Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material

A lithium-rich positive electrode material and anion technology, applied in battery electrodes, electrical components, electrochemical generators, etc., to achieve the effects of delaying decline, high capacity, and improving electrochemical performance

Inactive Publication Date: 2014-07-30
NANKAI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

CN201210216042.X adopts the method of doping chloride ions, but the material described in it can only

Method used

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  • Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material
  • Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material
  • Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Li[Li 017 Ni 0.25 mn 058 ]O 1.85 Cl 0.15 Preparation of:

[0026] Weigh 6.248 g of CH 3 COOLi·2H 2 O, 3.111 g Ni(CH 3 COO) 2 2H 2 O, 6.229 g Mn(CH 3 COO) 2 2H 2 O and 0.7422 g MnCl 2 4H 20, be mixed with 200 milliliters of aqueous solutions, then add citric acid of 200 milliliters of 1.0 moles per liter, add ammoniacal liquor and adjust the pH of the mixed solution to 9, stir evenly; Above-mentioned solution is injected into spray drier (Beijing Laiheng Science and Trade Co., Ltd. company, L-217) to obtain a uniformly mixed precursor; grind the resulting precursor into a powder, transfer it to a crucible, and bake it at 480°C for 7.5 hours. After cooling, the material is ground and the ground The material was sintered in a muffle furnace at 900°C for 10 hours, and finally the halogen anion-doped Li[Li 017 Ni 0.25 mn 0.58 ]O 1.85 Cl 0.15 Material. figure 1 is the X-ray diffraction (XRD) pattern of the prepared material, and no diffraction peaks of oth...

Embodiment 2

[0029] Li[Li 022 Ni 0.05 al 0.02 co 0.1 mn 0.61 ]O 1.94 Br 0.06 Preparation of:

[0030] CH in Example 1 3 COOLi·2H 2 The quality of O is changed to 6.5456 grams, Ni(CH 3 COO) 2 2H 2 O mass changed to 0.5807 grams, Mn(CH 3 COO) 2 2H 2 O mass is changed to 7.4889 grams. Add Co(CH 3 COO) 2 2H 2 O mass is 1.2454g, NH 4 The quality of Br is 0.2938g, Al(NO 3 ) 3 9H 2 O mass is 0.3751g. Other is with embodiment 1, can make Li [Li 022 Ni 0.05 al 0.02 co 0.1 mn 061 ]O 1.94 Br 0.06 Material. Figure 4 Showing its electrochemical performance, at a current density of 30 mA / g, Br-doped Li[Li 0.22 Ni 0.05 al 0.02 co 0.1 mn 0.61 ]O 1.94 Br 0.06 The discharge specific capacity of the material after 30 weeks is 223.0 mAh / g, and the cycle performance is excellent.

Embodiment 3

[0032] Li[Li 0.2 co 0.4 mn 0.4 ]O 1.98 I 0.02 Preparation of materials:

[0033] Remove Ni(CH in embodiment 1 3 COO) 2 2H 2 O, MnCl 2 4H 2 O. Mn(CH 3 COO) 2 2H 2 The quality of O is changed to 4.902 grams, adding Co(CH 3 COO) 2 2H 2 The mass of O is 4.9816g, and the mass of LiI is 0.1879g. CH 3 COOLi·2H 2 O quality is changed into 6.3246g, and other is with embodiment 1, can make Li [Li 0.2 co 0.4 mn 04 ]O 1.98 I 0.02 Material. Figure 5 Shown is the first-cycle charge-discharge curve of the material prepared in this example at a current density of 30 milliamperes per gram. It can be seen from the figure that after doping with I, the material also has a higher discharge specific capacity.

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Abstract

The invention relates to a halogen anion doped lithium-rich positive electrode material of a secondary battery as well as a preparation method and an application of positive electrode material. The expression formula of the halogen anion doped lithium-rich positive electrode material is Li[Li(1-2x)/3MxMn(2-x)/3]O2-zAz, wherein M is at least one or a combination of Co, Ni, Al, Mg, Zn, Ga, B, Zr, Ti, Ca, Ce, Y and Nb, A is at least one or a combination of Cl, Br or I, x is greater than 0 and less than 0.5, and z is greater than 0 and less than or equal to 0.5; when M is one or the combination of Ni and Co and A is Cl, x is not equal to 0.2. The preparation method comprises the following preparation steps: in the process of preparing a lamellar lithium-rich oxide positive electrode material Li[Li(1-2x)/3MxMn(2-x)/3]O2, introducing halogen anions A according to the stoichiometric ratio to prepare a solution, and then carrying out solidification, drying and calcination, thereby obtaining the halogen anion doped lithium-rich positive electrode material. If the halogen anion doped lithium-rich positive electrode material is used as the positive electrode material for a lithium battery, the first charge-discharge efficiency of the material can be improved; the structural transformation of the material in electrochemical cycle is inhibited. The electrochemical properties of the lithium-rich lamellar oxide positive electrode material are improved, and the lithium-rich lamellar oxide positive electrode material has the characteristics of high first charge-discharge efficiency, high capacity, good cycle performance, simple preparation process, good reproducibility and the like.

Description

technical field [0001] The invention relates to a halogen anion-doped lithium-rich cathode material for a secondary battery, a preparation method and application thereof. Background technique [0002] Due to the development of science and technology, people's requirements for energy storage are getting higher and higher. Lithium-ion batteries have become a research hotspot because of their advantages such as high energy density, relatively green environmental protection and long service life. As a key part of lithium-ion batteries, cathode materials play an important role. Layered lithium-rich oxide cathode materials Li[Li (1-2x) / 3 m x mn (2-x) / 3 ]O 2 Because of its high specific capacity exceeding 200mAh / g, it has become the most likely cathode material for the next generation of lithium-ion batteries. However, there are still some deficiencies in the current layered lithium-rich oxide cathode materials, mainly including: the first irreversible capacity loss caused by...

Claims

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Application Information

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IPC IPC(8): H01M4/131H01M4/1315H01M4/1391H01M4/13915
CPCH01M4/485H01M4/505H01M4/525H01M10/0525Y02E60/10
Inventor 高学平张洪周李国然叶世海
Owner NANKAI UNIV
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