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High-voltage lithium cobaltate based composite cathode material of lithium ion battery and preparation method of high-voltage lithium cobaltate based composite cathode material

A composite positive electrode material and lithium-ion battery technology, applied in battery electrodes, secondary batteries, circuits, etc., can solve the problems of unstudied electrochemical properties of positive electrode materials, inability to ensure uniform distribution of trace elements, and inability to synchronize surface coating production processes, etc. problems, to achieve excellent electrochemical performance, improve cycle performance, and good morphology

Active Publication Date: 2015-03-25
CENT SOUTH UNIV
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Problems solved by technology

The operating voltage range of existing lithium-ion batteries is basically between 3.0-4.3V, and lithium-ion batteries with lithium cobaltate as the positive electrode material can increase the capacity by about 20% when charged to 4.5V, but at this time lithium cobaltate is due to Deep deintercalation of Li+, accompanied by a phase transition process with poor reversibility, the material structure is extremely unstable, and the cycle performance of the battery also drops sharply
[0003] Chinese patent document CN102583585A and US patent document US6555269B2 all mention the use of doping with elements such as Mg and Ti to improve the high temperature performance and overcharge resistance of lithium cobaltate performance; but did not study the electrochemical performance of the prepared cathode material under high voltage
Coating was proposed in the non-patent literature ("Effect of AlF3 coating amount on high voltage cycling performance of LiCoO2". Electrochimica Acta 53 (2007) 1013-1019). Aluminum fluoride improves the cycle performance of lithium cobaltate at high voltage; however, the electrochemical performance at higher voltage (above 4.5 V) has not been studied, and the surface coating and positive electrode material production processes cannot be synchronized, and the preparation process is long
The Chinese patent document CN102751481A also proposes to form a composite material by introducing Li2MnO3 and LiCoO2 with a stable structure to suppress cobalt in the process of charging and discharging. Lithium acid phase transition; but the matrix LiCoO2 material is not modified, resulting in poor cycle performance under high voltage; in addition, the preparation method used in this patent document is a solid-phase mixed raw material, And after three stages of high-temperature sintering, it is impossible to ensure the uniform distribution of trace elements in the composite material, and the synthesis steps are complicated and energy-consuming

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  • High-voltage lithium cobaltate based composite cathode material of lithium ion battery and preparation method of high-voltage lithium cobaltate based composite cathode material
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  • High-voltage lithium cobaltate based composite cathode material of lithium ion battery and preparation method of high-voltage lithium cobaltate based composite cathode material

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Embodiment 1

[0031] A high-voltage lithium cobalt oxide-based composite cathode material for lithium ion batteries of the present invention, the molecular formula is 0.05Li 2 MnO 3 ·0.95LiCo 0.98 Mg 0.02 O 2 .

[0032]The preparation method of the above-mentioned composite positive electrode material, the specific steps are: taking lithium acetate, cobalt acetate, manganese acetate and magnesium acetate as raw materials, and weighing the raw materials according to the molar ratio of Li, Co, Mn and Mg as 1.10:0.931:0.05:0.019 and mixing them , adding deionized water and stirring to prepare a solution with a total metal concentration of 0.5mol / L; spray drying the solution, the air inlet temperature is 110°C, the outlet air temperature is 110°C, and the feed rate is 300mL / L during spray drying. h, after drying, a composite cathode material precursor is obtained; the precursor is pre-fired at 400 °C for 5 hours in an air atmosphere, ground after cooling, and then calcined at 900 °C for 10 ...

Embodiment 2

[0038] A high-voltage lithium cobalt oxide-based composite positive electrode material for lithium ion batteries of the present invention, the molecular formula is 0.01Li 2 MnO 3 ·0.99LiCo 0.995 Al 0.005 O 2 .

[0039] The preparation method of the above-mentioned composite positive electrode material includes the following steps: taking lithium nitrate, cobalt nitrate, manganese nitrate, and aluminum nitrate as raw materials, and weighing and mixing the raw materials according to the molar ratio of Li, Co, Mn, and Al of 1.01:0.98505:0.01:0.00495 , deionized water was added and stirred to prepare a solution with a total metal concentration of 0.1 mol / L; the solution was spray-dried, the air inlet temperature was 150 °C, the air outlet temperature was 110 °C, and the feed rate was 600 mL / h. After drying, the composite cathode material precursor is obtained; the precursor is pre-fired at 300 ° C for 1 hour in an air atmosphere, ground after cooling, and then calcined at 500 ...

Embodiment 3

[0042] A high-voltage lithium cobalt oxide-based composite positive electrode material for lithium ion batteries of the present invention, the molecular formula is 0.01Li 2 MnO 3 ·0.99LiCo 0.9 Zn 0.1 O 2 .

[0043] The preparation method of the above-mentioned composite positive electrode material, the specific steps are: using lithium chloride, cobalt chloride, manganese chloride, zinc chloride as raw materials, according to Li, Co, Mn, Zn molar ratio is 1.11:0.891:0.01:0.099 weighed Take the raw materials and mix them, add deionized water and stir to prepare a solution with a total metal concentration of 1 mol / L; the solution is spray-dried, and the air inlet temperature is 180°C during spraying, the air outlet temperature is 100°C, and the feeding speed is 100mL / h, dried to obtain a composite cathode material precursor; the precursor was pre-fired at 500 ° C for 8 hours in an air atmosphere, ground after cooling, and then calcined at 1000 ° C for 2 hours, after the mate...

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Abstract

The invention discloses a high-voltage lithium cobaltate based composite cathode material of a lithium ion battery. Metal element M is doped into lithium cobaltate; meanwhile, Li2MnO3 is introduced into lithium cobaltate to form the composite cathode material; the phase change of lithium cobaltate in a charging / discharging cyclic process under high voltage is inhibited, and the cyclic performance under high voltage (more than 4.5V) is improved; the molecular formula of the composite cathode material is xLi2MnO3.(1-x)LiCo(1-y)MyO2, wherein x is more than or equal to 0.01 and less than or equal to 0.20 and y is more than or equal to 0.005 and less than or equal to 0.10; and the doped metal element M is one or more of Mg, Ca, Ni, Mn, Cr, Fe, Al, Y, Ti, Zr, Cu, Zn, Ce, V, Nb and Mo. The lithium cobaltate based composite cathode material is prepared by a liquid phase mixing-spray drying-high temperature sintering combined method, and dual modification operations (material compounding and doping) are finished in one step, so that the preparation process of the material is simplified.

Description

technical field [0001] The invention belongs to the field of positive electrode materials for lithium ion batteries, in particular to a high-voltage lithium cobaltate-based composite positive electrode material for lithium ion batteries and a preparation method thereof. Background technique [0002] Lithium-ion batteries have been widely used in mobile phones, notebook computers, digital cameras and other portable electronic devices and electric vehicles due to their advantages such as high energy density, high working voltage, long cycle life, no memory effect and environmental friendliness. In the composition of lithium-ion batteries, the cathode material is an important factor that determines its electrochemical performance, safety performance and future development direction. Lithium cobalt oxide has dominated the cathode material market since it entered the market in the 1990s. In recent years, with the further miniaturization and multi-functionalization of electronic ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/131H01M4/1391H01M4/525
CPCH01M4/366H01M4/485H01M4/505H01M4/525H01M10/0525Y02E60/10
Inventor 王志兴王志国李新海郭华军彭文杰胡启阳
Owner CENT SOUTH UNIV
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