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High voltage Li-ion battery cathode materials with core-shell structure and preparation method thereof

A technology of lithium ion battery and core-shell structure is applied in the field of materials, which can solve the problems of increasing lattice parameters and reducing the cycle performance of materials, and achieves the effects of simple and feasible preparation method, excellent rate performance and cycle performance.

Active Publication Date: 2014-05-14
哈尔滨博尔特能源科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

mn 3+ The presence of content has contradictory effects on the material, on the one hand, due to the fact that Mn 3+ The radius of the ion is relatively large, which increases the lattice parameter, which is beneficial to Li + The transport of ions in the material, so it has a better rate performance, on the other hand, due to the Mn 3+ Disproportionation reaction is easy to occur, and the generated divalent manganese will dissolve in the electrolyte, migrate to the negative electrode, and deposit on the surface of the negative electrode, so Mn 3+ The presence of the material will reduce the cycle performance of the material

Method used

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Experimental program
Comparison scheme
Effect test

specific Embodiment approach 1

[0022] Embodiment 1: In this embodiment, electrode materials are prepared according to the following steps:

[0023] Weigh 0.03mol of manganese sulfate, 0.009mol of nickel sulfate and 0.001mol of cobalt sulfate and dissolve it in 1L of deionized water, add 1L of a solution containing 0.09mol of sodium hydroxide to it to obtain a suspension, and then dropwise add 0.5 L containing 0.003mol manganese sulfate and 0.001mol nickel sulfate solution and 0.5L containing 0.008mol sodium hydroxide solution. Filter, wash and dry to obtain a precipitate, mix the precipitate with 0.023mol lithium hydroxide to obtain a precursor, put the above precursor in a muffle furnace, pre-calcinate at 500 °C for 4 h, calcined at 850 °C for 12 h, and then at 650 °C After annealing for 24 h, a core-shell structure positive electrode material for high-voltage lithium-ion batteries was obtained.

specific Embodiment approach 2

[0024] Specific embodiment 2: In this embodiment, electrode materials are prepared according to the following steps:

[0025] Weigh 0.03 mol of manganese sulfate, 0.005 mol of nickel sulfate, 0.0045 mol of nickel nitrate and 0.0005 mol of aluminum chloride, dissolve them in 1 L of deionized water, add 1 L of a solution containing 0.1 mol of sodium hydroxide to it to obtain a suspension, and then add it to the solution. 0.5L solution containing 0.003mol manganese sulfate and 0.001mol nickel sulfate and 0.5L solution containing 0.004mol sodium carbonate were added dropwise to the suspension. Filter, wash, and dry to obtain a precipitate. Mix the precipitate with 0.023 mol of lithium nitrate to obtain a precursor. The above precursor is placed in a muffle furnace, pre-calcined at 400 °C for 4 h, calcined at 800 °C for 20 h, and then calcined at 700 °C. After annealing for 20 h, a core-shell structure positive electrode material for high-voltage lithium-ion batteries was obtained....

specific Embodiment approach 3

[0026] Embodiment 3: In this embodiment, electrode materials are prepared according to the following steps:

[0027] Weigh 0.02mol of manganese nitrate and 0.01mol of manganese chloride, 0.009mol of nickel sulfate and 0.001mol of chromium nitrate, dissolve them in 1L of deionized water, add 1L of a solution containing 0.05mol of sodium carbonate to it to obtain a suspension, and then add to the suspension. 0.5L of a solution containing 0.003mol of manganese sulfate and 0.001mol of nickel sulfate and 0.5L of a solution of 0.004mol of sodium bicarbonate were added dropwise to the turbid liquid. Filter, wash and dry to obtain a precipitate, mix the precipitate with 0.023mol lithium hydroxide to obtain a precursor, put the above precursor in a muffle furnace, pre-calcinate at 500 °C for 4 h, calcined at 850 °C for 12 h, and then at 650 °C After annealing for 24 h, a high-voltage core-shell structure lithium-ion battery cathode material was obtained.

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Abstract

The invention provides high voltage Li-ion battery cathode materials with a core-shell structure and a preparation method thereof, the high voltage Li-ion battery cathode materials are of the core-shell structure, core materials are made of LiNi0.5-xMxMn1.5O4, wherein x ranges from 0.002 and 0.12, M=Co, Al, Cr, Cu or Fe, shell materials are made of LiNi0.5Mn1.5O4, the core materials comprise, by mass percent, 2-20 of the shell materials. The preparation method is that the precursor of the core-shell structure is prepared through a co-precipitation method, and the high voltage Li-ion battery cathode materials of the core-shell structure are prepared by burning at high temperature and conducting annealing treatment. The core-shell materials of the high voltage Li-ion battery cathode materials are doped with high valence state elements, chemical valences of parts of Manganese are reduced to tetravalence from trivalence, the rate performance of the materials is improved by the existence of trivalent manganese, and the doped elements participate in the reaction in the ranges of charging and discharging of the high voltage, so that the material capacity is not be reduced. The shell materials do not contain Mn 3+, so that the Mn solution problem caused by the trivalent manganese is avoided, and the cyclic performance of materials is improved.

Description

technical field [0001] The invention belongs to the technical field of materials, and relates to a lithium ion battery positive electrode material and a preparation method thereof, in particular to a core-shell structure high-voltage lithium ion battery positive electrode material and a preparation method thereof. Background technique [0002] In response to the worldwide energy crisis, governments around the world are actively promoting the development of new energy vehicles, mainly electric vehicles. Power battery is an important part of electric vehicle, which directly affects the performance of electric vehicle. Lithium-ion batteries have the remarkable advantages of high working voltage, no memory effect, low self-discharge rate, high energy density and long cycle life. As a power battery, they have a wide range of application prospects. [0003] Among the cathode materials for lithium ion batteries, the spinel cathode material LiNi 0.5 Mn 1.5 O 4 It has a high disc...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/505H01M4/525H01M4/1397
CPCH01M4/366H01M4/505H01M4/525H01M10/0525Y02E60/10
Inventor 王振波薛原玉富达张音刘宝生
Owner 哈尔滨博尔特能源科技有限公司