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Large-particle single-crystal lithium cobalt oxide for lithium ion battery, and cation doping preparation method thereof

A lithium-ion battery, large particle technology, used in secondary batteries, single crystal growth, battery electrodes, etc., can solve problems such as discharge capacity attenuation, achieve large particle size, reduce side reactions, and be easy to control.

Active Publication Date: 2020-09-15
UNIV OF JINAN
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Although layered LiCoO 2 The theoretical specific capacity of the positive electrode material is as high as 274mAh / g, but when Li 1-x CoO 2 Middle Li + The irreversible transition from the hexagonal phase to the monoclinic phase will occur when the extraction amount x>0.5, resulting in a sharp decline in the discharge capacity, which limits the LiCoO 2 Improvement of practical specific capacity

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  • Large-particle single-crystal lithium cobalt oxide for lithium ion battery, and cation doping preparation method thereof
  • Large-particle single-crystal lithium cobalt oxide for lithium ion battery, and cation doping preparation method thereof
  • Large-particle single-crystal lithium cobalt oxide for lithium ion battery, and cation doping preparation method thereof

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preparation example Construction

[0023] As introduced in the summary of the invention, some methods studied by the inventor in the previous period are only suitable for the preparation of single crystal materials with a particle size of ≤10 μm. 2 The preparation of doped or undoped LiCoO can be significantly reduced with the increase of particle size 2 The side reaction between the electrode / electrolyte of the material under high voltage, in order to solve the above technical problems, in the first typical embodiment of the present invention, a layered LiCoO for lithium ion battery is provided 2 A method for preparing a large-grain single crystal or its cation doping, the general structural formula of the prepared layered positive electrode material is Li[Co 1-x m x ]O 2 , wherein M is one or more of Zn, Al, Mg, Ti, Zr, Nb, W, 0≤x≤0.1, and the preparation method comprises the following steps:

[0024] First, the precursor Co(OH) 2 or cation-doped precursors [Co1-x m x ](OH) 2 Mixed with a stoichiometric...

Embodiment 1

[0046] Embodiment 1: preparation precursor [Co 0.96 Mg 0.02 Al 0.02 ](OH) 2

[0047] Weigh 27.0Kg CoSO 4 ·7H 2 O, 0.296Kg Mg(NO 3 ) 2 and 0.751Kg Al(NO 3 ) 3 9H 2 The prepared concentration of O is 50L of 2M salt solution, wherein the Co-Al-Mg molar ratio is 0.96 / 0.02 / 0.02, and the above-mentioned salt solution is added dropwise to the continuous stirring reactor, and at the same time, the mixed solution of 10M NaOH and 1.5M ammonia water is used to control the reactor. The internal pH value is about 11.0, and the rotation speed is controlled at about 600rpm. When the above salt solution is completely consumed, the precipitate is centrifuged, washed, and dried to obtain the target precursor of magnesium-aluminum co-doping [Co 0.96 Mg 0.02 Al 0.02 ](OH) 2 .

Embodiment 2

[0048] Embodiment 2: Preparation of precursor Co(OH) 2

[0049] Weigh 28.1Kg CoSO 4 ·7H 2 O Prepare 50L of 2M salt solution, add the above salt solution dropwise to the continuous stirring reaction kettle, and control the pH value in the kettle at about 11.0 with a mixed solution of 10M NaOH and 1.5M ammonia water, and control the rotation speed at about 600rpm, until the above The salt solution is completely consumed, and the precipitate is centrifuged, washed, and dried to obtain the precursor Co(OH) 2 .

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Abstract

The invention relates to large-particle single-crystal lithium cobalt oxide for a lithium ion battery, and a cation doping preparation method thereof. The preparation method comprises the following steps: mixing a precursor Co(OH)2 or a cation-doped precursor [Co1-xMx](OH)2 with a lithium source, sintering to form spinel phase Li2y[Co1-xMx]2O4 small-particle single crystals, mixing and sintering the small-particle single crystals and spinel-phase Co3O4 to promote fusion of the two spinel phase particles to prepare spinel phase Li2y-2m[Co1-x+nMx-n]2O4 large-particle single crystals, supplementing a lithium source, and continuously sintering to prepare the cation-doped large-particle single-crystal lithium cobalt oxide. Cationic doping or co-doping can effectively inhibit conversion from a hexagonal phase to a monoclinic phase under high voltage of lithium cobalt oxide, and formation of large-particle single crystals can reduce side reaction between an electrode and an electrolyte underhigh voltage of lithium cobalt oxide, so that the specific discharge capacity and the structural stability of lithium cobalt oxide are improved.

Description

technical field [0001] The invention belongs to the technical field of lithium-ion battery electrode materials, and in particular relates to a preparation method of large-grain single-crystal lithium cobaltate and cation doping thereof. Background technique [0002] The information disclosed in this background section is only intended to increase some understanding of the general background of the present invention, and is not necessarily to be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to those skilled in the art. [0003] Lithium-ion batteries have the advantages of high energy density, long life, and no memory effect. They have been widely used in "3C" portable electronic devices, and are gradually expanding to power tools, automobiles, and high-efficiency energy storage systems. The basic structure of lithium-ion batteries includes positive and negative electrodes, separators and electrolytes. It i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C30B29/22C30B1/10H01M4/525H01M10/0525
CPCC30B1/10C30B29/22H01M4/525H01M10/0525H01M2004/021H01M2004/028Y02E60/10
Inventor 侯配玉黄金昭徐锡金
Owner UNIV OF JINAN
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