EP3308418A1 - Ncm à haute énergie dopé na et dopé nb, w et/ou mo - Google Patents

Ncm à haute énergie dopé na et dopé nb, w et/ou mo

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Publication number
EP3308418A1
EP3308418A1 EP16724429.2A EP16724429A EP3308418A1 EP 3308418 A1 EP3308418 A1 EP 3308418A1 EP 16724429 A EP16724429 A EP 16724429A EP 3308418 A1 EP3308418 A1 EP 3308418A1
Authority
EP
European Patent Office
Prior art keywords
active material
electrode
tungsten
niobium
lithium
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.)
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Application number
EP16724429.2A
Other languages
German (de)
English (en)
Inventor
Malte ROLFF
Anika Marusczyk
Thomas Eckl
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.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
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Filing date
Publication date
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of EP3308418A1 publication Critical patent/EP3308418A1/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Withdrawn legal-status Critical Current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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/485—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
    • 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
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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 present invention relates to an active material, an electrode material and an electrode for an electrochemical energy store, in particular a lithium cell, a manufacturing method thereof and an electrochemical energy store equipped therewith.
  • High-energy materials such as high-energy nickel-cobalt-manganese oxide (HE-NCM) of general chemical formula: x LiM0 2 : 1-x Li 2 Mn0 3 , where M is nickel (Ni), cobalt (Co) and Manganese (Mn), which is also referred to as Overlithiated Layered Oxide (OLO), are very interesting battery materials because of high starting energy densities and starting voltages, but so far have limited rate capability and exhibit lifetime performance a significant loss of voltage (English: Voltage Fade), which with a Capacity decline (English: Capacity Fade) goes along, why they are not yet used commercially.
  • HE-NCM high-energy nickel-cobalt-manganese oxide
  • OLO Overlithiated Layered Oxide
  • the document US 2009/0155691 Al relates to a process for producing a lithium alkali transition metal oxide as a positive electrode material for a lithium secondary battery.
  • Document US 2008/0090150 A1 relates to active material particles of a lithium-ion secondary battery, which comprises at least one first lithium-nickel composite oxide.
  • Document EP 2 720 305 A1 relates to a cathode active material and a nickel composite hydroxide as a precursor of the cathode active material.
  • US 2009/0297947 A1 relates to nanostructured, dense and spherically layered positive active materials.
  • the present invention is a, for example, overlithiated, for example, sodium-doped, in particular lithiierbares,
  • transition metal oxide based, active material in particular a
  • M is nickel (Ni) and / or cobalt (Co) and / or manganese (Mn), where M 'is niobium (Nb) and / or tungsten (W) and / or molybdenum (Mo), for example niobium ( Nb) and / or tungsten (W), and, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.5 and 0 ⁇ z ⁇ 1.
  • An active material may, in particular, be understood as meaning a material which participates in particular in a charging process or discharging process and thus may constitute the actually active material.
  • an electrochemical energy store may in particular be understood as any battery.
  • an energy store may comprise a primary battery or, in particular, a secondary battery, that is to say a rechargeable accumulator.
  • a battery can be a galvanic element or a plurality of
  • an energy store may comprise a lithium-based energy store, such as a lithium-ion battery.
  • a lithium-based energy store such as a lithium-ion battery
  • a lithium-based energy store can be understood to mean in particular an energy store whose electrochemical processes are at least partially based on lithium ions during a charging or discharging process.
  • Such an energy store can be used, for example, as a battery for laptop, PDA, mobile phone and other consumer applications, power tools, garden tools and vehicles, for example hybrid, plug-in hybrid vehicles and
  • a lithium cell may, in particular, be understood to mean an electrochemical cell whose anode (negative electrode) comprises lithium.
  • this may be a lithium-ion cell, a cell whose anode (negative electrode) comprises an intercalation material, for example graphite and / or silicon, in which lithium can be reversibly stored and displaced, or a lithium metal Cell, a cell with an anode (negative electrode) of lithium metal or a lithium alloy act.
  • anode negative electrode
  • an intercalation material for example graphite and / or silicon
  • lithium metal Cell a cell with an anode (negative electrode) of lithium metal or a lithium alloy act.
  • a lithiatable material may, in particular, be understood to be a material which reversibly absorbs and releases lithium ions.
  • a lithiatable material may be intercalatable with lithium ions and / or can be alloyed with lithium ions and / or lithium ions
  • a transition metal may, in particular, be understood as meaning an element which has an atomic number of 21 to 30, 39 to 48, 57 to 80 and 89 to 112 in the periodic table.
  • Such active materials for example high energy (HE) -NCM materials, advantageously a significantly improved rate capability and a stabilized active material structure and associated stabilization of the voltage and capacitance or a prevention or at least significant reduction in voltage drop and an improved output power, in particular an increased output voltage and output capacity and thus discharge capacity.
  • HE high energy
  • the life of a battery equipped with it can be increased and a high-energy battery, for example a high-energy lithium-ion battery, can be utilized for commercial applications.
  • electrochemical energy storage such as a lithium cell, for example, a lithium-ion cell, increased and, for example, a
  • Nickel, cobalt and manganese can advantageously form lithium layer oxides whose electrochemical potentials, for example those for automotive applications, in particular with regard to the highest possible
  • Lithium layer can be widened, resulting in a reduction of intrinsic Material resistance and thus a significant improvement in
  • x (LiM0 2): 1-x (y Na y Li2- Mni- z M 'z 0 3) based active material may, in particular, for on Li2- y Na y Mni- M' z 0 3 based Structures structurally integrated into LiM0 2 based areas. In this may, in particular, the doped Li2- y Na y Mni- z M 'z 0 3 -like regions, the stabilization of the active material structure and the associated
  • Niobium in particular niobium (IV), tungsten, in particular tungsten (IV), and molybdenum, in particular molybdenum (IV), can advantageously have a very similar ionic radius as the redoxin-active tin (IV) known as a structure stabilizer.
  • redoxin-active tin (IV) known as a structure stabilizer.
  • niobium (IV) in particular niobium (IV), tungsten, in particular tungsten (IV), and molybdenum, in particular molybdenum (IV), but redox-active - in particular with a small change in the ionic radius - and advantageously - in contrast to redoxin-active doping elements, such as tin and magnesium, additional
  • the electrochemically at the beginning with respect to the manganese still inactive Li2- y Na y Mni- z M 'z 0 3 - component under irreversible elimination of oxygen can be activated with a proportionate Mn (IV) by electrochemically active niobium, in particular niobium (IV), tungsten, in particular tungsten (IV), and / or molybdenum, in particular molybdenum (IV), can be replaced.
  • niobium in particular niobium (IV)
  • tungsten in particular tungsten (IV)
  • molybdenum in particular molybdenum
  • Transition metals in particular of manganese and / or nickel, and thereby a voltage drop, for example, by local structural transformations in the active material, would favor reduced. In particular, so can be achieved that less oxygen is irreversibly cleaved than in an undoped or with a redoxin-active element, such as tin (IV), doped material. This can advantageously lead to a stabilization of the structure and thus the voltage situation, since fewer defects in the active material or electrode material arise over which transition metals, especially manganese and / or nickel, migrate and thus change or destabilize the structure.
  • M ' may in particular stand for niobium (IV) and / or tungsten (IV) and / or molybdenum (IV).
  • Niobium (IV), tungsten (IV) and molybdenum (IV) may advantageously have an ionic radius, for example in a range of> 70 pm to ⁇ 85 pm, which is almost identical to the ionic radius of the ion
  • redoxin-active tin (IV) may be.
  • Widening of the crystal lattice which may be characterized, for example, by an increase in the lattice parameters a, b and / or c, may favor the migration of transition metals, in particular manganese and / or nickel, during the cyclization.
  • transition metals in particular manganese and / or nickel
  • Oxygen release during activation can advantageously both a widening of the crystal lattice in the active material or electrode material and thus a migration of transition metals, in particular of manganese and / or nickel, reduced, as well as a protection against a dissolution of transition metal, in particular manganese and / or nickel , will be realized. So can advantageously the capacity and
  • niobium (IV), tungsten (IV) and molybdenum (IV) can advantageously be used in at least two successive oxidation stages, in particular in the
  • successive oxidation stages have an ionic radius, which may each be, for example, in a range of> 70 pm to ⁇ 85 pm. Because a strong change in the ionic radius during cyclization, the migration would favor the transition metals further, a small change in the ionic radius can provide better protection against dissolution of the ion
  • transition metals and the active material or electrode material are further stabilized.
  • M may in particular stand for nickel (II) and / or cobalt (II) and / or manganese (II). For example, 0.2 ⁇ x ⁇ 0.7, for example, 0.3 ⁇ x ⁇ 0.55.
  • M may be manganese (Mn) and nickel (Ni) and / or cobalt.
  • M is nickel (Ni), cobalt (Co) and manganese (Mn).
  • the at least one active material is based on the general chemical formula:
  • a and b may be 1/3, for example, where LiNi a Co b Mni a - b 0 2 LiMni / 3 Nii / 3 Coi / 3 02.
  • 0.01 ⁇ z ⁇ 0.3. In particular, 0.01 ⁇ z ⁇ 0.2.
  • M ' is niobium, in particular niobium (IV), and / or tungsten, in particular tungsten (IV).
  • Another object of the invention is an electrode material, in particular a cathode material or an electrode material for a positive electrode, for an electrochemical energy storage, in particular for a lithium cell, for example for a lithium-ion cell comprising particles having at least one, for example, over-lithiated, in particular with sodium (Na) doped, lithiierbares, transition metal oxide-based, active material, wherein the particles or a particles having body is at least partially provided with a functional layer is, which lithium ions is conductive and niobium (Nb) and / or tungsten (W) and or molybdenum (Mo).
  • Nb niobium
  • W tungsten
  • Mo molybdenum
  • a particle may in particular a primary particle and / or a
  • a basic body may in particular be understood to mean, for example, a completely processed body of electrode material which contains or consists of particles which comprise the at least one active material.
  • a functional layer may, in particular, be understood as meaning a protective layer which prevents interaction of the active material with an electrolyte, for example when used in a lithium cell.
  • the functional layer which comprises lithium ions and comprises niobium, tungsten and / or molybdenum, it is advantageously possible to very effectively protect the active material or electrode material from loss or dissolution of the transition metals, in particular manganese and / or nickel, in an electrolyte which would otherwise result in deposition of lithium-containing transition metal compounds on the anode, and thus loss of available transition metal and / or lithium, and thus capacity degradation.
  • the functional layer can advantageously act as a kind of barrier, wherein the
  • Active material in particular in the Li 2 - y Na y Mni- z M 'z 0 3 - component are introduced.
  • two central problems of HE-NCM materials namely the capacity drop through the functional layer and the voltage drop due to doping with niobium, tungsten and / or molybdenum originating from the functional layer, can advantageously be counteracted in a very efficient and cost-effective manner by only one method step become.
  • the at least one active material, in particular the particle comprise or be at least one, for example, over-lithiated, for example sodium-doped, in particular lithiatable, transition-metal oxide-based, active material, for example manganese oxide, in particular nickel-cobalt-manganese oxide.
  • the at least one active material in particular the particle, is based on the general chemical formula:
  • LiMO 2 1-x (Li 2 -yNa y MnO 3 ), where M is nickel (Ni) and / or cobalt (Co) and / or manganese (Mn) and where 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.5.
  • M may be manganese (Mn) and nickel (Ni) and / or cobalt.
  • M is nickel (Ni), cobalt (Co) and manganese (Mn).
  • the at least one active material in particular, the at least one active material, in particular
  • Particles on the general chemical formula: x (LiNi a CobMni- a -b0 2) 1-x (Li 2 - y Na y Mn0 3) are based, where 0 ⁇ a ⁇ 1,
  • 0.2 ⁇ a ⁇ 0.8 for example, 0.3 ⁇ a ⁇ 0.45, and wherein 0 ⁇ b ⁇ 1, for example, 0 ⁇ b ⁇ 0.5, for example, 0.2 ⁇ b ⁇ 0 , 35, is.
  • the functional layer may in particular comprise niobium (IV) and / or tungsten (IV) and / or molybdenum (IV).
  • the functional layer comprises niobium, in particular niobium (IV), and / or tungsten, in particular tungsten (IV).
  • the at least one active material, in particular of the particles can be doped by niobium, tungsten and / or molybdenum from the functional layer.
  • the at least one active material, in particular the particles a, for example, überithiated, manganese oxide, in particular nickel-cobalt-manganese oxide, which with sodium and niobium and / or tungsten and / or molybdenum, for example with sodium and niobium and / or tungsten, is doped, include or be.
  • the at least one active material in particular the particle, comprises or is an active material according to the invention explained above.
  • the base body may for example comprise at least one conductive additive, for example elemental carbon, for example carbon black, graphite and / or carbon nanotubes, and / or at least one binder, for example selected from the group of natural or synthetic polymers, for example polyvinylidene fluoride (PVDF). , Alginates, styrene-butadiene rubber (SBR), polyethylene glycol and / or polyethyleneimine.
  • PVDF polyvinylidene fluoride
  • SBR styrene-butadiene rubber
  • the base body may, for example, have a gradient of niobium, tungsten and / or molybdenum pointing in its thickness direction.
  • the gradient in particular starting from the functional layer, can decrease, for example to a metal support, in particular serving as a current conductor. This may advantageously be sufficient because the interaction of the Active material with the electrolyte takes place predominantly in the surface region and thus the costs can be reduced by the redox-active doping elements.
  • a coating of the particles and / or of the basic body for example, which aluminum oxide (Al 2 0 3 ), aluminum fluoride (AIF 3 ), lithium aluminum oxide (LiAIO x ), zirconium dioxide (Zr0 2 ), titanium dioxide (Ti0 2 ), aluminum phosphate (AIPO4 ) and / or lithium phosphorous oxynitride (LiPON;
  • Lithium phosphorous oxynitride and / or another compound, for example, which can dissolve transition metal dissolution and / or other material-electrolyte interactions C, single particle coating ") may be present.
  • Another object of the invention is a method for producing an active material, in particular a cathode active material, and / or an electrode material, in particular a cathode material, and / or an electrode, in particular a cathode or positive electrode, for an electrochemical energy storage.
  • Electrode material and / or an electrode according to the invention.
  • the method may in particular include the method steps:
  • transition metal oxide-based active material or a body having the particles, wherein the at least one active material by means of a polymer pyrolysis method is prepared and / or doped with sodium or is;
  • Functional layer which is conductive to lithium ions and comprises niobium (Nb) and / or tungsten (W) and / or molybdenum (Mo),
  • the at least one active material in particular the particle, may comprise at least one, for example, over-lithiated, for example, sodium-doped, in particular lithiatable, transition-metal oxide-based, active material, for example
  • manganese oxide in particular nickel-cobalt-manganese oxide include or be.
  • a protective functional layer for the active material can be provided in a very simple manner in order to obtain a
  • the method can additionally offer the considerable advantage that a portion of the niobium and / or tungsten and / or molybdenum of the functional layer in the coating of the particles or the
  • Basic body can be introduced as a doping element in the active material.
  • doping of the active material with niobium and / or tungsten and / or molybdenum can advantageously be effected, which in turn can result in a structural stabilization.
  • the latter can be attributed, as explained above, to the fact that in the first formation cycle in which the electrochemically inactive Li 2 MnO 3 component is activated, less oxygen is irreversibly removed and thus fewer oxygen vacancies are formed than in the undoped HE NCM. Material.
  • two central problems of HE-NCM material namely the capacity drop by the coating of the particles or the
  • Tin compound can be omitted in order to introduce both a material doping for controlling the voltage loss layer and a protective layer for controlling the capacity drop in a single process step.
  • the polymer pyrolysis process comprises the process steps:
  • polymerizable monomer comprises;
  • the at least one polymerizable monomer may include or be acrylic acid.
  • the at least one polymer may in particular comprise or be a polyacrylate.
  • the fact that the salts are first dissolved in the monomer-containing solution and then the monomers are polymerized to form a polymer, may advantageously a polymer metal salt precursor, for example a
  • Polyacrylate are formed, in particular in which the metals are finely dispersed.
  • the solution may be, for example, an aqueous solution.
  • At least one lithium salt, a sodium salt and a transition metal salt, in particular manganese salt are dissolved and / or dispersed in the solution.
  • a transition metal salt in particular manganese salt
  • at least one nickel salt and / or cobalt salt may be dissolved and / or dispersed in the solution.
  • the lithium salt may, for example, include or be lithium hydroxide, for example LiOH-H 2 O.
  • the sodium salt may, for example, include or be sodium hydroxide, for example NaOH.
  • the manganese salt may, for example, comprise or be a manganese (II) salt and / or manganese nitrate, in particular manganese (II) nitrate, for example Mn (NO 3 ) 2 .
  • the nickel salt may, for example, comprise or be a nickel (II) salt and / or nickel nitrate, in particular nickel (II) nitrate, for example Ni (NO 3 ) 2 -6 H 2 O.
  • the cobalt salt may, for example, comprise or be a cobalt (II) salt and / or cobalt nitrate, in particular cobalt (II) nitrate, for example Co (NO 3 ) 2 -6 H 2 O.
  • the metal salts can be used, for example, in stoichiometric amounts.
  • the lithium salt in particular one, for example 5 greasy, excess can be used. So can advantageously a
  • Lithium loss can be compensated for later calcination.
  • At least one polymerization initiator may be added to the solution and / or dispersion.
  • at least one peroxodisulfate for example
  • Ammonium peroxodisulfate for example (NH 4 ) 2 S 2 0 8 , can be used.
  • the at least one polymer in particular before the pyrolysis, for example at a temperature of> 100 ° C, for example about 120 ° C, dried.
  • the pyrolyzing of the at least one polymer can be carried out in particular under an air atmosphere.
  • the pyrolyzing of the at least one polymer at a temperature of> 450 ° C, for example at about 480 ° C, to be performed.
  • the pyrolysis may be carried out for a period of> 4 hours, for example about 5 hours.
  • the calcining of the residue remaining after the pyrolysis can in particular also be carried out under an air atmosphere.
  • calcination of the residue remaining after pyrolysis may be carried out at a temperature of> 850 ° C, for example at about 900 ° C.
  • calcination may be performed for a period of> 4 hours, for example about 5 hours.
  • At least one active material in particular of the particles to the general chemical formula: x (LiM0 2) 1-x (Li 2 - y Na y Mn0 3) are based, where M is nickel (Ni) and / or cobalt (Co) and / or manganese (Mn) and wherein 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.5.
  • M can stand for manganese (Mn) and nickel (Ni) and / or cobalt (Co).
  • M can for
  • At least one active material in particular of the particles to the general chemical formula: x (LiNi a Co b Mni- a - b 0 2) 1-x (Li 2 - y Na y Mn0 3) are based, where 0 ⁇ a ⁇ 1, for example 0.2 ⁇ a ⁇ 0.8, for example 0.3 ⁇ a ⁇ 0.45, and wherein 0 ⁇ b ⁇ 1, for example 0 ⁇ b ⁇ 0.5, for example 0, 2 ⁇ b ⁇ 0.35, is.
  • the functional layer may in particular comprise niobium (IV) and / or tungsten (IV) and / or molybdenum (IV).
  • the functional layer comprises niobium, in particular niobium (IV), and / or tungsten, in particular tungsten (IV).
  • the coating of the particles for example of primary and / or
  • Secondary particles, with the functional layer can in particular be such that the particles, for example a powder obtained by the polymer pyrolysis process, for example in water and / or another
  • Dispersing medium together with at least one compound containing niobium (Nb) and / or tungsten (W) and / or molybdenum (Mo) are mixed. Then the solids of the dispersion can be separated off, for example filtered off. The solids or the residue can then optionally, for example at a temperature of> 100 ° C, for example at about 105 ° C, for example for several hours, for example about 10 h, dried. The solids may be (then) annealed at a temperature of> 450 ° C, for example for several hours, for example for about 5 hours.
  • the particles with the functional layer it is also possible to carry out other coating methods known to the person skilled in the art, such as sputtering, with at least one compound containing niobium and / or tungsten and / or molybdenum.
  • sputtering with at least one compound containing niobium and / or tungsten and / or molybdenum.
  • the coating of the base body or of the finished, for example laminated, electrode with the functional layer can be carried out by methods known to those skilled in the art, for example atomic layer deposition and / or sputtering, with at least one compound, which niobium and / or tungsten and / or
  • Molybdenum contains be carried out.
  • Li 7 La 3 Nb 2 0i 3 Li 7 Nb0 6 , Li 3 Nb0 4 , LiTiNb 2 0 9 and / or Li 8 - x Zri- x Nb x 0 6 are used.
  • tungsten compound for example, Li 6 W0 6 , Li 4 W0 5 and / or Li 6 W20 9 , are used.
  • the method may comprise the following method steps:
  • transition metal oxide-based active material or a body having the particles, wherein the at least one active material is prepared by means of a polymer pyrolysis process and / or doped with sodium or is;
  • the polymer pyrolysis process comprises the process steps: dissolving and / or dispersing at least one lithium salt and a
  • polymerizable monomer comprises;
  • Is lithium ion conductive and comprises niobium and / or tungsten and / or molybdenum, for example niobium and / or tungsten,
  • the process may comprise the following process steps:
  • transition metal oxide-based active material or a body having the particles, wherein the at least one active material is prepared by means of a polymer pyrolysis process and / or doped with sodium or is;
  • polymer pyrolysis process comprises the process steps:
  • polymerizable monomer comprises;
  • Lithium ion conducting and niobium and / or tungsten and / or molybdenum, for example niobium and / or tungsten, comprises.
  • Active material produced according to the method according to the invention and / or an electrode material produced by a method according to the invention are provided.
  • a further subject of the present invention is an electrode, in particular a cathode, which comprises at least one active material according to the invention and / or produced by an inventive method and / or an electrode material according to the invention and / or produced by a method according to the invention and / or produced by a method according to the invention is.
  • an electrode in particular a cathode, which comprises at least one active material according to the invention and / or produced by an inventive method and / or an electrode material according to the invention and / or produced by a method according to the invention and / or produced by a method according to the invention is.
  • the invention relates to an electrochemical energy storage, in particular a lithium cell and / or lithium battery, for example a
  • Lithium-ion cell and / or lithium-ion battery comprising
  • Inventive and / or according to the invention produced active material and / or an inventive and / or produced according to the invention electrode material and / or an electrode according to the invention and / or according to the invention.
  • FIG. 1 shows a schematic cross section through an embodiment of an electrode.
  • FIG. 2 shows a schematic cross section through an embodiment of a particle coated with a functional layer;
  • FIG. 3 shows a schematic cross section through a further embodiment of an electrode
  • FIG. 4 is a flowchart of an embodiment of a method according to the invention for producing an electrode shown in FIG. 1;
  • FIG. 1 shows an electrode 10 which has a metal carrier 12.
  • the metal carrier 12 can serve as Abieiter, in particular cathodes in a lithium cell or lithium battery.
  • the electrode 10 further includes a plurality of particles 14 disposed on the metal support 12.
  • the particles 14 have at least one, with sodium-doped, lithiierbares, transition metal oxide-based active material.
  • the particles 14 are with a
  • Functional layer 16 is lithium-ion conductive and comprises niobium and / or tungsten and / or molybdenum. Due to the redox-active niobium and / or tungsten and / or molybdenum, the functional layer 16 is designed such that it interacts with the active material
  • the particles 14 may be completely or only partially enclosed by the functional layer 16. For the sake of illustration, it has been omitted in FIG. 1 to individually draw in the functional layers 16 of all the particles 14. It is quite conceivable that a number of particles 14 are arranged on the surface of the electrode 10 and protrude from this, without being covered by the functional layer 16.
  • a majority of the particles 14 further comprise redox-active niobium and / or tungsten and / or molybdenum 18 as
  • the particles 14 have at least one Active material which is doped with niobium and / or tungsten and / or molybdenum 18.
  • the redox-active niobium and / or tungsten and / or molybdenum can originate in particular from the functional layer 16.
  • the electrode 10 may, for example, further comprise at least one conductive additive and at least one binder (not shown).
  • the at least one active material, the at least one conductive additive and the at least one binder form the electrode material of the electrode 10.
  • FIG. 3 shows an electrode 10 ' , which is 10 ' analogous to the electrode
  • a metal carrier 12 On the metal support 12, a base body 20 is arranged, which comprises the particles 14 or consists of the particles 14.
  • the individual particles 14 are uncoated here and also have the at least one, with sodium-doped, lithiatable transition metal oxide-based active material.
  • FIG. 3 further shows that the main body 20 is provided with the functional layer 16.
  • the functional layer 16 is analogous to the functional layer explained in connection with FIGS. 1 and 2.
  • Lithium ions conductive and includes niobium and / or tungsten and / or molybdenum.
  • the functional layer 16 may, in particular due to their composition, be designed in such a way that they prevent an interaction of the active material with an electrolyte, for example during use or in operation of a lithium cell, and thus prevent the electrode 10 'from being exposed
  • the electrode 10 ' can protect loss of transition metal.
  • the electrode 10 ' or the main body 20 furthermore has redox-active niobium and / or tungsten and / or molybdenum 18 as doping element.
  • the electrode 10 ' or the main body 20 furthermore has redox-active niobium and / or tungsten and / or molybdenum 18 as doping element.
  • Base body 20 or the particles 14 of the main body 20 at least one active material, which is doped with niobium and / or tungsten and / or molybdenum 18.
  • the redox-active niobium and / or tungsten and / or Molybdenum may originate in particular from the functional layer 16.
  • the main body 20 can have a gradient of the redox-active niobium and / or tungsten and / or molybdenum 18 pointing in its thickness direction.
  • the gradient of the redox-active niobium and / or tungsten and / or molybdenum 18 can decrease in particular from the functional layer 16 to the metal carrier 12.
  • FIG. 4 shows a flowchart of a method for producing an electrode 10, in particular a cathode for a lithium cell, according to FIG. 1C, single particle coating.
  • the method comprises a step of providing
  • transition metal oxide-based active material wherein the at least one active material by means of a polymer pyrolysis process
  • the polymer pyrolysis process comprises a
  • the method comprises the step 102 of coating 102 of the particles 14 with a functional layer 16, which is conductive to lithium ions and comprises niobium and / or tungsten and / or molybdenum, the step 104 of FIG.
  • FIG. 5 shows a flowchart of a method for producing an electrode 10 ' , in particular a cathode for a lithium cell, according to FIG. 3Caminate Coating. "The method has a step of providing 100 ' of particles 14 comprising at least one lithiatable,
  • transition metal oxide-based active material wherein the at least one active material by means of a polymer pyrolysis process
  • the polymer pyrolysis process comprises a step of dissolving and / or dispersing 100a 'at least one lithium salt and a transition metal salt in a solution comprising at least one polymerizable monomer; a step of polymerizing 100b 'of the at least one polymerizable monomer to at least one polymer; optionally a step of drying 100c 'of the at least one polymer, a step of pyrolyzing 100d' of the at least one polymer and a step of calcining 100e 'of the residue remaining after pyrolysis.
  • the method comprises the step of adding 102 ' a conductive additive and a binder, a step of dry-pressing 104 ' the components from the group consisting of the particles 14, the conductive additive and the binder, or a step of
  • Dispersing 104 ' the component from the group consisting of the particles 14, the conductive additive and the binder in a solvent, a step of applying 106' of the thus obtained press assembly or the application 106 ', in particular knife coating, the dispersion thus obtained on a metal support 12th to form a base 20 having the particles 14, optionally a step of drying the dispersion (not shown) and a step of coating 108 'of the base 20 with a functional layer 16 which is lithium ion conductive and niobium and / or tungsten and / or molybdenum.

Abstract

L'invention concerne une matière active pour un accumulateur d'énergie électrochimique, en particulier pour un élément au lithium. Pour accroître la durée de vie de l'accumulateur d'énergie électrochimique, ladite matière active est basée sur la formule chimique générale suivante : x (LiMO2) : 1-x (Li2-yNayMn1-zM'zO3), M représentant le nickel et/ou le cobalt et/ou le manganèse et M' représentant le niobium et/ou le tungstène et/ou le molybdène et 0 < x < 1, 0 < y < 0,5 et 0 < z < 1. L'invention concerne en outre une matière d'électrode et une électrode contenant cette matière active, un procédé de fabrication de ladite matière active, ainsi qu'un accumulateur d'énergie électrochimique doté de cette matière active.
EP16724429.2A 2015-06-15 2016-05-24 Ncm à haute énergie dopé na et dopé nb, w et/ou mo Withdrawn EP3308418A1 (fr)

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DE102015210895.3A DE102015210895A1 (de) 2015-06-15 2015-06-15 Na-dotiertes und Nb-, W- und/oder Mo-dotiertes HE-NCM
PCT/EP2016/061639 WO2016202536A1 (fr) 2015-06-15 2016-05-24 Ncm à haute énergie dopé na et dopé nb, w et/ou mo

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WO (1) WO2016202536A1 (fr)

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JP7310154B2 (ja) * 2019-01-29 2023-07-19 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質とその製造方法、およびリチウムイオン二次電池
JP2020123440A (ja) * 2019-01-29 2020-08-13 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質とその製造方法、およびリチウムイオン二次電池
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JP2018524769A (ja) 2018-08-30
WO2016202536A1 (fr) 2016-12-22
CN107710461A (zh) 2018-02-16
DE102015210895A1 (de) 2016-12-15
US20180138497A1 (en) 2018-05-17
KR20180017043A (ko) 2018-02-20

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