Multi-element in-situ co-doped ternary material precursor as well as preparation method and application thereof

A ternary material, co-doping technology, applied in chemical instruments and methods, electrical components, inorganic chemistry, etc., can solve the problems of easy change of crystal structure, difficult doping ion distribution, unstable crystal structure, etc. The effect of easy large-scale industrial production, excellent cycle performance, and excellent rate performance

Active Publication Date: 2019-02-15
圣戈莱(北京)科技有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] However, ternary materials also have some problems that need to be overcome: (1) The crystal structure of the material is unstable, and the crystal structure is easy to change during charging and discharging; (2) The surface structure of the material is unstable, and the compatibility between the material and the electrolyte is poor , due to LiPF 6 The electrolyte contains HF to corrode the electrode material, resulting in the dissolution of transition metal ions; (3) Ni 2+ Radius and Li + have similar radii, so Ni 2+ Very soluble in Li + Occupy each other, resulting in the occurrence of cation mixing phenomenon, Ni 2+ in Li + layer not only reduces the discharge specific capacity, but also hinders t

Method used

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  • Multi-element in-situ co-doped ternary material precursor as well as preparation method and application thereof
  • Multi-element in-situ co-doped ternary material precursor as well as preparation method and application thereof
  • Multi-element in-situ co-doped ternary material precursor as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] This embodiment prepares Zr 4+ with Al 3+ Co-doped modified ternary precursor (Ni 0.6 co 0.2 mn 0.2 ) 0.993 Zr 0.003 Al 0.004 (OH) 2.01 and ternary cathode material Li(Ni 0.6 co 0.2 mn 0.2 ) 0.993 Zr 0.003 Al 0.004 o 2 , including the following steps:

[0037] (1) Preparation of metal salt solution: Weigh 8.937mol nickel sulfate hexahydrate, 2.979mol cobalt sulfate heptahydrate, 2.979mol manganese sulfate monohydrate, 0.03mol aluminum sulfate octadecahydrate, 0.045mol zirconium sulfate tetrahydrate, dissolve in appropriate amount In pure water, 10 liters of salt solution A was prepared, and the total metal ion concentration in the salt solution was 1.5 mol / L.

[0038] (2) Precipitating agent preparation: Weigh 40 mol of sodium hydroxide, dissolve in pure water, and prepare 10 liters of sodium hydroxide aqueous solution B with a concentration of 4 mol / L.

[0039] (3) Complexing agent preparation: use ammonia water as a complexing agent, take an appropriat...

Embodiment 2

[0049] In this embodiment, the ternary cathode material LiNi 0.5 co 0.2 mn 0.3 o 2 (NCM523) as the substrate to prepare Zr 4+ , Zn 2+ with Al 3 + Co-doped ternary cathode material Li(Ni 0.5 co 0.2 mn 0.3 ) 0.99 Zr 0.003 Zn 0.002 Al 0.005 o 2 , including the following steps:

[0050] (1) Metal salt solution preparation: Weigh 9.9mol nickel sulfate hexahydrate, 3.96mol cobalt sulfate heptahydrate, 5.94mol manganese sulfate monohydrate, 0.05mol aluminum sulfate octadecahydrate, 0.06mol zirconium sulfate tetrahydrate, 0.04mol seven Zinc sulfate in water is dissolved in an appropriate amount of pure water to prepare 10 liters of metal salt solution A, and the total metal ion concentration in the solution is 2.0mol / L.

[0051] (2) Precipitating agent preparation: Weigh 60 mol of sodium hydroxide, dissolve in pure water, and prepare 10 liters of sodium hydroxide aqueous solution B with a concentration of 6 mol / L.

[0052] (3) Complexing agent preparation: use ammonia ...

Embodiment 3

[0058] In this embodiment, the ternary cathode material LiNi 0.6 co 0.2 mn 0.2 o 2 (NCM622) as the substrate, prepare Mg 2+ 、Sc 3+ 、Al 3+ with Ti 4+ Co-doped ternary cathode material Li(Ni 0.6 co 0.2 mn 0.2 ) 0.99 Mg 0.003 sc 0.002 al 0.004 Ti 0.001 o 2 , including the following steps:

[0059] (1) Metal salt solution preparation: Weigh 5.94mol nickel sulfate hexahydrate, 1.98mol cobalt sulfate heptahydrate, 1.98mol manganese sulfate monohydrate, 0.03mol magnesium sulfate, 0.02mol aluminum sulfate octadecahydrate, 0.01mol octahydrate Scandium sulfate and 0.01mol titanium tetrachloride were dissolved in an appropriate amount of pure water to prepare 10 liters of metal salt solution A. The total metal ion concentration in the salt solution was 1 mol / L.

[0060] (2) Precipitating agent preparation: Weigh 30 mol of sodium hydroxide, dissolve in pure water, and prepare 10 liters of sodium hydroxide aqueous solution B with a concentration of 3 mol / L.

[0061] (3) Co...

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Abstract

The invention discloses a multi-element in-situ co-doped ternary material precursor as well as a preparation method and an application thereof. The chemical formula of the precursor is (NixCoyMnz)(1-a-c)MaNc(OH)(2+k), wherein x is larger than or equal to 1/3 and smaller than or equal to 0.9, y is larger than 0 and smaller than or equal to1/3, z is larger than 0 and smaller than or equal to 0.4, the sum of x, y and z is 1, a is larger than or equal to 0.0001 and smaller than or equal to 0.01, and c is larger than or equal to 0.0001 and smaller than or equal to 0.01; radius of a doped ion M is close to that of the lithium ion, and M is selected from one or more of Mg<2+>, Zn<2+>, Zr<4+>, Nb<5+>, Ta<4+>, In<3+>, Sc<3+>, Y<3+>, Ce<4+> and Gd<3+>; radius of a doped ion N is close to that of metal ions Mn and Co in the ternary material, and N is selected from one or more of Al<3+>, Ti<4+>, Ge<4+>, W<6+> and V<5+>. In the preparation process of the ternary material precursor, two kinds metalions with different radii are introduced in situ, so that the doped metal ions are uniformly distributed in a precursor phase, and uniform mixing on the atomic grade is realized. The two kinds of metal ions with different radii are doped in different positions, cell parameters have coordinated variation, so that not only can a lithium ion transmission channel be expanded, but also good lattice structure of the ternary material can be kept, and the ternary material with excellent electrochemical performance is obtained.

Description

technical field [0001] The invention belongs to the technical field of lithium-ion battery electrode materials, and in particular relates to a multi-element in-situ co-doped ternary material precursor, a preparation method thereof, and an application thereof in preparing a lithium-ion battery ternary positive electrode material. Background technique [0002] At present, the commonly used and developed cathode materials for lithium-ion batteries mainly include lithium cobalt oxide (LiCoO 2 ), lithium nickelate, lithium manganate (Li x mn 2 o 4 ), lithium iron phosphate (LiFePO 4 ), etc., a lot of basic research has been carried out at home and abroad and industrialization has been basically realized. Compared with the traditional positive electrode materials mentioned above, the layered lithium nickel cobalt manganese oxide positive electrode material (hereinafter referred to as "ternary material" or "NCM") better combines the advantages of lithium cobalt oxide, lithium n...

Claims

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Application Information

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IPC IPC(8): C01G53/00H01M4/485H01M4/505H01M4/525H01M10/0525
CPCH01M4/485H01M4/505H01M4/525H01M10/0525C01G53/006C01P2006/40C01P2002/72C01P2004/03Y02E60/10
Inventor 闫东伟赵宜男吴志坚谷丰宏
Owner 圣戈莱(北京)科技有限公司
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