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Lithium titanium gallium phosphate modified ternary positive electrode composite material and preparation method thereof

A technology of titanium gallium lithium phosphate and composite materials, which is applied in the field of titanium gallium lithium phosphate modified ternary cathode composite materials and its preparation, can solve the problems of low initial discharge gram capacity and limited improvement effect, and achieve excellent rate performance and cycle performance. performance effect

Inactive Publication Date: 2020-11-27
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] In the above technical solution, lithium titanium phosphate is used to coat the nickel-cobalt-manganese ternary positive electrode material. Although the cycle stability of the positive electrode material is improved to a certain extent, the first discharge gram capacity is low, and the improvement effect is limited.

Method used

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  • Lithium titanium gallium phosphate modified ternary positive electrode composite material and preparation method thereof
  • Lithium titanium gallium phosphate modified ternary positive electrode composite material and preparation method thereof
  • Lithium titanium gallium phosphate modified ternary positive electrode composite material and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0042] (1) In terms of molar ratio, first mix 0.9moL of 1moL / L NiSO 4 ·6H 2 O, 0.05moL of CoSO 4 ·7H 2 O, 0.05moL of MnSO 4 ·H 2 O (Ni:Co:Mn=90:5:5) was evenly mixed, and NaOH solution (6mol / L) and NH 3 .H 2 O solution (5.5mol / L) was added in the reaction tank respectively. Adjust the pH value to 10.0 and the ammonia concentration to 1mol / L. Co-precipitation reaction is carried out, and the precursor Ni can be obtained after filtering, washing and drying with pure water 0.9 co 0.05 mn 0.05 (OH) 2 .

[0043] (2) In terms of molar ratio, weigh 0.01 mol of gallium nitrate according to the ratio of Ga:(Ni+Mn+Co)=0.01:1, mix it evenly with absolute ethanol, and mix 1 mol of the precursor prepared in step (1) Bulk material Ni 0.9 co 0.05 mn 0.05 (OH) 2 Dissolved in absolute ethanol, uniformly mixed gallium nitrate and 1mol of precursor material Ni 0.9 co 0.05 mn 0.05 (OH) 2 , adjust the solid-liquid ratio to 1:10; magnetically heat and stir at 68°C for 4.3h to ob...

Embodiment 2

[0050] (1) In terms of molar ratio, first mix 0.9moL of 1.5moL / L NiSO 4 ·6H 2 O, 0.05moL of CoSO 4 ·7H 2 O, 0.05moL of MnSO 4 ·H 2 O (Ni:Co:Mn=90:5:5) was evenly mixed, and NaOH solution (6.3mol / L) and NH 3 .H 2 O solution (5.8mol / L) is also added in the reaction tank respectively. Adjust the pH value to 10.0 and the ammonia concentration to 1mol / L. Co-precipitation reaction is carried out, and the precursor Ni can be obtained after filtering, washing and drying with pure water 0.9 co 0.05 mn 0.05 (OH) 2 .

[0051] (2) In terms of molar ratio, weigh 0.0075 mol of gallium sulfate according to the ratio of Ga:(Ni+Mn+Co)=0.015:1, mix it evenly with methanol, and mix 1 mol of the precursor material prepared in step (1) Ni 0.9 co 0.05 mn 0.05 (OH) 2 Dissolve in methanol, uniformly mix gallium sulfate and 1mol of precursor material Ni 0.9 co 0.05 mn 0.05 (OH) 2 , adjust the solid-liquid ratio to 1:11; magnetically heat and stir at 70°C for 4.5h to obtain a black ...

Embodiment 3

[0058] (1) In terms of molar ratio, first mix 0.9moL of 1.8moL / L NiSO 4 ·6H 2 O, 0.05moL of CoSO 4 ·7H 2 O, 0.05moL of MnSO 4 ·H 2 O (Ni:Co:Mn=90:5:5) is evenly mixed, and at the same time NaOH solution (6.5mol / L) and NH as a complexing agent 3 .H 2 O solution (6.0mol / L) was also added to the reaction tank respectively. Adjust the pH value at 10.1, and the concentration of ammonia water is 1.5mol / L. Co-precipitation reaction is carried out, and the precursor Ni can be obtained after filtering, washing and drying with pure water 0.9 co 0.05 mn 0.05 (OH) 2 . (2) In terms of molar ratio, weigh 0.01 mol of gallium sulfate according to the ratio of Ga:(Ni+Mn+Co)=0.02:1, mix it evenly with propanol, and mix 1 mol of the precursor prepared in step (1) MaterialNi 0.9 co 0.05 mn 0.05 (OH) 2 Dissolve in propanol, uniformly mix gallium sulfate and 1mol of precursor material Ni 0.9 co 0.05 mn 0.05 (OH) 2 , adjust the solid-liquid ratio to 1:12; magnetically heat and st...

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Abstract

The invention discloses a lithium titanium gallium phosphate modified ternary positive electrode composite material and a preparation method thereof. The chemical formula of the positive electrode composite material is LiNixCoyMnzGa0.01qO2.nLipGaqTiw(PO4)3, wherein x, y, z, p, q, w and n are mole numbers, x is greater than or equal to 0.6 and less than 1, y is greater than 0 and less than or equalto 0.2, z is greater than 0 and less than or equal to 0.2, x+y+z=1, (p+q+w) is greater than or equal to 3.2 and less than or equal to 3.6, p is greater than or equal to 1.2 and less than or equal to1.5, q is greater than or equal to 0.2 and less than or equal to 0.6, w is greater than or equal to 1.4 and less than or equal to 1.8, and n is greater than 0 and less than or equal to 0.05. The material is single crystal particles with the particle size of 2-3.5[mu]m, a uniform coating layer formed by lithium titanium gallium phosphate is arranged on the surface layer, and the thickness is 2.5-4nm. The method comprises the steps of coating the surface of a precursor or a positive electrode material with a gallium source, and then mixing and sintering with a lithium source to obtain a Ga<3+>-doped positive electrode material; and then sintering with a lithium source, a phosphorus source and a titanium source at high temperature to obtain the Ga<3+>-doped LipGaqTiw(PO4)3 surface-coated ternary positive electrode material. According to the invention, the rate capability and the cycle performance of the lithium ion battery are improved, and the performance is excellent at a high rate; andthe method is green, pollution-free, economical, applicable and suitable for large-scale production.

Description

technical field [0001] The invention relates to the field of battery materials, in particular to a ternary cathode composite material modified with lithium titanium gallium phosphate and a preparation method thereof. Background technique [0002] Ternary materials mainly rely on the price change of nickel element in the charge and discharge process, so increasing the nickel content in ternary materials can increase the reversible specific capacity of the material, so the development trend of ternary materials is from low nickel (111) to high nickel materials (622 / 811). In addition, the Co 3+ / Co 4+ transformation, and Mn 4+ The valence state of the material does not change, so an appropriate increase in the charge cut-off voltage can also increase the specific capacity of the material. Although high-nickel ternary materials have greater advantages in terms of energy density than other cathode materials, they also inherit LiNiO 2 Some shortcomings of high-nickel ternary ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/62H01M4/50H01M4/52H01M4/48C01B25/45C01G53/00
CPCC01B25/45C01G53/50C01P2002/72C01P2004/03C01P2004/04C01P2004/64C01P2004/80C01P2006/40H01M4/48H01M4/50H01M4/52H01M4/62Y02E60/10
Inventor 欧星范鑫铭刘赟张佳峰张宝
Owner CENT SOUTH UNIV
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