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Lithium-rich manganese-based positive electrode material and preparation method thereof, and lithium ion battery

A lithium-ion battery, lithium-rich manganese-based technology, applied in battery electrodes, secondary batteries, circuits, etc., can solve the problems of insignificant change in particle size, easy generation of impurity phases, and the occurrence of impurity phases, so as to reduce irreversible release and crystallization. Good sex, reduce the effect of activation

Active Publication Date: 2015-10-07
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Generally speaking, increasing the sintering temperature and sintering time can increase the primary particle size of lithium-rich materials, but this method consumes a lot of energy, has low efficiency, is prone to generate impurities, and is difficult to synthesize materials with uniform particle sizes above 400nm.
For example, in the literature (Chem.Mater.2013, 25, 3267), Arumugam Manthiram systematically investigated the effects of sintering time and sintering temperature on the synthesis of lithium-rich materials by using the sol-gel method. When the sintering temperature reaches 1000 ° C for 24 hours, Although the particle size reaches 500nm, the XRD spectrum shows that impurity phases appear, the 4.5V activation platform disappears, the first discharge capacity is lower than 100mAh / g, and when sintered at 900°C, the sintering time increases from 6h to 72h, and the particle size does not change significantly. , when the sintering time is 72h, the primary particle size is less than 300nm

Method used

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  • Lithium-rich manganese-based positive electrode material and preparation method thereof, and lithium ion battery
  • Lithium-rich manganese-based positive electrode material and preparation method thereof, and lithium ion battery
  • Lithium-rich manganese-based positive electrode material and preparation method thereof, and lithium ion battery

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preparation example Construction

[0066] The present invention also provides a method for preparing lithium-rich manganese-based cathode material, which includes the following steps:

[0067] a) Mixing the lithium source, the manganese source and the doping metal source and heating to obtain a manganese-based material;

[0068] The manganese-based material has the general formula shown in formula (III):

[0069] LiMn a M b O 4 Formula (III);

[0070] In formula (III), M is one or more of nickel, cobalt, iron, magnesium, titanium, aluminum and vanadium;

[0071] 1

[0072] b) Mixing the above-mentioned manganese-based material with a lithium source and sintering to obtain a lithium-rich manganese-based cathode material; the lithium-rich manganese-based cathode material has the general formula shown in formula (I):

[0073] Li 1+x Mn y M z O 2 Formula (I);

[0074] In formula (I), M is one or more of nickel, cobalt, iron, magnesium, titanium, aluminum and vanadium;

[0075] 0

Embodiment 1

[0144] (1) First, dissolve lithium acetate, nickel acetate, cobalt acetate and manganese acetate with a molar ratio of 1:1:1:6 in deionized water to obtain solution A; at the same time, combine citric acid with a molar ratio of 3:2 and Ethylenediaminetetraacetic acid (EDTA) is dissolved in 25%-28% ammonia water to obtain solution B; secondly, solution A is slowly added dropwise to solution B, and the pH is adjusted to 8 with ammonia water to make citric acid and solution A The molar ratio of metal ions is 1.5:1; then the above mixed solution is heated in an oil bath at 90°C for 18h to obtain a mixture gel; finally the mixture gel is dried and ground, and then sintered at 400°C to 550°C 3h~5h, then sintered at 900℃ for 20h to obtain manganese-based material LiNi 1 / 3 Co 1 / 3 Mn 4 / 3 O 4 .

[0145] (2) After mixing the manganese-based material with a molar ratio of 95:100 and lithium carbonate uniformly, sintering it at 900°C for 20 hours to obtain lithium-rich manganese-based cathode...

Embodiment 2

[0150] (1) First, dissolve lithium acetate, nickel acetate, cobalt acetate and manganese acetate with a molar ratio of 1:1:1:6 in deionized water to obtain solution A; at the same time, combine citric acid with a molar ratio of 1:4 and Ethylene glycol was mixed with deionized water to obtain solution B; secondly, solution A was slowly added dropwise to solution B so that the molar ratio of citric acid to metal ions in solution A was 1:1; then the above mixed solution was heated at 80°C Heated in an oil bath for 1 hour, and then heated in an oil bath at 140°C for 1 hour to obtain a mixture gel; finally, after drying and grinding the mixture gel, it is sintered at 400℃~550℃ for 3h~5h, and then at 800℃ Sintered for 48h to obtain manganese-based material LiNi 1 / 3 Co 1 / 3 Mn 4 / 3 O 4 .

[0151] (2) After mixing the manganese-based material with a molar ratio of 9:10 and lithium carbonate uniformly, sintering at 850°C for 20 hours to obtain lithium-rich manganese-based cathode material L...

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Abstract

The present invention provides a lithium-rich manganese-based positive electrode material and a preparation method thereof, wherein the general formula of the positive electrode material is Li(1+x)MnyMzO2, M is one or a plurality of materials selected from nickel, cobalt, iron, magnesium, titanium, aluminum and vanadium, x is more than 0 and is less than or equal to 0.5, y is more than 0.33 and less than 1, z is more than 0 and is less than 0.3, (x+y+z) is 1, and the primary particle diameter of the lithium-rich manganese-based positive electrode material is 400-3000 nm. According to the present invention, the lithium-rich manganese-based positive electrode material has characteristics of large primary particle diameter, low specific surface area and good crystallinity so as to improve the cycle performance and the first efficiency of the positive electrode material; and the cladding layer can be obtained through the surface modification and has the high ion conductivity so as to effectively improve the rate capability of the material. The present invention further provides a lithium ion battery.

Description

Technical field [0001] The invention relates to the technical field of lithium ion batteries, and more specifically, to a lithium-rich manganese-based cathode material, a preparation method thereof, and a lithium ion battery. Background technique [0002] At present, the cathode materials for commercial lithium-ion batteries are mainly lithium cobalt oxide, lithium manganate and nickel-cobalt-manganese ternary materials, and lithium iron phosphate. Among them, lithium cobalt oxide occupies the small-scale lithium-ion battery cathode material market, but due to its high price and low capacity , Poor safety and toxicity, and cannot be used as a positive electrode material for power lithium-ion batteries. The use of a mixture of lithium manganate and nickel-cobalt-manganese ternary materials can be used as a positive electrode material for power lithium-ion batteries, but due to its limited capacity, it restricts the range of electric vehicles. In addition, although lithium iron ph...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/505H01M4/525H01M10/0525
CPCH01M4/505H01M4/525H01M10/0525Y02E60/10
Inventor 潘凌超夏永高刘兆平
Owner NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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