EP3900077A1 - Unité cathodique et procédé pour la fabrication d'une unité cathodique - Google Patents

Unité cathodique et procédé pour la fabrication d'une unité cathodique

Info

Publication number
EP3900077A1
EP3900077A1 EP19829091.8A EP19829091A EP3900077A1 EP 3900077 A1 EP3900077 A1 EP 3900077A1 EP 19829091 A EP19829091 A EP 19829091A EP 3900077 A1 EP3900077 A1 EP 3900077A1
Authority
EP
European Patent Office
Prior art keywords
sis
polytetrafluoroethylene
cathode unit
percent
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19829091.8A
Other languages
German (de)
English (en)
Inventor
Felix HIPPAUF
Benjamin SCHUMM
Sebastian TSCHÖCKE
Holger Althues
Stefan Kaskel
Susanne DÖRFLER
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Technische Universitaet Dresden
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Technische Universitaet Dresden
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV, Technische Universitaet Dresden filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP3900077A1 publication Critical patent/EP3900077A1/fr
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a cathode unit and a method for producing a cathode unit.
  • Solid-state batteries represent a promising further development of lithium-ion batteries.
  • Solid-state batteries use a solid-state lithium ion conductor (or sodium ion conductor) as the electrolyte instead of a liquid electrolyte system. This also serves as an ion conductor between active material particles and as an ion-conductive separator between anode and cathode. What is important here is the possibility of large-scale processing of powdered electrode mixtures and the formation of an intimate contact area between solid electrolyte and active materials with as many contact points and as few cavities as possible.
  • Solid-state batteries can be used, among other things, based on the Categorize the electrolyte class (oxidic, sulfidic and polymer-based).
  • Oxide solid electrolytes have a high chemical and mechanical stability. Processing into non-porous and thin electrodes or solid electrolyte membranes, however, is a great challenge due to the high sintering temperatures. Sulfidic electrolyte materials can hardly be separated over a large area.
  • various binder-solvent mixtures for the anode, cathode and electrolyte layer are used, since otherwise the layer underneath may dissolve when the layer is applied.
  • a disadvantage of such processes is the comparatively high binder content of several percent by weight or mass and the resulting higher electrical and ionic resistances.
  • the present invention is therefore based on the object of proposing a cathode unit and a method for its production which overcomes the disadvantages mentioned ge, that is to say a large-scale production of the cathode unit with the lowest possible electrical and ionic resistances.
  • a cathode unit for a solid-state battery preferably an alkaline solid-state battery or lithium battery or sodium battery, has a layer made of a composite material.
  • the composite material has an electrode material, a solid electrolyte material, an electrically conductive conductive additive and polytetrafluoroethylene (PTFE) as a binder.
  • PTFE polytetrafluoroethylene
  • the composite material has less than 1 percent by weight of polytetrafluoroethylene and the polytetrafluoroethylene is at least partially present as a fibrillated polytetrafluoroethylene.
  • fibrillated polytetrafluoroethylene as a binder, the use of binders can be reduced, so that only small amounts are left less than 1 percent by weight of polytetrafluoroethylene of the cathode unit are necessary and therefore the electrical properties are improved.
  • the composite material is typically solvent-free to enable easier processing, application and formation of a free-standing film.
  • the cathode unit can have a current collector made of an electrically conductive material, to which the layer made of a composite material is applied.
  • electrically conductive is to be understood here to mean any material which has an electrical conductivity of more than 10 5 S / m at room temperature, ie 25 ° C.
  • the layer made of a composite material can also be electrically conductive by selecting a proportion of the conductive additive, which is typically also electrically conductive, to be correspondingly high.
  • polytetrafluoroethylene is present in the composite material as at least partially monoaxial and / or biaxially oriented poly tetrafluoroethylene in order to adjust the mechanical properties as desired.
  • the polytetrafluoroethylene is present in the composite material as at least partially monoaxial and / or biaxially oriented poly tetrafluoroethylene in order to adjust the mechanical properties as desired.
  • the polytetrafluoroethylene is present in the composite material as at least partially monoaxial and / or biaxially oriented poly tetrafluoroethylene in order to adjust the mechanical properties as desired.
  • the polytetrafluoroethylene is present in the composite material as at least partially monoaxial and / or biaxially oriented poly tetrafluoroethylene in order to adjust the mechanical properties as desired.
  • Polytetrafluoroethylene is present as completely monoaxial or completely biaxially oriented or aligned polytetrafluoroethylene.
  • the composite material can have the electrode material in an amount of 60 percent by weight to 99 percent by weight, preferably up to 100 percent.
  • the composite material typically has at least
  • the composite material preferably has less than 0.5 percent by weight of polytetrafluoroethylene, particularly preferably between 0.1 percent by weight and 0.4 percent by weight.
  • the electrode material can be sulfur, lithium sulfide (Li 2 S)
  • a transition metal oxide preferably LiCo0 2 , LiNi0 2 , LiNii_ x Co x 0 2 , LiFeP0 4 , LiMn0 2 , LiMn 2 0 4 , Li 2 Mn 3 Ni0 8 , LiNi x Co y Mn z 0 2 , LiNi x Co y Al z 0
  • corresponding sodium-containing analogs preferably Na 2 S, Na x Mn0 2 , Na 3 V 2 (P0 4 ) 3 , NaFeP0 4 , Na 2 FeP0 4 F, NaNiMn0 2 , Na 2 Ti0 7 and / or NaTi 2 (P0 4 ) 3 can be used.
  • the different materials mentioned can also generally be combined with one another to form the electrode.
  • the solid electrolyte material is typically in the powder mixture with between 1 percent by weight and 35 percent by weight.
  • Carbon nanotubes, carbon blacks, graphite, graphene and / or carbon nanofibers with between 1% by weight and up to
  • the solid electrolyte material is typically an electrochemically active material.
  • the leading additive can be an electrochemically inactive material.
  • the electrode material can have a protective layer which is applied to particles of this material. This protective layer is intended to prevent side reactions between the solid electrolyte material and the electrode material.
  • the protective layer can have, for example, Li 2 O-ZrO 2 or other metal oxides.
  • Each particle of the electrode material can have a protective layer with a thickness of typically 2-5 nm.
  • the electrically conductive current conductor typically comprises an electrically conductive material, preferably aluminum, or is made entirely of this material.
  • the current conductor can be designed as a, in particular flat, current conductor layer or current conductor film with a preferably double-sided coating, as expanded metal, as foam, as a fiber fabric, as a fiber fabric or as a current conductor layer provided with a primer layer.
  • the primer layer can also be flat.
  • Polytetrafluoroethylene produced as a binder The powder mixture here has a proportion of less than 1 percent by weight of polytetrafluoroethylene. At least partially fibrillated polytetrafluoroethylene is formed in the powder mixture by the action of shear forces on the powder mixture. The powder mixture is then formed into a flexible composite layer. Preferably, the flexible composite layer is applied to an electrically conductive current collector to form the cathode unit. Provision can also be made to subsequently compress the flexible composite layer and / or the current arrester.
  • a powder mixture which is to be understood as a material in granular form consisting of many small particles with a size of up to 15 pm or a granular or lumpy mixture or bulk material.
  • the powder mixture can be in dry form to simplify handling. In addition, the powder mixture cannot be free-flowing in the sense of the standard DIN EN ISO 6186.
  • dry is to be understood to mean that constituents of the powder mixture are in the form of solids free from liquids or materials that are in a liquid state of aggregation.
  • the powder mixture can be solvent-free, that is, it can be composed without solvent.
  • a "flexible composite layer” is to be understood as a composite layer which can be bent or folded and unfolded at room temperature by up to 180 ° without breaking. A bending radius is preferably 90 pm to 100 pm, particularly preferably 100 miti.
  • the at least partially fibrillated polytetrafluoroethylene can be formed by friction milling, mixing in a worm shaft or in a calender roll device, kneading device, mortar device or a combination of the methods mentioned in order to achieve efficient
  • the formation of the at least partially fibrillated polytetrafluoroethylene is typically carried out at room temperature, but preferably to achieve a binder content of less than 0.5 percent by weight, the formation at elevated temperatures of 60 ° C to 100 ° C, particularly preferably at 90 ° C to 100 ° C, especially at 100 ° C.
  • the polytetrafluoroethylene can also be completely fibrillated.
  • the forming of the powder mixture into the flexible composite layer is typically carried out by rolling, pressing or extrusion. However, a combination of the methods mentioned can also be used.
  • the application of the flexible composite layer to the electrically conductive current collector layer is typically carried out at temperatures between 60 ° C and 120 ° C, preferably 80 ° C to 100 ° C.
  • the described method can be used to produce the described cathode, i. H. the cathode described can be produced by the method described.
  • a solid-state battery or lithium battery according to the invention contains a cathode unit with the properties described.
  • Figure 1 is a schematic side view of a cathode. 2 shows a representation corresponding to FIG. 1, the cathode with a solid electrolyte membrane;
  • FIG. 3 shows a representation corresponding to FIG. 1, the cathode provided with the solid electrolyte membrane and an anode;
  • FIG. 1 shows a schematic lateral view of an electrically conductive current collector layer 1 made of aluminum as a substrate film or carrier film with a first electrode 2, which form a cathode unit.
  • the first electrode 2 is formed in the illustrated embodiment from a composite material in powder form.
  • the composite material has 85 percent by weight lithium-nickel-manganese cobalt (NCM), 13 percent by weight of a solid electrolyte material such as lithium U2S-P2S5,
  • the binder content here relates to the total mass at a ratio NCM: C: SE of 85: 2: 13 (SE is intended to indicate the solid electrolyte material as an abbreviation for "solid electrolyte”).
  • the composite material obtained is powdery, dry and solvent-free, but not free-flowing.
  • the composite material can be mixed in a mortar. Shear forces are exerted on the mixture or powder mixture forming the composite material, which cause fibril formation along the force vector.
  • the composite material is rolled out in a subsequent step on a plate with a roller to a desired layer thickness and laminated onto the carrier film 1.
  • the carrier film 1 has a thickness of less than 20 pm and is optionally provided with a carbon primer.
  • the cathode unit is finally assembled by punching or laser cutting.
  • the composite material can be added as a powder mixture or bulk material directly into a calender nip without solvent additives.
  • different rotation speeds of the two calender rolls are used, for example in a ratio of 10: 9 to 10: 4.
  • a shear force is exerted on the composite material in the gap, which causes fibrils to form along the direction of the roll.
  • the layer is laminated onto the substrate film 1 in a subsequent step and a final assembly takes place by punching or laser cutting.
  • the formation of a film in the calender nip also enables the layers involved to be compacted strongly during film formation. What is important here is coordinated particle size distributions of the powdery materials that are used for the composite material in order to fill gaps in the large particles with smaller ones as space-efficiently as possible and to keep porosity low.
  • the film therefore has a density of 1.7-1.9 g / cm 3 before pressing, which corresponds to a porosity of 50 to 55 percent. After pressing or compacting, the density is usually 3.5 g / cm 3 and the porosity approaches a value of up to 10 percent of the ideal value of 0 percent porosity.
  • the cathode unit obtained in this way thus has the layer sequence of substrate film 1 - first electrode 2.
  • the composition of the first electrode 2 is typically as follows: cathode active material: 60 to 99 percent by weight, solid electrolyte material 13 to 35 percent by weight, lead additive 2 to 5 percent by weight, the Binder (polytetrafluoroethylene) accounts for 0.1 to 1 percent by weight of the total mass.
  • the pressing mentioned above is typically carried out as a process step.
  • All processing steps in which the solid electrolyte material is involved preferably take place under protective gas, for example an inert gas, preferably argon, or nitrogen, or dry air with a dew point below -50 ° C.
  • protective gas for example an inert gas, preferably argon, or nitrogen, or dry air with a dew point below -50 ° C.
  • FIG. 2 the view corresponding to FIG. 1 shows the cathode unit comprising the carrier film 1 and the first electrode 2, a solid electrolyte membrane 3 now being in direct contact, that is to say in direct contact, on one side or surface of the first electrode 2 on which the Carrier film 1 is attached as a current conductor layer in direct contact, the opposite side or surface is arranged. While the carrier film 1 and the first electrode 2 lie flush one above the other, that is to say they have identical dimensions except for their respective thickness, the solid electrolyte membrane 3 is wider than the first electrode 2. Recurring features in this figure and in the following figures have identical reference numerals Mistake.
  • FIG. 3 shows in a view corresponding to FIGS. 1 and 2 a solid-state battery in which an anode unit is placed on the side opposite the solid electrolyte membrane 3 to the structure shown in FIG. 2.
  • the anode unit is formed from a second electrode 4 and a second substrate film 5 as a second current collector layer, which in turn are in direct contact with one another.
  • the second electrode 4 is in direct contact with the solid electrolyte membrane 3.
  • the solid electrolyte membrane ran 3 the second electrode 4 and the second carrier film 5 are aligned with one another, the second carrier film 5 having the smallest thickness, the second electrode 4 having the greatest thickness and the thickness of the solid electrolyte membrane 3 between the thickness of the second electrode 4 and the second carrier film 5.
  • the first electrode can have a thickness of 100 pm
  • the second electrode as a lithium anode, for example, up to 10 pm.
  • the thicknesses of the first carrier film 1 and the second carrier film 5 can also be identical.
  • the thickness of the first electrode 2 is greater than the thickness of the solid electrolyte membrane 3, which in turn has a greater thickness than the first carrier film 1.
  • FIG. 4 shows a scanning electron microscope image (SEM image) of a dry film made of NCM, solid electrolyte (SE), carbon fibers (CNF) in a mass ratio of 85: 13: 2 and 0.3 percent by weight of the total mass of polytetrafluoroethylene (PTFE).
  • SEM image scanning electron microscope image
  • SE solid electrolyte
  • CNF carbon fibers
  • FIGS. 5 to 9 each show discharge voltage profiles of test cells of the solid-state battery described. An electrical voltage is plotted against the capacitance.
  • the proportion of polytetrafluoroethylene in FIG. 5 is 0 percent by weight, in FIG. 6 0.1 percent by weight, in FIG. 7 0.3 percent by weight, in FIG. 8 0.7 percent by weight and in FIG. 10 1 percent by weight.
  • FIG. 10 shows an impedance measurement in a Nyquist diagram, in which an imaginary part is plotted over a real part.
  • the measurement curves show a test cell with a binder content of 0.1 percent by weight

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

La présente invention concerne une unité cathodique pour une batterie à électrolyte solide et un procédé pour la fabrication de l'unité cathodique. L'unité cathodique présente une couche en un matériau composite (2), qui présente un matériau d'électrode, un matériau d'électrolyte solide, un additif électriquement conducteur et du polytétrafluoroéthylène comme liant. Le matériau composite présente moins de 1 % en poids de polytétrafluoroéthylène et le polytétrafluoroéthylène se trouve au moins en partie sous forme de polytétrafluoroéthylène en forme de fibrilles.
EP19829091.8A 2018-12-18 2019-12-17 Unité cathodique et procédé pour la fabrication d'une unité cathodique Pending EP3900077A1 (fr)

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DE102018222129.4A DE102018222129A1 (de) 2018-12-18 2018-12-18 Kathodeneinheit und Verfahren zum Herstellen einer Kathodeneinheit
PCT/EP2019/085581 WO2020127215A1 (fr) 2018-12-18 2019-12-17 Unité cathodique et procédé pour la fabrication d'une unité cathodique

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EP (1) EP3900077A1 (fr)
JP (1) JP2022514855A (fr)
KR (1) KR20210114416A (fr)
CN (1) CN113424334A (fr)
DE (1) DE102018222129A1 (fr)
WO (1) WO2020127215A1 (fr)

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US20220029166A1 (en) 2022-01-27
KR20210114416A (ko) 2021-09-23
JP2022514855A (ja) 2022-02-16
CN113424334A (zh) 2021-09-21
DE102018222129A1 (de) 2020-06-18
WO2020127215A1 (fr) 2020-06-25

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