EP3942623A1 - Arrangement d'électrolyte multicouche pour batteries au lithium - Google Patents

Arrangement d'électrolyte multicouche pour batteries au lithium

Info

Publication number
EP3942623A1
EP3942623A1 EP20712911.5A EP20712911A EP3942623A1 EP 3942623 A1 EP3942623 A1 EP 3942623A1 EP 20712911 A EP20712911 A EP 20712911A EP 3942623 A1 EP3942623 A1 EP 3942623A1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
polymer
layer
lithium
ceramic material
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
EP20712911.5A
Other languages
German (de)
English (en)
Inventor
Mengyi ZHANG
Peter Bieker
Lei GUI
Martin Winter
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.)
Westfaelische Wilhelms Universitaet Muenster
Original Assignee
Westfaelische Wilhelms Universitaet Muenster
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 Westfaelische Wilhelms Universitaet Muenster filed Critical Westfaelische Wilhelms Universitaet Muenster
Publication of EP3942623A1 publication Critical patent/EP3942623A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • 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
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M50/449—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
    • H01M50/457—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
    • 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
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01G11/54—Electrolytes
    • 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
    • H01M2300/0048—Molten electrolytes used at high temperature
    • H01M2300/0051—Carbonates
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a polymer-based electrolyte for an electrochemical cell and an energy store containing it, in particular those with an anode
  • Lithium metal or lithium alloys Lithium metal or lithium alloys.
  • Promising electrode material and lithium-air batteries offer the advantage of a significantly higher specific capacity and energy compared to conventional lithium-ion batteries.
  • solid-state accumulators in which the electrolyte is a solid polymer electrolyte or a glass-ceramic material, the ion flow comes about through the movement of the ions of the conductive salt through the polymer or the glass ceramic.
  • the solid electrolyte here also serves as a separator.
  • DE 10 2012 107 848 A1 describes, for example, a multilayer separator comprising at least two individual layers lying on top of one another, at least one individual layer having a structure with a large number of contiguous pores for
  • a separator-anode composite can have a three-layer separator, the second individual layer also being formed from a porous material, the first individual layer being a polyolefin separator, the second individual layer being a polypropylene network and the third layer being a polypropylene network
  • Void volume is completely filled with lithium metal.
  • the anode material is rolled in here, for example.
  • this composite arrangement is not suitable for preventing dendrite growth through the separator.
  • US 2016/0056437 A1 describes an anode with an integrated two-layer separator for a lithium-ion battery, the two-layer separator being a porous one Comprises layer of separator particles and a porous polymer layer. To transport lithium ions, the separator is soaked with a liquid electrolyte. The rigid ceramic layer serves to suppress the dendrite growth through the separator. The bond between the ceramic separator layer and the anode must, however, be established by means of an additional thin polymer layer.
  • WO 2016/077663 A1 describes a composite separator and electrolyte. This comprises at least one electrolyte film in contact with a porous, self-supporting separator film, it being possible for the electrolyte film to contain a lithium salt and a polymer complexing agent such as PEO.
  • the separator can be dry or soaked in a liquid
  • Electrolyte composition can be used.
  • the porous, self-supporting separator film can have an electrolyte film on both sides.
  • the arrangement is very flexible, but piercing of the composite separator by lithium dendrites cannot be prevented. Furthermore, it is not disclosed whether cells containing the composite separator and electrolyte are rechargeable.
  • One object of the invention was therefore to provide an electrolyte arrangement with improved performance and safety.
  • the material of the polymer-based electrolyte layer (s) is a metal-ion-conductive ceramic material.
  • the electrolyte arrangement according to the invention can provide a reduction in the interface resistance between the electrolyte and the electrode, an improved thermal stability and also an increased cycle stability.
  • the ceramic material can prevent the electrolyte from shrinking, while at the same time improving the connection to the electrodes. This can significantly increase the safety as well as the cyclical life of a cell.
  • the electrolyte arrangement can prevent lithium dendrites, which arise during the cycling of a lithium battery, from piercing the electrolyte, which also functions as a separator in a solid cell, and causing a short circuit.
  • the electrolyte arrangement with high-voltage cathode materials and high cell voltages of up to 4.85 V was stable.
  • the electrolyte arrangement comprises at least three layers lying on top of one another.
  • the middle layer here comprises a porous, electrically non-conductive structure.
  • the pores of the porous structure can accommodate a polymer electrolyte.
  • Such a structure can be formed by a porous, electrically non-conductive membrane, for example a ceramic or polymer separator.
  • An advantage of the porous, electrically non-conductive membrane is that the mechanical properties of the electrolyte arrangement are improved. In this way, the layer thickness of the individual electrolyte layers and thus the total thickness of the electrolyte arrangement can be controlled. Furthermore, this enables a simple manufacturing process for the arrangement, since the polymer electrolytes can be applied to a mechanically stable middle layer.
  • At least one of the superposed layers of the electrolyte arrangement contains a ceramic material.
  • the ceramic material supports the stability of the arrangement. In this can advantageously significantly reduce what is known as thermal shrinkage of the electrolyte arrangement when the temperature rises during operation of a cell.
  • the ceramic material can be contained in the middle layer or in at least one of the polymer-based electrolyte layers. In embodiments in which the ceramic material is contained in the middle layer, this can be selected from a metal ion-conductive ceramic material, a ceramic material that does not conduct metal ions, and / or mixtures thereof.
  • the metal-ion-conductive ceramic material is in particular a lithium-ion-conductive ceramic material.
  • the ceramic material is contained in at least one of the polymer-based electrolyte layers, the ceramic material is a metal-ion-conductive, in particular a lithium-ion-conductive ceramic material.
  • the porous, electrically non-conductive structure of the middle layer can consist of a
  • the middle layer can contain a ceramic membrane such as an Al 2 O 3 membrane, which is surrounded on both opposite sides by a polymer electrolyte without a ceramic material, or at least one of the polymer-based electrolyte layers can contain a lithium ion-conductive ceramic material.
  • the middle layer can contain a polymer membrane, for example a polypropylene membrane, wherein in these embodiments at least one of the polymer-based electrolyte layers contains a lithium-ion-conductive ceramic material. In a preferred embodiment of the electrolyte arrangement is on both
  • the term “membrane” is generally understood to mean a thin layer.
  • Under a "porous" membrane is a membrane with a Understood pore structure.
  • the porosity represents the ratio of the void volume to the total volume of the membrane.
  • the porosity or the void fraction is preferably in the range from 3 30% by volume to 60% by volume, based on the total volume of the membrane.
  • Microporous membranes are preferred.
  • the pore size can range from 3 0.02 mm to £ 2 in.
  • An “electrically non-conductive” membrane is understood to mean that the electrical conductivity at 20 ° C. is less than 10 -7 ⁇ S cm -1 , so that an electrical separation of the electrodes is achieved and a short circuit is avoided. can.
  • the membrane can be formed from a polymer or a ceramic material or a composite material of polymer and ceramic.
  • Suitable polymers are, for example, selected from the group comprising polyolefins such as polypropylene or polyethylene, poly (vinylidene difluoride-co-hexafluoropropylene) (PVdF-HFP), polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), polyimide (PI), carboxymethyl cellulose (CMC) and / or polytetrafluoroethylene (PTFE) and / or their mixtures and copolymers.
  • the ceramic material of the middle layer can be selected from metal ion conductive
  • a metal-ion-conductive ceramic material is in particular a lithium-ion-conductive glass-ceramic material.
  • Metal ions that do not conduct can be selected from Al 2 O 3 , SiO 2 and / or mixtures thereof.
  • Polypropylene, polyethylene and combined polypropylene-polyethylene membranes are available from Celgard LLC, for example Celgard® 2500.
  • Ceramic Al 2 O 3 membranes are available for example under the name Separion®. Also
  • Polymer fleeces can be used as a porous, electrically non-conductive membrane.
  • a dispersion of the polymer is usually applied to the membrane and dried. It is assumed that the electrolyte dispersion during the
  • the pore diameter of the porous membrane is smaller than the particle diameter of the ceramic particles in the electrolyte dispersion, so that when using a polymer-based electrolyte containing particles of a ceramic material preferably only the proportion of polymer electrolyte comprising polymer, metal salt, and optionally plasticizers and / or crosslinkers and solvents, penetrates into the pores of the porous membrane.
  • a polymer-based electrolyte containing particles of a ceramic material preferably only the proportion of polymer electrolyte comprising polymer, metal salt, and optionally plasticizers and / or crosslinkers and solvents, penetrates into the pores of the porous membrane.
  • in the range from 3 50% by volume to £ 100% by volume preferably in the range from 3 70% by volume to £ 100% by volume, preferably in the range from 3 80% by volume.
  • the thickness of the porous, electrically non-conductive membrane can range from 3 5 mm to £ 50 mm.
  • the total thickness of the electrolyte arrangement is in the range from 3 5 mm to £ 300 mm, preferably in the range from 3 10 mm to £ 200 mm, preferably in the range from 3 15 mm to £ 100 mm.
  • the electrolyte / separator is as thin as possible.
  • a thickness of less than 200 mm or 100 mm allows the electrolyte arrangement to be easily bendable.
  • the layer thickness of the polymer electrolyte layer without lithium ion-conductive ceramic can be less than the layer thickness of the polymer-based electrolyte layer which contains a ceramic material, and can be in the range from 3 0.01 mm to £ 20 mm.
  • the layer thickness of the polymer-based electrolyte layer, which contains a glass-ceramic material, can be in the range from 0.1 mm to 50 mm.
  • polymer electrolyte or “polymer electrolyte” refers to solutions of salts in polymers such as polyethylene oxide (PEO).
  • PEO polyethylene oxide
  • the salts like lithium salts take care of the charge transport by moving the lithium ions through the layer.
  • the use of polymer electrolytes in rechargeable lithium batteries generally allows an improvement with regard to the safety aspect, as well as a simplification of cell production.
  • many other polymers such as polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride or polyvinylidene fluoride are described in the literature as a polymer matrix for gel electrolytes. The manufacture of polymer-based
  • Electrolyte layers can be created by pouring films (casting). Alternatively, polymer electrolyte layers can be produced by crosslinking polymerization of suitable monomers in the presence of plasticizers and conducting salt.
  • polymer-based electrolyte denotes a polymer electrolyte which can furthermore contain a ceramic material.
  • the polymer-based electrolyte layer (s) comprise a polymer selected from the group comprising polyethylene oxide (PEO), polyethylene glycol,
  • MEEP bis ((methoxyethoxy) ethoxy) phosphazene
  • PPO polypropylene oxide
  • Siloxane with an average molecular weight of 300 g / mol to 10,000 g / mol
  • polyolefins polyolefins
  • polypropylene or polyethylene poly (vinylidenedifluoride-co-hexafluoropropylene) (PVdF-HFP), polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), polyimide (PI), carboxymethyl cellulose (CMC) and / or polytetrafluoroethylene (PTFE) and / or mixtures thereof and copolymers.
  • PVdF-HFP polyethylene terephthalate
  • PVdF polyvinylidene fluoride
  • PI carboxymethyl cellulose
  • PTFE polytetrafluoroethylene
  • mixtures can have different proportions depending on the polymers used. For example, mixtures comprising polyethylene oxide (PEO) and polypropylene carbonate (PPC) are preferred.
  • a preferred polymer is polyethylene oxide (PEO).
  • PEO can dissolve lithium salts well.
  • the polymer-based electrolyte also has at least one metal salt or conductive salt.
  • the metal salt is preferably an organic or inorganic salt of lithium, sodium, magnesium, aluminum or zinc. Lithium salts are preferred. Basically are
  • Lithium salts suitable which can be dissolved in a polymer dispersion. Suitable
  • Lithium salts are selected, for example, from the group comprising LiAsF 6 , LiCIO 4 , LiSbF 6 , LiPtCl 6 , LiAlCl 4 , LiGaCl 4 , LiSCN, LiAIO 4 , LiCF 3 CF 2 SO 3 , Li (CF 3 ) SO 3 (LiTf), LiC (SO 2 CF 3 ) 3 , LiPF 6 , LiPF 3 (CF 3 ) 3 (LiFAP) and LiPF 4 (C 2 O 4 ) (LiTFOB), LiBF 4 , lithium bis (oxalato) borate (LiB (C 2 O 4 ) 2 , LiBOB), LiBF 2 (C 2 O 4 ) (LiDFOB), LiB (C 2 O 4 ) (C 3 O 4 ) (LiMOB), Li (C 2 F 5 BF 3 ) (LiFAB) and Li 2 B 12 F 12 (LiDFB) and / or lithium salts of
  • Sulfonylimides preferably lithium bis (fluorosulfonyl) imide (LiN (FSO 2 ) 2 , LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiN (SO 2 CF 3 ) 2 , LiTFSI) and / or LiN (SO 2 C 2 F 5 ) 2 (LiBETI).
  • Preferred lithium salts are those which do not decompose at elevated temperatures of, for example, 100.degree. C. or 120.degree.
  • the lithium salt is selected from the group comprising lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), LiClO 4 , LiBF 4 , LiPF 6 and lithium bis (oxalato) borate.
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • LiFSI lithium bis (fluorosulfonyl) imide
  • LiClO 4 LiBF 4
  • LiPF 6 lithium bis (oxalato) borate
  • the polymer-based electrolyte or comprise at least one polymer and metal salt as well as optionally plasticizers and / or crosslinkers.
  • the polymer-based electrolyte or electrolytes contain at least polymer and metal salt, in particular a lithium salt.
  • Plasticizers and / or crosslinkers can also be present. Plasticizers and crosslinkers can reduce the crystallization of the polymers.
  • Preferred plasticizers are organic solvents and ionic liquids.
  • Suitable organic solvents are, for example, selected from the group comprising
  • EC Ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • chloroform chloroform
  • DMC dimethyl carbonate
  • PYR 1A TFSI bis (trifluoromethanesulfonyl) imide
  • a preferred crosslinker is, for example, benzophenone. Benzophenone has proven to be particularly suitable for improving the mechanical stability of the electrolyte layers.
  • the polymer-based electrolytes comprise or comprise a polymer, a lithium salt and optionally plasticizers and / or crosslinkers, wherein the The molar ratio of polymer to lithium salt to plasticizer and to crosslinker is in the range of 3 0.5 to £ 20 to 1 to 3 0 to £ 10 to 3 0 to £ 1.
  • the molar ratio of polymer to lithium salt to plasticizer and to crosslinker can be 10: 1: 2: 0.121.
  • the term “molar ratio”, which is also referred to as “molar ratio”, is to be understood in the context of the present invention as the ratio of the amount of substance of one component to the amount of substance of the other components.
  • the molar ratio is based on the starting materials that are used to produce the polymer layer.
  • the lithium salt is used here as a reference to 1.
  • the polymer for example
  • Polyethylene oxide is used for the molar ratio based on the monomer or
  • Electrolyte layers which have been produced in accordance with this molar ratio show in particular good mechanical stability and ionic stability
  • One or both of the polymer-based electrolyte layers on the opposite sides of the porous, electrically non-conductive membrane can contain a ceramic material.
  • a layer containing lithium-ion-conducting ceramic supports the stability of the arrangement, so that this does not or at least significantly less
  • the ceramic contained can further prevent lithium dendrites from penetrating through the electrolyte layer and leading to a short circuit.
  • the lithium ion-conductive ceramic is preferably contained in the layer in the form of small particles, whereby sufficient flexibility of the layer can furthermore be provided.
  • Preferred lithium ion-conducting ceramics are glass ceramics with lithium compounds that have a structure similar to NASICON (sodium super ionic conductor) or a garnet-like structure of the crystal phase.
  • glass-ceramic material is to be understood as meaning a material which, starting from a starting glass produced using melting technology, is transformed into a glass-ceramic by temperature treatment Glass phase and a crystal phase is converted.
  • the glass ceramic can be produced by ceramizing from a starting glass or by ceramizing and sintering and / or pressing starting glass powder.
  • Such a glass ceramic has a conductivity for metal ions, in particular for lithium ions.
  • Corresponding glass ceramics are known to the Lachmann and are commercially available. In embodiments, the
  • Lithium-ion-conducting glass-ceramic a lithium-ion-conducting crystal phase, which is a NASICON-like phosphate glass-ceramic with the empirical formula Li 1 + X (Al, Ge) x (PO 4 ) 3 , where 0 £ x ⁇ 1 and (1 + x)> 1, a lithium compound with a garnet-like structure such as LLZO with various dopings or solid lithium sulfides such as Li 10 GeP 2 S 12 .
  • a preferred NASICON-like phosphate glass ceramic is, for example, lithium aluminum germanium phosphate (LAGP).
  • Lithium lanthanum zirconate (LLZO), Li 7 La 3 Zr 2 O 12 with or without doping of aluminum, niobium and / or have also proven to be particularly suitable
  • Proven tantalum oxide Proven tantalum oxide.
  • the lithium ion conductivity of such glass ceramics can be in a range from 3 10 -4 S / cm to £ 10 -2 S / cm at 20 ° C.
  • the proportion of ceramic material in the polymer-based electrolyte layer is in the range from 3 5% by weight to £ 80% by weight, preferably in the range from 3 35% by weight to £ 65% by weight, based on based on a total weight of the polymer-based electrolyte layer of 100% by weight.
  • the electrolyte arrangements show good mechanical stability and good lithium-ion conductivity.
  • the further components of a polymer-based electrolyte layer which contains a lithium ion-conductive ceramic can be the same or different in relation to the further polymer-based electrolyte layer. It is preferred that the components of the polymer-based electrolyte layers such as polymer, metal salt and optionally plasticizer and / or crosslinker, optionally with the exception of the ceramic, are the same. This makes it possible to provide a good bond and uniform ion conduction over the entire arrangement. Furthermore, an electrolyte layer that contains a lithium ion Conductive ceramic by simply dispersing the ceramic in the electrolyte composition used for the other side.
  • a polymer-based electrolyte layer containing a lithium ion-conductive ceramic preferably comprises:
  • polysiloxane with an average molecular weight of 300 g / mol to 10,000 g / mol, polyolefins, in particular polypropylene or polyethylene, PVdF-HFP, polyimide, PET , PVdF, CMC and / or PTFE and / or their mixtures and copolymers; and or
  • At least one metal salt preferably an organic or inorganic salt of lithium, sodium, magnesium or zinc; such as
  • the polymer-based electrolyte layer containing a ceramic material has a polymer selected from the group comprising polyolefins, in particular polypropylene or polyethylene, poly (vinylidene difluoride-co-hexafluoropropylene) (PVdF-HFP), polyimide (PI), polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), carboxymethyl cellulose (CMC) and / or polytetrafluoroethylene (PTFE).
  • polyolefins in particular polypropylene or polyethylene
  • PVdF-HFP poly (vinylidene difluoride-co-hexafluoropropylene)
  • PI polyimide
  • PET polyethylene terephthalate
  • PVdF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • PTFE polytetrafluoroethylene
  • the electrolyte arrangement can be a multilayer electrolyte arrangement.
  • the electrolyte arrangement is preferably in the form of a three-layer arrangement, at least one of the layers lying on top of one another containing a ceramic material.
  • At least one of the two outer polymer-based ones contains
  • Electrolyte layers a lithium ion conductive ceramic material.
  • the lithium ion-conductive ceramic-containing layer can be arranged on the cathode or contact it.
  • the lithium ion-conductive ceramic can reduce the interface resistance between the electrolyte and a cathode, prevent thermal shrinkage and / or enlarge the electrochemical stability window.
  • the lithium-ion-conductive ceramic is not compatible with lithium metal, it is preferred that direct contact between the lithium-ion-conductive ceramic and the anode is avoided.
  • a ceramic-free polymer-based electrolyte layer is arranged in a cell or an electrochemical energy store on the anode, in particular a lithium metal anode, and / or makes contact with the anode.
  • the ceramic-free polymer-based electrolyte layer is advantageously stable to lithium metal and can form good adhesion, in particular to a lithium metal electrode.
  • a layer containing ceramic material can be arranged on or contact the anode.
  • an LLTO-containing layer arranged on an anode can increase the cycle stability.
  • both layers contain lithium ion-conductive ceramic.
  • the electrolyte arrangement can be in the form of a four-layer or multilayer arrangement.
  • a further polymer-based electrolyte layer which preferably contains another lithium ion-conductive ceramic, can be arranged on the layer containing the lithium ion-conducting ceramic.
  • a fourth layer containing a lithium aluminum germanium phosphate glass ceramic (LAGP) can be applied. This preferably makes contact with the cathode in a cell.
  • LAGP lithium aluminum germanium phosphate glass ceramic
  • a further ceramic-free polymer-based layer can be applied to the lithium ion-conducting ceramic layer
  • Electrolyte layer be applied.
  • an electrolyte-electrode assembly comprising an anode, a cathode and an electrolyte arrangement according to the invention arranged between anode and cathode.
  • the electrolyte arrangement reference is made to the description above.
  • the polymer-based electrolyte layer containing a ceramic material can contact the anode or the cathode.
  • an electrolyte-electrode assembly comprises a lithium metal anode or an anode made from a lithium alloy.
  • the polymer-based electrolyte layer containing a ceramic material contacts the cathode, while the ceramic-free polymer-based
  • Electrolyte layer in particular contacted a lithium metal anode.
  • a layer containing ceramic material can be arranged on the anode or contact it.
  • Another object of the invention relates to a primary or secondary, in particular electrochemical energy store, comprising an electrolyte arrangement according to the invention.
  • energy storage includes primary and secondary electrochemical energy storage devices, that is to say batteries (primary storage) and accumulators (secondary storage).
  • accumulators are often referred to using the term “battery”, which is often used as a generic term.
  • the term lithium-air battery is used synonymously with lithium-air accumulator.
  • the term “lithium-air battery” can also refer to a “lithium-air battery” in the present case.
  • the term “electrochemical energy store” also includes in particular
  • electrochemical capacitors such as
  • Electrochemical capacitors also referred to as supercapacitors in the literature, are electrochemical energy storage devices that are distinguished from batteries by a higher power density and compared to conventional capacitors by a higher energy density.
  • the electrochemical energy store comprises at least one cell with a positive electrode and a negative electrode, and an electrolyte arrangement according to the invention, which is arranged between the electrodes.
  • the electrochemical energy store is preferably a lithium metal battery, a solid-state battery, a solid-state accumulator, a Fithium-Fuft, Fithium-Oxygen or Fithium-Sulfur battery or a Fithium-Fuft, Fithium-Oxygen or Fithium-sulfur accumulator, or a super capacitor.
  • the energy store is preferably a Fithium Fuft accumulator.
  • Fithium Fuft accumulator includes systems that are based on a reaction with oxygen.
  • Fithium-Fuft and Fithium-Oxygen systems comprise a negative fithium electrode and a positive gas diffusion electrode (GDE), which is often referred to as the "Fuft cathode”.
  • GDE positive gas diffusion electrode
  • the electrochemical reaction at the cathode includes a reaction with oxygen. This is usually via the
  • Ambient air supplied or can be supplied in the form of oxygen gas are generally referred to by the term “Fithium Fuft Battery”.
  • Figure 1 is a schematic representation of a Fithium metal battery, the one
  • Figure 2 is a schematic representation of a further Fithium-metal battery
  • FIG. 3 is a schematic representation of a further Fithium-metal battery
  • FIG. 4 shows an SEM cross-sectional image of a three-layer electrolyte arrangement according to an embodiment of the invention, which contains a glass-ceramic in layer 2.3.
  • FIG. 5 shows an SEM cross-sectional image of a three-layer comparative arrangement, the electrolyte in layer 2.3 not containing any glass-ceramic.
  • FIG. 6 in FIG. 6a an SEM surface image of the layer 2.3 of FIG. 4 and in
  • FIG. 6b an SEM surface image of the layer 2.3 from FIG. 5.
  • FIG. 7 shows the calculated specific conductivity of the three-layer electrolyte arrangements according to Example 1 and the comparison arrangement at different temperatures.
  • FIG. 9 cycle behavior of a Li-metal cell with LFP as cathode in
  • FIG. 12 Development of the cell voltage over time during galvanostatic
  • FIG. 13 cycle behavior of a Li metal cell with LFP as cathode in
  • FIG. 14 using a voltage profile of a Li-O 2 battery at room temperature
  • FIG. 15 voltage profile of a lithium metal-sulfur cell at 60 ° C. according to
  • Example 4 and a comparative arrangement.
  • FIG. 16 Voltage profile of an LFP lithium metal cell at 20 ° C. and at 60 ° C. below
  • FIG. 1 shows a schematic view of a lithium metal battery which contains a three-layer electrolyte arrangement 2 according to an embodiment of the invention.
  • the battery has a lithium metal anode 1 as a negative electrode and a cathode 3 as a positive electrode.
  • the electrolyte arrangement 2 comprising three layers 2.1, 2.2 and 2.3 lying on top of one another is arranged between anode 1 and cathode 3.
  • the middle layer 2.2 comprises a porous, electrically non-conductive membrane, on both sides of which layers 2.1 and 2.3 of a polymer-based electrolyte are arranged. At least 50% of the pore volume of the porous membrane of the layer 2.2 is filled with the polymer-based electrolyte that forms the layers 2.1.
  • the polymer-based electrolyte layer 2.3 contains a glass-ceramic material.
  • the polymer that is used to form the polymer-based electrolyte layers 2.1 and 2.3 can be the same or different.
  • the polymer-based electrolyte layer 2.3 containing glass-ceramic material is arranged on the cathode 3.
  • FIG. 2 shows a schematic view of a further lithium metal battery, with a three-layer electrolyte arrangement 2 arranged between a lithium metal anode 1 and a cathode 3.
  • Layer 2.2 comprises a porous, electrically non-conductive membrane, on both sides of which there are layers 2.1 and 2.3 of a polymer-based electrolyte arranged are.
  • the polymer-based electrolyte layer 2.3 containing glass-ceramic material is arranged on the anode 1.
  • FIG. 3 shows a schematic view of a lithium metal battery with a three-layer electrolyte arrangement 2 according to a further embodiment of FIG
  • the middle layer 2.2 contains a ceramic material that does not conduct lithium ions.
  • a material of the layer 2.2 can be a porous ceramic Al 2 O 3 membrane, for example a SEPARION® membrane.
  • the polymer-based electrolyte layers 1.2 and 2.3 do not contain any lithium-ion-conductive glass-ceramic material.
  • the lithium salt was set as 1 here.
  • the molecular weight of polyethylene oxide was calculated on the basis of the repeating units.
  • the solution was stirred at 60 ° C. for 24 hours to obtain a viscous dispersion for coating.
  • the dispersion of the electrolyte I was applied to one side of a porous polymeric polypropylene membrane (Celgard® 2500, thickness 25 mm, porosity 55%, pore diameter 64 nm according to the manufacturer's instructions) using a doctor blade (doctor blade coating) with a wet film thickness of 400 mm.
  • Electrolyte II containing glass ceramic The dispersion of the electrolyte I was also used for the non-ceramic part of the electrolyte II. A NASICON type was used for this Phosphorus glass ceramic (Li 1 + x A1 x Ti 2 - x (PO 4 ) 3 ; Schott AG, particle size approx. 0.2 mm) to the non-ceramic electrolyte I in a ratio of 64% by weight: 36% by weight added. The electrolyte dispersion II was applied to the other side of the porous polypropylene membrane by means of knife coating with a wet film thickness of 100 mm.
  • a comparative arrangement was made by applying the electrolyte dispersion I to both sides of the membrane.
  • the arrangements were each dried under vacuum at a temperature of 60 ° C. for 24 hours.
  • the membranes were then irradiated with UV light for 10 minutes in order to initiate the crosslinking of the polymer and to obtain crosslinked three-layer electrolyte arrangements.
  • Acceleration voltage was 3 kV, an "inlens" detector was used.
  • the electrolyte arrangements were each applied to a carbon adhesive pad for the SEM images.
  • FIG. 4 shows an SEM cross-sectional image of the three-layer electrolyte arrangement which contains a polymer electrolyte layer containing glass-ceramic, which is denoted by 2.3.
  • the layer 2.2 comprises the Celgard® membrane, and the layer 2.1 is formed from the polymer electrolyte I.
  • the total thickness of the three-layer electrolyte arrangement was 28 mm, layer 2.1 having a thickness of 2 mm, layer 2.2 having a thickness of 21 mm and layer 2.3 having a thickness of 5 mm. It is assumed that the electrolyte dispersion I penetrates into the pores of the porous membrane during the drying process.
  • FIG. 5 shows an SEM cross-sectional image of the three-layer comparison arrangement.
  • the layer 2.2 comprises a Celgard® membrane, but both layers 2.1 and 2.3 were formed from the polymer electrolyte I without glass-ceramic.
  • the total thickness of the comparison arrangement was 46 mm, with layer 2.1 having a thickness of 7 mm, layer 2.2 having a thickness of 26 mm and layer 2.3 having a thickness of 13 mm.
  • the polymer electrolyte I had penetrated into the pore volume of the membrane.
  • FIG. 6a shows an SEM surface image of the three-layer electrolyte arrangement, which contains a glass-ceramic in layer 2.3. As can be seen from FIG. 6a), the ceramic was homogeneously distributed in the layer.
  • FIG. 6b) shows an SEM surface image of the comparison arrangement without glass-ceramic in layer 2.3. This showed a smooth polymeric surface.
  • the filling fraction (FF) of the polymer electrolyte in the cavities of the separator was calculated according to the following method.
  • Porosity is defined as the ratio of void volume to apparent geometric volume.
  • the porosity is calculated as follows:
  • W separator is the weight of the dry separator
  • r PP is the density of the partially crystalline polypropylene
  • V separator is the apparent geometric volume of a 25 mm thick separator. r PP becomes this separator type according to the specified degree of crystallinity (X c ,%)
  • r c and r a refer to the density of the crystalline phase (0.936-0.946 g / cm 3 ) and the amorphous phase (0.850-0.855 g / cm 3 ). Therefore the value of r PP is estimated according to 0.88 g / cm3.
  • the fill fraction (FF) of the polymer-based electrolyte in the separator was calculated as:
  • W TSPE is the weight of the polymer-based electrolyte within the cavities of the
  • r TSPE is the measured density of the polymer-based electrolyte with a value of 1.40 g / cm 3 .
  • Celgard®2500 separator with a diameter of 1.6 cm (11.94 mg or 1.98 mg), the value F Celgard®2500 is 55% and the filling of the pore volume of the porous electrically non-conductive membrane with the polymer-based membrane Electrolyte was estimated to be 97%.
  • the ionic conductivity of the three-layer electrolyte arrangements produced in Example 1.1 was determined by measuring the electrochemical impedance with a Novocontrol Technologies impedance measuring device with temperature control.
  • the measuring cell passed made of two stainless steel electrodes with an area of 2 cm 2 .
  • the respective electrolyte arrangement was attached between these. The measurements were carried out at temperatures in the range from 0 ° C to 80 ° C.
  • FIG. 7 shows the calculated specific conductivity of the three-layer
  • Electrolyte arrangement with glass ceramic and the comparison arrangement without ceramic at different temperatures As can be seen from FIG. 7, the
  • the thermal shrinkage test can be used to determine the extent to which the membrane shrinks at a fixed temperature at a certain time.
  • the electrolyte arrangements produced according to Example 1.1 and an uncoated Celgard® membrane were kept under vacuum at 120 ° C. for 30 minutes. 3 tests were carried out in each case.
  • the transfer number denotes the fraction of the total electrical current carried by a certain type of ion like Li + .
  • the transfer number (t Li + ) of the three-layer electrolyte arrangements produced in Example 1.1 was determined using a symmetrical Li / Li cell (CR2032 button cell) according to the method of Evans, Vincent and Bruce, as described in: Evans, J., Vincent, CA & Bruce, PG (1987). Electrochemical measurement of transference numbers in polymer electrolytes. Polymer, 28 (13), 2324-2328.
  • Lithium metal foil served as a reference electrode.
  • the galvanostatic polarization took place at 0.1 mA cm -2 at 60 ° C.
  • the one produced according to Example 1.1 was examined
  • FIG. 8 shows the development of the cell voltage over time during the galvanostatic polarization.
  • the cell voltage vs. Li / Li + .
  • the electrolyte I in the symmetrical Li-Li cell showed a drop in the
  • the electrolyte which in the middle layer (2.2) comprises a Celgard® membrane, could withstand currents of up to 50 mAh / cm 2 without a
  • Lithium iron phosphate (LFP) and lithium-nickel-manganese-cobalt mixed oxide (NMC811) cathodes were made by adding a slurry of LFP or
  • NMC811 the electrolyte I and carbon black in a weight ratio of 8: 1: 1 (w / w / w) and applied to aluminum foil with the help of a doctor blade with a wet film thickness of 150 mm.
  • the electrodes were dried under vacuum at 110 ° C. for 24 hours before use. There were round electrodes with a
  • the button cells were built as follows: the LFP or NMC811 electrode served as the positive electrode, and Li-metal as the negative electrode. During the cell structure, the glass ceramic-containing layer 2.3 made contact with the positive electrode. There were constant current cycling at 60 ° C and at a rate of 0.1C with LFP as the cathode im
  • FIG. 9 shows the results of the cycling measurements with LFP as cathode over 50 cycles. As can be seen from FIG. 9, the cycle stability was increased by the glass-ceramic in layer 2.3.
  • FIG. 10 shows the voltage profile of the Li-metal cell with NMC811 as the cathode for the three-layer electrolyte arrangement with glass ceramic.
  • NMC811 can also be used as a positive electrode for this electrolyte arrangement.
  • the lithium salt was set as 1 here.
  • the molecular weight of polyethylene oxide was determined based on the
  • Electrolyte II containing glass ceramic the non-ceramic part was produced by mixing polyvinylidene fluoride (PVDF), LiTFSI and Py 1.4 TFSI with a molar ratio of 7.2: 1: 2 in acetone and the solution was stirred at 50 ° C. Subsequently, FFZO (Garnet type, Schott AG, particle size approx. 1 mm) was added as ion-conducting ceramic to the non-ceramic part of the electrolyte in a ratio of 65% by weight to 35% by weight
  • the coated membrane was dried under vacuum at a temperature of 60 ° C. for 24 hours. During this drying process, the electrolyte dispersion I diffused into the porous polypropylene membrane and took up approx. 80-100% of the pore volume. The membrane was then irradiated with UV light for 10 minutes in order to initiate the crosslinking of the polymer and to obtain crosslinked three-layer electrolyte arrangements.
  • the three-layer electrolyte arrangement with glass ceramic produced according to Example 2.1 was examined electrochemically in lithium metal full cells in button cell construction against a high-voltage lithium-nickel-manganese oxide (LNMO) cathode.
  • LNMO lithium-nickel-manganese oxide
  • the positive electrode was produced by mixing the active material LNMO, the conductivity additive Carbon Black and PVDF as a binder in a weight ratio of 8: 1: 1. After coating on aluminum foil and drying, the electrode was mixed with a mixture of LiTFSI in Pyr 1 TFSI in the ratio (1: 2) completely wetted and then dried under vacuum at a temperature of 60 ° C for 24 hours. In the cell structure of the button cell, the layer containing glass ceramic was arranged on the positive electrode. Lithium metal served as the negative electrode. A constant current Cyclization was carried out at 60 ° C and at a C rate of 0.1C in the potential range of 4.85V to 3.5V.
  • FIG. 11 shows the voltage profile of the Li metal cell with LNMO cathode and the three-layer electrolyte arrangement with glass ceramic. As can be seen from FIG. 11, the voltage profile showed that the cell could be cycled. Thus one could select the Li metal cell with LNMO cathode and the three-layer electrolyte arrangement with glass ceramic. As can be seen from FIG. 11, the voltage profile showed that the cell could be cycled. Thus one could select the Li metal cell with LNMO cathode and the three-layer electrolyte arrangement with glass ceramic. As can be seen from FIG. 11, the voltage profile showed that the cell could be cycled. Thus one could be seen from FIG. 11, the voltage profile showed that the cell could be cycled.
  • Rechargeable solid-state electrolyte cell with a 5V cathode can be made available.
  • Electrolyte II containing glass ceramic The dispersion of the electrolyte I was also used for the non-ceramic part of the electrolyte II.
  • a lithium-ion conductive ceramic LLZO Gamet type, Schott AG, particle size approx. 1 mm
  • Ratio 64% by weight 36% by weight to the non-ceramic electrolyte I added.
  • the electrolyte dispersion II was applied to the other side of the porous polypropylene membrane by means of knife coating with a wet film thickness of 250 mm.
  • the coated membrane was dried under vacuum at a temperature of 60 ° C. for 24 hours. During this drying process, the electrolyte dispersion I diffused into the porous polypropylene membrane and took up about 80-100% of the
  • Pore volume The membrane was then crosslinked for 10 minutes under UV light.
  • FIG. 12 shows the development of the cell voltage over time during the
  • the three-layer electrolyte arrangement with LLZO ceramic produced according to Example 3.1 was examined in full cells with a negative electrode made of lithium metal and a positive electrode made of lithium iron phosphate (LFP).
  • the LFP cathodes were produced by mixing a slurry of LFP, electrolyte I and carbon black in a weight ratio of 8: 1: 1 (w / w / w) and using a doctor blade with a wet film thickness of 150 mm on aluminum foil was coated.
  • the electrode was dried under vacuum at 110 ° C. for 24 hours. Round electrodes with a diameter of 12 mm and an area loading of approximately 2 mg cm -2 were punched out.
  • the cell was installed in a button cell, with the electrolyte layer containing LLZO ceramic facing the negative electrode.
  • the constant current measurement was carried out in the potential range of 4.2 - 2.0 V and a C rate of 0.1 and at 60 ° C.
  • FIG. 13 shows the voltage profile of the LFP lithium metal cell at 60.degree.
  • the electrolyte containing LLZO glass ceramic could be
  • the electrolyte arrangement was also examined in a lithium / air cell with an air cathode (ECC-Air cell, EL-CELL GmbH).
  • ECC-Air cell ECC-Air cell
  • EL-CELL GmbH A commercial Co 3 O 4 / C coated on a nickel mesh with PTFE as a binder (gas diffusion cathode (GDE, MEET Co., Ltd.) was used as the cathode.
  • GDE gas diffusion cathode
  • 2 M LiTFSI in DMSO was used as the catholyte.
  • Constant current cycling (CCC) was performed at a current of 0.2 mA / cm 2 and a cut-off current of 3 mAh / cm 2 under a constant flow of oxygen
  • FIG. 14 shows the voltage profile of the lithium / air cell at room temperature. As can be seen from FIG. 14, the cell showed a rechargeable behavior. The result shows that the three-layer electrolyte arrangement, the LLZO ceramic containing
  • Electrolyte layer to negative electrode shows an ion-conducting path available represents.
  • the electrolyte can act as a protective layer for the side reactions between the lithium metal and the DMSO, as well as the oxygen in the diffusion cell.
  • Electrolyte I The dispersion of Electrolyte I was also used for the non-ceramic part of Electrolyte II.
  • a lithium-ion conductive ceramic LLZO Garnet type, Schott AG, particle size approx. 1 mm
  • the electrolyte dispersion II was applied to the other side of the porous polypropylene membrane by means of a doctor blade coating with a
  • the electrolyte dispersion I diffused into the porous polypropylene membrane and took up approx. 80-100% of the pore volume.
  • the polymer was then crosslinked for 10 minutes under UV light.
  • a second polymer-based electrolyte layer 2.2 containing lithium aluminum germanium phosphate ceramic (LAGP) was formed on the cathode.
  • the electrode was dried under vacuum at 40 ° C. for 12 hours.
  • the arrangement of the polymer-based electrolyte layer containing LLZO was placed on the polypropylene membrane on the LAGP-containing polymer-based electrolyte layer of the coated cathode, with the LLZO-containing electrolyte layer facing the negative electrode.
  • the three-layer electrolyte arrangement with cathode was installed and examined in a button cell with a negative electrode made of lithium metal. A corresponding full cell without a layer containing LAGP was examined as a speaker.
  • the constant current measurement was carried out in the potential range of 3.0-1.5 V and a C-rate of 0.1 and a temperature of 60 ° C.
  • FIG. 15 shows the voltage profile of the lithium metal-sulfur cells below
  • Example 5 three-layer electrolyte arrangement ("with LAGP-containing layer") at 60 ° C. As can be seen from FIG. 15, the full cell with the LAGP-containing layer showed a higher capacity. It is believed that this is due to the fact that the LAGP-containing layer prevents a “polysulfide shuttle effect”.
  • Example 5
  • the electrolyte was made by dissolving polypropylene carbonate (PCC,
  • the positive electrode was made by mixing the active material LFP, des
  • the cell was built as a button cell with the LFP electrode as the positive electrode and a lithium metal anode.
  • the constant current measurements were in the range of 3.8-2.5 V at a C rate of 0.1 and at a temperature of 20 ° C and 60 ° C
  • FIG. 16 shows the voltage profile of the LFP lithium metal cells at 20.degree. C. and at 60.degree.
  • the polymer-based electrolyte layer without glass ceramic material was compatible with an LFP cathode with a discharge plateau at 3.3 V at 20 ° C and at 3.4 V at 60 ° C.

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Abstract

L'invention concerne un arrangement d'électrolyte pour une cellule ayant au moins une anode (1) et au moins une cathode (3) comprenant au moins trois couches (2.1, 2.2, 2.3) superposées. La couche centrale (2.2) comprend une structure poreuse non conductrice d'électricité, et une couche d'un électrolyte à base de polymère (2.1, 2.3) est disposée sur les deux côtés opposés de la structure poreuse non conductrice d'électricité. Au moins l'une des couches (2.1, 2.2, 2.3) superposées contient un matériau céramique. Le matériau céramique de la couche centrale (2.2) est choisi parmi un matériau céramique conducteur d'ions métalliques, un matériau céramique qui ne conduit pas les ions métalliques et/ou des mélanges de ceux-ci, et le matériau céramique de la ou des couches d'électrolyte à base de polymère (2.1, 2.3) est un matériau céramique conducteur d'ions métalliques.
EP20712911.5A 2019-03-19 2020-03-18 Arrangement d'électrolyte multicouche pour batteries au lithium Pending EP3942623A1 (fr)

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