Preparation method for nickel-manganese-cobalt anode material of lithium ion battery

A positive electrode material, nickel-manganese-cobalt technology, applied in battery electrodes, electrical components, circuits, etc., can solve physical indicators such as difficult control of particle size and morphology characteristics, inability to form a homogeneous eutectic, and unstable batch product quality and other problems to achieve high tap density, stable cycle performance and low cost

Inactive Publication Date: 2012-01-04
HEFEI GUOXUAN HIGH TECH POWER ENERGY
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Problems solved by technology

However, direct sintering of the above-mentioned raw materials by high-temperature solid-phase method is prone to problems such as uneven mixing, failure to form a homogeneous eutectic, and unstable product quality in each batch.
The publication number is: CN1851962A discloses a doped lithium-nickel-manganese-cobalt composite oxide positive electrode material and its preparation method. The method is to mix a compound capable of decomposing to produce tin oxide at high temperature with nickel-manganese-cobalt lithium oxide, and then carry out high-temperature solidification. The positive electrode material obtained by the corresponding reaction has a capacity of about 125mAh / g in 3C discharge, but the high-temperature solid-phase method consumes a lot of energy and the material is mixed unevenly, which makes it difficult to control its physical indicators such as particle size and morphology.
The publication number is: CN101450815A discloses a method for preparing nickel-manganese-cobalt acid lithium by using waste lithium-ion batteries as raw materials. 1C discharge has a capacity of about 150mAh / g, and the capacity remains at about 130 after 30 cycles, but the preparation process is more complicated. Suitable for industrial production

Method used

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  • Preparation method for nickel-manganese-cobalt anode material of lithium ion battery
  • Preparation method for nickel-manganese-cobalt anode material of lithium ion battery
  • Preparation method for nickel-manganese-cobalt anode material of lithium ion battery

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Embodiment 1

[0032](1) Dissolve equimolar amounts of manganese sulfate (MnSO4·H2O), cobalt sulfate (CoSO4·7H2O), and nickel sulfate (NiSO4·6H2O) in deionized water to form a mixed solution of 1 mol·L. Water Mixed solution of 2 mol L-1 NaOH and 0.48 mol L-1 ammonia water, the volume ratio of the mixed solution and ammonia water is 1:4;

[0033] (2) With a constant current pump, the above-mentioned nickel-manganese-cobalt ion mixed solution and ammonia solution mixed solution are added respectively in the reaction vessel of the nitrogen atmosphere of high-speed stirring, and NaOH solution is added dropwise to adjust the pH to be 12, aged for 10h, and controlled aging The pH of the chemicalization process is 12. The precipitate obtained in the above steps is fully washed, filtered, and dried in vacuum at 100~110°C for 12 hours to obtain the Ni1 / 3Co1 / 3Mn1 / 3(OH)2 precursor;

[0034] (3) Weigh 30 g of nickel-manganese-cobalt hydroxide, 12.11 g of lithium carbonate, add 0.2105 g of alumina ball m...

Embodiment 2

[0038] According to the molar ratio Ni:Co:Mn=1:1:1, prepare a mixed aqueous solution of nickel sulfate, manganese sulfate, and cobalt sulfate with a total concentration of 1.3mol / L, prepare a NaOH solution with a concentration of 4mol / L, and prepare a concentration of 0.66mol / L of ammonia solution. The volume ratio of the mixed solution and ammonia water is 1:3.5.

[0039] Add the above-mentioned nickel-manganese-cobalt ion mixed solution and ammonia solution into the reactor to stir and react with a constant-current pump, add NaOH solution dropwise to adjust the pH to 14, age for 18 hours, and control the pH of the aging process to be 14. The precipitate was fully washed, filtered, and dried in vacuum at 100-110°C for 12 hours to obtain the Ni1 / 3Co1 / 3Mn1 / 3(OH)2 precursor.

[0040] Weigh 20 g of nickel-manganese-cobalt hydroxide, 8.235 g of lithium carbonate, add 0.2258 g of chromium oxide ball mill and mix, place in an air atmosphere muffle furnace, and then heat up to Ins...

Embodiment 3

[0044] According to the molar ratio Ni:Co:Mn=1:1:1, prepare a mixed aqueous solution of nickel chloride, manganese chloride, and cobalt chloride with a total concentration of 1.1mol / L, prepare a NaOH solution with a concentration of 6mol / L, and prepare a concentration of It is a 0.24mol / L ammonia solution, and the volume ratio of the mixed solution to the ammonia solution is 1:3.

[0045] Add the above-mentioned nickel-manganese-cobalt ion mixed solution and ammonia solution into the reactor to stir and react with a constant flow pump, add NaOH solution dropwise to adjust the pH to 13, age for 18 hours, and control the pH of the aging process to be 13, the above steps are obtained The precipitate was fully washed, filtered, and dried in vacuum at 100-110°C for 12 hours to obtain Ni 1 / 3 co 1 / 3 mn 1 / 3 (OH) 2 Precursor.

[0046] Weigh 60g of nickel-manganese-cobalt hydroxide, 25.43g of lithium carbonate, add 0.68334g of zinc oxide ball mill and mix, place in an oxygen atmosph...

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Abstract

The present invention relates to a preparation method for a nickel-manganese-cobalt anode material of a lithium ion battery. According to the present invention, in the presence of nitrogen atmosphere, a mixed solution containing nickel iron, manganese iron and cobalt ion reacts with a precipitating agent, then processes of aging, washing, drying and the like are performed to obtain a nickel-manganese-cobalt hydroxide precursor, the synthesized precursor material has spherical morphology, ideal particle size distribution and high tap density; the precursor, a lithium compound and a doped compound are mixed, then the sintering processing is performed for twice to prepare the nickel-manganese-cobalt three-element composite anode material. The method has characteristics of simple synthesis process, easy process controlling, low energy consumption, high efficiency and low cost, and is applicable for the industrial production; the prepared precursor material has characteristics of spherical morphology, uniform particle distribution and high tap density; the discharge capacity of the battery is improved through doping the metals; the cycle performance of the battery is stable.

Description

technical field [0001] The invention relates to the field of lithium-ion battery positive electrode materials, in particular to a preparation method of nickel-manganese-cobalt lithium-ion positive electrode material. technical background [0002] At present, there are many research systems used as cathode materials for lithium-ion batteries, but only lithium cobaltate (LiCoO 2 ). LiMn 2 o 4 Compared with LiCoO 2 The raw material is relatively cheap, and the thermal stability of the material is slightly higher, but the capacity of LiMn2O4 is lower. LiFePO 4 Synthetic raw materials are rich in resources, low in cost, environmentally friendly, high in capacity, and good in cycle performance, but their volumetric energy density is low. LiNiO 2 Because of the difficulty of synthesis and the ratio of LiCoO 2 The worse overcharge safety problem limits its application. New ternary composite oxide LiNi 1 / 3 co 1 / 3 mn 1 / 3 o 2 with LiCoO 2 have the same structure, it has L...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/505H01M4/525
CPCY02E60/122Y02E60/10
Inventor 陈海涛曹贺坤张羽
Owner HEFEI GUOXUAN HIGH TECH POWER ENERGY
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