EP2489092A1 - Electrode cathodique et cellule électrochimique correspondante - Google Patents

Electrode cathodique et cellule électrochimique correspondante

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Publication number
EP2489092A1
EP2489092A1 EP10771331A EP10771331A EP2489092A1 EP 2489092 A1 EP2489092 A1 EP 2489092A1 EP 10771331 A EP10771331 A EP 10771331A EP 10771331 A EP10771331 A EP 10771331A EP 2489092 A1 EP2489092 A1 EP 2489092A1
Authority
EP
European Patent Office
Prior art keywords
cathodic electrode
lithium
nmc
active material
lmo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10771331A
Other languages
German (de)
English (en)
Inventor
Tim Schaefer
Andreas Gutsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Li Tec Battery GmbH
Original Assignee
Li Tec Battery GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Li Tec Battery GmbH filed Critical Li Tec Battery GmbH
Publication of EP2489092A1 publication Critical patent/EP2489092A1/fr
Withdrawn legal-status Critical Current

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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
    • H01M4/36—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49117—Conductor or circuit manufacturing
    • Y10T29/49204—Contact or terminal manufacturing

Definitions

  • the present invention relates to a cathodic electrode for an electrochemical cell comprising at least one support on which at least one active material is deposited or deposited, wherein the active material is a mixture of a lithium-nickel-manganese-cobalt mixed oxide (NMC), which does not is present in a spinel structure, with a lithium manganese oxide (LMO) in spinel structure.
  • NMC lithium-nickel-manganese-cobalt mixed oxide
  • LMO lithium manganese oxide
  • the present invention also relates to an electrochemical cell having a cathodic electrode with this active material and an anodic electrode and a separator which is at least partially disposed between these electrodes.
  • Said cathodic electrode or said electrochemical cell find 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”).
  • batteries with high energy and / or power density are preferably used in power tools and electric vehicles, for example in hybrid-powered vehicles.
  • Lithium-ion batteries are examples of such batteries.
  • lithium-ion cells and in lithium-ion batteries are particularly preferred.
  • said Lithium-ion cells and lithium-ion batteries are used in power tools and for driving vehicles, both fully or predominantly 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.
  • active materials for example, active materials, for example, active materials, for
  • lithium cobalt oxides eg L1C0O2
  • lithium manganese oxides eg LiMn 2 0 4
  • lithium (nickel) cobalt aluminum oxides NCA
  • Electric vehicles or vehicles with hybrid drives suitable.
  • An active material for cathodic electrodes which can be used in principle for electrochemical cells and batteries that can be used in power tools, electrically driven vehicles or vehicles with hybrid drive, mixed oxides of lithium with nickel, manganese and cobalt (lithium-nickel-manganese Cobalt mixed oxides, "NMC").
  • lithium-nickel-manganese-cobalt mixed oxides are preferable in particular to lithium cobalt oxides, and, for reasons of energy density, to lithium polyanion compounds likewise conceivable as active materials, for example LiFePO 4 ("LiPF" has an approximately 50th strength % lower energy density than lithium-nickel-manganese-cobalt mixed oxides, which is particularly important for non-stationary applications).
  • NCM nickel-manganese-cobalt mixed oxides of Lithium
  • an electrochemical cell having cathodic and anodic electrodes and separator the reduced stability of NMC as cathodic electrode material may result in the use of a separator of increased layer thickness.
  • an object of the present invention can be seen to provide improved cathodic electrode active material.
  • advantages of the improved active material for a cathodic electrode this should be as safe as possible, have a comparatively high energy and / or power density and / or be improved in terms of aging resistance (service life).
  • Another object of the present invention is to provide an improved electrochemical cell.
  • the improved electrochemical cell it should, if possible, have smaller dimensions and thus an improved energy density and / or power density with an improved service life.
  • a cathodic electrode for an electrochemical cell comprising at least one support on which at least one active material is applied or deposited, wherein the active material comprises a 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.
  • NMC lithium-nickel Manganese-cobalt mixed oxide
  • LMO lithium manganese oxide
  • an electrochemical cell with a cathodic electrode comprising at least one support on which at least one active material is applied or deposited, the active material comprising a mixture of a lithium nickel manganese cobalt mixed oxide (NMC), which is not in a spinel structure, with a lithium manganese oxide ( LMO) in spinel structure; an anodic electrode; and a separator disposed at least partially between these electrodes.
  • NMC lithium nickel manganese cobalt mixed oxide
  • LMO lithium manganese oxide
  • the said separator comprises at least one porous ceramic material, preferably in a layer applied to an organic carrier material.
  • Said cathodic electrode or said electrochemical cell find a preferred application in batteries, which are preferably used in power tools and electrically driven vehicles, including vehicles with hybrid drive or with fuel cells. They should do this
  • Batteries have a high energy and / or power density.
  • cathodic electrode refers to the electrode that receives electrons when it is connected to a load, for example when operating an electric motor, and the cathodic electrode is therefore the "positive electrode” in this case.
  • An “active material” of cathodic and anodic electrode according to the present invention is a material which can store lithium in ionic or metallic or any intermediate form, in particular in a lattice structure can store ("intercalation").
  • the active material thus participates “actively” in the electrochemical reactions occurring during charging and discharging (in contrast to other possible components of the
  • Electrode such as binder, stabilizer or carrier.
  • the cathodic electrode according to the present invention comprises at least one active material, wherein the active material is a 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.
  • NMC Lithium-nickel-manganese-cobalt mixed oxide
  • LMO lithium manganese oxide
  • the active material comprises at least 30 mol%, preferably at least 50 mol% NMC and at least 10 mol%, preferably at least 30 mol% LMO, in each case based on the total moles of the active material of the cathodic electrode (ie not based on the cathodic Total electrode, which in addition to the active material may also comprise conductivity additives, binders, stabilizers, etc.).
  • 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 total cathodic electrode, which in addition to the active material may also comprise conductivity additives, binders, stabilizers, etc.).
  • the active material essentially consists of NMC and LMO, ie contains no other active materials in an amount of more than 2 mol%.
  • the material applied to the support is essentially active material, ie 80 to 95 percent by weight of the material deposited on the support of the cathodic electrode is said active material, more preferably 86 to 93 percent by weight, based in each case on the total weight of the Materials (that is, based on the cathodic electrode without carrier total, which may in addition to the active material still Leitmaschines- keitszu accounts, binders, stabilizers, etc.).
  • NMC NMC
  • NMC 3 (LMO) up to 3 (NMC): 7 (LMO)
  • 6 (NMC): 4 (LMO) up to 4 (NMC): 6 (LMO) being more preferred.
  • the mixture according to the invention of the lithium-nickel-manganese-cobalt mixed oxide (NMC) preferred as active material 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.
  • the composition of the lithium-nickel-manganese-cobalt mixed oxide there are no restrictions with respect to the composition of the lithium-nickel-manganese-cobalt mixed oxide, except that this oxide in addition to 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 metals 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: Li [Coi / 3Mni 3 ii 3] O 2 , where the proportion of Li, Co, Mn, Ni and O is in each case about ⁇ 5% can vary.
  • lithium-nickel-manganese-cobalt mixed oxides are not present in a spinel structure. Rather preferably, these lithium-nickel-manganese-cobalt mixed oxides of the present invention, even during unloading and loading operation are not subject to any appreciable (ie, not in the scope of more than In contrast to this, lithium manganese oxides (LMO) are present in a spinel structure, while lithium manganese oxides in spinel structure and in the sense of the present invention
  • 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 moles of transition metals present in total in the oxide.
  • 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 closest-packing of the chalcogenide (here oxygen) ions whose tetrahedral and octate gaps 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 may exemplarily have 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 O has the disadvantage that under some 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.
  • known stabilization methods reference is made by way of example to WO 2009/011157, US Pat. No. 6,558,844, US Pat. No.
  • Preferred mixtures are present as homogeneous powders or pastes or dispersions.
  • the mixture is produced continuously by means of paste extrusion, optionally without previous mixing and drying phase, and drawn up and compacted to the electrode.
  • the lithium-nickel-manganese-cobalt mixed oxide and the lithium-manganese oxide are each in particle form, preferably as particles having an average diameter of 1 pm to 50 pm, preferably 2 pm to 40 ⁇ m , 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 two phases, in particular of the two phases in particle form, contributes to the aging resistance of the lithium-nickel-manganese-cobalt mixed oxide being particularly advantageously influenced in this mixture.
  • the active material is "applied” to a carrier and there are no restrictions on this "application” of the active material to the carrier.
  • the active material can be applied as a paste or as a powder, or be deposited from the gas phase or a liquid phase, for example as a dispersion.
  • the active material is applied as a paste or dispersion directly onto the cathodic electrode. Coextrusion with the other constituents of the electrochemical cell, in particular anodic electrode and separator, then produces a laminate composite (see discussion of extrudates and laminates below). Such methods are disclosed, for example, in EP 1 783 852.
  • the terms "paste” and "dispersion” are used synonymously.
  • 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 3
  • Percent by weight based in each case on the total weight of the cathodic electrode mass applied to the support.
  • this stabilizer comprises the separator described below, that is to say a separator comprising at least one porous ceramic workpiece.
  • a separator comprising at least one porous ceramic workpiece.
  • the "separation" described below as a pulverulent admixture, preferably in a weight ratio of 1 weight percent to 5 weight percent, more preferably 1 weight percent to 2.5 weight percent, each based on the total weight of the applied to the carrier mass of the cathodic electrode
  • an electrochemical cell having a separator layer comprising at least one porous ceramic material as described below, this results in particularly stable and safe cells
  • Such conductive additives include, for example, carbon black (Enasco) or graphite (KS 6), preferably in one Weight ratio of 1 weight percent to 6 weight percent, more preferably 1 weight percent to 3 weight percent
  • 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 regard to the carrier or the carrier material, except that this or this must be suitable for accommodating the at least one active material, in particular the at least one active material of the cathodic electrode.
  • said carrier during operation of the cell or battery, ie in particular in the discharge and charging operation, compared to the active material substantially or largely be inert.
  • the support may be homogeneous, or comprise a layered structure or be or include 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 may be coated or uncoated and may be a composite material.
  • the cathodic electrode described above is used in an electrochemical cell, this electrochemical cell then having:
  • a cathodic electrode comprising at least one
  • Carrier on which at least one active material is deposited or deposited wherein the active material comprises a mixture of a lithium nickel manganese cobalt mixed oxide (NMC), which is not in a spinel structure, with a lithium manganese oxide (LMO) in
  • anodic electrode means the electrode that emits electrons when connected to a load such as an electric motor, and thus the anodic electrode is the “negative electrode” in this case.
  • the anodic electrode preferably comprises carbon and / or lithium titanate, more preferably coated graphite.
  • 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.” In this case, this harder carbon / hard carbon has a Hardness of
  • the "conventional” graphite can be natural graphite such as Kropfmühl's UFG8, optionally with a C-fiber content of up to 38%.
  • the proportion of "hard carbon” relative to “hard carbon” + “soft carbon” is preferably at most 15%
  • An anodic electrode comprising conventional graphite ("soft carbon", natural graphite), which is coated with “hard carbon”, increases in interaction
  • the cathodic electrode according to the invention the stability of the electrochemical cell is particularly pronounced.
  • the electrodes, as well as the separator are present in layers as films or layers. This means that the electrodes as well as the separator are in the form of a layer or in the form of a layer Layers are made of the corresponding materials or substances In the electrochemical cell, these layers or layers can be superposed, laminated or wound. For the purposes of the present invention, it is preferable if the layers or layers are stacked without laminating them.
  • the separators used therein which separate the cathodic electrode from the 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. In the case of the present electrochemical cell operating with lithium ions, the separator allows the passage of lithium ions through the separator.
  • the separator comprises at least one inorganic material, preferably a ceramic material. It is preferred that the separator comprises at least one porous ceramic material, preferably in a layer applied to an organic carrier material.
  • a separator of this type is known in principle from WO 99/62620 A1 or can be prepared by the methods disclosed therein. Such a separator is also commercially available under the trade name Separion® Evonik.
  • the ceramic material 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.
  • silicates especially zeolites
  • borates and phosphates are disclosed in EP 1 783 852.
  • 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 ,
  • thicknesses of 2 to 50 ⁇ m are preferred for the separator, in particular 5 to 25 ⁇ m, more preferably 10 to 20 ⁇ m.
  • 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).
  • PET polyethylene glycol terephthalate
  • PO polyolefin
  • PEI polyetherimide
  • the carrier material is advantageously formed as a film or thin layer.
  • said organic material is a polyethylene glycol terephthalate (PET).
  • PET polyethylene glycol terephthalate
  • the organic material is preferably coated with an inorganic ion conducting material which is preferably ion conducting in a temperature range of -40 ° C to 200 ° C.
  • 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 the polyetherimide.
  • magnesium oxide may be replaced by calcium oxide, barium oxide, barium carbonate, lithium, sodium, potassium, magnesium, calcium, barium phosphate, or by lithium, sodium, potassium borate, or mixtures of these compounds be.
  • the polyetherimide with which the layer of the inorganic substance is coated on one or both sides in the preferred embodiment, is preferably present in the form of the above-described nonwoven fabric in the separator.
  • nonwoven fabric means that the fibers are in nonwoven fabric (non-woven fabric)
  • nonwoven fabrics are known in the art and / or can be prepared by the known methods, for example, by a spunbonding process or Meltblowing process as described in DE 195 01 271 A1.
  • 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 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 further polymer.
  • 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 starts to melt, the polyetherimide which is very stable against 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 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 (sometimes 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. This also reduces electrical currents between the edges of electrodes of an electrode coil.
  • methods known in principle may be used, such as, for example, the methods described in Handbook of Batteries, Third Edition, McGraw-Hill, Editors: D. Linden, TB Reddy, 35.7. 1.
  • 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 onto the negative electrode and / or the positive electrode. Coextrusion then forms a laminate composite. In this case, 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 each other.
  • 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 continuously and separately supplied to a processor unit, wherein the merged negative electrode with the separator and the positive electrode are laminated into a cell assembly.
  • the processor unit preferably comprises or consists of laminating rollers. Such a method is known from WO 01/82403. Examples
  • a significantly smaller separator thickness can be selected (than when lithium-nickel-manganese-cobalt mixed oxide is used alone for the cathodic electrode), thus achieving a higher overall energy and power density.
  • Disperser dispersed until a homogeneous dispersion is formed.
  • a dispersion prepared under b) is prepared on the under a)
  • 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 lie between the coatings of the products according to d) and e), the polyetherimide nonwoven contacted the coating of the product according to Example e).
  • the metal foils are provided with Abieitern and the system housed in a shrink film.
  • the total content NMC / LMO is LMO 86 to 93%, the latter in reduction of the remaining components in the ratio and preferably in highly dynamic cells.
  • one of the constituents of the electrolyte can be used as a flow aid, but also a mixture, for example EC / EMC 3: 1.
  • Preference is given to processing in kneaders which are essentially quasi anhydrous, TP-65 grd. TP and be guided or acted upon.
  • the electrodes or the cell lamintas by paste extrusion.
  • a paste extruder for example Common Tee
  • the active materials are metered, used and then squeezed out 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 service life of the aggregates and the cells. It saves energy because it can be extruded at room temperature and a complex, controlled homogeneous heating is eliminated.
  • the odor load by plasticizer vapors on the extruder is minimized.
  • 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 components in the amount of the described additives or stabilizers, or of additives such as vinylene carbonate or Fire retardants, such as firesorb, also as nanometer-structured material in microcapsules, the encapsulation of which may consist of polymeric substances such as stoba, which diffuse out only at excessive temperature and wet or ionically seal the electrode.
  • collector tapes in copper and aluminum of 30 and 20 ⁇ m, respectively were selected, which at the same time better cool the cell and the electrode material, which thereby are correspondingly current carrying capacity. Electrodes in the thickness range cathode 55 to 125 pm and anode 18 to 80 pm after calendering were produced on the collector baffles. The upper electrodes in the upper part of the mentioned thicknesses were built into "high energy" cells, conversely the thin electrodes turned into "high power” cells.
  • the anode is advantageously a graphite system made of a "soft carbon” coated with a “hard carbon”, with “hard carbon” being present only up to 15%.
  • the cathode is designed for large-sized stacked cells, ie in particular coated 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 injected polymers and failed to form a sectoral "hot spot.”
  • the "high power" design is extremely cycle stable and resilient, beyond> 20C.
  • electrolyte With regard to the electrolyte it could be shown that it is sufficient to use simple mixtures such as EC / EMC 1: 3 with an additive such as VC or "redox shuttle" (without further, partly harmful to the environment, questionable additives), since the additive effect on the As a result, the electrolyte becomes more environmentally friendly and cheaper and a very good result in overcrowding the cold cranking test can be detected.
  • an additive such as VC or "redox shuttle”

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne une électrode cathodique, comprenant au moins un support sur lequel au moins un matériau actif est appliqué ou déposé, ledit matériau actif comprenant un mélange d'oxyde mixte de lithium-nickel-manganèse-cobalt (NMC) qui ne se présente pas en structure spinelle, avec un oxyde de lithium-manganèse (LMO) en structure spinelle. L'invention concerne également une cellule électrochimique présentant cette électrode cathodique et un séparateur comprenant au moins un matériau céramique poreux.
EP10771331A 2009-10-14 2010-10-12 Electrode cathodique et cellule électrochimique correspondante Withdrawn EP2489092A1 (fr)

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DE102009049326A DE102009049326A1 (de) 2009-10-14 2009-10-14 Kathodische Elektrode und elektrochemische Zelle hierzu
PCT/EP2010/006220 WO2011045028A1 (fr) 2009-10-14 2010-10-12 Electrode cathodique et cellule électrochimique correspondante

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US (1) US20120282513A1 (fr)
EP (1) EP2489092A1 (fr)
JP (1) JP2013507745A (fr)
KR (1) KR20120102631A (fr)
CN (1) CN102549830A (fr)
BR (1) BR112012008436A2 (fr)
DE (1) DE102009049326A1 (fr)
WO (1) WO2011045028A1 (fr)

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WO2011045028A1 (fr) 2011-04-21
KR20120102631A (ko) 2012-09-18
JP2013507745A (ja) 2013-03-04
BR112012008436A2 (pt) 2016-03-29
US20120282513A1 (en) 2012-11-08
CN102549830A (zh) 2012-07-04
DE102009049326A1 (de) 2011-04-21

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