Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery

Abstract

The invention discloses a preparation method of a layered lithium-rich manganese base oxide of a positive material of a lithium ion battery. The preparation method comprises the following steps of: slowly adding transition metal brine solution, alkali liquor and ammonia water which conform to a stoichiometric ratio into a stirring reactor respectively; stirring and heating; aging, filtering, washing and drying the obtained precipitate to obtain a nickel cobalt and manganese composite precursor; proportioning and mixing with a lithium source according to the stoichiometric ratio; adding a fluxing agent of a certain proportion and uniformly mixing in a mechanical mode; placing mixed powder in a furnace for sintering; cooling to room temperature; fully washing with water; and removing remaining fluxing agent to obtain the layered lithium-rich manganese base oxide Li1+xNialphaCobetaMngammaO2 (wherein x is greater than 0 and is less than or equal to 0.33, alpha is greater than or equal to 0 and is less than 1, beta is greater than or equal to 1 and is less than 1, gamma is greater than 0 and is less than 1, and alpha and beta are not zero simultaneously.). According to the preparation method, the heating efficiency is greatly increased, the energy consumption is reduced, and meanwhile, the electrochemical performance of the material is improved; the prepared spherical layered lithium-rich manganese base oxide has no doped phase; and a product has a uniform average particle diameter and superior circulation performance.

Description

technical field

[0001] The invention belongs to the field of preparation of secondary battery materials, and in particular relates to a method for preparing a layered lithium-rich manganese-based oxide as a high-capacity lithium-ion battery anode material. Background technique

[0002] Lithium-ion batteries are widely used in people's daily life due to their high energy density, such as common mobile phones, digital cameras, notebook computers and power tools. Recently, in order to further increase its energy density, lithium-ion battery cathode materials have shifted from commercialized lithium cobalt oxide, lithium manganese oxide, and lithium nickel manganese cobalt oxide to other new cathode materials. Among them, the layered lithium-rich manganese-based oxide Li 1+x Ni α co β mn γ o 2 (where 0<x≤0.33, 0≤α<1, 0≤β<1, 0<γ<1, α.β are not zero at the same time) because of its ultra-high capacity, low cost, excellent cycle performance and thermal stability...

Examples

Embodiment 1

[0021] Mix nickel sulfate and manganese sulfate with a molar ratio of 1:3, add deionized water to prepare a 2mol / L mixed solution, use 2mol / L sodium carbonate solution as a precipitant, and 0.2mol / L ammonia water as a complex The reagent was added dropwise into the continuously stirred reactor at the same time, and the pH value of the reaction system was controlled to be 8, and the mixture was heated at a constant temperature of 60°C for 10h. The resulting precipitate was aged, filtered, washed, and dried to obtain the nickel-manganese carbonate precursor (Ni 0.25 mn 0.75 )CO 3 . Will (Ni 0.25 mn 0.75 )CO 3 Placed in an air atmosphere furnace at 500°C for constant temperature calcination for 5 hours to obtain the nickel manganese oxide precursor (Ni 0.25 mn 0.75 ) 3 o 4 .

[0022] Mix the obtained nickel-manganese oxide precursor, lithium carbonate and potassium chloride uniformly in a certain proportion, wherein the mass of potassium chloride is 5 times the total ma...

Embodiment 2

[0024] Mix nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 1:1:4, add deionized water to prepare a 2mol / L mixed solution, use 2mol / L sodium carbonate solution as a precipitant, 0.2mol / L Ammonia water was used as a complexing agent, and was added dropwise into a continuously stirred reactor at the same time, and the pH of the reaction system was controlled to be 8, and heated at a constant temperature of 60° C. for 12 hours. The resulting precipitate was aged, filtered, washed, and dried to obtain the nickel-cobalt-manganese carbonate precursor (Ni 1 / 6 co 1 / 6 mn 4 / 6 )CO 3 .

[0025] Mix the obtained nickel-cobalt-manganese carbonate precursor, lithium carbonate and sodium chloride uniformly in a certain proportion, wherein the quality of sodium chloride is 10 times of the total mass of the nickel-cobalt-manganese carbonate precursor and lithium carbonate, at 5°C Raise the temperature at a rate of 1 / min, then place the obtained powder in an air atmos...

Embodiment 3

[0027]Mix nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 2:1:7, add deionized water to prepare a 2mol / L mixed solution, use 2mol / L sodium carbonate solution as a precipitant, and 2mol / L Ammonia water was used as a complexing agent, and was added dropwise into a continuously stirred reactor at the same time, and the pH of the reaction system was controlled to be 8, and heated at a constant temperature of 60° C. for 8 hours. The resulting precipitate was aged, filtered, washed, and dried to obtain the nickel-cobalt-manganese carbonate precursor (Ni 0.2 co 0.1 mn 0.7 )CO 3 .

[0028] Mix the obtained nickel-cobalt-manganese carbonate precursor, lithium carbonate and potassium chloride uniformly in a certain proportion, wherein the quality of potassium chloride is 5 times the total mass of the nickel-cobalt-manganese carbonate precursor and lithium carbonate. Raise the temperature at a rate of 1 / min, then place the obtained powder in an air atmosphere...

technical field

[0001] The invention belongs to the field of preparation of secondary battery materials, and in particular relates to a method for preparing a layered lithium-rich manganese-based oxide as a high-capacity lithium-ion battery anode material. Background technique

[0002] Lithium-ion batteries are widely used in people's daily life due to their high energy density, such as common mobile phones, digital cameras, notebook computers and power tools. Recently, in order to further increase its energy density, lithium-ion battery cathode materials have shifted from commercialized lithium cobalt oxide, lithium manganese oxide, and lithium nickel manganese cobalt oxide to other new cathode materials. Among them, the layered lithium-rich manganese-based oxide Li 1+x Ni α co β mn γ o 2 (where 0<x≤0.33, 0≤α<1, 0≤β<1, 0<γ<1, α.β are not zero at the same time) because of its ultra-high capacity, low cost, excellent cycle performance and thermal stability...

Examples

Embodiment 1

[0021] Mix nickel sulfate and manganese sulfate with a molar ratio of 1:3, add deionized water to prepare a 2mol / L mixed solution, use 2mol / L sodium carbonate solution as a precipitant, and 0.2mol / L ammonia water as a complex The reagent was added dropwise into the continuously stirred reactor at the same time, and the pH value of the reaction system was controlled to be 8, and the mixture was heated at a constant temperature of 60°C for 10h. The resulting precipitate was aged, filtered, washed, and dried to obtain the nickel-manganese carbonate precursor (Ni 0.25 mn 0.75 )CO 3 . Will (Ni 0.25 mn 0.75 )CO 3 Placed in an air atmosphere furnace at 500°C for constant temperature calcination for 5 hours to obtain the nickel manganese oxide precursor (Ni 0.25 mn 0.75 ) 3 o 4 .

[0022] Mix the obtained nickel-manganese oxide precursor, lithium carbonate and potassium chloride uniformly in a certain proportion, wherein the mass of potassium chloride is 5 times the total ma...

Embodiment 2

[0024] Mix nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 1:1:4, add deionized water to prepare a 2mol / L mixed solution, use 2mol / L sodium carbonate solution as a precipitant, 0.2mol / L Ammonia water was used as a complexing agent, and was added dropwise into a continuously stirred reactor at the same time, and the pH of the reaction system was controlled to be 8, and heated at a constant temperature of 60° C. for 12 hours. The resulting precipitate was aged, filtered, washed, and dried to obtain the nickel-cobalt-manganese carbonate precursor (Ni 1 / 6 co 1 / 6 mn 4 / 6 )CO 3 .

[0025] Mix the obtained nickel-cobalt-manganese carbonate precursor, lithium carbonate and sodium chloride uniformly in a certain proportion, wherein the quality of sodium chloride is 10 times of the total mass of the nickel-cobalt-manganese carbonate precursor and lithium carbonate, at 5°C Raise the temperature at a rate of 1 / min, then place the obtained powder in an air atmos...

Embodiment 3

[0027]Mix nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 2:1:7, add deionized water to prepare a 2mol / L mixed solution, use 2mol / L sodium carbonate solution as a precipitant, and 2mol / L Ammonia water was used as a complexing agent, and was added dropwise into a continuously stirred reactor at the same time, and the pH of the reaction system was controlled to be 8, and heated at a constant temperature of 60° C. for 8 hours. The resulting precipitate was aged, filtered, washed, and dried to obtain the nickel-cobalt-manganese carbonate precursor (Ni 0.2 co 0.1 mn 0.7 )CO 3 .

[0028] Mix the obtained nickel-cobalt-manganese carbonate precursor, lithium carbonate and potassium chloride uniformly in a certain proportion, wherein the quality of potassium chloride is 5 times the total mass of the nickel-cobalt-manganese carbonate precursor and lithium carbonate. Raise the temperature at a rate of 1 / min, then place the obtained powder in an air atmosphere...

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