Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
  • H01M4/623—Binders being polymers fluorinated polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • 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
  • H01M10/056—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
  • 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
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • 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
  • H01M4/62—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
• • 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
  • H01M2300/0085—Immobilising or gelification of electrolyte
• • 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 cathode and a solid-state battery with the cathode.
• solid-state battery is used synonymously for all designations commonly used in the prior art for galvanic elements and cells that use at least one solid-state electrolyte as an ion-conducting connection between cathode and anode, such as metal-solid-state battery, metal-solid-state accumulator , all solid state battery (ASSB), cell, solid state cell, polymer cell and accumulator.
• ASSB all solid state battery
• cell solid state cell
• polymer cell and accumulator solid state battery
• rechargeable batteries secondary batteries
• Solid-state batteries are a further development of batteries with liquid electrolytes.
• the porous liquid-soaked separator which is intended for ion transport and thus for charge equalization between cathode and anode, is replaced by an ion-conducting solid.
• a preferred variant of the solid-state battery is the lithium-ion solid-state battery.
• Lithium ion solid state batteries known from the prior art have two different electrodes, a positive electrode (cathode) and a negative electrode (anode).
• the cathode comprises a cathode active material capable of reversibly accepting and donating lithium ions.
• the anode may include an anode active material, where the anode active material comprises either lithium metal, a lithium-containing alloy, or an alternative material that is also intended to reversibly accept or release lithium ions.
• Materials customary in the prior art are, for example, graphite, silicon and silicon suboxide (SiOx with O ⁇ x ⁇ 2).
• lithium-free in this context means that the anode is free of metallic lithium in the uncharged state after manufacture and before formation of the cell.
• the metallic lithium is only formed by a corresponding charging process at the anode.
• the two electrodes are connected to one another in a lithium-ion-conducting manner via a solid-state separator.
• the solid-state separator spatially separates the cathode from the anode.
• the solid separator ensures lithium ion transport between the cathode and the anode.
• the solid-state separator thus conducts the electric current by transporting lithium ions in the solid.
• the solid-state separator thus represents a solid-state lithium ion conductor.
• Solid state separators can be divided into ceramic, polymer-based and gel-based solid electrolytes.
• sulfidic and oxidic solid electrolytes are used as ceramic solid electrolytes, which are becoming more and more important due to their electrochemical stability combined with high lithium ion conductivity.
• Polymer-based solid electrolytes are solvent-free and are based on ionic conduction along polymer chains.
• polyethylene oxide to which a lithium-containing conductive additive has been added can be used as the polymer-based solid electrolyte.
• Gel-based solid electrolytes contain a solid polymer matrix interspersed with a liquid electrolyte that ensures ionic conduction.
• US 2019/0157723 A1 describes a lithium-ion solid state battery that contains a cathode with a cathode active material and an anode with an anode active material.
• the anode includes an anode current collector.
• the anode active material is selected in such a way that it can form an alloy or a compound with metallic lithium.
• the anode active material and the cathode active material are spatially separated from one another by a solid electrolyte.
• the solid electrolyte consists of a sulfidic material such as LiePSsCI with an argyrodite structure.
• the cathode active material consists in particular of known layer oxides containing lithium, such as NMC.
• the anode active material can be selected from the Group consisting of amorphous carbon, gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin and zinc and combinations thereof.
• the lithium-ion solid-state battery described above uses a lithium-free anode concept, since metallic lithium is deposited between the anode current collector and the anode active material during the initial charging processes. The metallic lithium is therefore initially not present in the cell after production.
• WO 2020 0725524 A1 discloses a lithium-ion solid-state battery comprising an anode current collector, a solid-state electrolyte and a transition layer between the anode current collector and the solid-state electrolyte.
• the transition layer is selected from the group consisting of zinc, tin, magnesium, silver, aluminum, indium, bismuth, lithium alloy, lithium oxide, and lithium peroxide, and combinations thereof.
• the solid electrolyte consists of a lithium-containing garnet, preferably lithium lanthanum zirconate (LLZO) with the chemical formula Li?La3Zr20i2, which ensures charge equalization between the anode and cathode by transporting lithium ions.
• LLZO lithium lanthanum zirconate
• a lithium-free anode concept is also used here.
• Ceramic solid electrolytes are known from US 2021/01226281 A1, which can be described with the general formula:
• WO 2019/051305 A1 discloses a cathode, anode and a solid electrolyte which is arranged between the cathode and the anode. At least one of the cathode, anode, and solid electrolyte comprises a ceramic material that includes lithium (Li), boron (B), and sulfur (S). The ceramic exhibits multiple crystalline phases and has an overall composition characterized by an a:b:c molar ratio of Li:B:S, where c/b ranges from about 1 to about 3.
• EP 3 496 202 A1 describes lithium ion-conducting lithium yttrium halides of the general formula Li6-3zY z Xe, where 0 ⁇ z ⁇ 2 and X is CI or Br. The lithium yttrium halides are used as a solid electrolyte in a solid state lithium ion battery.
• US 10 811 688 B2 and US 2017/0338492 A1 disclose a lithium-ion solid-state battery with a solid-state electrolyte based on an ion-conducting polymer, an ion source such as U2O, Na2Ü, MgO, CaO, ZnO, KOH, NaOH, CaCl 2 , AICI 3 , MgCl 2 , LiTFSI (lithium bis-trifluoromethanesulfonimide), LiBOB (lithium bis(oxalate)borate) or combinations thereof and an electron acceptor.
• an ion source such as U2O, Na2Ü, MgO, CaO, ZnO, KOH, NaOH, CaCl 2 , AICI 3 , MgCl 2 , LiTFSI (lithium bis-trifluoromethanesulfonimide), LiBOB (lithium bis(oxalate)borate) or combinations thereof and an electron acceptor.
• Liquid-crystal polymers polyetheretherketone (PEEK), polyphenylene sulfide (PPS) and semi-crystalline polymers with a crystallinity of more than 30% are mentioned as lithium-ion-conducting polymers.
• US 2019/0051939 A1 shows a lithium-ion solid-state battery that contains a polylithium acrylate as a polymer-based solid-state electrolyte.
• the solid electrolyte further includes a hydrophilic polymer, a lithium salt, and a Lewis acid.
• the solid electrolyte is integrated into the cathode. This is done by providing so-called composite electrodes, i.e. a mixture of the solid electrolyte and the active material.
• Either organic binders or polymer electrolytes such as polyethylene oxide (PEO) in the cathode composite can help.
• organic binders lack ionic conductivity, and polymers such as PEO often do not have sufficient oxidative stability for the potentials of the electrode materials on the cathode side (> 4V).
• the object of the invention is to avoid the disadvantages of the solid-state batteries known from the prior art and to provide a solid-state battery that is easy to manufacture and can be operated stably over a longer period of time.
• the object is achieved according to the invention by providing a cathode for a solid-state battery according to claim 1.
• the cathode for a solid-state battery comprises the following components:
• M is a cation selected from the group consisting of proton and alkali metals; n is an integer from 1 to 4;
• Z represents a central ion selected from the group consisting of aluminum and boron
• R represents a monovalent optionally fluorine-substituted hydrocarbon radical and is selected from the group consisting of C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 2 -C 4 alkynyl, C 6 -C 12 cycloalkyl and C 6 -C 12 aryl; wherein the ionic group is connected to the backbone of the first fluorine-containing polymer through at least one bridging oxygen atom of the ionic group.
• the invention is based on the basic idea of providing a combination of a cathode active material and a first fluorine-containing polymer for the cathode of a solid-state battery, with the combination proposed according to the invention having a number of advantageous properties.
• the fluorine-containing polymer has ionic groups as an essential feature.
• the ionic groups enable almost unhindered ion transport within the cathode.
• the first fluorine-containing polymer is thus an ion conductor.
• the addition of classic conductive salts such as lithium hexafluorophosphate is therefore not necessary.
• the ion conduction takes place via the fluorine-containing polymer.
• the first fluorine-containing polymer also has a transport number close to 1 due to these ionic functional groups.
• fluorine-containing polymers with an at least partially fluorinated or perfluorinated basic structure have high chemical and electrochemical stability. Consequently, these are particularly suitable for use in a cathode for a solid-state battery.
• the first fluorine-containing polymer is also mechanically flexible and elastic.
• the polymers can therefore compensate for changes in the volume of the cathode active material during cell operation.
• the cathode active material can therefore expand and contract again unhindered during re- and de-lithiation.
• the combination of cathode active material and the former fluorine-containing polymer can compensate for these volume changes and prevent mechanical stresses within the cell.
• the cathode active material as the "rigid” component
• the fluorine-containing polymer as the "soft” component
• the fluorine-containing polymer as a "soft” component can preferentially adapt to the rigid shape of the cathode active material.
• the contact area can be increased and the ion conduction between the fluorine-containing polymer and the cathode active material is thus ensured.
• Suitable cathode active materials for the cathode can be any cathode active materials known in the prior art.
• Preferred cathode active materials for the inventive cathode include lithium cobalt oxide (LOO), lithium nickel oxide (LNO), lithium nickel cobalt aluminum oxide (NCA), lithium nickel manganese cobalt oxide (NMC), lithium and manganese rich lithium nickel -Manganese cobalt oxide or lithium nickel manganese oxide (LMR), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium manganese iron phosphate (LMFP), lithium nickel manganese oxide spinel ( LNMO) and derivatives and combinations thereof.
• LEO lithium cobalt oxide
• LNO lithium nickel oxide
• NCA lithium nickel cobalt aluminum oxide
• NMC lithium nickel manganese cobalt oxide
• LMR lithium nickel manganese oxide
• LMO lithium iron phosphate
• LMFP lithium manganese iron phosphate
• LNMO lithium nickel manganese oxide spinel
• NMC Lithium-nickel-manganese-cobalt compounds
• NCM Lithium-nickel-manganese-cobalt compounds
• NMC-based cathode materials are used in particular in lithium-ion batteries for vehicles.
• NMC as a cathode material has an advantageous combination of desirable properties, for example a high specific capacity, a reduced cobalt content, a high high-current capability and high intrinsic safety, which is reflected, for example, in sufficient stability in the event of overcharging.
• Certain stoichiometries are given in the literature as triples of numbers, for example NMC 811, NMC 622, NMC 532 and NMC 111.
• the triple of numbers indicates the relative content of nickel:manganese:cobalt in each case.
• lithium and manganese-rich NMCs or LMR with the general formula unit Lii + £ (NixMn y Coz) i- £ O2 can be used, where E is in particular between 0.1 and 0.6, preferably between 0.2 and 0.4.
• These lithium-rich layered oxides are also known as Overlithitated (Layered) Oxides (OLO).
• the first fluorine-containing polymer contains at least one ionic group represented by general formula (I).
• the ionic group is an ion comprising a cation M + and an anion [-(O) n - Z-(OR) 4 -n]-.
• the negative charge of the anion is stoichiometrically balanced by the positive charge of the cation.
• the cation is selected from the group consisting of proton and alkali metals.
• the cation is preferably lithium.
• Z in formula (I) means a central ion selected from the group consisting of aluminum and boron.
• the ionic groups are thus either aluminates or borates and the anions of formula (I) are correspondingly singly negatively charged.
• the radicals R each represent a monovalent optionally fluorine-substituted hydrocarbon radical and are independently selected from the group consisting of Ci-Cs-alkyl, C2-C-alkenyl, C2-C-alkynyl, C6-C12-cycloalkyl and Ce-Ci4-aryl .
• monovalent means that the hydrocarbon radicals R each bond to the central ion Z via a single oxygen atom.
• Ci-Cs-alkyl includes linear or branched saturated hydrocarbon radicals having one to eight carbon atoms.
• Preferred hydrocarbon radicals include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, iso- hexyl, 2-ethylhexyl, n-heptyl, iso-heptyl, n-octyl and iso-octyl.
• C2-C -alkenyl includes linear or branched at least partially unsaturated hydrocarbon radicals having two to ten carbon atoms, the hydrocarbon radicals having at least one CC double bond.
• Preferred hydrocarbon radicals include, for example, ethenyl, 1-propenyl, 2-propenyl, 1-n-butenyl, 2-n-butenyl, isobutenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, and 1-nonenyl 1-decenyl.
• C2-C-alkynyl encompasses linear or branched, at least partially linear, unsaturated hydrocarbon radicals having two to ten carbon atoms, the hydrocarbon radicals having at least one C-C triple bond.
• Preferred hydrocarbon radicals include, for example, ethynyl, 1-propynyl, 2-propynyl, 1-n-butynyl, 2-n-butynyl, isobutynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl, and 1-nonynyl 1-decynyl.
• C6-Ci2-cycloalkyl encompasses cyclic, saturated hydrocarbon radicals having six to twelve carbon atoms.
• Preferred hydrocarbon radicals include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexyl, cyclononyl and cyclodecanyl.
• Ce-Ci4-aryl encompasses aromatic hydrocarbon radicals having six to twelve carbon atoms.
• Preferred hydrocarbon radicals include, for example, phenyl, naphthyl and anthracyl.
• the hydrocarbon radicals R are at least partially fluorine-substituted, preferably completely fluorine-substituted.
• Fluorine-substituted hydrocarbon radicals yield anions which form particularly stable ionic groups of formula (I).
• n is an integer from 1 to 4.
• n defines a number of bonds of the central ion Z to the at least partially fluorinated or perfluorinated backbone of the first fluorine-containing polymer.
• the central ion Z is always bonded to the first fluorine-containing polymer via at least one bridging oxygen atom of the ionic group.
• the number of -OR radicals in the general formula (I) is given as 4-n.
• the number of -OR radicals is directly linked to the number of bonds (n) of the central ion Z to the at least partially fluorinated or perfluorinated backbone of the first fluorine-containing polymer.
• n the degree of linkage of the ionic group can be adjusted.
• two types of operations are given by the choice of n:
• the first fluorine-containing polymer has at least one ionic end group of general formula (I) where n is equal to 1.
• n in formula (I) is 1, the central ion Z is connected to the backbone of the first fluorine-containing polymer via a bridging oxygen atom in the ionic group. Such a central ion Z then binds to three -OR residues.
• An example of such an ionic end group is given by the following formula (II):
• the first fluorine-containing polymer has at least one ionic crosslinking group of general formula (I) wherein n is 2, 3 or 4.
• n in formula (I) is 2, the central ion Z is connected to the backbone of a first fluorine-containing polymer via two bridging oxygen atoms in the ionic group. Such a central ion Z then binds to two radicals -OR.
• formula (III) An example of such an ionic structure is given by the following formula (III):
• the first fluorine-containing polymer can have both ionic end groups of the formula (II) and ionic crosslinking groups of the formulas (III) to (V).
• the first fluorine-containing polymer contains only ionic end groups or only ionic crosslinking groups.
• the general formula (I) has at least one or more of the following features:
• R represents a linear, branched or cyclic C1-C4 perfluoroalkyl radical.
• C 1 -C 4 -perfluoroalkyl includes linear or branched saturated perfluorinated hydrocarbon radicals having 1 to 4 carbon atoms.
• perfluoroalkyl radicals examples include trifluoromethyl, perfluoro-ethyl, perfluoro-propyl, perfluoro-isopropyl, perfluoro-n-butyl, perfluoro-sec-butyl, perfluoro-iso-butyl and perfluoro-tert-butyl.
• the ionic group is an ionic end group of the following formula (VI):
• the backbone of the first fluorine-containing polymer is fully fluorinated and has repeating units of tetrafluoroethylene (-C2F4-).
• the basic structure of the first fluorine-containing polymer is therefore derived from polytetrafluoroethylene (PTFE).
• PTFE polytetrafluoroethylene
• the basic structure is unbranched (linear) and essentially consists of fluorine and carbon.
• the first fluorine-containing polymer may include at least one perfluorinated side chain.
• the perfluorinated side chain serves to link the basic structure and an ionic group of general formula (I).
• the invention is not limited with respect to the perfluorinated side chain. Any of the perfluorinated side chains known in the art for perfluorinated polymers may be present. In particular, the perfluorinated side chains known from DE 28 17 315 can be used, to which reference is made here.
• the backbone of the first fluorine-containing polymer contains at least one side chain of the following formula (VII): wherein
• Y is a fluorine atom or a linear, branched or cyclic Ci-Cs-perfluoroalkyl radical; m is 0, 1 or 2; and v is 0 or 1; wherein the ionic group of general formula (I) is attached to the CY2 residue of the side chain.
• the central ion Z of an ionic group of the general formula (I) can be bonded to the CY2 radical of the side chain via a bridging oxygen atom of the ionic group.
• the side chain thus represents a linking element between the basic structure and the ionic group.
• An ionic end group is attached to the backbone of the first fluorine-containing polymer only through a side chain.
• Ionic crosslinking groups are instead attached to a backbone of a fluorine-containing polymer through multiple side chains.
• the ionic crosslinking groups crosslink the backbones of several first fluorine-containing polymers with one another.
• n 2
• the ionic crosslinking group is bonded to the backbone of a first polymer through two side chains.
• the first fluorine-containing polymer is a copolymer of the following formula (VIII) or (IX): wherein, m is 0, 1 or 2; - p is from 1 to 10; r is 1 to 10; s is 1 to 15; and
• - Y represents a fluorine atom or a linear, branched or cyclic Ci-Cw-perfluoroalkyl radical
• - T represents an ionic group of general formula (I).
• the ionic group T of the general formula (I) is bonded to the —CY2 radical.
• the ionic group of the general formula (I) can thus be easily integrated into the fluorine-containing polymer.
• the side chains are chemically stable to the oxidative stresses during cell operation.
• the first fluorine-containing polymer can be produced via the synthesis of hydroxyl-containing fluoropolymers, which can be reacted with lithium aluminum hydride (UAIH4) in perfluorohexane (C6F14) at 70-80° C. in the presence of perfluoroalcohols.
• the cathode can also be a second fluorine-containing polymer, wherein the second fluorine-containing polymer is selected from the group of sulfonated perfluorinated polymers.
• the invention is not further limited. In principle, all sulfonated perfluorinated polymers customary in the prior art can be used.
• polymers known from DE 28 17 315 can be used.
• the sulfonated perfluorinated polymers are based on, or derived from, polytetrafluoroethylene such as NAFION®.
• the sulfonated perfluorinated polymers have perfluoroalkyl side chains with functional groups.
• the second fluorine-containing polymer is not limited with respect to the functional groups of the perfluoroalkyl side chains.
• all functional groups customary in the prior art can be used for perfluoroalkyl side chains, as long as they are ionic and have lithium ions as cations.
• the sulfonated perfluorinated polymers based on polytetrafluoroethylene preferably have SOsLi-containing, SO2-N'Li + -SO2CF3-containing and/or SO2C(CN)2Li-containing perfluoroalkyl side chains.
• SO2C(CN)2Li-containing perfluoroalkyl side chains are structures of the following formula (X):
• SOsLi-containing perfluoroalkyl side chains are structures of the following formula (XI):
• Suitable examples of SO2-N'Li + -SO2CF3-containing perfluoroalkyl side chains are structures of the following formula (XII):
• the perfluoroalkyl side chains are not limited with respect to the above examples, particularly not to the perfluoroethoxy and perfluoroisopropoxy groups shown.
• the proposed SO3U-containing, SO2-N'Li + -SO2CF3-containing and/or SO2C(CN)2Li-containing perfluoroalkyl side chains can have any branched or unbranched perfluoroalkoxy groups.
• the lithium content of the cathode can preferably be adjusted in a targeted manner by introducing a second fluorine-containing polymer.
• the lithium ion conductivity of the cathode can also be adjusted.
• the lithium ion conductivity is primarily adjusted via the choice of the functional group of the perfluoroalkyl side chains.
• the second fluorine-containing polymer thus represents a second lithium ion conductor.
• the cathode comprises at least one solvent component, the solvent component being selected from the group consisting of perfluorocarbonates, perfluoroaromatics, perfluoroethers and perfluoroesters, and combinations and derivatives thereof.
• Hexafluorobenzene for example, can be used as the perfluoroaromatic.
• the solvent component forms a gel with the first and/or second fluorine-containing polymer.
• the gel fulfills the function of a gel electrolyte with the task of ion transport in the cathode guarantee.
• the gel electrolyte is mechanically flexible, which means it can compensate for changes in the volume of the cathode active material during cell operation. Damage to the solid-state cell due to mechanical stress can thus be avoided.
• the cathode comprises the following components, each based on the total weight of the cathode:
• (C) 0-30% by weight of at least one second fluorine-containing polymer, preferably selected from the group of sulfonated perfluorinated polymers, preferably based on polytetrafluoroethylene (PTFE) with SOsLi-containing, SO2-N'Li + -SO2CF3-containing and/or SO2C(CN)2Li- containing perfluoroalkyl side chains; and
• PTFE polytetrafluoroethylene
• (D) 0-70% by weight, preferably 0.1-70% by weight, of at least one solvent component consisting of perfluorocarbonates, perfluoroaromatics, perfluoroethers and perfluoroesters and combinations and derivatives thereof; where the proportions of components (A) to (D) add up to 100% by weight.
• the cathode can contain other additives, as are known from the prior art, for example binders and conductive additives.
• the invention is not restricted with regard to the further additives.
• the invention also relates to a solid-state battery with a cathode, an anode and a solid-state separator which spatially separates the cathode from the anode and is in ion-conducting contact with the cathode and anode.
• the solid separator comprises at least one ceramic, polymer-based or gel-based solid electrolyte or combinations thereof.
• the invention is not restricted. Basically can all separators known in the prior art based on solid electrolytes can be used.
• the solid separator can comprise at least one solid electrolyte, in particular at least one ceramic, polymer-based or gel-based solid electrolyte and combinations thereof.
• the solid electrolyte comprises a lithium phosphorus sulfide and/or a lithium boron sulfide with the general formula LicTySzRq, where T is boron or phosphorus, and R is a halogen, and where 2 ⁇ c ⁇ 7, 1 ⁇ y ⁇ 7, 3 ⁇ z ⁇ 13, 0 ⁇ q ⁇ 1.
• suitable solid electrolytes include the compounds of the general formula known from US 2021/0126281 A1:
• Lil-a-b-c-dP aTbAcXd where 0 ⁇ a ⁇ 0.129, 0 ⁇ b ⁇ 0.096, 0.316 ⁇ c ⁇ 0.484, 0.012 ⁇ d ⁇ 0.125 and where T is an element from the group consisting of As, Si, Ge, Al and B means, X means one or more halogens or N, and A is one or more of S and Se, and the compositions known from WO 2019/051305 A1 based on lithium (Li), boron (B) and sulfur (S ) characterized by an a:b:c molar ratio of Li:B:S, where c/b ranges from about 1 to about 3.
• the solid electrolyte comprises a lithium-containing garnet with the general formula Li n LamM′pM′′ q Zr s Ot, where 4 ⁇ n ⁇ 8.5.1.5 ⁇ m ⁇ 4.0 ⁇ p ⁇ 2.0 ⁇ q ⁇ 2,0 ⁇ s ⁇ 2.5 and 10 ⁇ t ⁇ 13, and wherein M' and M'' are independently selected from the group consisting of aluminum, molybdenum, tungsten, niobium, antimony, calcium, barium, strontium , cerium, hafnium, rubidium, gallium and tantalum.
• the lithium-containing garnet comprises a compound with the general formula Li w La v ZrkOh ⁇ gALOa, where 5 ⁇ w ⁇ 8, 2 ⁇ v ⁇ 5, 0 ⁇ k ⁇ 3, 10 ⁇ h ⁇ 13 and 0 ⁇ g ⁇ 1.
• the solid electrolyte is a lithium-containing garnet with the general formula LijLaaZrbOia ⁇ gALOa, where 5 ⁇ j ⁇ 8, 0 ⁇ b ⁇ 2.5, and 0 ⁇ g ⁇ 1.
• mixtures of polyethylene oxide and derivatives thereof with a lithium-containing conductive salt can be used as polymer-based solid electrolytes.
• Further examples include ion-conducting polymers based on liquid crystal polymers, polyetheretherketone (PEEK), polyphenylene sulfide (PPS) and semicrystalline polymers with a crystallinity of more than 30%, such as the compositions known from US 2017/0338492 A1 and US 10,811,688 B2, referred to.
• solid electrolytes described in US 2019/0051939 A1 which contain a polylithium acrylate together with a hydrophilic polymer, a lithium salt and a Lewis acid, can also be used.
• lithium ion-conducting lithium yttrium halides of the general formula Lie- 3zYzX6 described in EP 3 496 202 A1 can be used as solid electrolyte, where 0 ⁇ z ⁇ 2 and X is CI or Br.
• the lithium yttrium halides can be used as a solid electrolyte in a lithium ion battery.
• the solid separator comprises at least one solid electrolyte. However, it is also conceivable that several different solid electrolytes are used.
• the solid-state separator preferably comprises one of the abovementioned oxidic solid-state electrolytes, particularly preferably a lithium-containing garnet such as lithium lanthanum zirconate (LLZO).
• LLZO lithium lanthanum zirconate
• the solids separator is preferably designed as a layer that can have one or more layers. In particular, several layers with different solid separators can be present. The composition of the layers can vary stepwise or gradually.
• An oxidic solid electrolyte is preferably arranged on the anode side.
• the anode includes an anode current collector and optionally an anode layer.
• the anode current collector can be made of any material known in the prior art for anode current collectors.
• the anode current collector is made of copper.
• the anode layer of the solid state battery may comprise any anode structure and material known in the art.
• the anode layer may include an anode active material and/or a seed layer.
• anode layer can be present as a composite layer, which comprises a mixture of anode active materials and other components such as binders, conductive additives and solid electrolytes and combinations thereof.
• the anode layer can have one or more layers.
• Preferred components for the anode active material in the solid state lithium ion battery include lithium metal, zinc, magnesium, silver, aluminum, indium, tin, bismuth, silicon, silicon suboxide, graphite, silicon-carbon composite, tin-carbon composite, silicon alloy and lithium alloy, and combinations of that.
• the anode in the uncharged state after fabrication, does not include lithium metal.
• the lithium metal is only deposited on the anode by a charging process after the lithium-ion solid-state battery has been manufactured.
• lithium metal is deposited onto the anode current collector or optionally onto a seed layer which may be deposited onto the anode current collector.
• the seed layer is not able to completely absorb the lithium metal deposited on the anode during charging of the solid-state lithium-ion battery.
• the seed layer fulfills a different function than the anode active material, namely to control the lithium deposition at the anode during the charging process of the lithium-ion solid-state battery.
• This can already be achieved by using a seed layer with a layer thickness of 1 nm-10 ⁇ m, preferably 5 nm-3 ⁇ m, particularly preferably 10-2000 nm.
• a porous seed layer can be provided.
• the seed layer may include the same components as the anode active material described above, except for lithium or lithium alloys.
• Suitable examples of the seed layer components include zinc, magnesium, silver, aluminum, indium, tin, bismuth, silicon, silicon suboxide, graphite, silicon-carbon composite, tin-carbon composite, silicon alloy, and combinations thereof.
• the cathode includes a cathode current collector and a cathode layer on the one cathode current collector.
• the cathode current collector can be made of any material known in the art for cathode current collectors.
• the cathode current collector is made of aluminum.
• the cathode layer includes at least a cathode active material and a first fluorine-containing polymer.
• Suitable cathode active materials for the cathode of the invention include lithium cobalt oxide (LOO), lithium nickel oxide (LNO), lithium nickel cobalt alumina (NCA), lithium nickel manganese cobalt oxide (NMC), lithium and manganese rich lithium nickel -Manganese cobalt oxide or lithium nickel manganese oxide (LMR), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium manganese iron phosphate (LMFP), lithium nickel manganese oxide spinel ( LNMO) and derivatives and combinations thereof.
• LEO lithium cobalt oxide
• LNO lithium nickel oxide
• NCA lithium nickel cobalt alumina
• NMC lithium nickel manganese cobalt oxide
• LMR lithium nickel manganese oxide
• LMO lithium iron phosphate
• LMFP lithium manganese iron phosphate
• LNMO lithium nickel manganese oxide spinel
• the solid-state battery is a lithium-ion solid-state battery.
• the lithium-ion solid-state battery comprises a cathode with a cathode layer, which comprises a cathode active material and a first fluorine-containing polymer, an anode and a solid-state separator based on a ceramic, in particular an oxidic, solid-state electrolyte.
• the cathode according to the invention there is a synergistic effect between the cathode according to the invention and the ceramic solids separator.
• the fluorine-containing polymer enables an ionic connection of the cathode to the oxidic separator
• the solid-state separator be manufactured separately from the cathode.
• the ceramic solid separator in particular an oxidic solid electrolyte, can be sintered separately at high temperatures and only subsequently joined to the cathode. Consequently, the cathode does not have to be exposed to high temperatures during manufacture. Nevertheless, because of the solid electrolyte used in the cathode according to the invention and based on a fluorine-containing polymer, there is intimate contact with the ceramic solid electrolyte.
• a further advantageous combination results from the composition of a lithium-ion solid-state battery consisting of the cathode described above, an oxidic solid-state separator and an anode which comprises an anode layer, the anode layer comprising a lithium metal.
• the ceramic, in particular oxidic, solid separator serves as a particularly stable protective layer between the lithium metal of the anode layer and the active material of the cathode layer.
• An undesired reaction between the components of the cathode and the lithium metal of the anode can thus be avoided. Consequently, no oxidative decomposition takes place on the anode side.
• the first fluorine-containing polymer remains intact since it is spatially separated from the lithium metal of the anode by the protective layer. The performance of the lithium-ion solid-state battery is therefore only slightly or not at all restricted.
• the proposed lithium-ion solid-state batteries are easy to manufacture and have improved cycle stability.
• the cyclic aging resistance of the test cells can be determined via the number of cycles.
• the test cells are initially charged with a constant charging current up to a maximum permissible cell voltage.
• the upper switch-off voltage is kept constant until a charging current has fallen to a specified value or the maximum charging time has been reached. This is also known as I/U loading.
• the test cells are then discharged with a constant discharge current intensity up to a given switch-off voltage. Depending on the desired number of cycles, charging can be repeated.
• the upper cut-off voltage and the lower cut-off voltage as well as the given charging or discharging currents must be taken into account be chosen experimentally. This also applies to the value to which the charging current has dropped.
• FIG. 1 in a schematic representation of a lithium ion
• FIG. 3 shows a schematic representation of the lithium-ion solid-state battery from FIG. 2 with a solvent component.
• FIG. 1 shows a lithium ion solid state battery 10.
• the lithium ion solid state battery 10 has an anode 16 and a cathode 26 on.
• the anode 16 and the cathode 26 are connected to one another in an ionically conductive manner via a solid-state separator 18 .
• the solid separator 18 spatially separates the anode 16 from the cathode 26.
• ionically conductive means the conduction of lithium ions within the solid-state separator 18 .
• the anode 16 includes an anode current collector 12 and an anode layer 14 on the anode current collector 12.
• Anode current collectors are known and usually consist of a metallic material.
• the anode current collector 12 is provided for making electrical contact with the anode layer 14 .
• the anode current collector 12 can be made of copper, for example.
• the anode layer 14 includes at least one anode active material.
• the anode active material is intended to reversibly absorb lithium ions and release them again.
• the anode active material is preferably composed of components from the group consisting of lithium metal, zinc, magnesium, silver, aluminum, indium, tin, bismuth, silicon, silicon suboxide, graphite, silicon-carbon composite, tin-carbon composite, silicon alloy, and lithium alloy, and combinations thereof.
• the anode active material preferably comprises a lithium metal.
• the cathode 26 includes a cathode current collector 24 and a cathode layer 25 on the cathode current collector 24.
• Cathode current collectors usually consist of a metallic material such as aluminum.
• the cathode layer 25 is present as a composite and comprises a mixture of a cathode active material 20 and a first fluorine-containing polymer 22.
• the cathode active material 20 is distributed in a matrix of the first fluorine-containing polymer 22.
• the cathode active material 20 is preferably selected from the group consisting of lithium cobalt oxide (LOO), lithium nickel oxide (LNO), lithium nickel cobalt aluminum oxide (NCA), lithium nickel manganese cobalt oxide (NMC), lithium and manganese-rich lithium nickel manganese cobalt oxide or lithium nickel manganese oxide (LMR), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium manganese iron phosphate (LMFP), lithium nickel manganese oxide Spinel (LNMO) and derivatives and combinations thereof.
• the cathode active material 20 is intended to reversibly absorb lithium ions and release them again.
• the first fluorine-containing polymer 22 has a partially fluorinated or perfluorinated backbone and contains at least one ionic group of the general formula (I): wherein,
• M is a cation selected from the group consisting of proton and alkali metals; n is an integer from 1 to 4; Z means a central ion selected from the group consisting of
• R represents a monovalent optionally fluorine-substituted hydrocarbon radical and is selected from the group consisting of C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 2 -C 4 alkynyl, C 6 -C 12 cycloalkyl and C 6 -C 12 aryl; wherein the ionic group is connected to the backbone of the first fluorine-containing polymer through at least one bridging oxygen atom of the ionic group.
• M is lithium, n is 1 and Z is aluminum.
• the hydrocarbon radical R is particularly preferably a trifluoromethyl radical and/or a perfluoro-tert-butyl radical.
• the first fluorine-containing polymer is a lithium ion conductor.
• the cathode layer 25 can comprise at least one binder (not shown here), the binder being selected from the group consisting of polyvinylidene fluoride (PVDF), hydrogenated acrylonitrile butadiene rubber (HNBR), carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR ), polyacrylate (PAA), lithium polyacrylate (LiPAA) and polyvinyl alcohol (PVA) and combinations thereof.
• PVDF polyvinylidene fluoride
• HNBR hydrogenated acrylonitrile butadiene rubber
• CMC carboxymethyl cellulose
• SBR styrene butadiene rubber
• PAA polyacrylate
• LiPAA lithium polyacrylate
• PVA polyvinyl alcohol
• the cathode layer 25 may also include a conductive additive (not shown here), where the conductive additive is selected from the group consisting of conductive carbon black, carbon nanotubes, graphene, graphite, and carbon nanofibers, and combinations thereof.
• the solid state separator 18 is arranged between the anode 16 and the cathode 26, and comprises at least one ceramic, polymer-based or gel-based solid state electrolyte or combinations thereof.
• compositions can be used as the solid electrolyte:
• Li c T y S z Rq a lithium phosphorus sulfide and/or a lithium boron sulfide having the general formula Li c T y S z Rq, where T is boron or phosphorus, and R em is halogen and where 2 ⁇ c ⁇ 7, 1 ⁇ y ⁇ 7, 3 ⁇ z ⁇ 13, 0 ⁇ q ⁇ 1;
• T is a member from the group consisting of from As, Si, Ge, Al and B, X is one or more halogens or N, and A is one or more of S and Se;
• lithiated garnet having the general formula LinLa m M'pM" q Zr s Ot, where 4 ⁇ n ⁇ 8.5.1.5 ⁇ m ⁇ 4.0 ⁇ p ⁇ 2.0 ⁇ q ⁇ 2.0 ⁇ s ⁇ 2.5 and 10 ⁇ f ⁇ 13, and wherein M' and M'' are independently selected from the group consisting of aluminum, molybdenum, tungsten, niobium, antimony, calcium, barium, strontium, cerium, hafnium, rubidium , gallium and tantalum;
• Li w La v ZrkOh gAhOa having the general formula Li w La v ZrkOh gAhOa, where 5 ⁇ w ⁇ 8, 2 ⁇ v ⁇ 5, 0 ⁇ 3, 10 ⁇ /? ⁇ 13 and 0 ⁇ g ⁇ 1;
• LijLaaZrbOi2 gALOa having the general formula LijLaaZrbOi2 gALOa, where 5 ⁇ y ⁇ 8, 0 ⁇ b ⁇ 2.5, and 0 ⁇ g ⁇ 1;
• lithium yttrium halide of the general formula Li6-3zY z X6, where 0 ⁇ z ⁇ 2 and X is CI or Br;
• the solid separator 18 conductively connects the cathode 26 to the anode 16.
• the solid separator 18 represents a protective layer between the anode layer 14 of the anode 16 and the cathode layer 25 of the cathode 26.
• the solids separator 18 can have one or more layers. In particular, several layers with different solid separators can be present. The composition of the layers can vary stepwise or gradually.
• the solids separator 18 may comprise an anode-side region having a higher resistance to lithium metal than a cathode-side region of the solids separator.
• the area arranged on the anode side preferably comprises an oxidic solid electrolyte, particularly preferably a lithium-containing garnet such as lithium lanthanum zirconate (LLZO).
• LLZO lithium lanthanum zirconate
• the lithium-ion solid-state battery 10 shown here shows a particularly good ionic connection of the cathode 26 to the solid-state separator 18. It is particularly advantageous that the first fluorine-containing polymer 22 is mechanically flexible and can be adapted to the rigid and inflexible shape of the solid-state separator 18 and can reliably compensate for changes in volume.
• Figure 2 shows the lithium-ion solid-state battery 10 from Figure 1 with a changed composition of the cathode 26.
• the cathode 26 in FIG. 2 comprises a cathode layer 25 which is present as a composite and comprises a mixture of a cathode active material 20 , a first fluorine-containing polymer 22 and a solvent component 28 .
• the lithium-ion solid-state battery 10 can contain the same components as already described above.
• the cathode in FIG. 2 has a solvent component 28 .
• the solvent component 28 is preferably selected from the group consisting of perfluorocarbonates, perfluoroaromatics, perfluoroethers and perfluoroesters and combinations and derivatives thereof.
• the solvent component 28 forms a gel electrolyte with the first fluorine-containing polymer.
• the gel electrolyte preferably has a gel-like consistency. The gel electrolyte is therefore dimensionally stable, but also mechanically flexible and stretchable.
• the presence of a gel electrolyte with a gel-like consistency makes it possible to compensate for the volume expansion of the cathode active material 20 during regular operation of the lithium-ion solid-state battery 10 .
• Figure 3 shows the lithium ion solid state battery 10 from Figure 2 with a different composition of the cathode 26.
• the cathode 26 in FIG. 3 comprises a cathode layer 25 which comprises a mixture of a solvent component 28 , a cathode active material 20 , a first fluorine-containing polymer 22 and a second fluorine-containing polymer 30 .
• the lithium-ion solid-state battery 10 can contain the same components as already described above.
• the second fluorine-containing polymer 30 is preferably selected from the group of sulfonated perfluorinated polymers with SOsLi-containing and/or SO2C(CN)2Li-containing perfluoroalkyl side chains, preferably a polytetrafluoroethylene (PTFE) such as National®, or polymers derived from National®.
• PTFE polytetrafluoroethylene
• Other possible side chains are SO2-N'Li + -SO2CF3-containing perfluoroalkyl side chains.
• the second fluorine-containing polymer 30 contains perfluorinated side chains saturated with lithium ions.
• the second fluorine-containing polymer 30 is thus also a lithium ion conductor.
• the second fluoropolymer 30 forms a gel with the first fluoropolymer 22 and the solvent component 28 .
• the cathode active material 20 is present in a gel consisting of the first fluorine-containing polymer 22 , the second fluorine-containing polymer 30 and the solvent component 28 .
• the gel enables ionic bonding of the cathode active material 20 to the solid separator 18 and the cathode current collector 24.

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