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Composite lithium ion battery cathode material and preparation method and application thereof

A technology for lithium-ion batteries and positive electrode materials, applied in battery electrodes, positive electrodes, secondary batteries, etc., can solve the problems of reducing mass specific capacity, material cycle stability, etc., to reduce oxygen precipitation, improve stability and safety properties, good crystal plane orientation

Active Publication Date: 2019-12-31
INST OF PROCESS ENG CHINESE ACAD OF SCI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

HNO by Kang S H et al. 3 to 0.5Li 2 MnO 3 0.5LiNi 0.44 co 0.25 mn 0.31 o 2 After pretreatment, the first coulombic efficiency of the material increased from 81% to 100%, but the cycle stability of the material decreased after treatment
Manthiram uses VO 2 (B) The main body completely eliminates the first irreversible capacity loss, but adds other lithium intercalation materials, reducing the mass specific capacity

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0081] (1) According to the molecular formula Li 1.2 mn 0.55 Ni 0.15 co 0.1 o 2 Molar ratio Weigh manganese sulfate, nickel sulfate and cobalt sulfate, add deionized water to dissolve and make a mixed metal solution with a total metal ion molarity of 2mol, add 2mol of NaOH precipitant to the mixed metal solution, and react at a speed of 500rpm Stir continuously, adjust the pH of the reaction solution to 10.5 with complexing agent ammonia water, and the reaction temperature is 50°C, then dry the obtained product at 110°C for 12h to obtain Mn 0.688 Ni 0.188 co 0.124 (OH) 2 Precursor;

[0082] (2) According to the molecular formula Li 1.2 mn 0.55 Ni 0.15 co 0.1 o 2 Weigh 5% Li in excess of theoretical moles 2 CO 3 , will Li 2 CO 3 with the Mn 0.688 Ni 0.188 co 0.124 (OH) 2 After the precursors are mixed, heat up to 500°C and sinter for 6 hours at a heating rate of 5°C / min in an air atmosphere, and then heat up to 800°C for 20 hours to obtain a layered lithium-...

Embodiment 2

[0087] (1) According to the molecular formula Li 1.2 mn 0.55 Ni 0.15 co 0.1 o 2 Molar ratio Weigh manganese chloride, nickel chloride and cobalt chloride, add deionized water to dissolve and make a mixed metal solution with a total metal ion molarity of 2mol, add 6mol of Na to the mixed metal solution 2 CO 3 The precipitation agent was reacted and stirred continuously at a speed of 800 rpm, the pH of the reaction solution was adjusted to 8 with complexing agent ammonium bicarbonate, and the reaction temperature was 50°C, and then the obtained product was dried at 110°C for 12 hours to obtain Mn 0.688 Ni 0.188 co 0.124 (OH) 2 Precursor;

[0088] (2) according to step (1) molecular formula, take compared with theoretical molar excess 8% Li 2 CO 3 , will Li 2 CO 3 with the Mn 0.688 Ni 0.188 co 0.124 (OH) 2 After the precursors are mixed, in an oxygen-containing atmosphere at a heating rate of 6°C / min, the temperature is raised to 550°C for sintering for 5 hours, a...

Embodiment 3

[0093] (1) According to the molecular formula Li 1.2 mn 0.64 Ni 0.08 co 0.08 o 2 Weigh manganese chloride, nickel chloride and cobalt chloride in molar ratio, add deionized water to dissolve and make a mixed metal solution with a total metal ion molar weight of 2mol, add 4mol of NaOH precipitant to the mixed metal solution to react and continuously stirred at a rotation speed of 1000 rpm, adjusted the pH of the reaction solution to 11 with complexing agent ammonia water, and the reaction temperature was 45° C., and then dried the obtained product at 100° C. for 12 hours to obtain Mn 0.8 Ni 0.1 co 0.1 (OH) 2 Precursor;

[0094] (2) take by weighing the LiOH of excessive 8% mol ratio by step (1) molecular formula, combine LiOH and described Mn 0.8 Ni 0.1 co 0.1 (OH) 2 After the precursors are mixed, heat up to 600°C for 5 hours at a heating rate of 9°C / min in an air atmosphere, and then heat up to 950°C for 10 hours to obtain a layered lithium-rich material intermedia...

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Abstract

The invention discloses a composite lithium ion battery cathode material and a preparation method and an application thereof. The composite lithium ion battery positive electrode material comprises alithium-rich manganese-based positive electrode material with a layered structure and a 5V high-voltage positive electrode material with a spinel structure, a chemical formula of the 5V high-voltage positive electrode material with the spinel structure is LiMaNbMn<2-a-b>O<4-c>S<c>, wherein a is greater than 0.01 and less than 0.5, b is greater than 0.1 and less than 1, c is greater than 0.001 andless than 0.5, M comprises any one or a combination of at least two of Ni, Cr, V, Fe, Cu and Co, N is doped cations, and S is doped anions. The obtained coating material has good crystal orientation,irreversible capacity loss of a lithium-rich phase can be effectively improved, moreover, oxygen atoms in the positive electrode material of the lithium battery are doped with polyanion groups, so loss of charging and discharging oxygen octahedrons under a high-voltage platform is reduced, a problem of voltage attenuation is relieved, and stability and the rate capability of the material are improved.

Description

technical field [0001] The invention belongs to the field of lithium-ion battery materials, and in particular relates to a composite lithium-ion battery cathode material, its preparation method and application. Background technique [0002] Lithium-ion batteries have the advantages of high working voltage, high specific energy, long cycle life, and no memory effect. Since the commercialization of lithium-ion batteries, they have been widely used in electronic products, such as mobile phones, digital cameras, and notebook computers. The positive electrode materials of lithium-ion batteries mainly include the following categories: LiCO 2 , LiNiO 2 , ternary materials, LiMn 2 o 4 and LiFePO 4 Wait. Lithium-rich manganese-based cathode material xLi 2 MnO 3 ·(1-x)LiAO 2 (A=Co, Ni, Cr, Fe) has high specific capacity, high working voltage, low price and environmental friendliness, so it has been widely studied. However, lithium-rich manganese-based cathode materials also h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/505H01M4/525H01M4/62H01M10/0525
CPCH01M4/362H01M4/505H01M4/525H01M4/628H01M10/0525H01M2004/028Y02E60/10
Inventor 谭强强纪雪倩冯海兰
Owner INST OF PROCESS ENG CHINESE ACAD OF SCI
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