present invention.
  • the system 150 has a first unwind station 12-1, which is a first
  • the unwind stations 12-1, 12-2 and the preprocessing sections 16-1, 16-2 are constructed the same or similar to the corresponding system parts of the system 10 of FIG. 1; the post-processing section 108 and the reeling station 112 correspond to the same system parts of the system 100 of FIG. 5, so that in order to avoid repetition of the explanations made to this corresponding reference can be made, as far as the following
  • the coating and Lam inierumble 152 has two input stations 26- 1, 26-2 for detecting the coming from the Vorbearbeitungsumblen 16-1, 16-2 Shinfolienbs 14-1, 14-2 (from there as a semi-finished 34-1, 34- 2), multiple injection units 28-1 1, 28-12, 28-13, 28-14 to
  • the input stations 26-1, 26-2 correspond to the input station 26 of the system 10 of FIG. 1, the pair of printing rollers 118, the output unit 122, the supply unit and the heater 126 correspond to the respective system components of the laminating path 106 of the system 100 of FIG. so that in order to avoid repetition to the explanations made there, reference can be made accordingly, as far as the following
  • Carrier film tape 14-1, 14-2 each one polyimide film (primed), wherein the first carrier film tape 14-1 the construction of a cathode side and the second carrier film tape 14-1 the construction of an anode side of the finished strip 110 is used.
  • the coating and laminating section 152 the
  • the first injection units 28-1, 28-21 of each side in the sequence serve in each case for double-sided coating of the semi-finished products 34-1, 34-2 with a conductivity additive such as carbon nanotubes and an adhesion promoter.
  • the adhesion promoter essentially serves for wetting the carrier film and the adhesion of the additive particles; it may partially volatilize during subsequent drying.
  • the additive particles have a maximum length which is greater than a height of the adhesion promoter after drying. Thus, the additive particles protrude after completion of the layer in different directions in space from the adhesive layer.
  • the successive second injection units 28-12, 28-22 of each side serve respectively to coat the semifinished products 34-1, 34-2 on both sides with a conductor material (containing copper for the anode side and aluminum for the cathode side, respectively), and the third injection units 28-13, 28-23 each side are each the two-sided coating of the semi-finished products 34-1, 34-2 with an electrochemically active electrode material (cathode or anode material).
  • the length of the additive particles is such that they still through the
  • Conductor layer project into the electrode layer, but at least substantially not beyond.
  • the additive particles serve the toothing and thus the improvement of an electrical connection between the conductor layer (collector layer) and the respective electrode layer.
  • conductivity additives such as nano-Sl, magnesia, alumina, carbon black, certain ionic liquids, etc. More preferably, the conductivity additives have three-dimensional structures, such as nanotubes, that are at least partially in a direction orthogonal or oblique to a plane of the
  • Carrier film strips 14-1, 14-2 extend.
  • the conductivity additive is used as
  • the semi-finished products 34-1, 34-2 are each fed to an intermediate processing unit 153-1, 153-2.
  • the intermediate processing units 153-1, 153-2 have, for example, but not only, an abrasive device 153a for removing excess additive particles, and a calendering device 153b for compacting the previously applied layers, as shown in the figure for the intermediate processing unit 153-1. From the intermediate processing units 153-1, 153-2, the intermediate processing units 153-1, 153-2, the
  • Semi-finished 34-1, 34-2 each supplied to the fourth injection units 28-14, 28-24. These injection units 28-14, 28-24 are used for one-sided coating of the semi-finished products 34-1, 34-2 with a separator material. After that, the
  • Pressure (arrows 120) and supported by the heater 126 are pressed together and connect to each other.
  • the laminate After the connection (lamination) of the two semi-finished products 34-1, 34-2, the laminate is fed to the last injection unit 28-30, where the laminate, which still has free electrode layers on the outer sides, is coated on both sides with a separator material. In the subsequent output unit 122, the coated laminate is calendered again (calender assembly 154).
  • the post-processing section 108 of this system 150 has a
  • FIG. 10 is a schematic representation of a processing line 160 for a semifinished product 34 that may be used, for example, but not limited to, instead of or as part of one of the initial stations or finishing lines of the above
  • the processing section 160 serves for processing an already coated semifinished product 34 which has a conductor or collector layer 2, an electrode layer 4 (dashed line) and a separator layer 6.
  • the conductor layer 2 is exposed as a discharge region 84 at a lateral edge of the semifinished product 34 and is covered in the remaining region by the separator layer 6, just like the
  • interposed electrode layer 4 which is less wide than the
  • Separator layer 6 is (see dashed line in Fig. 10).
  • the processing section 160 has a memory unit 162, a punching unit 164 and a drive unit 166.
  • the storage unit 162 has at least one storage roller and corresponding guide rollers (not shown in detail).
  • the drive unit 166 keeps the semi-finished product 34 taut.
  • Punching unit 164 has a punching unit (not shown in detail), which punch out rectangular recesses 168 from the discharge area 84.
  • Recesses 168 cover the entire width of the diverter region 84 and extend into the separator layer 6, but not as far as the electrode layer 4. The region remaining between the recesses 168 is referred to as
  • Ableitfahnen 169 of the electrode assembly (electrode belt 22).
  • the punches are made with a cycle length I (hereinafter also referred to as pitch I), wherein a length li of the recesses 168 (also referred to as a punching) is greater than a length l 2 of the remaining Ableitfahnen 169 (hereinafter also referred to as the contact width l 2 ) plus one
  • the electrode belt 22 leaving the processing section 160 can be wound up on a coil or continuously processed further, as in the system 10 shown in FIG. FIG. 11 shows, in a three-dimensional view, schematic processing steps for the further processing of two electrode bands 22, which were produced as shown in FIG. 10.
  • a first electrode tape 22-1 is supplied from the left side in the figure, and a second electrode tape 22-2 is fed from the right side in the figure (arrow directions 170-1, 170-2 symbolize) also corresponding conveyors).
  • the first electrode band 22-1 be a cathode band and let the second electrode band 22-2 be an anode band.
  • each electrode band 22-1, 22-2 a piece of a length I is separated in each case, the length I corresponding to the cycle length or the pitch I in FIG. 10.
  • the separation takes place between two Ableitfahnen 169-1 or 169-2, as close as possible to a counter to the feed direction 170-1 or 170-2 next Ableitfahne (dashed dividing lines 172-1, 172-2 in Fig. 1 1
  • band sections 174-1, 174-2 of a length which corresponds to pitch I are formed.
  • the location of the dividing lines 172-1, 172-2 is determined so that each severed tape portion 174-1, 174-2 has a complete (ie, unseparated) bleed tab 169-1, 169-2 and the bleed tabs 169-1, 169 -2 completely on one side of the length (the pitch) I of the band portion 174-1, 174-2 bisecting center line 175-1, 175-2 comes to rest.
  • the band sections 174-1, 174-2 cut off from the electrode bands 22-1, 22-2 are alternately conveyed to a stacking station (arrow directions 176-1, 176-2 also symbolize corresponding conveying devices) and placed on top of each other so that they form a stack 178 (an arrow direction 180 also symbolizes a corresponding stacking device).
  • Belt section 174-1 to lie over one of a Ableitfahne 22-2 free half of a stacking direction next or previous band portion 174-2 and vice versa.
  • discharge lugs 22-1 of the first band sections 174-1 oppose each other in the stacking direction
  • respective discharge lugs 22-2 of the second band sections 174-2 in the stack 178 oppose each other in the stacking direction.
  • stacks 178 having a predetermined number of tape sections 174-1, 174-2 therein
  • the number of tape sections 174-1, 174-2 of a stack 178 is determined by the desired capacity of the battery or cell.
  • Fig. 12 shows schematically an exemplary plant 200 for the continuous production of a finished strip 212 from three carrier film strips 14-1, 14-2, 14-3 as a further embodiment of the present invention.
  • the carrier film tapes 14-1, 14-2, 14-3 of coils 202-1 become. 202-2, 202-3 and in each case a Vorbearbeitungsumble 204-1, 204-2, 204-3 supplied.
  • the first carrier film strip 14-1 comprises aluminum or an aluminum alloy or is produced therefrom.
  • Carrier film strip 14-2 comprises copper or a copper alloy or is produced therefrom.
  • the third carrier tape 14-3 has PET
  • the carrier film belts 14-1, 14-2 can therefore also be used as collector belts
  • the cathode collector belt 14-1 in two successive spray stations 28-1 1, 28-12 successively on one side Carbon Nanotubes (NanoC) and a cathode material (Kath.) Coated as described above. Likewise, that will be described above.
  • resulting semi-finished products 34-1, 34-2 can thus also be referred to as electrode strips (cathode strip 34-1, anode strip 34-2).
  • the carbon nanotubes serve as a conductivity additive; they protrude into the respective
  • Electrode layers applied by the spray stations 28-12, 28-22 are not longer than the thickness of the electrode layers in this embodiment.
  • the third carrier film strip 14-3 is coated after pretreatment in a spray station 28-30 on both sides with zirconium oxide (ZrO), wherein the particle size is preferably not more than 100 nm.
  • ZrO zirconium oxide
  • Carrier film tape 14-3 is an organic carrier material which is a poor electron conductor (ie an insulator). It is processed so that the material of the third carrier sheet 14-3 at least partially
  • ZrO is an inorganic material which is a good ion conductor in a typical temperature working range of -40 ° C to 200 ° C for high performance batteries.
  • the resulting semi-finished product 34-3 after coating can also be referred to as a separator belt.
  • ZrO for zirconia is used here as an abbreviation, not necessarily as a molecular formula.
  • Anode belt 34-1 and the cathode belt 34-2 is arranged and the Electrode layers of the electrode bands 34-1, 34-2 facing the Separatorband 34-3.
  • the laminate is then coated on both sides with an insulator material (ISO) in a spray station 28-40 and rolled up after passing through a reworking section 210 as a finished strip 212 on a coil 214.
  • ISO insulator material
  • the finished strip 212 of this embodiment has a structure in
  • the collector strips 14-1, 14-2 are each coated in such a way that an edge remains free as a contact region or discharge region.
  • the PET tape 14-3 is coated all over and is slightly wider than the electrode layers on the electrode tapes 34-1, 34-2, but narrower than the collector tapes 14-1, 14-2. During lamination, the contact areas of the
  • Electrode bands 34-1, 34-2 to opposite sides beyond the edges of the separator band 34-3.
  • the separator band 34-3 In a preferred, unspecified modification, the
  • Electrode bands 34-1, 34-2 also on the outside with a
  • Coating with the insulator layer Can be omitted in this modification.
  • the electrode structure of the resulting finished strip corresponds to the layer structure shown in FIG. 4G, but with the difference that the middle separator layer is formed by the separator strip 34-3.
  • a finished strip with such an electrode structure can be wound directly without requiring an insulating layer or a corresponding finished strip of mirror-image layering.
  • the contact areas of the electrode bands 34-1, 34-2 are punched out prior to lamination, as shown in FIG.
  • the electrode bands 34-1, 34-2 are thus punched out the separator belt 34-3 laminates that the contact portions protrude to the same side and the Ableitfahnen (169 in Fig. 10) of the electrode bands 34-1, 34-2 are staggered.
  • Fig. 13A shows a portion of an electrode tape 220 in a preferred embodiment of the invention in a plan view
  • Fig. 13B shows the electrode tape 220 of this alternative embodiment in a cross-sectional view taken along a bold dotted line in Fig. 13A looking in the direction of an associated arrow.
  • the electrode tape 220 of this alternative embodiment has a structure similar to that shown in FIG. 4E. In other words, on one
  • Carrier tape 14 are on both sides in the following order one
  • Electrode tape 220 is provided. In the middle of the electrode strip 220 in the width direction, the layer structure is interrupted by a trench (longitudinal trench) 222 in each case.
  • the ditch 222 extends to the
  • delimited segments can be created in the transverse direction, which can be addressed or controlled separately, for example, in a finished cell.
  • the segmentation in the transverse direction can be realized, for example, but not only, by the fact that between individual
  • Spray devices which are arranged distributed over the width of the semifinished product (34), are arranged panels which shield a selected region of the semifinished product, so that delimited injection zones are defined.
  • the conductor layer 2 is designed to be continuous in the width direction and extends the trench 222 only to the conductor layer 2.
  • this modification although a separate control of the two segments is not possible. However, it is conceivable that in the event of a deterioration of one segment, for example (but not only) due to overheating or other overloading, the other segment may continue to work.
  • FIG. 14A shows a portion of an electrode tape 230 in a preferred modification of the alternative embodiment of FIG. 13 in a plan view.
  • FIG. 14B shows the electrode tape 230 of this alternative embodiment in one Cross-sectional view, and
  • Fig. 14C shows the electrode tape 230 of this
  • Electrode layer 4 on one side of the trench 232 of an anode side, on the other side of the trench 232 of a cathode side of a galvanic cell, as shown in Fig. 14B. After the layer structure has been formed, contact areas on each side of the trench 232 are punched out analogously to the illustration in FIG. 10, the remaining discharge lugs 96 being formed offset in the longitudinal direction.
  • the electrode tape 230 is folded along the trench 232, and the two halves are folded on each other (curved arrows in Fig. 14B) and bonded together by pressure, heat, binder, or the like, as shown in Fig. 14C. In this way, a more complete
  • Electrode layer structure (finished tape 238, Fig. 14C) of a galvanic cell with prepared for contacting Ableitfahen in a continuous
  • Fig. 15 shows a portion of a finished strip 240 in another
  • the layer structure of the finished strip 240 corresponds - without limiting the generality - that of the finished strip 22 in Fig. 4E. In contrast, extend through the layer structure transverse trenches 242 across the width of the finished strip 240. In this way, a segmentation of the finished strip 240 in
  • segments 244 of a length s Longitudinal realized to form segments 244 of a length s.
  • the segments 244 can be controlled separately, for example in a finished galvanic cell, it can 244 in case of failure of a segment
  • Other segments 244 continue to work, and / or the transverse trenches 242 may serve as markers for orientation or synchronization in subsequent
  • Process steps such as punching, cutting, lamination and / or the like are used.
  • Segmentation in the longitudinal direction can be realized, for example, but not only, by interrupting the application in a timed manner by the spray guns, so that uncoated zones (trenches as separating regions of the segments) remain, and / or in that the feed or
  • Feed rate of the semifinished product is briefly increased in a predetermined cycle, so that zones arise in which the spray application is thinner, and / or in that in temporal timing a mask is pushed between the spray guns and the semi-finished, which
  • the layer structure of the electrode band 240 changes from segment 244 to segment 244 between an anode assembly and a cathode assembly, contact regions 84 are formed on both edges of the electrode band 240 and alternately becomes the contact region 84 of one segment 244 or the other segment 244 punched out.
  • the segments 244 of this modification can be zigzagged along the transverse trenches 242 (fanfold or accordion folding) and connected to each other by pressure, heat, bonding or the like. By the number of segments 244 thus connected, the capacity of such a structure can be determined.
  • the layer structure alternating in the feed direction can, for example, but not only, be controlled by pulsed activation of several
  • Fig. 16 shows a portion of an electrode tape 250 as a preferred modification of the alternative embodiment shown in Fig. 15 in a plan view, and Fig. 17 illustrates an effect of this arrangement.
  • segments 254 of constant length s are formed in the electrode belt 250 by transverse trenches 252.
  • the measure of a gap ti, t 2 , t, (length of the transverse trenches 252) between segments 254 changes as the feed x progresses.
  • FIG. 17 shows a preferred application of the configuration shown in FIG.
  • two electrode belts 250-1, 250-2 are wound on a flat winding core 256 to form the active part of a galvanic cell.
  • the electrode bands 250-1, 250-2 may be connected to a finished strip.
  • the detailed depiction of the layer structure was omitted in the figure; he is on the
  • Reverse sections of a roll produced in this way can be separated, for example, at parting lines 258 in order to obtain a parallelepiped-shaped film stack. (Separation at parting lines 258 is advantageous if the
  • Carrier film tapes of the electrode strips 250-1, 250-2 have a collector material, as they would otherwise touch and contact in the area of the reversing sections. On the other hand, if the carrier film tapes are nonconductive, the turnarounds may also remain.
  • a similar effect as shown in Fig. 17 can also be achieved if the transverse trenches each have equal lengths t in that the finished strip or electrode strip is stretched during the winding at the transverse trenches in accordance with a growing thickness of the coil. Stretching can be supported, for example, but not only, by heating.
  • injection units 28 can be combined in a single housing.
  • injection units 28 can be divided to the front and back of the strip and / or first several or all layers of the front side of the semifinished product 34 applied successively and then several or all layers of the back of the semifinished product 34 are applied successively.
  • the supply of plant components, apparatus and components takes place in varying degrees of centralization or decentralization.
  • calendering of the semifinished product can take place after each injection step or can be provided at selected points in the process sequence. There may be intercooling or intermediate heating be provided the slides.
  • the spray rolls (wet rolls) can be cooled or heated.
  • Layers are applied to one of the front or back of the backing sheet, all or only selected layers are dried immediately after application, and then some or all of the layers are applied to the other of the front and back, all or only selected layers be dried immediately after application. In preferred developments is between
  • a winding core on which an electrode strip or finished strip is wound in order to form an active part of a galvanic cell can be produced from a good heat conductor.
  • a method according to the invention for producing a multi-layered, preferably in the direction of symmetry, electrode structure, in particular for a galvanic cell advantageously has a step of forming at least two layers of the electrode structure on one another by thermal spraying or deposition.
  • the invention is also directed to an electrode assembly produced by the method described, to a galvanic cell having such an electrode assembly, and to an apparatus for carrying out the method. Described above
  • Plasma or other spray guns, series or other arrangements thereof, as well as all equipment parts and apparatuses containing them, such as coating and laminating lines or the like, can be used as thermal spraying or depositing arrangements in the sense of
  • Carrier film strips, intermediates and semi-finished products can be understood as a carrier substrate in the context of the invention.
  • Electrode strips, finished strips, film stacks or intermediate products can be understood as an electrode structure in the sense of the invention. Coils can be understood as roles within the meaning of the invention. Trenches (longitudinal and transverse trenches) can be understood as separation areas in the sense of the invention.
  • Ceramic layers or electrodes of all kinds for ionic batteries are produced by thermal spraying. These ceramic layers such as Separion can be deposited on the electrodes or separately as a separator, such as in a multilayer or
  • the method advantageously takes advantage of the fact that the materials are produced in a melted or doughy state, by paste extrusion or doughed by means of ionic liquids.
  • Layers are applied to existing substrates such as collector foil material or polyimide foils as substrate carriers. In this case, preferably a minimum thermal influence of the materials themselves. Layer thicknesses are in the range of 10 to 150 ⁇ .
  • the preferred method is carried out according to a particular embodiment as a plasma spraying of air such that preconditioned or dried air is removed from a dry room for this plasma spraying process. Thus, moisture ranges are reached, which are in the range of an absolute dew point from -60 to -100. This can also be avoided that arise micro inclusions in the materials or
  • Moisture traces between layers are formed or remain.
  • a special inert atmosphere can be produced, which can optionally be supported by negative pressure.
  • the dense layers and the adhesive strength can be adjusted defused in the process by material or according to the
  • particular conductivity additives are added in their own injection stages or together with other additives.
  • These are conductivity additives such as nano-Si or MgO, their magnesium oxide, aluminum oxide, carbon black, nanotubes or ionic liquids. These can also be used to absorb additional water, contribute to the stability of the layer, contain the ionic conductivity component lithium-ion or promote the later interpretation of ionic electrochemical systems or allow.
  • the method is preferably used for double-sided coating, but it is also applicable in a further preferred modification for one-sided coating.
  • the subject is run on plates or the like, with a preferred arrangement in the area in the sense of drying is preferred.
  • the layers are optionally recalendered directly after the thermal spraying. Thereafter, the electrodes may be processed into either wound, stacked, prismatic wound cells, and the like.
  • Substrate films, the copper or aluminum foils (in general the collector foils) or the absorption of moisture, which can settle between the layers and then later affect the quality of the electrical determinant significance can be excluded by the described method also completely or at least partially , In that regard, the production process is supported, especially the time-critical shift is slowing down.
  • a preferred embodiment is to previously deposit, shave or carbon nanotubes or the like on the substrate
  • the invention has been described in terms of a preferred example of an electrode assembly for a lithium-ion cell, the invention is in all its forms on electrode foils and all types of galvanic cells, in which a multilayer electrode structure is required or advantageous, applicable.
  • Separion is a registered trademark of Evonik Litarion GmbH.
  • 169 (169-1, 169-2) discharge lance (cathode side, anode side)
  • 250 250-1, 250-2 electrode band (cathode, anode side)

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Abstract

L'invention concerne un procédé pour fabriquer une structure d'électrode multicouche, de préférence une structure d'électrode symétrique dans le sens de l'empilage, notamment pour une cellule galvanique. Le procédé selon l'invention présente une étape de formation d'au moins deux couches de la structure d'électrode les unes sur les autres par pulvérisation thermique ou précipitation. L'invention concerne également une structure d'électrode fabriquée au moyen du procédé décrit, une cellule galvanique qui présente une telle structure d'électrode et un dispositif pour mettre en œuvre le procédé.
PCT/EP2011/003308 2010-07-29 2011-07-04 Procédé et dispositif pour fabriquer une structure d'électrode multicouche, cellule galvanique WO2012013286A1 (fr)

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DE102010032770A DE102010032770A1 (de) 2010-07-29 2010-07-29 Verfahren und Vorrichtung zur Herstellung eines mehrschichtigen Elektrodenaufbaus, galvanische Zelle

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CN112534606A (zh) * 2020-03-12 2021-03-19 宁德新能源科技有限公司 电极组件和电池
CN113013381A (zh) * 2019-12-20 2021-06-22 英特赛尔股份有限公司 用于制造锂离子电池组的电极的方法和设备
US11621411B2 (en) 2019-12-23 2023-04-04 Intecells, Inc. Method of insulating lithium ion electrochemical cell components with metal oxide coatings
CN115896703A (zh) * 2022-11-07 2023-04-04 江阴纳力新材料科技有限公司 一种用于多层结构集流体的生产装置及生产方法

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DE102012213111B4 (de) * 2012-07-26 2016-04-14 Leichtbau-Zentrum Sachsen Gmbh Verfahren und Anordnung zur effizienten Herstellung von Folienstapeln zur Bildung einer Lithium-Ionen-Batteriezelle
DE102012112954A1 (de) * 2012-12-21 2014-06-26 Dritte Patentportfolio Beteiligungsgesellschaft Mbh & Co.Kg Verfahren zur Herstellung einer Anodenbeschichtung
WO2017202444A1 (fr) * 2016-05-23 2017-11-30 Applied Materials, Inc. Procédé de fabrication d'une batterie, appareil de traitement sous vide et batterie
DE102016225221A1 (de) * 2016-12-16 2018-06-21 Robert Bosch Gmbh Verfahren zur Herstellung eines Elektrodenstapels für eine Batteriezelle und Batteriezelle
DE102017118320A1 (de) * 2017-08-11 2019-02-14 Friedrich-Alexander-Universität Erlangen Verfahren zur Herstellung von Bauteilen sowie danach hergestellte Bauteile
EP4016664A1 (fr) 2020-12-17 2022-06-22 VARTA Microbattery GmbH Dispositif et procédé de compression d'une matière d'électrode appliqué à une bande collectrice
DE102022122308A1 (de) 2022-09-02 2024-03-07 Bayerische Motoren Werke Aktiengesellschaft Elektrode für eine elektrochemische Speicherzelle, Elektrochemische Speicherzelle und Verfahren zum Herstellen einer Elektrode

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CN115896703A (zh) * 2022-11-07 2023-04-04 江阴纳力新材料科技有限公司 一种用于多层结构集流体的生产装置及生产方法
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