Classifications

• • 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
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/04—Construction or manufacture in general
  • H01M10/0486—Frames for plates or membranes
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  • 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
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/60—Heating or cooling; Temperature control
  • H01M10/61—Types of temperature control
  • H01M10/613—Cooling or keeping cold
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/60—Heating or cooling; Temperature control
  • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
  • H01M10/625—Vehicles
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/60—Heating or cooling; Temperature control
  • H01M10/65—Means for temperature control structurally associated with the cells
  • H01M10/651—Means for temperature control structurally associated with the cells characterised by parameters specified by a numeric value or mathematical formula, e.g. ratios, sizes or concentrations
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/60—Heating or cooling; Temperature control
  • H01M10/65—Means for temperature control structurally associated with the cells
  • H01M10/655—Solid structures for heat exchange or heat conduction
  • H01M10/6553—Terminals or leads
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
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  • 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
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
  • H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
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  • 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
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
  • H01M50/105—Pouches or flexible bags
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  • 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
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  • 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
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/04—Construction or manufacture in general
  • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
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  • 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
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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  • 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
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
  • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/70—Carriers or collectors characterised by shape or form
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/44—Fibrous material
• • H—ELECTRICITY
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  • 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
  • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
• • H—ELECTRICITY
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  • 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
  • H01M50/463—Separators, membranes or diaphragms characterised by their shape
  • H01M50/469—Separators, membranes or diaphragms characterised by their shape tubular or cylindrical
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
• • 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
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/60—Other road transportation technologies with climate change mitigation effect
  • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

• the present invention relates to an electrochemical cell for a
• Lithium ion battery comprising at least:
• At least one separator arranged between or on the cathodic electrode and / or anodic electrode, wherein said separator comprises at least one porous ceramic material, preferably in one on an organic one
• Carrier material applied layer is present, wherein this organic carrier material preferably comprises or is a non-woven polymer.
• the electrolyte, electrodes and separator (s) are in a pressure-resistant
• Enclosure enclosed gas-tight, said housing and said electrochemical cell comprise no means for pressure reduction in the enclosure, in particular no bursting device, pressure valve, one-way valve, central pin, mandrel or the like.
• Safety valves in the enclosure are described by way of example in US 5,853,912 or in US 2006/0263676. Bursting devices, pressure valves, predetermined breaking points and the like are according to the prior art mounted laterally in the enclosure and / or in the lid of the cell.
• Electrochemical cell for a lithium-ion battery at least comprising: an electrolyte and
• At least one anodic electrode as well
• separator arranged between or on the cathodic electrode and / or anodic electrode, wherein said separator comprises at least one porous ceramic material, preferably in one on an organic one
• Carrier material applied layer is present, wherein this organic carrier material preferably comprises or is a non-woven polymer.
• the electrolyte, electrodes and separator (s) are in a pressure-resistant
• Enclosure enclosed gas-tight, said housing and said electrochemical cell comprise no means for pressure reduction in the enclosure, in particular no bursting device, pressure valve, one-way valve, central pin, mandrel or the like.
• a "flameproof" housing is any conceivable enclosure, cladding with frame, frame structure, sealed structure comprising deep-drawn shell parts, etc., which are the inside of the cell (and thus inside the housing located) active components of the lithium-ion cell, ie in particular cathode, anode, separator and electrolyte before material, in particular chemical, actions and
• Ambient pressure is reduced or increased. These prints can be both inside and outside the enclosure.
• gas-tight means that the enclosure also functions in the underpressure or overpressure mentioned in the last paragraph, ie, the active components of the lithium-ion cell, ie in particular the cathode, Anode, separator and electrolyte to protect against material, especially chemical agents and interactions, not lose, and permanently over the entire intended life of the cell
• a housing is advantageously in the form of a composite film (laminate film) formed ("pouch cell "," coffee bag “), or as frame cell with frame and cladding or as a sealed composite of shell pieces, or as any combination or modification thereof.
• the cathodic electrode comprises at least one support on which at least one active material is deposited or deposited, wherein the active material is either:
• Li lithium-nickel-manganese-cobalt mixed oxide
• NMC lithium-nickel-manganese-cobalt mixed oxide
• NMC lithium nickel manganese cobalt composite oxide
• LMO lithium manganese oxide
• lithium-nickel-manganese-cobalt composite oxide is a slightly “overlithiated” stoichiometry of Li 1 + x [Co 1/3 Mn 1/3 Ni 1/3] 0 2 with x in the range of 0.01 to 0.10 particularly preferred because by such
• the support for the cathodic electrode comprises a metallic material, in particular aluminum, and that said carrier has a thickness of 5 ⁇ to 100 ⁇ , preferably 10 [im to 75 [im, more preferably 15 ⁇ to 45 ⁇ having.
• the carrier is formed as a collector foil.
• the anodic electrode comprises at least one support on which at least one carbon-containing
• Active material is applied or deposited.
• the carrier for the anodic electrode comprises a metallic material, in particular copper, and that said carrier has a thickness of 5 ⁇ to 100 ⁇ , preferably 10 ⁇ to 75 ⁇ , more preferably 15 ⁇ to 45 ⁇ .
• the carrier is formed as a collector foil.
• the anode comprises pure metallic lithium. This eliminates the substrate described for the anode.
• the metallic lithium is preferably used as a thin strip, foil, expanded metal or sponge.
• the thickness of the cathodic electrode (carrier and active material) and the thickness of the anodic electrode (carrier and active material) is less than 300 ⁇ , preferably less than 200 ⁇ , more preferably less than 150 ⁇ and more preferably less than 100, and finally less than 50 ⁇ .
• the small thickness of the carrier and the electrodes in total allows a particularly effective cooling of the active materials. This also contributes to that
• a Z-winding according to the invention should not be laminated.
• the separator of the present invention comprising the porous ceramic material has sufficient porosity for the function of the electrochemical cell, but is much more temperature resistant and less shrinking at higher temperatures as compared with conventional separators which do not comprise a ceramic material.
• a ceramic separator has In addition, advantageously a high mechanical strength. Both are for the underlying task of the present invention of the "intrinsic"
• the present combination "hermetic containment" in the enclosure / enclosure according to the invention with particularly thin electrodes and the ceramic separators mounted between the electrodes ensures that even in the event of abuse (overcharge, deep discharge, mechanical stress , thermal breakthrough or the like) no or only a slight gas pressure is built up inside the housing / enclosure, which in any case does not necessitate the presence of a pressure relief valve or a bursting protection or the like, so that the present cell is not only reliable but also structurally simpler than the cells of the prior art.
• the active material coming into contact with the electrolyte contains cathode and / or anode (as well as
• the porous ceramic material of the separator in the form of the active material optionally also the electrolyte itself
• the porous ceramic material of the separator in the form of the active material optionally also the electrolyte itself
• added particles see also below the detailed description of the application of the active materials on the support.
• the anode and / or cathode active material in contact with the electrolyte comprises a proportion of 0.01 to 5 percent by weight (based on the total weight of active material), preferably 0.05 to 3 percent by weight, more preferably 0.1 to 2
• Percent by weight of particulate porous ceramic material which substantially corresponds to the porous ceramic material of the separator. In a preferred embodiment, at least 50% of that in the
• electrochemical cell freely present electrolytes from the porous received ceramic material of the separator, preferably at least 70%, more preferably at least 90%, more preferably at least 95%.
• the electrolyte is bound in such a way that it does not take part in the abuse of the cell in the then possibly occurring undesirable reactions (or at least not to such an extent that participates "Going through” or "blowing through” the entire cell is possible).
• the protection against overpressure in the cell is thus not achieved via a defense reaction after damage by reducing an overpressure, but rather intrinsically in the overall design of the cell through targeted material selection and geometric arrangement in the cell created.
• the cell as a whole is so applied (small thickness of electrodes, carrier and
• the lithium-ion electrochemical cell according to the invention finds a preferred application in batteries, in particular in batteries with high energy density and / or high power density (so-called “high power batteries” or “high energy batteries”).
• said lithium-ion cells and lithium-ion batteries are used in power tools and for driving vehicles, both of fully or predominantly electrically driven vehicles or vehicles in the so-called “hybrid" - operation, ie together with a combustion engine.
• Hybrid electrically driven vehicles or vehicles in the so-called "hybrid" - operation, ie together with a combustion engine.
• An application of such batteries together with fuel cells and in stationary operation is included.
• cathodic electrode refers to an electrode that receives electrons when connected to a consumer ("discharge"), that is, for example, during the operation of an electric motor.
• the cathodic electrode is therefore in this case the "positive electrode” into which the ions deposit during discharge.
• An "active material” of cathodic or anodic electrode in the sense of the present invention is a material which contains lithium in ionic or metallic
• Electrode such as binder, stabilizer or carrier.
• the selection of the cathodic electrode material is of importance for the particular application envisaged. Such are, for example
• lithium-cobalt oxides eg LiCoO 2
• lithium (nickel) cobalt-aluminum oxides NCA
• Active materials plays a bigger role. Also with regard to high performance, some of these conventional materials are limited.
• electrodes which can be used for electrochemical cells and batteries are mixed lithium oxides with nickel, manganese and cobalt (lithium-nickel-manganese-cobalt mixed oxides, "NMC").
• NMC lithium-nickel-manganese-cobalt mixed oxides
• lithium-nickel-manganese-cobalt mixed oxides are preferable to lithium-cobalt oxides and are within the meaning of
• NMC cobalt, manganese and nickel
• NMC cobalt, manganese and nickel
• single-phase lithium-nickel-manganese-cobalt mixed oxides are known in principle as possible active materials for electrochemical cells in the prior art (see, for example, WO 2005/056480 and the corresponding publications
• the composition (stoichiometry) of the lithium nickel manganese cobalt mixed oxide there are no restrictions in the present case with regard to the composition (stoichiometry) of the lithium nickel manganese cobalt mixed oxide, except that this oxide besides lithium at least 5 mol%, preferably in each case at least 15 mol%, more preferably in each case at least 30 mol% of nickel .
• Manganese and cobalt must contain, in each case based on the total number of moles of transition metal components in the lithium-nickel-manganese-cobalt mixed oxide.
• the lithium-nickel-manganese-cobalt mixed oxide can be doped with any other metals, in particular transition metals, as long as it is ensured that the abovementioned molar minimum amounts of Ni, Mn and Co are present.
• a lithium-nickel-manganese-cobalt mixed oxide of the following stoichiometry is particularly preferred: wherein the proportion of Li, Co, Mn, Ni and O can each vary by +/- 5%.
• a slightly “overithiated” stoichiometry with Li + x [Coi / 3Mni / 3Ni / 3 ] O 2 with x in the range from 0.01 to 0.10 is particularly preferred, since such "overithithiation” compared to the 1: 1 stoichiometry better cycle properties and a greater stability of the cell (see problem of the invention) is achieved.
• lithium nickel manganese cobalt mixed oxides are not present in a spinel structure. Preferably, they are rather in a "layered structure prior to, for example, a" 03 "structure. More preferably this lithium-nickel-manganese-cobalt mixed oxides of the present invention are also subject to during the unloading and loading operation no significant (ie not within the scope of more 5%) Phase transformation into another structure, especially not a spinel structure
• An alternative - particularly inexpensive - cathodic electrode active material that can be used for electrochemical cells and batteries used in power tools, electric vehicles or hybrid vehicles can, are
• the lithium polyanion compound is preferably selected from the group comprising:
• X is a hetero atom such as P, N, S, B, C or Si and "XO"
• M is at least one transition metal cation of the first row of the Periodic Table of the Elements.
• the transition metal cation is preferably from Group consisting of Mn, Fe, Ni or Ti or a combination of these elements selected.
• the compound preferably has an olivine structure.
• the said polyanionic compounds are particularly preferred because they are characterized by low cost and good availability, especially against such active materials containing cobalt. These criteria (costAvailability) may be for
• At least one polyanion is used as the main active material for the cathodic electrode, i. At least 50%, preferably at least 80%, more preferably at least 90% of the active material of the cathode comprise the at least one polyanionic material (in each case mol%).
• the active material of the cathodic electrode comprises at least one lithium-polyanion compound together with at least (i) a lithium-nickel-manganese-cobalt mixed oxide (NMC), which is not present in a spinel structure, and / or with (ii) a spinel-type lithium-manganese oxide (LMO).
• NMC lithium-nickel-manganese-cobalt mixed oxide
• LMO spinel-type lithium-manganese oxide
• a mixture of (i) with (ii) improves the stability of the associated electrochemical cell while at the same time allowing a thinner application of the active material to the substrate.
• Low layer thicknesses reduce the impedance ("internal resistance") of the cell, which has a positive effect in all applications of the cell, but especially in "high power” applications.
• At least 20 mol%, preferably at least 40 mol%, more preferably at least 60 mol%, of active material in the form of at least one polyanion are preferably present in such a mixture.
• the ratios of lithium nickel-manganese-cobalt mixed oxide to lithium manganese oxides the preferred ranges given below apply.
• the active material for the cathodic electrode comprises at least one mixture of a lithium-nickel-manganese-cobalt mixed oxide (NMC), which is not present in a spinel structure, with a lithium manganese oxide (LMO) in spinel structure ,
• this mixture is preferably the essential active material for the cathodic electrode, i. at least 80%, preferably at least 90% of the
• Active material of the cathode comprise the at least one mixture of a lithium-nickel-manganese-cobalt mixed oxide (NMC), which is not in one
• LMO lithium manganese oxide
• the active material comprises at least 30 mol%, preferably at least 50 mol% NMC , as well as at least 10 mol%, preferably at least 30 mol% LMO, in each case based on the total number of moles of the active material of the
• Cathodic electrode (ie not based on the cathodic electrode in total, which may in addition to the active material still conductivity additives, binders, stabilizers, etc.).
• the proportion of the lithium-manganese oxide in the active material is 5 to 25 mol%.
• NMC and LMO together account for at least 60 mole% of the active material, more preferably at least 70 mole%, more preferably at least 80 mole%, even more preferably at least 90 mole%, each based on the total moles of active material of the cathodic electrode (ie not based on the cathodic electrode in total, which in addition to the active material may still comprise conductivity additives, binders, stabilizers, etc.).
• the material applied to the carrier is essentially active material, ie that 80 to 95 percent by weight of the on the support of the cathodic electrode
• the applied material is the said active material, more preferably 86 to 93 weight percent, each based on the total weight of the material (ie based on the cathodic electrode without carrier total, which in addition to the active material nor conductivity additives, binders,
• Stabilizers etc. may include). With regard to the ratio in parts by weight of NMC as active material to LMO as active material, it is preferred that this ratio ranges from 9 (NMC): 1 (LMO) to 3 (NMC): 7 (LMO), where 7 (NMC) : 3 (LMO) up to 3 (NMC): 7 (LMO) is preferred and with 6 (NMC): 4 (LMO) up to 4 (NMC): 6 (LMO) being more preferred.
• a mixture of lithium nickel manganese cobalt mixed oxide (NMC) with at least one lithium manganese oxide (LMO) leads to increased stability, in particular improved lifetime of the cathodic electrode. Without being bound to any theory, it is believed that these improvements are due to the increased manganese content over pure NMC. In this case, the high energy density and the other advantages of lithium-nickel-manganese-cobalt-mixed oxide (NMC) over lithium-manganese oxides (LMO) are largely retained in the mixture.
• a combination of these materials with the abovementioned proportions of polyanion active materials is particularly preferred, since this also minimizes the costs without having to make any significant limitations with regard to the performance of the battery.
• Lithium manganese oxides are usually present in a spinel structure.
• Lithium manganese oxides in spinel structure and for the purposes of the present invention comprise as transition metal at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol% of manganese, in each case based on the total number of moles of oxide present in total
• a preferred stoichiometry of the lithium-manganese oxide is Li 1 + x Mn 2 -y MyO 4 where M is at least one metal, in particular at least one transition metal, and -0.5 (preferably -0.1) ⁇ x ⁇ 0.5 (preferred 0.2), 0 ⁇ y ⁇ 0.5.
• spinel structure is well-known to the person skilled in the art as a widely-used crystal structure, named after its main agent, the mineral "spinel” (magnesium aluminate, MgAl 2 O 4 ), for compounds of the type AB 2 X 4 .
• the structure consists of a cubic close packing of the chalcogenide (here oxygen) ions whose tetrahedral and Okatederlücken are (partially) occupied by the metal ions.
• Spinels as cathode materials for lithium-ion cells are exemplified in Chapter 12 of "Lithium Batteries", published by Nazri / Pistoia (ISBN: 978-1-4020-7628-2).
• Pure lithium manganese oxide can have, for example, the stoichiometry LiMn 2 O 4 .
• the lithium-manganese oxides used in the present invention are preferably modified and / or stabilized, since pure LiMn 2 0 4 has the disadvantage that under certain circumstances Mn ions are released from the spinel structure.
• this stabilization of the lithium-manganese oxides can be effected, as long as the lithium-manganese oxide can be kept stable under the operating conditions of a Li-ion cell for the desired service life.
• stabilization methods reference is made by way of example to WO 2009/011 157, US Pat. No. 6,558,844, US Pat. No. 6,183,718 or EP 816,292. These describe the use of stabilized lithium manganese oxides in spinel structure as sole active material for cathodic electrodes in lithium-ion batteries.
• Particularly preferred stabilization methods include doping and coating.
• the active materials for example, lithium polyanion compound, NMC, and LMO
• the active materials for example, lithium polyanion compound, NMC, and LMO
• the active material is "applied” to a carrier for the purposes of the present invention.
• the active material can be applied as a paste or as a powder, or deposited from the gas phase or a liquid phase, for example as a dispersion. Preference is given to an extrusion process.
• the active material is applied as a paste or dispersion directly onto the cathodic electrode. Coextrusion with the other components of the electrochemical cell, in particular anodic electrode and separator, then results in a laid or laminated composite (see discussion of extrudates and laminates below).
• the terms "paste” and "dispersion” are used interchangeably herein.
• a "laid" electrode stack is not permanently bonded but the layers (cathode-separator-anode etc.) are merely superimposed and optionally pressed.
• an adhesive and / or a heat treatment is carried out in a "laminate", so that the stack is permanently laminated ("glued") and thus held together irrespective of possible compression (achieved, for example, by applying a vacuum to a vacuum-tight covering around the electrode stack) becomes.
• the electrodes and the separator are wound, preferably in a flat coil.
• the active material is not applied as such to the support, but in common with other non-active (i.e., non-lithium intercalating) other components.
• the cathodic electrode comprises a stabilizer, for example Aerosil or Sipernat. It is preferred if these stabilizers in a weight ratio of up to 5 weight percent, preferably up to
• the active material for the cathodic and / or anodic electrode contains the separator described below, ie a separator comprising at least one porous ceramic material, in particular the "separation" described below, as powdery admixture, preferably in a weight ratio from
• Such conductivity additives include, for example, conductive carbon black (Enasco) or graphite (KS 6), preferably in a weight ratio of 1 weight percent to 6 weight percent, more preferably 1 weight percent to 3 weight percent, each based on the total weight of the cathodic electrode applied to the carrier. It also can
• Structural materials particularly structural materials in the nanometer range or conductive carbon 'nanotubes "are introduced, for example, Bayer” Baytubes ® ".
• the above-defined active materials for the electrodes, in particular for the cathodic electrode, are present on a support.
• the carrier or the carrier material there are no restrictions with respect to the carrier or the carrier material, except that this or this must be suitable for receiving the at least one active material, in particular the at least one active material of the cathodic electrode and that the carrier has a thickness of 5 ⁇ m to 100 ⁇ m ⁇ , preferably 10 m to 75 ⁇ , more preferably 15 m to 45 ⁇ , so must be dimensioned comparatively thin.
• the carrier is preferably formed as a collector foil.
• the support may be homogeneous, or comprise a layered structure, or be or comprise a composite material.
• the carrier preferably also contributes to the removal or supply of electrons.
• the carrier material is therefore preferably at least partially electrically conductive, preferably electrically conductive.
• the support material in this embodiment preferably comprises aluminum or copper or consists of aluminum or copper.
• the carrier is preferably connected to at least one electrical Abieiter.
• the carrier preferably also serves for heat removal from the interior of the cell.
• the carrier may be coated or uncoated and may be a composite material.
• anodic electrode means the electrode which, when connected to a consumer ("discharging"), for example an electric motor, Emit electrons.
• the anodic electrode is thus in this case the "negative electrode” into which the ions are incorporated during charging.
• the anodic electrode preferably comprises carbon and / or lithium titanate, more preferably coated graphite, or consists of Li metal.
• an anodic electrode comprising coated graphite is used in the electrochemical cell. It is particularly preferred that the anodic electrode comprises conventional graphite or so-called “soft" carbon ("soft carbon"), which is coated with harder carbon, in particular with “hard carbon”. The harder carbon / hard carbon has a hardness of
• the "conventional” graphite may be natural graphite such as UFG8 from Kropfmühl or may have a C-fiber content or carbon nanotubes (CNT) of up to 38% or CNT proportionally.
• CNT carbon nanotubes
• Anodic electrode comprising conventional graphite ("soft carbon”, natural graphite), which is coated with “hard carbon”, increases the stability of the electrochemical cell to a particular extent in cooperation with the cathodic electrode according to the invention.
• the electrodes, as well as the separator are in layers as films or layers.
• the electrodes as well as the separator in the form of a layer or in the form of layers of the corresponding Materials or substances are constructed.
• these layers or layers can be superimposed, laminated or wound.
• the separators used therein which separate a cathodic electrode from an anodic electrode, should be designed so that they allow easy passage of charge carriers.
• the separator is ion-conducting and preferably has a porous structure.
• the separator allows the passage of lithium ions through the separator.
• the separator comprises at least one inorganic material, preferably at least one ceramic material. It is preferred that the separator comprises at least one porous ceramic material, preferably in an applied on an organic carrier material
• a separator of this type is known in principle from WO 99/62620 or can be prepared by the methods disclosed therein. Such a separator is commercially available under the trade name Separion ® Evonik.
• the ceramic material for the separator is selected from the group of oxides, phosphates, sulfates, titanates, silicates, aluminosilicates, borates of at least one metal ion.
• oxides of magnesium, calcium, aluminum, silicon, zirconium and titanium are used, and silicates (especially zeolites), borates and phosphates.
• This ceramic material has a sufficient porosity for the function of the electrochemical cell, but compared to conventional separators, which do not comprise ceramic material, substantially more temperature-resistant and shrinks at higher temperatures less.
• a ceramic separator also advantageously has a high mechanical strength.
• the ceramic separator in conjunction with the cathodic electrode active material according to the invention, which causes increased thermal stability and aging resistance, can be reduced in its layer thickness so that the cell size can be reduced and the energy density can be increased with superior safety and mechanical strength , This allows, inter alia, to achieve the desired according to the invention small thicknesses of the carrier / electrodes, without affecting the safety of the cell.
• thicknesses of 2 pm to 50 pm are preferred for the separator, in particular 5 pm to 25 pm, more preferably 10 pm to 20 pm.
• the increased thermal stability and aging resistance of the cathodic electrode-as stated above- makes it possible in the present case to make the separator layer, with its intrinsic resistance, thinner and thus of lower cell impedance than the separators of the prior art.
• the inorganic substance or the ceramic material is present in the form of particles having a maximum diameter of less than 100 nm.
• the inorganic substance, preferably the ceramic particles, is / are preferably present on an organic carrier material.
• the separator is preferably coated with polyetherimide (PEI).
• PEI polyetherimide
• an organic material is used, which is preferably configured as a nonwoven web, wherein the organic material preferably comprises a polyethylene glycol terephthalate (PET), a polyolefin (PO) or a polyetherimide (PEI), or mixtures thereof.
• the carrier material is advantageously formed as a film or thin layer.
• said organic material is or comprises a polyethylene glycol terephthalate (PET).
• this separator which is preferably present as a composite of at least one organic carrier material with at least one inorganic (ceramic) substance, is formed as a layered composite in film form, which is preferably coated on one or both sides with a polyetherimide.
• the separator consists of a layer of magnesium oxide, which is further preferably coated on one or both sides with polyetherimide.
• 50 to 80 percent by weight of the magnesium oxide may be replaced by calcium oxide, barium oxide, barium carbonate, lithium,
• the polyetherimide with which the inorganic substance is coated on one or both sides in the preferred embodiment is preferably in the form of the above-described (nonwoven) nonwoven fabric in the separator.
• nonwoven here means that the fibers in non-woven Form present (non-woven fabric).
• Such nonwovens are known from the prior art and / or can be prepared by the known methods, for example by a spunbonding method or a
• Polyetherimides are known polymers and / or can be prepared by known methods. For example, such methods are disclosed in EP 0 926 201. Polyetherimides are commercially available, for example under the trade name Ultem ®. According to the invention, said polyetherimide may be present in the separator in one layer or in several layers, in each case on one side and / or on both sides on the layer of the inorganic material.
• the polyetherimide comprises a further polymer.
• This at least one further polymer is preferably selected from the group consisting of polyester, polyolefin, polyacrylonitrile, polycarbonate, polysulfone, polyethersulfone, polyvinylidene fluoride, polystyrene.
• the further polymer is a polyolefin.
• Preferred polyolefins are polyethylene and polypropylene.
• the polyetherimide preferably in the form of the nonwoven fabric, is preferably coated with one or more layers of the further polymer, preferably of the polyolefin, which is preferably also present as nonwoven fabric.
• the coating of the polyetherimide with the further polymer, preferably the polyolefin can be achieved by gluing, lamination, by a chemical reaction, by welding or by a mechanical connection.
• Such polymer composites and processes for their preparation are known from EP 1 852 926.
• the nonwovens are made of nanofibers or of technical glasses of the polymers used, whereby nonwovens are formed, which have a high porosity with formation of small pore diameters.
• the fiber diameters of the polyletherimide nonwoven are larger than the fiber diameter of the further polymer nonwoven, preferably of the polyolefin nonwoven.
• the nonwoven fabric made of polyetherimide then has a higher pore diameter than the nonwoven fabric, which is made of the other polymers.
• a polyolefin in addition to the polyetherimide ensures increased safety of the electrochemical cell, since undesirable or excessive heating of the cell, the pores of the polyolefin contract and the charge transport through the separator is reduced or terminated. Should the temperature of the electrochemical cell increase to such an extent that the polyolefin begins to melt, the polyetherimide, which is very stable to the action of temperature, effectively counteracts the melting together of the separator and thus an uncontrolled destruction of the electrochemical cell.
• the ceramic separator is formed of a flexible ceramic composite material.
• a composite material (composite material) is made of different, firmly bonded materials. Such a material may also be referred to as a composite material.
• this composite material is formed from ceramic materials and from polymeric materials. It is known to provide a web of PET with a ceramic impregnation or support. Such composite materials can withstand temperatures of over 200 ° C (in some cases up to 700 ° C).
• a separator layer or a separator at least partially extends over a boundary edge of at least one in particular adjacent electrode. Particularly preferably, a separator layer or a separator extends beyond all boundary edges, in particular of adjacent electrodes. Thus, electrical currents between the edges of electrodes of an electrode stack are reduced or prevented.
• the separator layer is formed directly on the negative or the positive electrode or the negative and the positive electrode.
• the inorganic substance of the separator is applied as a paste or dispersion directly to the negative electrode and / or the positive electrode. Coextrusion then forms a laminate composite.
• a paste extrusion is particularly preferred for the present invention.
• the laminate composite then comprises an electrode and the separator or the two electrodes and the separator between them.
• the resulting composite can be dried or sintered according to the usual methods, if necessary.
• the anodic electrode and the cathodic electrode as well as the layer of the inorganic substance, ie the separator, separately from one another.
• the inorganic substance or the ceramic material is / are then preferably in the form of a film.
• the Separately prepared electrodes and the separator are then supplied continuously and separately to a processor unit, wherein the merged negative electrode with the separator and the positive electrode to a cell composite (preferred) or laminated or wound.
• the processor unit preferably comprises or consists of laminating rollers. Such a method is known from WO 01/82403.
• the mixture is by way of paste extrusion, optionally without prior mixing and
• one of the components of the electrolyte can be used as the flow aid, but also a mixture, for example, ethyl carbonate (EC) / ethyl methyl carbonate (EMC) in a ratio of 3: 1 (+/- 20%).
• EC ethyl carbonate
• EMC ethyl methyl carbonate
• the active materials are metered, used and then squeezed through a nozzle.
• the lubricant still containing extrudate is freed of lubricant in a drying zone and then sintered and / or calendered. This ensures that the abrasion is minimized, which contributes to an increased life of the aggregates and the cells. It saves energy, since it can be extruded at room temperature and a complex, controlled homogeneous heating eliminates. Also the
• further substances such as free-radical scavengers or ionic liquids are preferably extruded, which effect a prolonged life of the cells, for example by injection over an area / mass of extruded constituents in the amount of the described additives or stabilizers, or of additives such as vinylene carbonate or fire retardants, such as "firesorb", or nanometer-structured material in microcapsules, the encapsulation of which may consist of polymeric substances which diffuse out only at excessive temperature and the " wet" or ionically seal the electrode.
• Electrodes in the thickness range of cathode 50 ⁇ m to 125 ⁇ m and anode 10 ⁇ m to 80 ⁇ m are preferably produced on the substrates / substrates after calendering.
• the electrodes in the upper area of the mentioned thicknesses are built into “high energy” cells, conversely the thin electrodes become “high power” cells.
• Injected are the o.a. Stabilizers and Conductivity additives preferred according to recipe content of 3% maximum.
• the active materials and in particular the lithium-nickel-manganese-cobalt mixed oxide and the lithium-manganese oxide are each in particulate form, preferably as particles having an average diameter of 1 pm to 50 pm 2 pm to 40 pm, more preferably 4 pm to 20 pm.
• the particles may also be secondary particles which are composed of primary particles. The above mean diameters then refer to the secondary particles.
• a homogeneous and intimate mixing of the phases, in particular the phases in particle form, contributes to the fact that the aging resistance of the lithium-nickel-manganese-cobalt mixed oxide is particularly advantageously influenced in this mixture.
• Other types of "blending,” such as alternating deposition of layers on a support or coating of particles, are also possible.
• an electrochemical cell according to the invention comprising the two electrodes, in particular here the cathodic electrode and the separator in an electrolyte with a gas-tight enclosure, will be described.
• dimethylformamide From dimethylformamide are electrostatically spun polyetherimide fibers having a mean fiber diameter of about 2 pm and this processed into a nonwoven fabric having a thickness of about 15 pm.
• Disperser dispersed until a homogeneous dispersion is formed.
• a dispersion prepared under b) is applied to the fleece produced under a), so that the applied layer has a thickness of approximately 20 ⁇ m (separator).
• NMC lithium nickel manganese cobalt mixed oxide
• LMO lithium manganese oxide
• the layers produced according to c), d) and e) are wound on a winding machine, so that the product according to c) comes to rest between the coatings of the products according to d) and e), the polyetherimide nonwoven covering the Coating the product according to Example e) contacted.
• the metal foils (collector foils) are connected and provided with Abieitern and the system housed in a shrink film.
• the enclosure does not include any device for dismantling one
• the anode is advantageously a graphite system of a "soft carbon” coated with a “hard carbon”, with “hard carbon” being present only up to 15%.
• the cathode is designed for large format stack cells, i. especially coated as or in pattern form.
• the resulting cells even in the "high energy” version, have a high load capacity up to 10C, are resistant to aging and have outstanding cycle properties> 5,000 full cycles (80%).
• Manipulated entry of a copper lobe or chip was enveloped by the polymers that were injected and failed to form a sectoral "hot spot”.
• the "high-power" version is extremely cycle-stable and resilient, beyond> 20C.

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