Modified lithium ion battery ternary positive electrode material precursor and preparation method thereof

A technology for lithium ion batteries and positive electrode materials, which is applied in battery electrodes, electrical components, secondary batteries, etc., can solve the problems of uneven distribution of material components, affect the performance of positive electrode materials, and poor consistency of precursors, and achieve cost Low, guaranteed high consistency, simple operation effect

Pending Publication Date: 2021-10-29
ZHUJI PAWA NEW ENERGY
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  • Description
  • Claims
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Problems solved by technology

[0003] The Chinese invention patent application of CN112174223A discloses a kind of preparation method of high-nickel ternary cathode material NCA precursor, by preparing raw material nickel-cobalt salt solution, aluminum salt solution, precipitant solution, complexing agent solution, will obtain nickel-cobalt salt solution , aluminum salt solution, complexing agent solution and precipitating agent solution are respectively added to the reaction kettle for co-precipitation reaction to obtain a nickel-cobalt-aluminum ternary precursor. The invention obtains an aluminum salt solution by dissolving aluminum sulfate in sodium hydroxide as The aluminum source of the nickel-cobalt-aluminum ternary precursor, the precursor produced by the one-step co-precipitation method has poor consistency, the bulk phase distribution of the material components is uneven, and the gap between the bulk phase structure of the material is significantly different, which affects the subsequent lithium-mixed sintering process of the positive electrode Material properties

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  • Modified lithium ion battery ternary positive electrode material precursor and preparation method thereof

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Embodiment 1

[0038] A modified ternary material precursor, including a substrate and a molybdenum trioxide coating on the surface of the substrate, whose chemical formula is Ni 0.88 co 0.09 mn 0.03 Mo 0.002 Nb 0.002 (OH) 2 • nMoO 3 , the primary particles on the surface of the ternary material precursor are in the form of flakes, the shape of the secondary particles is spherical, the particle size of the secondary particles is 3-6 μm, and the Mo and Nb ions are evenly distributed in the matrix bulk phase structure. The molybdenum oxide coating is 3% of the mass of the base material.

[0039] A method for preparing the aforementioned modified ternary material precursor, which is specifically prepared through the following steps:

[0040](1) Prepare 3mol / L nickel sulfate solution, 3mol / L cobalt sulfate solution and 3mol / L manganese sulfate solution according to the molecular formula of the ternary precursor and the preparation amount of the ternary precursor; The cobalt solution and t...

Embodiment 2

[0045] A modified ternary material precursor preparation method, comprising the steps of:

[0046] (1) Prepare 5mol / L nickel sulfate solution, 5mol / L cobalt sulfate solution and 5mol / L manganese sulfate solution according to the molecular formula of the ternary precursor and the preparation amount of the ternary precursor. solution and manganese sulfate solution (Ni:Co:Mn=88:9:3) were uniformly mixed in the first reaction kettle, and NaOH solution (7 mol / L) and NH 3 •H 2 O solution (7 mol / L) was sent to the first reactor in parallel flow through the metering pump for nucleation and co-precipitation reaction, the stirring speed was controlled at 480 rpm, the reaction temperature was 55 °C, and the pH value was adjusted at 12.5-12.8 , the ammonia value was 13-18 g / L, and the co-precipitation reaction time was controlled to be 2.5 h until uniform fine nano-crystal nuclei were formed, and the D50 of the nuclei was 80 nm;

[0047] (2) Pass the unreacted slurry in the first reacto...

Embodiment 3

[0051] A modified ternary material precursor preparation method, comprising the steps of:

[0052] (1) According to the molecular formula of the ternary precursor and the preparation amount of the ternary precursor, prepare 5.5 mol / L nickel sulfate solution, cobalt sulfate solution and manganese sulfate solution, and the nickel sulfate solution, cobalt sulfate solution and manganese sulfate solution according to ( Ni:Co:Mn=88:9:3) were uniformly mixed, and at the same time NaOH solution (7 mol / L) and NH 3 •H 2 O solution (7 mol / L) was sent to the first reactor in parallel flow through the metering pump for nucleation and co-precipitation reaction, the stirring speed was controlled at 450 rpm, the pH value was adjusted at 12.5-12.8, and the reaction temperature was 50 °C , the ammonia value is 13-18 g / L, and the co-precipitation reaction time is controlled to be 2 hours until uniform fine nano-crystal nuclei are formed, and the D50 of the crystal nuclei is 80 nm;

[0053] (2)...

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Abstract

The invention discloses a modified lithium ion battery ternary positive electrode material precursor, which comprises a matrix and a molybdenum trioxide coating layer on the surface of the matrix, wherein the chemical formula of the ternary positive electrode material precursor is NixCoyMnzMopNbq(OH)2.n MoO3. According to the invention, Nb and Mo ions uniformly doped in a precursor body phase can effectively stabilize the crystal structure of the material, inhibit the mixed arrangement phenomenon of Ni < 2 + > ions and Li < + > in a lithium layer in the charging and discharging process of the ternary material and improve the cycling stability of the ternary positive electrode material, and a formed MoO3 uniform coating layer can reduce the diffusion barrier of Li < + > and accelerate the diffusion of Li < + > from a surface interface to the interior of the bulk phase, so that the rate capability of the positive electrode material is improved. The invention also provides a preparation method of the precursor. The preparation method is short in process, low in cost and suitable for large-scale production.

Description

technical field [0001] The invention relates to the field of battery materials, in particular to a modified lithium-ion battery ternary precursor and a preparation method thereof. Background technique [0002] The nickel-cobalt-manganese ternary precursor is the most important raw material for the preparation of lithium-ion battery cathode materials. The main preparation method of the ternary precursor is to add nickel-cobalt-manganese metal salt solution, liquid caustic soda, and ammonia water into the reactor at the same time for co-precipitation reaction. Due to the limitations of equipment and process conditions, microcracks are usually generated during the nucleation process of co-precipitation reaction. In order to give full play to the excellent performance of the ternary cathode material, the preparation of its precursor is crucial to the production of the ternary cathode material, because the quality of the precursor (morphology, particle size, particle size distrib...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/505H01M4/525H01M4/485H01M4/62H01M10/0525C01G53/00C01G39/02
CPCH01M4/505H01M4/525H01M4/485H01M4/62H01M10/0525C01G53/006C01G39/02C01P2004/32C01P2004/61C01P2004/80Y02E60/10
Inventor 张宝邓鹏程诚林可博丁瑶周亚楠
Owner ZHUJI PAWA NEW ENERGY
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