US20090302267A1 - Inorganic Compounds - Google Patents

Inorganic Compounds Download PDF

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US20090302267A1
US20090302267A1 US11/990,273 US99027306A US2009302267A1 US 20090302267 A1 US20090302267 A1 US 20090302267A1 US 99027306 A US99027306 A US 99027306A US 2009302267 A1 US2009302267 A1 US 2009302267A1
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chemical compound
mixed metal
powder
hydroxide
lithium
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Sven Albrecht
Michael Kruft
Stefan Malcus
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Toda Kogyo Corp
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    • 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
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    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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Definitions

  • the present invention relates to a chemical compound of the formula Ni b M1 c M2 d (O) x (OH) y , a process for the preparation thereof and the use thereof as a precursor for the preparation of cathode material for lithium secondary batteries.
  • Lithium secondary batteries with non-aqueous electrolyte liquids have the desired properties.
  • This type of secondary batteries is distinguished by a positive electrode, the active material of which can reversibly embed and release lithium ions.
  • Composite oxides which in each case comprise lithium and at least one transition metal are known as suitable active substances for the positive electrodes of such secondary batteries.
  • suitable active substances for the positive electrodes of such secondary batteries.
  • Examples are LiCoO 2 , LiNiO 2 or also LiNi 0.8 Co 0.2 O 2 .
  • LiCoO 2 which is currently still used most frequently in lithium secondary batteries, has the disadvantage of a very high price of cobalt.
  • Nickel is indeed less expensive than cobalt, but the high nickel-containing active masses have the disadvantage that when they are employed in secondary batteries they have the effect of an inadequate heat stability of the battery.
  • JP 10-27611 proposes employing an at least bimetallic mixed hydroxide as a precursor for the synthesis of the lithium mixed metal oxide to improve the electrochemical properties.
  • the elements nickel and cobalt the elements aluminium and manganese, inter alia, are also mentioned in this context as a third metallic component for co-precipitation of the mixed metal hydroxide.
  • the amount of doping elements is 10-30 mol % of the total amount of metal. At an amount of these metallic doping components of less than 10 mol %, a battery with this active mass has an inadequate cycle stability, while at an amount of greater than 30 mol %, the spherical particle shape is difficult to maintain in the precursor.
  • US 2002/0053663 A1 and US 2003/0059490 A1 propose composite oxides which comprise lithium, nickel, cobalt and manganese.
  • co-precipitated mixed hydroxides of nickel, cobalt and manganese form the starting substance for the later mixed oxides.
  • Both the electrochemical charging/discharging properties of the secondary battery and the high temperature stability are said to be improved by the doping elements cobalt and manganese in the lithium mixed metal oxide.
  • higher concentrations of cobalt and manganese are required compared with the compounds mentioned in JP 10-27611.
  • the upper limit mentioned for cobalt and manganese in US 2002/0053663 A1 is in each case 33 mol %, based on the total amount of the metallic transition elements.
  • US 2003/0054251 A1 describes an optimized process route for the synthesis of nickel- and manganese-containing mixed oxides as an active mass for lithium secondary batteries.
  • the main aim of this invention is to heat-treat the co-precipitated mixed hydroxides (e.g. comprising Ni, Co, Mn) at 300-500° C. before the actual oven process. i.e. before the conversion into the lithium mixed metal oxide, in order to obtain the so-called dry precursor.
  • a lithium component is then added to this dry precursor and the mixture is converted into the mixed metal oxide by calcining.
  • WO 2004/092073 A1 also relates to mixed metal precursors for the synthesis of lithium mixed metal oxide.
  • an ideal precursor for the synthesis of this compound class is sought here.
  • US 2003/0054251 A1 is mentioned, inter alia, as prior art. Since the heat treatment of the precursor, as described in US 2003/0054251, is very involved and the subsequent use of LiOH is very expensive compared with Li 2 CO 3 , an oxidation of the co-precipitated Ni—Co—Mn hydroxide to give an Ni—Co—Mn oxyhydroxide is proposed as an alternative here.
  • the oxidation is carried out using an oxidizing agent such as dissolved air, sodium hypochlorite, hydrogen peroxide solution, potassium peroxodisulfate or bromine.
  • an oxidizing agent such as dissolved air, sodium hypochlorite, hydrogen peroxide solution, potassium peroxodisulfate or bromine.
  • a gamma-NiOOH phase also additionally forms.
  • This phase has a significant expansion in volume compared with the beta-NiOOH phase because of an interlaminar expansion, which facilitates embedding of foreign ions, such as e.g. Na + etc.
  • the interlaminar expansion is already known from J. Power Sources, 8 (1982), 229.
  • US 2002/0053663 A1 discloses co-precipitated nickel-cobalt-manganese hydroxides, emphasis being placed on being able to synthesize a co-precipitated nickel-cobalt-manganese hydroxide having a high tap density.
  • the hydroxide serves as a precursor for the lithium mixed metal oxides, which in turn is employed as an active mass in lithium secondary batteries.
  • the tap density of the lithium mixed metal oxide is in turn of great importance and is influenced quite considerably by the tap density of the precursor.
  • further important parameters of the mixed hydroxide as a precursor for lithium mixed metal oxides are not dealt with.
  • the object of the present invention is therefore to provide a mixed metal compound, as a precursor for the preparation of cathode material for lithium secondary batteries, which contains no gamma-oxyhydroxide structures and/or alpha-hydroxide structures, is distinguished by a high tap density, has low sodium contents and allows the synthesis of a high-quality lithium mixed metal compound.
  • the object of the present invention is furthermore to provide a economical process for the preparation of partly oxidized mixed metal hydroxides.
  • Advantageous compounds are chemical compounds of the formula Ni b M1 c M2 d (O) x (OH) y , wherein
  • Particularly preferred compounds are chemical compounds of the formula Ni b M1 c M2 d (O) x (OH) y wherein x is a number between 0.3 and 0.6 and y is a number between 1.4 and 1.7.
  • the chemical compounds according to the invention are partly oxidized mixed metal hydroxides, later also called precursor(s).
  • the average degree of oxidation is also an indicator for evaluation of the quality of the precursor for lithium secondary batteries. Precise adjustment of this parameter during the preparation process is therefore necessary.
  • the average degree of oxidation of the partly oxidized mixed metal hydroxide according to the invention should not be below a certain level in order to ensure good further processability and finally a good quality of the end product. It has also been found that the average degree of oxidation should not be too high, since a secondary phase, such as a gamma-oxyhydroxide, may increasingly occur in the precursor at degrees of oxidation which are too high.
  • a secondary phase such as a gamma-oxyhydroxide
  • the presence of the gamma phase alongside the desired beta phase means an inhomogeneity of the precursor and finally also influences the homogeneity of the end product obtainable therefrom. Due to the interlaminar extension of the crystal lattice compared with the beta phase, the existence of a gamma phase furthermore promotes the undesirable inclusion of ionic impurities.
  • the average degree of oxidation is 2.2 to 2.7, particularly preferably 2.3 to 2.6.
  • the determination of the average degree of oxidation over all the metallic components is based on the Rupp method of manganese dioxide determination.
  • the degree of oxidation determined by means of the method mentioned is the basis for evaluation of the empirical formula of the present chemical compound.
  • NiCoMn(O) 0.5 (OH) 1.5 NiCoMn(O) 0.5 (OH) 1.5 .
  • FIG. 1 shows by way of example an x-ray diffraction spectrum (XDS) of a partly oxidized mixed metal hydroxide according to the invention, which was prepared according to Example 1 and in which no gamma phase is detectable.
  • XDS x-ray diffraction spectrum
  • Preferred partly oxidized mixed metal hydroxides according to the invention contain no alpha phase.
  • the presence of the alpha phase alongside the desired beta phase means an inhomogeneity of the precursor and finally also influences the homogeneity of the end product obtainable therefrom.
  • the degree of oxidation increases, e.g. when the latter reaches a value of e.g. 3.0 in the oxidized mixed metal hydroxide, the ionic impurities, those such as e.g. sodium, in the product increase, since in the phase conversion to the gamma-oxyhydroxide greater distances between layers in the crystal lattice render possible the incorporation of undesirable foreign ions.
  • the gamma phase leads to a considerable expansion in volume due to an interlaminar extension and thereby promotes the embedding of foreign ions.
  • the partly oxidized mixed metal hydroxides according to the invention are also distinguished in that they have low sodium contents.
  • they contain ⁇ 2,000 ppm, particularly preferably ⁇ 1,000 ppm of sodium, in particular ⁇ 500 ppm of sodium.
  • the partly oxidized mixed metal hydroxides according to the invention are preferably in powder form, the average particle size of the secondary particles, measured in accordance with ASTM B822, preferably being 2 to 30 ⁇ m, particularly preferably 3 to 15 ⁇ m.
  • Secondary particles are understood as meaning particles which are composed of primary particles.
  • a particular feature of the mixed metal hydroxide powder according to the invention is its high tap density, which has a direct influence directly on the tap density of the end product, e.g. a lithium mixed metal oxide.
  • the high tap density is necessary in order to achieve a high volumetric energy density in the battery.
  • the partly oxidized mixed metal hydroxide powders according to the invention have a tap density, determined in accordance with ASTM B527, of greater than 1.7 g/cm 3 , particularly preferably greater than 1.9 g/cm 3 .
  • the pulverulent mixed metal hydroxides according to the invention can be prepared both in a spherical and in a regular (non-spherical) particle shape.
  • the preferred powders according to the invention are distinguished in particular by the spherical shape of the powder particles, the shape factor of which has a value of greater than 0.7, particularly preferably of greater than 0.9.
  • the shape factor of the secondary particles can be determined by the method mentioned in U.S. Pat. No. 5,476,530, columns 7 and 8 and FIG. 5. This method determines a shape factor of the particles which is a measure of the sphericity of the particles.
  • the shape factor of the particles can be determined from the SEM photographs of the materials.
  • the shape factor is determined by evaluation of the particle circumference and the particle area and of the determination of the diameter deduced from the particular parameters.
  • the diameters mentioned result from
  • the shape factor of the particles f is deduced from the particle circumference U and the particle area A according to:
  • d A and d U are equal and a shape factor of precisely one would result.
  • FIG. 2 shows by way of example a photograph of the partly oxidized mixed metal hydroxide powder according to the invention prepared according to Example 1 taken with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the partly oxidized mixed metal hydroxide powders according to the invention have a standardized width of the particle size distribution, defined according to the formula
  • D denotes the diameter of the powder particles, of less than 1.8, particularly preferably of less than 1.2.
  • the invention furthermore relates to an efficient and economical process for the preparation of the partly oxidized mixed metal hydroxides according to the invention.
  • the invention therefore also provides a process for the preparation of the partly oxidized mixed metal hydroxides according to the invention comprising the following steps:
  • the partly oxidized mixed metal hydroxides according to the invention can be prepared both in a spherical and in a non-spherical particle shape, the preparation of the former being carried out in the presence of ammonia or ammonium salts.
  • Mixed hydroxides are prepared by precipitation from aqueous metal salt solutions by adjusting the pH to 8-14, particularly preferably to 9-13, by addition of alkali hydroxide solutions.
  • the process can be carried out discontinuously or continuously.
  • metal salt solution and the alkali hydroxide solution are added simultaneously to a precipitating reactor, with continuous removal of the product suspension.
  • Suitable metal salts are water-soluble metal salts, e.g. sulfates, nitrates, halides, such as e.g. chlorides or fluorides.
  • Alkali metal salt solutions which are employed for carrying out the precipitation are hydroxides of the alkali metals, preferably sodium hydroxide, as well as ammonium hydroxide.
  • An oxidation of the metals should be avoided during the precipitation process, in order to be able to achieve a high tap density of the partly oxidized mixed metal hydroxide.
  • the oxidation is therefore carried out after the precipitation in a further reactor.
  • the invention provides a process which is particularly suitable in respect of simple ease of integration into the existing production process.
  • the partial oxidation of the co-precipitated mixed metal hydroxide can still take place in the product suspension.
  • the process is realized by transferring the product suspension with the co-precipitated mixed metal hydroxide from the precipitating reactor into a subsequent stirred tank. An oxidizing agent is fed into this tank via an inlet tube. Air, oxygen, hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate and/or mixtures thereof are particularly suitable oxidizing agents.
  • the reaction temperature of the suspension during the partial oxidation is 25 to 65° C., particularly preferably 30 to 60° C.
  • the pH of the suspension during the partial oxidation of the mixed metal hydroxide is preferably 7-13, particularly preferably 8-12.
  • the dwell time of the product suspension in the reaction tank likewise plays an important role during the partial oxidation. It has now been found that the dwell time of from 1 to 10 hours, preferably of from 2 to 8 hours and particularly preferably of from 4 to 6 hours leads to partly oxidized mixed metal hydroxides according to the invention.
  • the partly oxidized mixed metal hydroxide is removed continuously. However, it is also possible to remove the product in portions.
  • the partly oxidized mixed metal hydroxide according to the invention is then washed on a suction filter and dried in a drying cabinet.
  • the preparation of partly oxidized mixed metal hydroxides according to the invention can also be carried out via another process by separating off the co-precipitated mixed metal hydroxides from the suspension, washing them and drying them under an oxygen-containing atmosphere, such as e.g. air.
  • the invention therefore provides a further process comprising the following steps:
  • the partly oxidized mixed metal hydroxides according to the invention are particularly suitable for the synthesis of end products having the chemical formula Li a Ni b M1 c M2 d (O) 2 , also called end product, which are employed as the active material for positive electrodes in secondary batteries.
  • the partly oxidized mixed metal hydroxides according to the invention are conceived such that the end product obtainable therefrom—lithium mixed metal oxide—can be prepared via a simple synthesis route.
  • the invention furthermore provides a process for the preparation of active materials for secondary batteries comprising the following steps:
  • the chemical reaction of the precursor proceeds to a chemical compound Li a Ni b M1 c M2 d (O) 2 , wherein M1 is at least one element chosen from the group consisting of Fe, Co, Mg, Zn, Cu and mixtures thereof and/or M2 is at least one element chosen from the group consisting of Mn, Al, B, Ca, Cr and mixtures thereof, the particle shape and/or particle size distribution being retained.
  • the end product can be prepared by mixing the partly oxidized mixed metal hydroxide according to the invention with a lithium-containing component and then calcining and sieving the mixture.
  • Suitable lithium-containing components are, in particular, lithium hydroxide, lithium carbonate, lithium nitrate and/or mixtures thereof.
  • the calcining can be carried out at temperatures of greater than 600° C., preferably of greater than 700° C.
  • the end product obtainable from the partly oxidized mixed metal hydroxide according to the invention is distinguished in particular by very good sieving properties.
  • the sieving yield of the end product is greater than 90%, preferably greater than 95%, particularly preferably greater than 98%.
  • the partly oxidized mixed metal hydroxides according to the invention are preferably employed as a precursor for cathode active material in lithium secondary batteries, together with materials known to the person skilled in the art.
  • the average degrees of oxidation stated in the following examples are determined by the Rupp method. This method is based on the method of determination of manganese dioxide. In this, metal ions of higher valency (valency +3 or +4 in this case) are reduced to metal(II) ions by iodide, the iodide being oxidized to elemental iodine. The iodine formed is determined by means of titration against sodium thiosulfate standard solution. The equivalent point is indicated with starch solution.
  • test material 0.2 g is weighed into a 500 ml conical flask with a ground glass joint on an analytical balance. 50 ml of potassium iodide solution and 25 ml of dilute sulfuric acid are added by means of a 50 ml measuring cylinder. The conical flask is then closed with a glass stopper.
  • test material is dissolved at room temperature by occasional swirling of the conical flask.
  • the dissolving time is 30 to 60 min.
  • the average degree of oxidation over all the metals of the compound can be calculated via the following formula:
  • a ′ 2 + ( V ⁇ ( Na 2 ⁇ S 2 ⁇ O 3 , sample ) - V ⁇ ( Na 2 ⁇ S 2 ⁇ O 3 , blank ) ) ⁇ titre ⁇ ( Na 2 ⁇ S 2 ⁇ O 3 ) ⁇ c ⁇ ( Na 2 ⁇ S 2 ⁇ O 3 ) ⁇ M ⁇ ( sample ) m ⁇ ( sample )
  • a solution which is in each case 0.7 molar in NiSO 4 , CoSO 4 and MnSO 4 is fed continuously to a precipitating reactor.
  • a 2.5 molar NaOH solution and a 12.5% strong NH 3 solution are simultaneously fed continuously into the reactor. These streams are metered such that an ammonia concentration of 30 g/l and a free sodium hydroxide solution concentration of 1.4 g/l are established in the stationary operating state. Under these conditions, a pH of 12.4 is established. The high pH ensures that the metallic components are precipitated as hydroxides from the metal-containing solutions.
  • the addition of the various feed solutions results in a solids concentration in the reactor of 40 g/l.
  • the temperature in the reactor is regulated to 50° C. by means of an external supply of heat.
  • the average dwell time of the solid in the reactor is 6 h.
  • the product suspension is removed continuously from the reactor and first fed to washing on a suction filter. Washing is necessary in order to separate the solid from adhering impurities.
  • the solid synthesized in this way has an average oxidation level over all the metals, determined by experiment, of 2.7.
  • the tap density of the material was measured as 1.74 g/cm 3 .
  • the SEM photograph in FIG. 2 shows the particular sphericity and also the pronounced compactness of the particles of the material synthesized in this way.
  • the shape factor determined for the material is 0.85.
  • the precursor was first mixed mechanically with technical-grade lithium carbonate (Chemetall).
  • the molar ratio of the lithium compound to the precursor in this case was 1.05:1.00.
  • the mechanical mixture was then calcined at 890° C. under an oxygen-containing atmosphere for 30 hours.
  • the sieving yield was 97.5%. 2.5% of the material could not be sieved through a 50 ⁇ m sieve. After the sieving, the material was subjected to a second calcining at 890° C. under an oxygen-containing atmosphere for 4 hours. Thereafter, sieving was carried out again with a sieving yield of 99.6%.
  • the tap density of the end product here was 2.0 g/cm 3 . It can be seen from the SEM photographs of the end product, FIGS. 3 and 4 , that the conversion of the precursor into the end product has taken place with retention of the spherical shape of the secondary particles of the precursor.
  • a solution which is in each case 0.7 molar in NiSO 4 , CoSO 4 and MnSO 4 is fed continuously to a precipitating reactor.
  • a 2.5 molar NaOH solution and a 12.5% strong NH 3 solution are simultaneously fed continuously into the reactor. These streams are metered such that an ammonia concentration of 8.3 g/l and a free sodium hydroxide solution concentration of 0.5 g/l are established in the stationary operating state. Under these conditions, a pH of 12.0 is established. The high pH ensures that the metallic components are precipitated as hydroxides from the metal-containing solutions.
  • the addition of the various feed solutions results in a solids concentration in the reactor of 80 g/l.
  • the temperature in the reactor is regulated to 45° C. by means of an external supply of heat.
  • the average dwell time of the solid in the reactor is 12 h.
  • the product suspension is removed continuously from the reactor and first fed to a filtration and washing. Washing is necessary in order to separate the solid from adhering impurities.
  • the mixed hydroxide synthesized in this way had an average oxidation level over all the metals, determined by experiment, of 2.07.
  • the x-ray diffraction spectrum for the compound synthesized is shown in FIG. 5 .
  • the precursor was first mixed mechanically with technical-grade lithium carbonate (Chemetall).
  • the molar ratio of the lithium compound to the mixed metal compound in this case was 1.07:1.00.
  • the mechanical mixture was then calcined at 860° C. under an oxygen-containing atmosphere for 30 hours.
  • FIG. 8 A comparison of the electrochemical performance data of half cells which comprise the material synthesized according to Example 1 and that according to Comparison Example 1 as the cathode active material is shown in FIG. 8 . It can be seen from the figure that a half cell produced with the substance from Example 1 shows better performance data compared with a half cell produced with the substance from Comparison Example 1.
  • a solution which is in each case 0.7 molar in NiSO 4 , CoSO 4 and MnSO 4 is fed continuously to a precipitating reactor.
  • a 2.5 molar NaOH solution and a 12.5% strong NH 3 solution are simultaneously fed continuously into the reactor.
  • These streams are metered such that an ammonia concentration of 8 g/l and a free sodium hydroxide solution concentration of 0.5 g/l are established in the stationary operating state. Under these conditions, a pH of 12.0 is established.
  • the high pH ensures that the metallic components are precipitated as hydroxides from the metal-containing solutions.
  • the addition of the various feed solutions results in a solids concentration in the reactor of 50 g/l.
  • the temperature in the reactor is regulated to 50° C. by means of an external supply of heat.
  • the average dwell time of the solid in the reactor is 5 h.
  • the product suspension is fed continuously from the precipitating reactor to a second reactor, in which the pH is adjusted to 12.0 by means of pH control and metering in of 2.5 molar NaOH solution and the temperature is adjusted to 50° C. by means of an external supply of heat.
  • the average dwell time is adjusted to 10 h.
  • Air is introduced into this second reactor with a volume flow of 0.5 litre/min. During this procedure, the suspension changes its colour from pale brown in the first reactor to dark brown to black in the second reactor.
  • the suspension is removed continuously from the second reactor, and initially fed to washing on a suction filter. Washing is necessary in order to separate the solid from adhering impurities. After washing of the product, the solid is dried for 24 h in a vacuum drying cabinet at 100° C.
  • the solid synthesized in this way has an average oxidation level over all the metals, determined by experiment, of 2.39.
  • the sodium content of the product is 70 ppm.
  • FIG. 9 only peaks which can be assigned to a ⁇ structure are detected. No further phases are to be found in the XDA spectrum.
  • a solution which is in each case 0.7 molar in NiSO 4 , CoSO 4 and MnSO 4 is fed continuously to a precipitating reactor.
  • a 2.5 molar NaOH solution and a 12.5% strong NH 3 solution are simultaneously fed continuously into the reactor.
  • These streams are metered such that an ammonia concentration of 8 g/l and a free sodium hydroxide solution concentration of 0.5 g/l are established in the stationary operating state. Under these conditions, a pH of 12.0 is established.
  • the high pH ensures that the metallic components are precipitated as hydroxides from the metal-containing solutions.
  • the addition of the various feed solutions results in a solids concentration in the reactor of 50 g/l.
  • the temperature in the reactor is regulated to 50° C. by means of an external supply of heat.
  • the average dwell time of the solid in the reactor is 5 h.
  • the product suspension is fed continuously from the precipitating reactor to a second reactor, in which the pH is adjusted to 12.5 by means of pH control and metering in of 2.5 molar NaOH solution and the temperature is adjusted to 70° C. by means of an external supply of heat.
  • the average dwell time is adjusted to 15 h.
  • Air is introduced into this second reactor with a volume flow of 0.5 litre/min. During this procedure, the suspension changes its colour from pale brown in the first reactor to dark brown to black in the second reactor.
  • the suspension is removed continuously from the second reactor, and initially fed to washing on a suction filter. Washing is necessary in order to separate the solid from adhering impurities. After washing of the product, the solid is dried for 24 h in a vacuum drying cabinet at 100° C.
  • the solid synthesized in this way has an average oxidation level over all the metals, determined by experiment, of 2.83.
  • the sodium content of the product is 3,000 ppm.
  • FIG. 10 contents of a gamma phase are detected, in addition to the peaks, which can be assigned to a beta structure.

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  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100310869A1 (en) * 2007-10-12 2010-12-09 H.C. Starck Gmbh POWDER NiaMbOx(OH)y COMPOUNDS, PROCESSES FOR MAKING THE SAME, AND USES THEREOF IN BATTERIES
US20110180748A1 (en) * 2007-08-21 2011-07-28 H.C. Starck Gmbh Powdered niam1 bm2c(o)x(oh)ycompounds, method for the production thereof and use thereof in batteries
US20130168600A1 (en) * 2010-09-22 2013-07-04 Omg Kokkola Chemicals Oy Mixed Metal Oxidized Hydroxide and Method for Production
US8592085B2 (en) 2009-10-22 2013-11-26 Toda Kogyo Corporation Nickel-cobalt-maganese-based compound particles and process for producing the nickel-cobalt-manganese-based compound particles, lithium composite oxide particles and process for producing the lithium composite oxide particles, and non-aqueous electrolyte secondary battery
US20150364761A1 (en) * 2011-06-07 2015-12-17 Sumitomo Metal Mining Co., Ltd. Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueous-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery
US9698420B2 (en) 2012-10-17 2017-07-04 Toda Kogyo Corp. Li-Ni composite oxide particles and process for producing the same, and non-aqueous electrolyte secondary battery
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US9941515B2 (en) 2013-06-19 2018-04-10 Sumitomo Metal Mining Co., Ltd. Nickel-cobalt-manganese composite hydroxide and method for producing same
US9966600B2 (en) * 2012-07-09 2018-05-08 Lg Chem, Ltd. Precursor for preparing lithium composite transition metal oxide, method for preparing the precursor, and lithium composite transition metal oxide
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US20120231340A1 (en) * 2009-11-20 2012-09-13 Sumitomo Chemical Company, Limited Transition-metal-containing hydroxide and lithium-containing metal oxide
JP5747918B2 (ja) * 2010-08-09 2015-07-15 日本ゼオン株式会社 二次電池用多孔膜、製造方法、及び用途
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WO2016013674A1 (ja) * 2014-07-25 2016-01-28 住友金属鉱山株式会社 ニッケルマンガン複合水酸化物粒子およびその製造方法
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US20240400411A1 (en) * 2023-05-31 2024-12-05 Sylvatex, Inc. Method for the Manufacture of Cathode Materials
KR20250053587A (ko) * 2023-10-13 2025-04-22 (주)에코프로머티리얼즈 리튬 이차 전지용 양극 활물질 전구체 및 이의 제조 방법

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6348284B1 (en) * 1999-12-23 2002-02-19 Alcatel Non-sintered nickel electrode for a secondary electro-chemical cell having an alkaline electrolyte
US20020039683A1 (en) * 2000-08-08 2002-04-04 Masaru Kihara Manufacturing method of positive active material for alkaline storage battery, nickel electrode using the same material and alkaline storage battery using the same nickel electrode
US20020053663A1 (en) * 2000-11-06 2002-05-09 Tanaka Chemical Corporation High density cobalt-manganese coprecipitated nickel hydroxide and process for its production
US20030186125A1 (en) * 2002-03-19 2003-10-02 Tanaka Chemical Corporation Process for producing nickel oxyhydroxide by electrolytic oxidation
US20030206852A1 (en) * 1999-12-29 2003-11-06 Kimberly-Clark Worldwide, Inc. Nickel-rich quaternary metal oxide materials as cathodes for lithium-ion and lithium-ion polymer batteries
US20040241545A1 (en) * 2001-09-03 2004-12-02 Seijiro Ochiai Nickel electrode material,and production method therefor, and nickel electrode and alkaline battery
US20050026039A1 (en) * 2003-07-31 2005-02-03 Matsushita Electric Industrial Co., Ltd. Cobalt oxyhydroxide, method for producing the same and alkaline storage battery using the same
US20060083989A1 (en) * 2003-04-17 2006-04-20 Seimi Chemical Co., Ltd. Lithium-nickel-cobalt-maganese containing composite oxide, material for positive electrode active material for lithium secondary battery, and methods for producing these

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002201028A (ja) * 2000-11-06 2002-07-16 Tanaka Chemical Corp 高密度コバルトマンガン共沈水酸化ニッケル及びその製造法
NZ520452A (en) 2002-10-31 2005-03-24 Lg Chemical Ltd Anion containing mixed hydroxide and lithium transition metal oxide with gradient of metal composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6348284B1 (en) * 1999-12-23 2002-02-19 Alcatel Non-sintered nickel electrode for a secondary electro-chemical cell having an alkaline electrolyte
US20030206852A1 (en) * 1999-12-29 2003-11-06 Kimberly-Clark Worldwide, Inc. Nickel-rich quaternary metal oxide materials as cathodes for lithium-ion and lithium-ion polymer batteries
US20020039683A1 (en) * 2000-08-08 2002-04-04 Masaru Kihara Manufacturing method of positive active material for alkaline storage battery, nickel electrode using the same material and alkaline storage battery using the same nickel electrode
US20020053663A1 (en) * 2000-11-06 2002-05-09 Tanaka Chemical Corporation High density cobalt-manganese coprecipitated nickel hydroxide and process for its production
US20040241545A1 (en) * 2001-09-03 2004-12-02 Seijiro Ochiai Nickel electrode material,and production method therefor, and nickel electrode and alkaline battery
US20030186125A1 (en) * 2002-03-19 2003-10-02 Tanaka Chemical Corporation Process for producing nickel oxyhydroxide by electrolytic oxidation
US20060083989A1 (en) * 2003-04-17 2006-04-20 Seimi Chemical Co., Ltd. Lithium-nickel-cobalt-maganese containing composite oxide, material for positive electrode active material for lithium secondary battery, and methods for producing these
US20050026039A1 (en) * 2003-07-31 2005-02-03 Matsushita Electric Industrial Co., Ltd. Cobalt oxyhydroxide, method for producing the same and alkaline storage battery using the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9352977B2 (en) 2007-08-21 2016-05-31 H.C. Starck Gmbh Powered compounds, method for the production thereof, and use thereof in lithium secondary batteries
US20110180748A1 (en) * 2007-08-21 2011-07-28 H.C. Starck Gmbh Powdered niam1 bm2c(o)x(oh)ycompounds, method for the production thereof and use thereof in batteries
US9028710B2 (en) * 2007-08-21 2015-05-12 H.C. Starck Gmbh Powdered NiaM1bM2c(O)x(OH)y compounds, method for the production thereof and use thereof in batteries
US8545794B2 (en) 2007-10-12 2013-10-01 H.C. Starck Gmbh Powder NiaMbOx(OH)γcompounds, processes for making the same, and uses thereof in batteries
US20100310869A1 (en) * 2007-10-12 2010-12-09 H.C. Starck Gmbh POWDER NiaMbOx(OH)y COMPOUNDS, PROCESSES FOR MAKING THE SAME, AND USES THEREOF IN BATTERIES
US8592085B2 (en) 2009-10-22 2013-11-26 Toda Kogyo Corporation Nickel-cobalt-maganese-based compound particles and process for producing the nickel-cobalt-manganese-based compound particles, lithium composite oxide particles and process for producing the lithium composite oxide particles, and non-aqueous electrolyte secondary battery
US20130168600A1 (en) * 2010-09-22 2013-07-04 Omg Kokkola Chemicals Oy Mixed Metal Oxidized Hydroxide and Method for Production
US9287555B2 (en) * 2010-09-22 2016-03-15 OMG Kokkola Chemical Oy Mixed metal oxidized hydroxide and method for production
US11038168B2 (en) 2011-06-07 2021-06-15 Sumitomo Metal Mining Co., Ltd. Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueos-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery
US10128501B2 (en) * 2011-06-07 2018-11-13 Sumitomo Metal Mining Co., Ltd. Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueous-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery
US12288876B2 (en) 2011-06-07 2025-04-29 Sumitomo Metal Mining Co., Ltd Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueos-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery
US11876222B2 (en) 2011-06-07 2024-01-16 Sumitomo Metal Mining Co., Ltd. Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueos-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery
US11545663B2 (en) 2011-06-07 2023-01-03 Sumitomo Metal Mining Co., Ltd. Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueos-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery
US20150364761A1 (en) * 2011-06-07 2015-12-17 Sumitomo Metal Mining Co., Ltd. Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueous-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery
US9966600B2 (en) * 2012-07-09 2018-05-08 Lg Chem, Ltd. Precursor for preparing lithium composite transition metal oxide, method for preparing the precursor, and lithium composite transition metal oxide
US9698420B2 (en) 2012-10-17 2017-07-04 Toda Kogyo Corp. Li-Ni composite oxide particles and process for producing the same, and non-aqueous electrolyte secondary battery
US9941515B2 (en) 2013-06-19 2018-04-10 Sumitomo Metal Mining Co., Ltd. Nickel-cobalt-manganese composite hydroxide and method for producing same
US10122016B2 (en) 2013-07-18 2018-11-06 Tosoh Corporation Nickel-manganese composite oxyhydroxide, its production method, and its application
US10153490B2 (en) 2016-04-29 2018-12-11 Lg Chem, Ltd. Composite transition metal oxide-based precursor, preparing method thereof, and cathode active material using the same
US10727475B2 (en) 2016-08-10 2020-07-28 Umicore Precursors for lithium transition metal oxide cathode materials for rechargeable batteries
US20180047975A1 (en) * 2016-08-10 2018-02-15 Umicore Precursors for Lithium Transition Metal Oxide Cathode Materials for Rechargeable Batteries
EP3281915A1 (en) 2016-08-10 2018-02-14 Umicore Precursors for lithium transition metal oxide cathode materials for rechargeable batteries
US11476461B2 (en) 2017-03-14 2022-10-18 Umicore Precursors for cathode material with improved secondary battery performance and method to prepare the precursors
US11848448B2 (en) 2018-03-09 2023-12-19 Lg Energy Solution, Ltd. Lithium secondary battery
US20210328216A1 (en) * 2019-01-22 2021-10-21 Tanaka Chemical Corporation Composite hydroxide small particle for non-aqueous electrolyte secondary battery

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