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Anion-cation compound-doped spinel lithium manganese and preparation method thereof

A spinel lithium manganate, compound doping technology, applied in electrical components, electrochemical generators, battery electrodes, etc., can solve the problems of unsatisfactory performance of positive electrode materials, complicated processes, difficult recycling, etc., and achieve excellent charging and discharging. The effect of cycle performance and high temperature performance, rational and scientific process design, and high initial discharge specific capacity

Active Publication Date: 2016-12-14
HUNAN SHANSHAN NEW ENERGY CO LTD
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  • Abstract
  • Description
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Problems solved by technology

Spinel lithium manganese oxide has the advantages of low cost, easy synthesis, high working voltage, high safety performance, no pollution to the environment, and high capacity. It is considered to be the most likely substitute for lithium cobalt oxide and has the greatest application potential. However, the capacity fading and poor electrochemical performance of lithium manganate have always been the bottlenecks that limit its application. The Jahn-Teller distortion effect and the dissolution of manganese have not been well resolved.
[0004] According to the comprehensive literature, the synthesis methods of spinel lithium manganese oxide mainly include the following types: (1) High temperature synthesis method: mix lithium hydroxide and manganese oxide, and calcinate at high temperature for several hours to obtain Lithium manganate; (2) Melt impregnation method: using LiNO with a lower melting point 3 As a lithium source, pre-treatment is carried out at about the melting point of lithium salt, and then the lithium source is impregnated into the porous surface of manganese dioxide to increase the contact of reactants and improve the reaction efficiency. The synthesized lithium manganate has excellent electrochemical properties; (3 ) Sol-gel method: This method is to form a chelate with metal ions and organic acids, then esterify and further polymerize into a polymer to prepare a precursor, and finally roast the precursor to obtain lithium manganate, but the initial discharge capacity of the product Low, at the same time a large amount of organic solvents, difficult to recycle, high cost, the preparation process needs to be improved; (4) co-precipitation method: by adjusting the pH value of the solution to co-precipitate lithium ions and manganese ions, so that lithium and manganese are mixed at the atomic level , to prepare lithium manganate, but the process is complicated, and it needs to go through steps such as filtration, washing and drying, and the performance of the positive electrode material is not ideal

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  • Anion-cation compound-doped spinel lithium manganese and preparation method thereof
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Embodiment 1

[0035] A kind of anion and cation complex doping spinel lithium manganese oxide of the present invention, its molecular formula is expressed as LiMn 1.98 (Al) 0.02 o 3.96 (Cl) 0.04 , and the doped cations and anions all enter the spinel lattice of spinel lithium manganese oxide, forming a stable spinel single-phase compound.

[0036] The preparation method of the anion-cation composite doped spinel lithium manganate of the present embodiment comprises:

[0037] Take electrodeposited manganese dioxide, lithium carbonate, aluminum oxide, lithium chloride, the molar ratio of these raw materials is MnO 2 : Li 2 CO 3 :Al 2 o 3 :LiCl=1.98:0.5:0.01:0.04, wherein the purity of each substance is above 98%. Grind thoroughly in an agate mortar and mix well to obtain a mixture doped with lithium manganese oxide; then add ethanol solution (mass concentration: 70%) and mix with the mixture evenly to make a slurry, then place it in a muffle furnace for pre-calcination , within 50 mi...

Embodiment 2

[0044] A kind of anion and cation complex doping spinel lithium manganese oxide of the present invention, its molecular formula is expressed as LiMn 1.94 (Ni) 0.06 o 3.96 (I) 0.04 , and the doped cations and anions all enter the spinel lattice of spinel lithium manganese oxide, forming a stable spinel single-phase compound.

[0045] The preparation method of the anion-cation composite doped spinel lithium manganate of the present embodiment comprises:

[0046] Take chemical manganese dioxide, lithium acetate, nickel oxide, lithium iodide, the molar ratio of these raw materials is MnO 2 :CH 3 COOLi:NiO:LiI=1.94:1.0:0.06:0.04, the purity of each substance is above 98%. Grind thoroughly in an agate mortar and mix well to obtain a mixture doped with lithium manganese oxide; then add ethanol solution (mass concentration: 70%) and mix with the mixture evenly to make a slurry, then place it in a muffle furnace for pre-calcination , within 50 minutes, the temperature rose to the...

Embodiment 3

[0050] A kind of anion and cation complex doping spinel lithium manganese oxide of the present invention, its molecular formula is expressed as LiMn 1.94 (Cr) 0.06 o 3.98 (F) 0.02 , and the doped cations and anions all enter the spinel lattice of spinel lithium manganese oxide, forming a stable spinel single-phase compound.

[0051] The preparation method of the anion-cation composite doped spinel lithium manganate of the present embodiment comprises:

[0052] Take electrodeposited manganese dioxide, manganese trioxide, lithium hydroxide, chromium oxide, and lithium fluoride, and the molar ratio of these raw materials is (MnO 2 +Mn 2 o 3 ):LiOH:Cr 2 o 3 : LiF=1.94 (manganese element in manganese source): 1.0:0.03:0.02, and the purity of each substance is above 98%. Grind thoroughly in an agate mortar and mix well to obtain a mixture doped with lithium manganese oxide; then add ethanol solution (mass concentration: 70%) and mix with the mixture evenly to make a slurry, ...

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Abstract

The invention provides anion-cation compound-doped spinel lithium manganese. A molecular formula of the anion-cation compound-doped spinel lithium manganese is represented as LiMn<2-x>(M)<x>O<4-y>(N)<y>, wherein M and N represent doped cations and anions respectively; and the cations and the anions enter spinel lattices of spinel lithium manganese to form a stable spinel single-phase compound. The preparation method comprises the following steps of firstly, fully grinding and evenly mixing a manganese source, a lithium source, a cation material and an anion material to obtain a lithium manganese oxide-doped mixture; adding an organic solvent to adjust into paste, fully mixing the paste, pre-sintering for several hours, carrying out cooling and grinding, gradually warming a pre-sintered product by stages again for multi-step sintering and slowly cooling the obtained pre-sintered product; and finally crushing and screening the pre-sintered product to obtain the anion-cation compound-doped spinel lithium manganese. The product provided by the invention has relatively high initial discharge specific capacity and also has excellent charge-discharge cycle performance and high temperature performance.

Description

technical field [0001] The invention relates to a lithium ion battery cathode material and a preparation method thereof, in particular to a cathode material lithium manganate and a preparation method thereof. Background technique [0002] With the continuous development of the economy, people are paying more and more attention to energy issues. The soaring oil price has made people have a deeper understanding of new energy, especially in the 2008 national "863 Plan" modern transportation technology field "energy saving and new energy vehicles" major The project regards lithium manganese oxide cathode material as the preferred material for power batteries, and lithium-ion battery materials are facing a development opportunity. Represented by electric vehicle power batteries, the field of lithium-ion batteries is taking shape. At present, the commercialized lithium-ion cathode material is mainly lithium cobalt oxide, which has relatively mature technology and the best electro...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/505H01M4/62H01M10/0525
CPCH01M4/364H01M4/505H01M4/628H01M10/0525Y02E60/10
Inventor 蔡振勇李艳石慧袁荣忠李旭谭欣欣蒋湘康
Owner HUNAN SHANSHAN NEW ENERGY CO LTD
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