Particulate matter, its production method and use

Abstract

Composition (Li a Mg b ) 1+x (Ni c M 1 d M 2 e ) 1-x O2 (In the formula, M 1 is selected from Ti, Zr, Nb, Mo, W, and combinations of at least two of the foregoing; M 2 is selected from Al, Co, Mn, and combinations of at least two of the foregoing; a:b is in the range of 100:1 to 400:1, and a+b=1; c:d is in the range of 40:1 to 250:1, and c:e is in the range of 12:1 to 50:1; c+d+e=1, (Li+Mg) and (Ni+M 1 +M 2 ) in a range of 1:1 to 1.05:1; 0.00≦x≦0.05) A particulate matter comprising: The particulate matter has an average particle size (D50) in the range of 2 to 20 μm.

Description

[Technical field]

[0001] The present invention relates to a composition (Li a Mg b ) 1+x (Ni c M 1 d M 2 e ) 1-x O2 (In the formula, M 1 is selected from Ti, Zr, Nb, Mo, W, and combinations of at least two of the foregoing; M 2 is selected from Al, Co, Mn, and combinations of at least two of the foregoing; a:b is in the range of 100:1 to 400:1, and a+b=1; c:d is in the range of 40:1 to 250:1, and c:e is in the range of 12:1 to 50:1; c+d+e=1, (Li+Mg) and (Ni+M 1 +M 2 ) in a range of 1:1 to 1.05:1; 0.00≦x≦0.05) With regard to particulate matter, Here, the particulate matter has an average particle size (D50) in the range of 2 to 20 μm. [Background technology]

[0002] Lithiated transition metal oxides are currently used as electrode active materials in lithium-ion batteries. Extensive research and development has been carried out over the past few years to improve properties such as charge density, specific energy, and other properties such as cycle life degradation and capacity loss that adversely affect the life or applicability of lithium-ion batteries. Further efforts are being made to improve the manufacturing methods.

[0003] Many of the electrode active materials currently under discussion are of the lithiated nickel-cobalt-manganese oxide ("NCM material") or lithiated nickel-cobalt-aluminum oxide ("NCA material") type.

[0004] In a typical process for the preparation of cathode materials for lithium-ion batteries, a so-called precursor is first formed by co-precipitation of a transition metal as a carbonate, oxide, or preferably as a hydroxide, which may or may not be basic. This precursor is then mixed with a lithium salt, such as, but not limited to, LiOH, Li2O or especially Li2CO3, and calcined at high temperature. The lithium salt(s) can be used as hydrate(s) or in dehydrated form. The calcination or calcination, also commonly referred to as thermal or heat treatment of the precursor, is usually carried out at temperatures in the range of 600-1000°C. During the heat treatment, a solid-state reaction takes place to form the electrode active material. If hydroxides or carbonates are used as precursors, the solid-state reaction is followed by removal of water or carbon dioxide. The heat treatment is carried out in a heated zone of an oven or kiln. Summary of the Invention [Problem to be solved by the invention]

[0005] To improve the capacity of the cathode active material, it has been proposed to increase the nickel content as much as possible, but materials such as LiNiO2 have been found to have short cycle life, significant gas evolution, and a large increase in internal resistance during cycling, posing significant challenges to their practical application. [Means for solving the problem]

[0006] Thus, a particulate material as defined at the outset has been found, which is also referred to in the following as "inventive material" or "material according to the invention". The inventive material is explained in more detail below.

[0007] The substance of the present invention has the formula (Li a Mg b )1+x (Ni c M 1 d M 2 e ) 1-x O2 (In the formula, M 1 is selected from Ti, Zr, Nb, Mo, W, and combinations of at least two of the foregoing; M 2 is selected from Al, Co, Mn, and combinations of at least two of the foregoing; a:b is in the range of 100:1 to 400:1, and a+b=1; c:d is in the range of 40:1 to 250:1, and c:e is in the range of 12:1 to 50:1; c+d+e=1, (Li+Mg) and (Ni+M 1 +M 2 ) in a range of 1:1 to 1.05:1; 0.00≦x≦0.05) The composition is Here, the particulate matter has an average particle size (D50) in the range of 2 to 20 μm.

[0008] This is the formula (Li a Mg b ) 1+x TM 1-x O2, where TM is (Ni 1-x1-x2 M 1 x1 M 2 x2 ), x1≧0.0025, x2≧0.05, and x1+x2≦0.0525. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The substances of the present invention will now be described in more detail.

[0010] In one embodiment of the invention, the material of the invention is composed of spherical particles, i.e. particles having a spherical shape, including not only particles that are precisely spherical, but also particles in which the difference between the maximum and minimum diameters of at least 90% (number average) of a representative sample is 10% or less.

[0011] The substances of the invention have an average particle size (D50) in the range of 2 to 20 μm, preferably 5 to 16 μm. The average particle size can be determined, for example, by light scattering or laser diffraction or electroacoustic spectroscopy. The particles are usually composed of agglomerates from primary particles, and the particle size mentioned above refers to the particle size of the secondary particles.

[0012] In one embodiment of the invention, the material of the invention is composed of secondary particles which are agglomerates of primary particles. Preferably, the material of the invention is composed of spherical secondary particles which are agglomerates of primary particles. Even more preferably, the material of the invention is composed of spherical secondary particles which are agglomerates of spherical primary particles or platelets.

[0013] In one embodiment of the invention, the primary particles of the substance of the invention have an average diameter in the range of 1-2000 nm, preferably 10-1000 nm, particularly preferably 50-500 nm. The average primary particle size can be determined, for example, by SEM or TEM. SEM is an abbreviation for scanning electron microscope, TEM is an abbreviation for transmission electron microscope, and XRD is an abbreviation for X-ray diffraction.

[0014] In one embodiment of the present invention, the substance of the present invention is 0.1 to 2.0 m 2 / g. The BET surface area can be determined by nitrogen adsorption after outgassing the sample at 200 °C for 30 minutes and beyond, according to DIN ISO 9277:2010.

[0015] M 1is selected from Ti, Zr, Nb, Mo, W, and a combination of at least two of the foregoing, preferably M 1 is selected from a combination of at least two of Ti, Zr, Nb, Mo, and W, for example, a combination of Ti and Zr, or a combination of Zr and Mo, or a combination of Ti, Zr, and Mo.

[0016] M 2 is selected from Al, Co, Mn, and combinations of at least two of the foregoing; a:b is in the range of 100:1 to 400:1, and a+b=1; c:d is in the range of 40:1 to 250:1, and c:e is in the range of 12:1 to 50:1; c+d+e=1, (Li+Mg) and (Ni+M 1 +M 2 ) in a range of 1:1 to 1.05:1; 0.00≦x≦0.05.

[0017] Some metals are ubiquitous, e.g. sodium, calcium or zinc, but such trace amounts are not considered in the present specification. Trace amounts in this context mean amounts of 0.05 mole % or less, based on the total metal content TM. Preferably, the calcium content of the material of the present invention is only a trace amount, and no compounds of calcium are intentionally added during manufacture.

[0018] In one embodiment of the invention, the substance has formula (I): (Ni c M 1 d M 2 e ) (I) (In the formula, M 2 is selected from Mn and Co; c is in the range of 0.95 to 0.995, d is in the range of 0.002 to 0.04, e is in the range of 0.002 to 0.02, and c+d+e=1) In a preferred embodiment, b≦c.

[0019] M 1 is selected from Nb, Ti, Zr, W, Mo, and preferably a combination of at least two of the foregoing; M 2 is selected from Al, Mn, Co, and a combination of at least two of the foregoing.

[0020] In one embodiment of the present invention, M 1 is selected from Ti, Zr, W, and a combination of any two of the foregoing.

[0021] In one embodiment of the present invention, the number of metals other than Ni, Mg and Li is at least 3 and at most 5. More preferably, one element M 2 Only exists.

[0022] In one embodiment of the present invention, the metal(s) M 1 Each of these is present in an amount of 0.1 to 0.5 mol % relative to Ni.

[0023] In one embodiment of the present invention, the metal(s) M 2 Each of these is present in an amount of 0.5 to 2 mol % relative to Ni.

[0024] In one embodiment of the present invention, M 1 and M 2 is uniformly dispersed within the material of the present invention. 1 and M 2 is dispersed more or less uniformly on the particles of the material of the invention.

[0025] In one embodiment of the present invention, M 1 and M 2 At least one of these is concentrated at the particle boundaries of the particles of the material of the invention.

[0026] In certain embodiments of the invention, the secondary particles of the material of the invention are coated with a metal oxide, preferably a metal oxide that does not function as a cathode active material. Examples of suitable metal oxides include LiBO2, B2O3, Al2O3, Y2O3, LiAlO2, TiO2, ZrO2, Li2ZrO3, Nb2O5, and LiNbO3.

[0027] The material of the present invention is particularly suitable as a cathode active material in lithium-ion batteries, as it combines excellent cycling stability with high energy density.

[0028] In one embodiment of the present invention, the cathode active material of the present invention contains Li2CO3 in the range of 0.001 to 1% by mass, based on the material of the present invention, as determined by titration as Li2CO3.

[0029] Another aspect of the invention relates to a method for producing a substance of the invention, hereinafter also referred to as the method of the invention or the method according to the (present) invention, which comprises several steps, hereinafter also referred to as step (a), step (b) etc.

[0030] Steps (a) to (c) have the following characteristics: (a) providing a particulate nickel hydroxide, nickel(II) oxide, or nickel oxyhydroxide; (b) The nickel oxide / hydroxide is reacted with Mg, M 1 and M 2 and a lithium source; (c) heat treating the mixture resulting from step (b).

[0031] Steps (a) to (c) will be described in more detail below.

[0032] In step (a), particulate nickel hydroxide, nickel(II) oxide or nickel oxyhydroxide, hereinafter also collectively referred to as nickel oxide / hydroxide, is provided. In the context of the present invention, the term nickel oxyhydroxide is not limited to stoichiometric NiOOH, but also means any nickel compound having only oxide and hydroxide counterions and an individual content of metal impurities such as Mn or Mg of up to 2% by weight, based on the total metal content of said nickel hydroxide, nickel(II) oxide or nickel oxyhydroxide. Preferably, the nickel hydroxide, nickel(II) oxide or nickel oxyhydroxide has a maximum total impurity content of 2% by weight, based on the total metal content of said nickel hydroxide, nickel(II) oxide or nickel oxyhydroxide.

[0033] The nickel oxide / hydroxide provided in step (a) has an average particle size (D50) in the range of 2-20 μm, preferably 4-16 μm. The average particle size can be determined, for example, by light scattering or laser diffraction or electroacoustic spectroscopy. The particles are composed of agglomerates from primary particles, and the particle size mentioned above refers to the particle size of the secondary particles.

[0034] The preferred nickel oxide / hydroxide is freshly precipitated nickel hydroxide.

[0035] In one embodiment of the present invention, the nickel oxide / hydroxide provided in step (a) has a residual water content in the range of 50-1,000 ppm, preferably 100-400 ppm. The residual water content can be determined by Karl Fischer titration.

[0036] In step (b), the nickel oxide / hydroxide is reacted with Mg, Mg in the absence of a solvent, such as water or an organic solvent. 1 and M 2 is mixed with the compound.

[0037] Suitable compounds of Mg are Mg(OH)2, MgO, Mg(NO3)2, and oxalates such as MgC2O4.

[0038] M 1 Suitable compounds of are the oxides, (oxy)hydroxides and nitrates of Ti, Zr, W, Mo and Nb, such as TiO2, Ti2O3, TiO(OH)2, ZrO2, Zr(OH)4, TiO(NO3)2, Ti(NO3)4, niobic acid, Nb2O5, WO3, Li2WO4 and MoO3. 1 Further examples of compounds of the formula (I) are, for example, ammonium metatungstate (hydrate), ammonium orthomolybdate, ammonium heptamolybdate, ammonium dimolybdate, ammonium niobate oxalate, ammonium zirconium(IV) carbonate, but are not limited thereto, either as such or as hydrates.

[0039] M 2 Suitable compounds of are nitrates, oxides, hydroxides and oxyhydroxides, such as, but not limited to, Al2O3, Al(OH)3, AlOOH, Al2(SO4)3, KAl(SO4)2 and Al(NO3)3, alkanolates of Al, such as, but not limited to, Al(C2H5O)3, Al-tris-isopropoxide, mixed salts of at least two cations, such as aluminum magnesium isopropoxide. Examples of cobalt compounds are Co(OH)2, Co2O3, Co3O4, and examples of Mn compounds are Mn2O3, MnO2 and Mn(NO3)2. 2 Alkanolates of the formula (I) can also be used.

[0040] In addition, a lithium source is added.

[0041] Examples of lithium sources are Li2O, LiOH, and Li2CO3, each free of water or optionally as a hydrate, e.g., LiOH·H2O. A preferred example is lithium hydroxide.

[0042] The amounts of lithium source and powdered residue are selected to provide a molar ratio of Li to TM of (1+x):1, where x is in the range of 0.98 to 1.05.

[0043] Preferably, the lithium source is in particulate form, for example having an average diameter (D50) in the range of 3 to 10 μm, preferably 5 to 9 μm.

[0044] In one embodiment of the present invention, step (b) is carried out at a temperature in the range of 5 to 85°C, preferably 10 to 60°C.

[0045] In one embodiment of the invention, step (b) is carried out at normal pressure, however, it is preferred to carry out step (b) under elevated pressure, for example at a pressure between 10 mbar and 10 bar above normal pressure, or under suction, for example at a pressure between 50 and 250 mbar below normal pressure, preferably at a pressure between 100 and 200 mbar below normal pressure.

[0046] Step (b) can be carried out in a vessel located above the filter device, allowing easy drainage from the vessel. Such vessels can be loaded with the nickel oxide / hydroxide from step (a) and subsequently with the lithium source, Mg, M 1 and M 2 In another embodiment, such a container contains a source of lithium, Mg, M 1 and M 2 In another embodiment, the nickel oxide / hydroxide from step (a) and Mg, M 1 and M 2 and a lithium source are introduced simultaneously.

[0047] Nickel oxide / hydroxide and Mg, M 1 and M 2 Mixing of this compound with the lithium source can be carried out for a period of from 1 minute to 3 hours, preferably from 5 minutes to 1 hour, and even more preferably from 5 minutes to 30 minutes.

[0048] Step (b) may be supported by a mixing operation, such as shaking, especially stirring or shearing.

[0049] From step (b) a powdery mixture is obtained.

[0050] Examples of suitable equipment for carrying out step (b) are high shear mixers, tumbler mixers, ploughshare mixers and free fall mixers.

[0051] In one embodiment of the present invention, step (b) is carried out at a temperature ranging from room temperature to 200°C, preferably from 20 to 50°C.

[0052] A mixture is obtained.

[0053] Step (c) comprises subjecting the mixture from step (b) to a thermal treatment. An example of step (c) is a thermal treatment at a temperature in the range of 600-800° C., preferably 650-750° C. The terms "thermal treatment" and "thermal treatment" are used interchangeably in the context of the present invention.

[0054] In one embodiment of the present invention, the mixture obtained from step (b) is heated to 600-800° C. at a heating rate of 0.1-10° C. / min.

[0055] In one embodiment of the present invention, the temperature is increased before reaching a desired temperature of 600 to 800° C., preferably 650 to 750° C. For example, the mixture obtained from step (c) is first heated to 350 to 550° C., then kept constant for 10 minutes to 4 hours, then increased to 650 to 800° C., and then kept at 650 to 800° C. for 10 minutes to 10 hours.

[0056] In one embodiment of the present invention, step (c) is carried out in a roller hearth kiln, a pusher kiln or a rotary kiln, or a combination of at least two of them. A rotary kiln has the advantage that the homogenization of the material produced therein is very good. In roller hearth kilns and pusher kilns, different reaction conditions for different steps can be set very easily. In laboratory scale experiments, box furnaces, tube furnaces and split tube furnaces can also be used.

[0057] In one embodiment of the present invention, step (c) is carried out in an oxygen-containing atmosphere, such as a nitrogen-air mixture, a noble gas-oxygen mixture, air, oxygen or oxygen-enriched air. In a preferred embodiment, the atmosphere in step (c) is selected from air, oxygen and oxygen-enriched air. The oxygen-enriched air can be, for example, a 50:50 volumetric ratio of air and oxygen. Other options include a 1:2 volumetric ratio of air and oxygen, a 1:3 volumetric ratio of air and oxygen, a 2:1 volumetric ratio of air and oxygen, and a 3:1 volumetric ratio of air and oxygen.

[0058] In one embodiment of the present invention, step (c) is carried out under a gas flow, such as air, oxygen and oxygen-enriched air. Such a gas flow is also called a forced gas flow. Such a gas flow is represented by the general formula (Li a Mg b ) 1+x (Ni c M 1 d M 2 e ) 1-x O2 per kg of material, 0.5-15m 3 The gas flow can have a specific flow rate in the range of 1000 rpm / h. The volume is determined under normal conditions (298 Kelvin and 1 atm). The gas flow is useful for removing gaseous decomposition products such as water and carbon dioxide.

[0059] The process of the present invention may comprise a further step following step (c), such as but not limited to a further calcination step at a temperature in the range of 650-800°C.

[0060] In one embodiment of the invention, step (c) has a duration ranging from 1 hour to 30 hours, preferably from 10 hours to 24 hours. The time at temperatures above 600°C counts the heating and holding time, but the cooling time is ignored in this context.

[0061] A material is obtained that is highly suitable as a cathode active material for lithium ion batteries.

[0062] In one embodiment of the invention, the material of the invention can be treated with water and then dried. In another embodiment, the particles of the material of the invention can be at least partially coated, for example, by mixing with an oxide or hydroxide, such as aluminum hydroxide or alumina, or with boric acid, followed by heat treatment at 150-400° C. In another embodiment of the invention, the particles of the material of the invention can be at least partially coated by atomic layer deposition, for example by alternating treatment(s) with trimethylaluminum and water.

[0063] A further aspect of the present invention is an electrode comprising at least one material according to the present invention.These are particularly useful in lithium-ion batteries.The lithium-ion batteries comprising at least one electrode according to the present invention show very good discharge and cycle behavior, and they show good safety behavior.

[0064] In one embodiment of the present invention, the cathode of the present invention comprises (A) at least one substance of the invention as defined above, (B) carbon in a conductive state, and (C) binder, (D) Current collector Contains:

[0065] In a preferred embodiment of the present invention, the cathode of the present invention comprises, based on the sum of (A), (B) and (C), (A) 80 to 98% by mass of the substance of the present invention; (B) 1 to 17 mass% carbon, (C) 1 to 10 mass % of a binder material Contains:

[0066] The cathode according to the invention contains a conductive modified carbon, also called carbon (B) for short. Carbon (B) can be selected from soot, activated carbon, carbon nanotubes, graphene and graphite. Carbon (B) can be added directly during the preparation of the electrode material according to the invention.

[0067] The electrodes according to the invention may contain further components. They may contain a current collector (D), for example (but not limited to) an aluminum foil. They may further contain a binder material (C), also called binder (C) below. The current collector (D) will not be described further here.

[0068] Suitable binders (C) are preferably selected from organic (co)polymers. Suitable (co)polymers, i.e. homopolymers or copolymers, can be selected, for example, from (co)polymers obtainable by anionic, catalytic or free radical (co)polymerization, in particular from polyethylene, polyacrylonitrile, polybutadiene, polystyrene and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth)acrylonitrile and 1,3-butadiene. Polypropylene is also suitable. Polyisoprene and polyacrylates are furthermore suitable. Polyacrylonitrile is particularly preferred.

[0069] In the context of the present invention, polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers but also copolymers of acrylonitrile with 1,3-butadiene or with styrene. Polyacrylonitrile homopolymers are preferred.

[0070] In the context of the present invention, polyethylene refers not only to homopolyethylenes, but also to copolymerized ethylene with at least 50 mol % and up to 50 mol % of at least one further comonomer, such as α-olefins, such as propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, and also isobutene, vinyl aromatics, such as styrene, and also (meth)acrylic acid, vinyl acetate, vinyl propionate, C1-C2 copolymers of (meth)acrylic acid. 10-alkyl esters, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and also copolymers of ethylene with maleic acid, maleic anhydride and itaconic anhydride. The polyethylene may be HDPE or LDPE.

[0071] In the context of the present invention, polypropylene is understood to mean not only homopolypropylene but also copolymers of propylene with at least 50 mol % copolymerized propylene and up to 50 mol % of at least one further comonomer, such as ethylene, and α-olefins, such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene. The polypropylene is preferably isotactic polypropylene or essentially isotactic polypropylene.

[0072] In the context of the present invention, polystyrene refers not only to homopolymers of styrene, but also to C1-C4 copolymers of acrylonitrile, 1,3-butadiene, (meth)acrylic acid, and (meth)acrylic acid. 10 -alkyl esters, divinylbenzene, in particular 1,3-divinylbenzene, 1,2-diphenylethylene and α-methylstyrene copolymers are also understood to mean.

[0073] Another preferred binder (C) is polybutadiene.

[0074] Other suitable binders (C) are selected from polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyimides and polyvinyl alcohol.

[0075] In one embodiment of the invention, the binder (C) has an average molecular weight M ranging from 50,000 g / mol to 1,000,000 g / mol, preferably up to 500,000 g / mol. W The (co)polymers are selected from those having the formula:

[0076] The binder (C) may be a crosslinked or non-crosslinked (co)polymer.

[0077] In a particularly preferred embodiment of the present invention, the binder (C) is selected from halogenated (co)polymers, in particular fluorinated (co)polymers.Halogenated or fluorinated (co)polymers are understood to mean (co)polymers that contain at least one (co)polymerized (co)monomer with at least one halogen atom or at least one fluorine atom per molecule, more preferably at least two halogen atoms or at least two fluorine atoms per molecule.Examples include polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymer, perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and ethylene-chlorofluoroethylene copolymer.

[0078] Suitable binders (C) are especially polyvinyl alcohol and halogenated (co)polymers such as polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.

[0079] The electrode of the present invention may contain 3 to 10 mass % of binder(s) (d) based on the total mass of the component (a), the component (b) and carbon (c).

[0080] A further aspect of the present invention is (A) at least one cathode comprising a cathode active material (A) of the present invention, carbon (B) and a binder (C); (B) at least one anode; and (C) at least one electrolyte It is a battery containing

[0081] The embodiment of the cathode (1) has already been described in detail above.

[0082] The anode (2) may contain at least one anode active material, such as carbon (graphite), TiO2, lithium titanium oxide, silicon, or tin. The anode (2) may further contain a current collector, such as a metal foil, such as copper foil.

[0083] The electrolyte (3) may include at least one non-aqueous solvent, at least one electrolyte salt, and optionally additives.

[0084] The non-aqueous solvent for the electrolyte (3) may be liquid or solid at room temperature and is preferably selected from polymers, cyclic or acyclic ethers, cyclic and acyclic acetals, and cyclic or acyclic organic carbonates.

[0085] Examples of suitable polymers are in particular polyalkylene glycols, preferably poly-C1-C4-alkylene glycols and in particular polyethylene glycols, where the polyethylene glycols may contain up to 20 mol % of one or more C1-C4-alkylene glycols.The polyalkylene glycols are preferably polyalkylene glycols with two methyl or ethyl end caps.

[0086] The molecular weight M of suitable polyalkylene glycols, particularly suitable polyethylene glycols, W may be at least 400 g / mol.

[0087] The molecular weight M of suitable polyalkylene glycols, particularly suitable polyethylene glycols, W can be up to 5,000,000 g / mol, preferably up to 2,000,000 g / mol.

[0088] Examples of suitable acyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, with 1,2-dimethoxyethane being preferred.

[0089] Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.

[0090] Examples of suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.

[0091] An example of a suitable cyclic acetal is 1,3-dioxane, and especially 1,3-dioxolane.

[0092] Examples of suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate.

[0093] Examples of suitable cyclic organic carbonates are compounds of the general formulae (II) and (III) [ka] (In the formula, R 1 , R 2 and R 3 can be the same or different and are selected from hydrogen and C1-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably R 2 and R 3 (Both cannot be tert-butyl).

[0094] In a particularly preferred embodiment, R 1 is methyl, R 2 and R 3 are each hydrogen or R 1 , R 2 and R 3 are hydrogen.

[0095] Another preferred cyclic organic carbonate is vinylene carbonate of formula (IV).

[0096] [ka]

[0097] Preferably, the solvent or solvents are used in an aqueous state, ie with a water content in the range of 1 ppm to 0.1% by weight, which can be determined, for example, by Karl Fischer titration.

[0098] The electrolyte (3) further comprises at least one electrolyte salt. Suitable electrolyte salts are in particular lithium salts. Examples of suitable lithium salts are LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, LiC(C n F 2n+1 SO2)3, lithium imide, e.g. LiN(C n F 2n+1 SO2)2 (wherein n is an integer ranging from 1 to 20), LiN(SO2F)2, Li2SiF6, LiSbF6, LiAlCl4, and compounds of the general formula (C n F 2n+1 SO2) t Salt of YLi where t=1 when Y is selected from oxygen and sulfur; when Y is selected from nitrogen and phosphorus, t=2; When Y is selected from carbon and silicon, t=3).

[0099] Preferred electrolyte salts are selected from LiC(CF3SO2)3, LiN(CF3SO2)2, LiPF6, LiBF4, LiClO4, with LiPF6 and LiN(CF3SO2)2 being particularly preferred.

[0100] In a preferred embodiment of the present invention, the electrolyte (3) contains at least one flame retardant. Useful flame retardants may be selected from trialkyl phosphates (wherein the alkyls are different or the same), triaryl phosphates, alkyl dialkyl phosphonates, and halogenated trialkyl phosphates. Preferred are tri-C1-C4-alkyl phosphates (wherein the C1-C4-alkyls are different or the same), tribenzyl phosphate, triphenyl phosphate, C1-C4-alkyl di-C1-C4-alkyl phosphonates, and fluorinated tri-C1-C4-alkyl phosphates.

[0101] Preferably, the electrolyte (3) contains at least one flame retardant selected from trimethyl phosphate, CH3-P(O)(OCH3)2, triphenyl phosphate, and tris-(2,2,2-trifluoroethyl) phosphate.

[0102] The electrolyte (3) may contain 1 to 10 mass % of a flame retardant based on the total mass of the electrolyte.

[0103] In an embodiment of the invention, the battery according to the invention comprises one or more separators (4) by means of which the electrodes are mechanically separated. Suitable separators (4) are polymer films, in particular porous polymer films, which are unreactive towards metallic lithium. Particularly suitable materials for the separators (4) are polyolefins, in particular film-forming porous polyethylene and film-forming porous polypropylene.

[0104] The separator (4) made of polyolefin, particularly polyethylene or polypropylene, may have a porosity in the range of 35 to 45%. The suitable pore size is, for example, in the range of 30 to 500 nm.

[0105] In another embodiment of the present invention, the separator (4) can be selected from PET nonwoven fabrics filled with inorganic particles. Such separators can have a porosity in the range of 40-55%. Suitable pore sizes are, for example, in the range of 80-750 nm.

[0106] The battery according to the invention may further comprise a housing which may have any shape, for example a cube or a cylindrical disk. In one variant, a metal foil configured as a pouch is used as the housing.

[0107] The battery according to the invention exhibits very good discharge and cycling behaviour, especially with regard to capacity loss, especially at high temperatures (above 45° C., for example up to 60° C.).

[0108] The battery according to the invention may comprise two or more electrochemical cells that are combined with each other, for example connected in series or connected in parallel. A series connection is preferred. In the battery according to the invention, at least one electrochemical cell contains at least one electrode according to the invention. Preferably, in the electrochemical cell according to the invention, the majority of the electrochemical cells contain electrodes according to the invention. Even more preferably, in the battery according to the invention, all electrochemical cells contain electrodes according to the invention.

[0109] The present invention further provides a method for using the battery according to the present invention in equipment, especially mobile equipment.Examples of mobile equipment are vehicles, such as automobiles, bicycles, aircraft, or water vehicles, such as boats or ships.Other examples of mobile equipment are manually operated, such as computers, especially laptops, phones, or powered hand tools, for example in the construction sector, especially drills, battery-powered drivers, or battery-powered staplers.

[0110] The present invention is further illustrated by the following examples. EXAMPLES

[0111] The average particle size (D50) was determined by dynamic light scattering ("DLS"). Percentages are by weight unless otherwise stated. All heat treatments were performed in an oven under a flow rate of 5 liters per minute of oxygen.

[0112] Step (a.1): Spherical Ni(OH)2 precursor was obtained by combining aqueous nickel sulfate (1.65 mol / kg solution) with 25 wt% NaOH aqueous solution, using ammonia as a complexing agent. The pH value was set to 12.6. The freshly precipitated Ni(OH)2 was washed with water, sieved, and dried at 120 °C for 12 h. p-CAM.1 was Ni(OH)2 with a D50 of 8 μm.

[0113] Preparation of comparative cathode active material C-CAM.1: Comparative cathode active material C-CAM.1 (Li 1.01 Ni 0.95 Al 0.005 Co 0.02 Mn 0.02 Zr 0.005 O2) was synthesized. The mixture was then poured into a zirconia crucible and heated from 25°C to 400°C at 3°C / min, then held at 400°C for 4 hours. The mixture was then heated from 400°C to 692°C at 3°C / min, then held at 692°C for 6 hours. Finally, the mixture was cooled from 692°C to 120°C at a cooling rate of more than 10°C / min, then transferred to a glove box to obtain the comparative material C-CAM.1 with a D50 of 8 μm.

[0114] Step (b.2): The precursor p-CAM.1 is reacted with a lithium source LiOH HO and Mg, M 1 and M 2 Sources: Mg(OH)2, Al2O3, Co3O4, MnO2, Zr(OH)4, and WO3 were mixed in appropriate stoichiometric ratios in a ball mill for 3 h.

[0115] Step (c.2): The mixture obtained from step (b.2) was then poured into a zirconia crucible and heated from 25° C. to 400° C. at 3° C. / min, then held at 400° C. for 4 hours. The mixture was then heated from 400° C. to 675° C. at 3° C. / min, then held at 675° C. for 6 hours. Finally, the mixture was cooled from 675° C. to 120° C. at a cooling rate of more than 10° C. / min, then transferred to a glove box to obtain the material CAM.2 of the present invention having a D50 of 8 μm. The cathode active material CAM.2 of the present invention (Li 1.030 Mg 0.020 )Ni 0.970 Al 0.005 Co 0.005 Mn 0.010 Zr 0.005 W 0.005 O2) was obtained.

[0116] Electrode preparation: The electrodes contained 94% CAM, 3% carbon black (Super C65) and 3% binder (polyvinylidene fluoride, Solef 5130). The CAM, carbon black and binder were slurried in N-methyl-2-pyrrolidone and cast onto aluminum foil with a doctor blade. The electrodes were dried in vacuum at 105° C. for 6 hours, after which circular electrodes were punched out, weighed and dried in vacuum at 120° C. for 12 hours before being placed in an Ar-filled glove box.

[0117] Electrochemical measurements of half-cells: A coin-type electrochemical cell was assembled in an argon-filled glove box. The positive electrode (loading capacity 8.0 ± 0.5 mg cm) with a diameter of 14 mm was used. -2 ) was separated from the Li foil with a thickness of 0.58 mm by a glass fiber separator (Whatman GF / D). As electrolyte, 1 M LiPF6 in ethylene carbonate (EC):ethyl methyl carbonate (EMC) with a mass ratio of 3:7 was used in a volume of 95 μl. The cells were galvanostatically cycled in a Maccor 4000 battery cycler at room temperature from 3.1 to 4.3 V by applying the following C-rates until 70% of the initial discharge capacity was reached at the specific discharge step:

[0118] [Table 1]

[0119] After charging at the stated C-rate, all charging steps except the first step were performed using constant voltage steps (CV * ) for 1 hour or until the current reached 0.02C.

[0120] During the resistance measurements (performed every 25 cycles at 25°C), the cells were charged at 0.1C to reach a state of charge of 50% of the previous discharge capacity. This was followed by a 30 min open circuit step to allow the cells to equilibrate. Finally, a discharge current of 2.5C was applied for 30 s and the resistance was measured. At the end of the current pulse, the cells were again equilibrated at open circuit for 30 min and further discharged at 0.1C to 3.0 V.

[0121] To calculate the resistance, we took the voltage V0s before applying the 2.5C pulse current, the voltage V30s after applying the 2.5C pulse current for 30 seconds, and the current value of 2.5C (j is expressed in A). The resistance was calculated according to Equation 3 (V: voltage, j: 2.5C pulse current).

[0122] R=(V0s-V30s) / j (Formula 3)

[0123] The results show improved 1C rate and high stability after 140 (1C) and 141 (0.1C) cycles. Furthermore, there is less increase in resistance compared to the control experiment.

[0124] [Table 2]

Claims

1. Composition (Li ａ Mg ｂ ) １＋ｘ (Ni ｃ M １ ｄ M ２ ｅ ) １－ｘ O ２ (wherein M １ is selected from Ti, Zr, Nb, Mo, W, and combinations of at least two of the foregoing, M ２ is selected from Al, Co, Mn, and combinations of at least two of the foregoing, a:b is in the range of 100:1 to 400:1, a + b = 1, c:d is in the range of 40:1 to 250:1, c:e is in the range of 12:1 to 50:1, c + d + e = 1, the total molar ratio of (Li + Mg) to (Ni + M １ + M ２ ) is in the range of 1:1 to 1.05:1, 0.00 ≦ x ≦ 0.05) is a particulate material, wherein the particulate material has an average particle size (D50) in the range of 2 to 20 μm. Particulate material.

2. The substance is represented by the general formula (I), (Ni c M 1 d M 2 e ) (I) (wherein M ２ is selected from Mn and Co, c is in the range of 0.95 to 0.995, d is in the range of 0.002 to 0.04, e is in the range of 0.002 to 0.02, and c + d + e = 1) The particulate material according to claim 1, comprising a combination of metals according to.

3. M １ is selected from Ti, Zr, W, and combinations of at least two of the foregoing, the particulate matter according to claim 1 or 2.

4. The particulate matter according to claim 1 or 2, wherein the number of metals other than Ni, Mg, and Li is at least three and at most five.

5. The substance has an integrated peak width in the differential capacity plot (dQ) / (dV) of at least 25 mV between 4.1 and 4.25 V in the second charge cycle at a 0.2 C rate 第２充電 IPW ４．１－４．２５Ｖ The particulate matter according to claim 1 or 2.

6. The particulate matter according to claim 1 or 2, wherein the substance is coated with a metal oxide.

7. The following steps: (a) providing particulate nickel hydroxide, nickel(II) oxide, or nickel oxyhydroxide; (b) mixing the nickel oxide / hydroxide or nickel oxyhydroxide with compounds of Mg, M １ and M ２ and a lithium source; (c) heat-treating the mixture obtained from step (b) A method for producing the particulate matter according to claim 1 or 2, comprising.

8. The method according to claim 7, wherein step (c) is carried out at a maximum temperature in the range of 650 to 750 °C.

9. (A) at least one particulate matter according to claim 1 or 2, (B) carbon in a conductive state, (C) a binder material A cathode containing.

10. Based on the total of (A), (B), and (C), (A) 80 to 98% by mass of a cathode active material, (B) 1 to 17% by mass of carbon, (C) 3 to 10% by mass of a binder material The cathode according to claim 9, containing the same.

11. An electrochemical cell containing at least one cathode according to claim 9.