High-density doped trimanganese tetroxide and preparation method thereof

Abstract

The invention discloses high-density doped trimanganese tetroxide. The chemical formula of the high-density doped trimanganese tetroxide is Mn3O4*zMxOy, wherein z is within the range of 0.01-0.3; and MxOy is one or several of MgO, Ni2O5, Co3O4, Cr2O3, Al2O3, ZrO2, V2O5 and TiO2, or rare earth oxide. The physical indexes of the high-density doped trimanganese tetroxide are as follows: D50 (particle size) is within the range of 3-25 microns; the tap density is within the range of 2.1-2.6 g / cm3; BET is within the range of 1 to 4 m<2> / g; and the particle morphology is a spherical shape. The invention further discloses a preparation method for the trimanganese tetroxide; the method enables manganese to be continuously agglomerated with doped oxide in the process of being converted to the trimanganese tetroxide; and the growth direction and the growth speed of agglomerates are controlled by using the pH value, the reaction temperature and the adding quantity of ammonium salt catalyst to obtain the doped trimanganese tetroxide with good doping uniformity, good particle morphology and high density.

Description

technical field

[0001] The invention relates to trimanganese tetroxide raw material for lithium manganese oxide, a positive electrode material of batteries, and a preparation method thereof. Background technique

[0002] Lithium manganate is one of the more promising cathode materials for lithium-ion batteries. With the advancement of lithium manganate material technology, the amount of lithium manganate is also increasing year by year. However, the manganese source selected for traditional lithium manganate materials is manganese dioxide, and its capacity performance and cycle performance limit the further expansion of lithium manganate materials. In recent years, with the deepening of research, lithium manganese oxide manufacturers have found that lithium manganese oxide materials prepared using trimanganese tetraoxide as a manganese source have better capacity and cycle performance. The main reason is that compared with manganese dioxide, the crystal form of trimanganese...

Examples

preparation example Construction

[0017] The preparation method of high-density doped trimanganese tetraoxide of the present invention comprises the following steps:

[0018] (1) Grinding: mix metal manganese and doped oxides by molar ratio Mn:M x o y =3:0.01~0.3 is added to the mill, and the mixture is wet-ground to a certain particle size;

[0019] (2) Reaction: Add the ground slurry into the reactor, then add ammonium salt as a catalyst according to 0.5% to 10% of the total weight of manganese metal, and feed air or oxygen to control the reaction temperature at 70°C±10°C , control the pH value of 6.5-7.0, and carry out the catalytic oxidation reaction;

[0020] (3) Washing: Use washing equipment to perform one or more washings to remove the impurity elements doped in the trimanganese tetroxide;

[0021] (4) Drying: Use drying equipment to dry the manganese tetraoxide after washing to obtain a high-density, uniformly doped manganese tetraoxide product.

[0022] Wherein, in step (1): the metal manganese i...

Embodiment 1

[0028] (1) Grinding: Metal manganese flakes with a purity of 99.1% and aluminum oxide with a purity of 99.8% are mixed according to the molar ratio Mn:Al 2 o 3=3:0.07 for proportioning, the total weight is 1200Kg, put it into the ball mill, grind for 6 hours, and control the slurry D50 (particle size) to 0.93 um;

[0029] (2) Reaction: Add the ground slurry into the reactor, then add 50Kg of ammonium chloride, and start the air reaction. During the reaction process, the pH value is controlled to be 6.6±0.1, and the reaction temperature is 75°C±3°C. When the reaction pH is less than or equal to 6.4, it is judged as the end point, and the reaction lasts for 12 hours;

[0030] (3) Washing: Use a counter-current washing machine to wash the reacted slurry to control various impurities, especially Cl - , controlled below 200ppm;

[0031] (4) Drying: Use spray drying equipment to dry the washed slurry. The inlet temperature is controlled at 300°C±5°C, the outlet temperature is con...

Embodiment 2

[0034] (1) Grinding, manganese metal powder with a purity of 99.1%, aluminum oxide with a purity of 99.8%, and magnesium oxide with a purity of 99.6%, according to the molar ratio Mn:Al 2 o 3 :MgO=3:0.05:0.02 for proportioning, the total weight is 600Kg, add it to the ball mill, grind for 4 hours, and control the D50 (particle size) of the slurry to 0.92um;

[0035] (2) For reaction, add the ground slurry into the reactor, then add 30Kg of ammonium chloride, and start the air reaction. During the reaction process, the pH value is controlled to be 6.9±0.1, and the reaction temperature is 70°C±3°C. When the reaction pH is less than or equal to 6.4, it is judged as the end point, and the reaction lasts for 10 hours;

[0036] (3) Washing, using a counterflow washing machine to wash the reacted slurry to control various impurities, especially Cl - , controlled below 200ppm;

[0037] (4) Drying. Use spray drying equipment to dry the washed slurry. The inlet temperature is control...

technical field

[0001] The invention relates to trimanganese tetroxide raw material for lithium manganese oxide, a positive electrode material of batteries, and a preparation method thereof. Background technique

[0002] Lithium manganate is one of the more promising cathode materials for lithium-ion batteries. With the advancement of lithium manganate material technology, the amount of lithium manganate is also increasing year by year. However, the manganese source selected for traditional lithium manganate materials is manganese dioxide, and its capacity performance and cycle performance limit the further expansion of lithium manganate materials. In recent years, with the deepening of research, lithium manganese oxide manufacturers have found that lithium manganese oxide materials prepared using trimanganese tetraoxide as a manganese source have better capacity and cycle performance. The main reason is that compared with manganese dioxide, the crystal form of trimanganese...

Examples

preparation example Construction

[0017] The preparation method of high-density doped trimanganese tetraoxide of the present invention comprises the following steps:

[0018] (1) Grinding: mix metal manganese and doped oxides by molar ratio Mn:M x o y =3:0.01~0.3 is added to the mill, and the mixture is wet-ground to a certain particle size;

[0019] (2) Reaction: Add the ground slurry into the reactor, then add ammonium salt as a catalyst according to 0.5% to 10% of the total weight of manganese metal, and feed air or oxygen to control the reaction temperature at 70°C±10°C , control the pH value of 6.5-7.0, and carry out the catalytic oxidation reaction;

[0020] (3) Washing: Use washing equipment to perform one or more washings to remove the impurity elements doped in the trimanganese tetroxide;

[0021] (4) Drying: Use drying equipment to dry the manganese tetraoxide after washing to obtain a high-density, uniformly doped manganese tetraoxide product.

[0022] Wherein, in step (1): the metal manganese i...

Embodiment 1

[0028] (1) Grinding: Metal manganese flakes with a purity of 99.1% and aluminum oxide with a purity of 99.8% are mixed according to the molar ratio Mn:Al 2 o 3=3:0.07 for proportioning, the total weight is 1200Kg, put it into the ball mill, grind for 6 hours, and control the slurry D50 (particle size) to 0.93 um;

[0029] (2) Reaction: Add the ground slurry into the reactor, then add 50Kg of ammonium chloride, and start the air reaction. During the reaction process, the pH value is controlled to be 6.6±0.1, and the reaction temperature is 75°C±3°C. When the reaction pH is less than or equal to 6.4, it is judged as the end point, and the reaction lasts for 12 hours;

[0030] (3) Washing: Use a counter-current washing machine to wash the reacted slurry to control various impurities, especially Cl - , controlled below 200ppm;

[0031] (4) Drying: Use spray drying equipment to dry the washed slurry. The inlet temperature is controlled at 300°C±5°C, the outlet temperature is con...

Embodiment 2

[0034] (1) Grinding, manganese metal powder with a purity of 99.1%, aluminum oxide with a purity of 99.8%, and magnesium oxide with a purity of 99.6%, according to the molar ratio Mn:Al 2 o 3 :MgO=3:0.05:0.02 for proportioning, the total weight is 600Kg, add it to the ball mill, grind for 4 hours, and control the D50 (particle size) of the slurry to 0.92um;

[0035] (2) For reaction, add the ground slurry into the reactor, then add 30Kg of ammonium chloride, and start the air reaction. During the reaction process, the pH value is controlled to be 6.9±0.1, and the reaction temperature is 70°C±3°C. When the reaction pH is less than or equal to 6.4, it is judged as the end point, and the reaction lasts for 10 hours;

[0036] (3) Washing, using a counterflow washing machine to wash the reacted slurry to control various impurities, especially Cl - , controlled below 200ppm;

[0037] (4) Drying. Use spray drying equipment to dry the washed slurry. The inlet temperature is control...

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