Lithium zirconium phosphate fast ionic conductor coated lithium nickel cobalt aluminate positive electrode material and preparation method thereof

A technology of nickel cobalt lithium aluminate and lithium zirconium phosphate, applied in battery electrodes, electrical components, electrochemical generators, etc., can solve the problem of difficulty in film formation or uniform mixing, limited improvement in ternary cycle performance, and impact on ternary cycle. performance and other issues, to achieve good high-rate discharge performance, good cycle stability, and the effect of reducing side reactions

Active Publication Date: 2019-01-11
CENT SOUTH UNIV
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Problems solved by technology

[0003] Patent CN105406069 A discloses a method for coating ternary materials with lithium manganese iron phosphate. In this method, ascorbic acid is mixed with lithium manganese phosphate, mixed with ternary materials, and then vacuum-dried. The method involves the participation of acidic substances in the coating process. The ternary material is an oxide and is easily corroded by acidic substances. Therefore, the method has shortcomings and the improvement of the ternary material is limited.
[0004] CN107230771 A discloses a kind of method of vanadium phosphate coating ternary material, this method mixes vanadium salt and phosphate reducing agent in deionized water, after stirring, filter, wash, dry and ternary material according to 1~10: The ingredient ratio is 100, mixed in a high-speed mixer, and then heat-preserved and sintered at 200-400 degrees under a non-oxygen atmosphere to obtain a coated ternary coated modified material. Mixing, uneven coating, weak interaction between solid particles, it is difficult to achieve film formation or uniform mixing, and the residual lithium on the solid-phase mixed ternary surface still exists in the solid phase on the ternary surface, which still affects the cycle performance of the ternary. This coating method has limited improvement in the cycle performance of the ternary, and there is a problem of uneven coating
[0005] Patent CN105047864 A discloses a method of using lithium zirconate to coat ternary materials. This method utilizes the nickel-cobalt-manganese precursor prepared by oxalate and tetrabutyl zirconate to react hydrothermally at 180 degrees to form a zirconia coating layer. Then sinter at high temperature to obtain the coating material of lithium zirconate. This method uses a liquid phase zirconium source, and tetrabutyl zirconate is used as the coating material, because the liquid phase should have better dispersion relative to the solid phase. solution, so better coating can be achieved, but the electrochemical performance after coating still needs to be further improved

Method used

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  • Lithium zirconium phosphate fast ionic conductor coated lithium nickel cobalt aluminate positive electrode material and preparation method thereof
  • Lithium zirconium phosphate fast ionic conductor coated lithium nickel cobalt aluminate positive electrode material and preparation method thereof
  • Lithium zirconium phosphate fast ionic conductor coated lithium nickel cobalt aluminate positive electrode material and preparation method thereof

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Experimental program
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Embodiment 1

[0038] (1) Weigh 0.90513g (0.002108287mol) zirconium nitrate pentahydrate (relative molecular mass 429.32), add water to dissolve, transfer to a 50ml volumetric flask, add deionized water to volume, weigh 0.32867g (0.003162431mol) dihydrogen phosphate Lithium (relative molecular mass: 103.93), dissolved in water, transferred to a 50ml volumetric flask, added water to volume. The ratio of zirconium and phosphorus is 2:3, (under the condition of this ratio, 1ml of zirconium nitrate and 1ml of lithium dihydrogen phosphate are mixed to obtain the required ratio of 1wt% lithium zirconium phosphate coated on the ternary material, that is, two Mix 1ml of each solution, which is the required amount for 1wt% coating. 0.5ml of each of the two solutions is the required amount for 0.5wt% coating, and the rest of the coating amount can be deduced in the same way. The volume of the solution can be used as the proportioning amount, and the operation is simplified, the same below, and will no...

Embodiment 2

[0042] (1) Weigh 0.9051g (0.002108mol) zirconium nitrate pentahydrate, add water to dissolve and transfer to a 50ml volumetric flask, add deionized water to volume, weigh 0.3287g (0.00316mol) lithium dihydrogen phosphate, add water to dissolve and transfer To a 50ml volumetric flask, add water to volume. The molar ratio of phosphorus to zirconium is 2:3.

[0043] (2) Use a pipette to take 0.5ml of the zirconium nitrate solution described in (1) above, add 75ml of alcohol, stir well, then add 0.5ml of the lithium dihydrogen phosphate solution described in (1) above, and stir slowly.

[0044] (3) Take 0.5g lithium nickel cobalt aluminate and add it to the above solution (2), heat and stir at 90°C for 1.5h until evaporated to dryness, then directly transfer to a tube furnace, under an oxygen atmosphere, heat at 5°C / min heating rate, heated to 650 degrees and kept for 1 hour, to obtain nickel cobalt lithium aluminate cathode material coated with lithium zirconium phosphate fast ...

Embodiment 3

[0046] (1) Weigh 0.9051g (0.002108mol) zirconium nitrate pentahydrate, add water to dissolve and transfer to a 50ml volumetric flask, add deionized water to volume, weigh 0.3287g (0.00316mol) lithium dihydrogen phosphate, add water to dissolve and transfer To a 50ml volumetric flask, add water to volume. The molar ratio of phosphorus to zirconium is 2:3.

[0047] (2) Use a pipette to take 0.5ml of the zirconium nitrate solution described in (1) above, add it to 75ml of alcohol, stir evenly, then add 0.5ml of the lithium dihydrogen phosphate solution described in (1) above, and stir slowly.

[0048] (3) Add 0.5g lithium nickel-cobalt aluminate to the solution of (2) above, heat, stir and evaporate to dryness at 90°C for 1.5h, and when the mixed slurry becomes viscous, about 3-5ml, stop stirring, Slowly evaporate the solution to dryness, and then transfer it to an oven for drying. After drying, transfer it to a tube furnace, heat it to 650 degrees for 1 hour at a heating rate o...

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Abstract

The invention relates to a lithium zirconium phosphate fast ionic conductor coat lithium nickel cobalt aluminate positive electrode material and a preparation method thereof, wherein that mass of thelithium zirconium phosphate fast ionic conductor is 0. 1-10wt%, and the lithium zirconium phosphate fast ionic conductor form a coating layer with a thickness of 5-30nm and is coated on the lithium nickel cobalt aluminate. The positive electrode material is spherical particles with a particle diameter of 5 to 15 mum. The preparation method comprises the following steps: (1) preparing a solution containing phosphorus source and zirconium source, adding zirconium source solution into an organic solvent or water, adding phosphorus source solution, stirring, adding lithium nickel cobalt aluminate,heating and stirring, slowly evaporating and drying, and placing the obtained powder in an oven for drying; (2) placing the powder obtained in the step (1) in a tubular furnace for low-temperature rapid sintering. The positive electrode material of the invention has good cycle stability and rate discharge performance; as that method of the invention can effectively reduce the problem of low circulation stability of the surface residual lithium and ternary materials dure conventional coating, the process cost is low, the process is simple, and the method is suitable for large-scale industrialproduction.

Description

technical field [0001] The invention relates to a positive electrode material and a preparation method thereof, in particular to a lithium zirconium phosphate fast ion conductor coated nickel-cobalt lithium aluminate positive electrode material and a preparation method thereof. Background technique [0002] Lithium-ion batteries are considered to be one of the most promising energy storage cycle systems that can realize power batteries. They have the advantages of high energy density, high working voltage, good safety performance, stable cost, and low toxicity. The development of lithium-ion batteries is of great significance for solving energy shortages and reducing environmental pollution. Among them, the cathode material is the key factor that determines the electrochemical performance, safety performance and price cost of lithium-ion batteries. However, the ternary cathode materials that currently dominate the market still cannot meet the needs of the development of elec...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/525H01M4/58H01M10/0525
CPCH01M4/366H01M4/525H01M4/5825H01M10/0525Y02E60/10
Inventor 张佳峰张建永张宝欧星彭春丽
Owner CENT SOUTH UNIV
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