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A kind of doping modification method of spinel type lithium manganese oxide cathode material

A type of lithium manganate and positive electrode material technology, applied in the nanometer field, can solve the problems of difficult to accurately control the stoichiometry of doped ions, complex sol-gel process, and limited application, and achieve excellent electrochemical performance and good dispersion , low-cost effect

Active Publication Date: 2016-08-24
ANHUI UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The co-precipitation method is difficult to accurately control the stoichiometry of dopant ions, while the sol-gel method is complicated and inefficient
These shortcomings of the liquid phase method limit its application in industrial production

Method used

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  • A kind of doping modification method of spinel type lithium manganese oxide cathode material
  • A kind of doping modification method of spinel type lithium manganese oxide cathode material
  • A kind of doping modification method of spinel type lithium manganese oxide cathode material

Examples

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Effect test

Embodiment 1

[0030] (1) According to the chemical formula LiMn doped lithium manganate 1.95 co 0.05 o 4 , weigh lithium hydroxide (LiOH·H 2 O) 4.1941g, cobalt nitrate (Co(NO 3 ) 2 ·6H 2 O) 1.4552g, citric acid (C 6 h 8 o 7 ·H 2 (2) 11.0324g, lithium hydroxide, cobalt nitrate and citric acid are dissolved in 50mL deionized water respectively, are mixed with solution, the citric acid solution is magnetically stirred, add lithium hydroxide solution first, then add cobalt nitrate solution, use dilute nitric acid (HNO 3 ) and dilute ammonia (NH 3 ·H 2 O) adjust the pH value to 6, add ethylene glycol (C 2 h 6 o 2 ) 1.6294g, stirred at a constant temperature of 65°C for 1h to form a sol;

[0031] (2) Manganese tetraoxide (Mn 3 o 4 ) powder (primary particle size ≤ 200nm, specific surface area ≥ 10m 2 / g) 14.8727g was added to the above-mentioned sol, mixed evenly, placed in a ball mill tank, and ball milled on a planetary ball mill for 3h, the ball-to-material ratio was 5:1, and...

Embodiment 2

[0036] (1) According to the chemical formula LiMn doped lithium manganate 1.91 co 0.055 Al 0.035 o 4 , weigh lithium hydroxide (LiOH·H 2 O) 4.1941g, cobalt nitrate (Co(NO 3 ) 2 ·6H 2 O) 1.6007g, aluminum nitrate (Al(NO 3 ) 3 9H 2 O) 1.3130g, citric acid (C 6 h 8 o 7 ·H 2 (2) 13.7431g, lithium hydroxide, cobalt nitrate, aluminum nitrate and citric acid are dissolved in 50mL deionized water respectively, are mixed with solution, citric acid solution is magnetically stirred, add lithium hydroxide solution first, then add cobalt nitrate, nitric acid Aluminum solution, dilute nitric acid (HNO 3 ) and dilute ammonia (NH 3 ·H 2 O) adjust the pH value to 5, add ethylene glycol (C 2 h 6 o 2 ) 2.4356g, stirred at 70°C for 1.5h to form a sol;

[0037] (2) Manganese tetraoxide (Mn 3 o 4 ) powder (primary particle size ≤ 200nm, specific surface area ≥ 10m 2 / g) 14.5676g was added to the above-mentioned sol, mixed evenly, placed in a ball mill tank, and ball milled on ...

Embodiment 3

[0042] (1) According to the chemical formula LiMn doped lithium manganate 1.95 Ni 0.05 o 4 , weigh lithium nitrate (LiNO 3 )6.895g, nickel acetate (Ni(CH 3 COO) 2 4H 2 O) 1.2442g, citric acid (C 6 h 8 o 7 ·H 2 (2) 15.4519g, lithium nitrate, nickel acetate and citric acid were dissolved in 60mL of deionized water respectively, prepared into a solution, the citric acid solution was magnetically stirred, lithium nitrate solution was added, then nickel acetate solution was added, and dilute ammonia (NH 3 ·H 2 O) adjust the pH value to 6, add ethylene glycol (C 2 h 6 o 2 ) 1.3035g, stirred at a constant temperature of 70°C for 2h to form a sol;

[0043] (2) Manganese tetraoxide (Mn 3 o 4 ) powder (primary particle size ≤ 200nm, specific surface area ≥ 10m 2 / g) 14.8727g was added to the above-mentioned sol, mixed evenly, placed in a ball mill tank, and ball milled on a planetary ball mill for 2 hours, the ball-to-material ratio was 9:1, and the rotating speed was 25...

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Abstract

The invention discloses a doping modification method of spinel lithium manganate anode material, and belongs to the field of nanotechnology. The method mainly comprises the following steps: respectively adding a saline solution of lithium-ion and doping ion into a citric acid solution, regulating pH values, adding ethylene glycol into the solution, heating and stirring the solution so as to form sol, mixing manganous-manganic oxide with the sol, performing ball milling, and performing microwave dehydration and subsequent heat treatment on products subjected to ball milling so as to obtain the doped spinel lithium manganate anode material. The method has the advantages that the prepared spinel lithium manganate anode material has high specific capacity, good rate capability and excellent cycling performance, meanwhile the technology is simple, the cost is low, the efficiency is high, and the method can be directly applied to industrial production.

Description

technical field [0001] The invention belongs to the field of nanotechnology, and relates to a preparation method of a positive electrode material of a lithium ion battery, in particular to a sol-solid phase hybrid synthesis method of spinel lithium manganate doped with mono- or binary metal ions. technical background [0002] Spinel-type lithium manganese oxide has a large specific capacity (theoretical capacity 148mAh g -1 ) higher redox potential (4V vs. Li / Li + ), low cost, environmental friendliness and good safety. As a cathode material for lithium-ion batteries, spinel lithium manganese oxide is expected to replace expensive lithium cobalt oxide. However, due to the dissolution of Mn ions, Jahn-Teller distortion, and decrease in crystallinity, the capacity fading of spinel lithium manganate cathode materials is very serious during cycling, especially at higher temperatures (≥55 °C). Studies have shown that the modification of lithium manganate can be achieved by dop...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/505H01M4/525
CPCH01M4/505H01M4/525Y02E60/10
Inventor 方道来郑翠红檀杰闫勇
Owner ANHUI UNIVERSITY OF TECHNOLOGY
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