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Two-layer coated modified ternary cathode high-nickel material and preparation method thereof

A double-layer coating, high-nickel technology, applied in electrical components, battery electrodes, circuits, etc., can solve the problems of high residual alkali content, a large amount of gas and heat, instability and other problems, and achieve the improvement of the first discharge specific capacity, The effect of improving electrochemical stability and less demanding production equipment

Active Publication Date: 2019-05-31
TIANJIN GUOAN MGL NEW MATERIALS TECH CO LTD
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Problems solved by technology

At the same time, when the Ni content exceeds 60%, the positive electrode is in the delithiated state. 4+ The content will also increase, and Ni4 + It is very unstable and highly oxidizing, which can easily cause side reactions between the electrode and the electrolyte, which will sharply reduce the cycle performance and thermal stability of the material, thereby affecting the practical use of materials with high nickel content.
[0003] At the same time, materials with high nickel content (>60%) are prone to excessive residual alkali content on the surface during sintering, because during the cooling stage, materials with high nickel content (>60%) will interact with moisture in the air And carbon dioxide, and then generate lithium hydroxide, lithium carbonate and other impurities, which will cause the residual alkali content of the sintered material to be too high
During the battery manufacturing process, the residual alkali on the surface will decompose to varying degrees during the charging and discharging process, thereby producing CO 2 Such gases make the material easy to produce gas in actual use, causing the thickness of the battery to change and affecting the actual use of the material
If under the environmental conditions such as overcharging, the residual alkali on the surface can easily cause rapid side reactions and generate a large amount of gas and heat, resulting in thermal runaway of the battery, eventually leading to combustion and explosion of the battery, etc.
In order to reduce the amount of residual alkali on the surface of materials with high nickel content (>60%), the amount of lithium added during the sintering process can be reduced, but this often loses the electrical properties of the obtained materials, that is, cycle stability and discharge are often not obtained. The material with the best specific capacity

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  • Two-layer coated modified ternary cathode high-nickel material and preparation method thereof
  • Two-layer coated modified ternary cathode high-nickel material and preparation method thereof
  • Two-layer coated modified ternary cathode high-nickel material and preparation method thereof

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preparation example Construction

[0032] The present invention also provides the preparation method of the above-mentioned double-layer coating modified ternary positive high-nickel material, comprising the following three steps:

[0033] Step 1, the precursor nickel-cobalt-manganese hydroxide is mixed with manganese salt to obtain a precursor coated with manganese salt;

[0034] Step 2, the product of step 1 is mixed with lithium salt, and sintered to obtain a ternary positive high-nickel material coated with manganese oxide;

[0035] In step 3, the product obtained in step 2 is mixed with metal oxide and sintered to obtain a double-layer coated ternary positive high-nickel material.

[0036] Above-mentioned preparation method comprises the following steps:

[0037] Step 1, the manganese salt is uniformly dissolved in the solvent I first, then the precursor nickel cobalt manganese hydroxide is added, stirred, heated, and the solvent I is removed to obtain a ternary cathode material precursor coated with the ...

Embodiment 1

[0077] First, ultrasonically dissolve 20g of manganese acetate in 400g of ethanol solvent, and then slowly add high-nickel ternary cathode material precursor Ni 0.65 co 0.20 mn 0.15 (OH) 2 1000g,

[0078] After stirring at 500rpm for 30min, heat at 70°C until the solvent is completely evaporated to obtain a precursor of manganese acetate;

[0079] Then the precursor of manganese acetate bag that obtains is pulverized, crosses 300 mesh sieves, weighs 800g again, weighs required lithium carbonate 332g by lithium proportioning 1.05 again. After ball milling and mixing evenly, sintering at a high temperature of 870°C for 15 hours in a muffle furnace with 45% oxygen, and after natural cooling, a ternary positive high-nickel material coated with manganese oxide is obtained;

[0080] Pass the obtained manganese oxide-coated ternary positive high-nickel material through a 300-mesh sieve, then weigh out 700g, then accurately weigh 1.4g of nano-alumina and mix it with it, and use a ...

Embodiment 2

[0082] Dissolve 25g of manganese acetate uniformly in 400g of water solvent, then slowly add Ni 0.70 co 0.20 mn 0.10 (OH) 2 1000g, after stirring at 500rpm for 30min, heat at 70°C until the solvent is completely evaporated to obtain a precursor of manganese acetate;

[0083] Then the precursor of the bag manganese acetate that obtains is pulverized, crosses 300 mesh sieves, then weighs the precursor 800g of the bag manganese acetate that obtains, weighs required lithium carbonate 332g by lithium proportioning 1.05 again. After mixing uniformly by ball milling, sintering at 840°C for 15 hours in a muffle furnace with 45% oxygen, and after natural cooling, a ternary positive high-nickel material coated with manganese oxide is obtained;

[0084] The ternary anode high-nickel material of cladding manganese oxide obtained is passed through a 300 mesh sieve, and then weighed and taken out 700g. Accurately weigh 1.4g of nano-titanium oxide additive, then mix the titanium oxide ad...

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Abstract

The invention provides a two-layer coated modified ternary cathode high-nickel material and a preparation method thereof. The double-layer coated modified ternary cathode high-nickel material has a double-layer coated structure which is composed of a Ni-Co lithium manganate substrate, a manganese oxide layer coating layer and a metal oxide outer layer coating layer. The preparation method comprises coating the ternary cathode material precursor NixCoyMn1-x-y(OH)2 as a precursor with the manganese oxide and the metal oxide. The method not only reduces the residual alkali on the surface of the material, but also stabilizes the Ni4+ generated by the material when fully charged, improves the high temperature storage performance and the safety performance. Further, the coated nano metal oxide at the outer layer effectively prevents the electrolyte from reacting with the material, improves the cycle performance of the material, increases the material capacity retention rate, and reduces thecost.

Description

technical field [0001] The invention relates to the field of positive electrode materials for batteries, in particular to a high-nickel positive electrode material in a lithium ion battery and a preparation method thereof. Background technique [0002] Since the commercial application of lithium-ion secondary batteries for the first time, it has rapidly become the current electronic consumer products such as mobile phones, computers, The main provider of electrical energy required by devices such as cameras. In recent years, with the vigorous development of electric vehicles and other industries, the current commercial lithium-ion battery cathode materials can no longer meet the requirements of high-power batteries, and high-capacity cathode materials have become a current research hotspot. Among them, nickel-cobalt-manganese ternary cathode material LiMO 2 (M=Ni, Co, Mn) has become the most promising cathode material for lithium-ion secondary batteries due to its higher t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/48H01M4/505H01M4/525
CPCY02E60/10
Inventor 王辉周宏宝吴朋朋沙金周玉林苏迎春
Owner TIANJIN GUOAN MGL NEW MATERIALS TECH CO LTD
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