Preparation method of oxide-cladding lithium ion battery positive material

An ion battery, cathode material technology, applied in battery electrodes, circuits, electrical components, etc., can solve the problem of cycle performance, poor thermal stability and high temperature performance, poor battery safety and thermal stability, difficult to achieve cobalt acid Lithium replacement and other issues, to achieve good market promotion value, good product stability, and improved cycle performance.

Active Publication Date: 2016-01-27
DAXIN MANGANESE MINE BRANCH OF CITIC DAMENG MINING IND
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AI Technical Summary

Problems solved by technology

[0003] Lithium cobalt oxide (LiCoO 2 ), lithium manganate (LiMn 2 o 4 ) and lithium iron phosphate (LiFePO 4 ); Lithium cobaltate is currently widely used as a positive electrode material for small lithium-ion batteries, but because cobalt is toxic, resource reserves are limited and expensive, and batteries assembled with lithium cobaltate materials as positive electrode materials have poor safety and thermal stability. Oxygen will be generated at high temperature, which cannot meet the technical requirements of power batteries; although lithium manganate is cheap, environmentally friendly, safe, and has good rate performance and safety performance, its theoretical capacity is not high, and its cycle performance, thermal stability and high temperature performance are relatively low. Poor, the biggest problem in application is poor cycle performance, especially at high temperature, the trivalent manganese ions in the material and the divalent manganese ions formed on the particle surface during high-rate discharge make the material dissolve significantly in the electrolyte , eventually destroying the structure of lithium manganate and reducing the cycle performance of the material; the lithium manganate materials that can be used in the market are all obtained through modification measures. On the one hand, such modification measures require high-standard Synthetic equipment, on the other hand, also needs to be at the cost of reducing the reversible capacity of the material, so these materials have been difficult to replace lithium cobalt oxide; lithium iron phosphate is a new lithium-ion battery cathode material that has attracted widespread attention in recent years. It has superior safety performance and good recycling performance, and has a good application prospect, but the material has a small tap density and a low voltage platform, so the specific energy after being made into a battery is low, making it unsuitable for high-voltage applications. Where energy density is required
[0004] As far as the current technology is concerned, the voltage of these commercially available cathode materials relative to the graphite anode is below 4V, which limits the power of the battery. Therefore, the development of high voltage, high capacity, safety and good cycle performance Ni-doped Miscellaneous LiMn 2 o 4 with 5V grade LiNi 0.5 mn 1.5 o 4 , which has important practical significance for the development of high-power lithium-ion power batteries for electric vehicles

Method used

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  • Preparation method of oxide-cladding lithium ion battery positive material

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Embodiment 1

[0032] (1) Preparation of manganese salt and nickel salt materials: mix manganese sulfate and nickel sulfate materials with a Mn:Ni molar ratio of 3:1;

[0033] (2) The sol-gel method prepares the nickel-manganese precursor: the mixture obtained in step (1) is added in the chelating agent polyethylene glycol-1000, and the quality of the chelating agent is 120% of the metal Mn+Ni quality, with ammonium bicarbonate Adjust the pH to 8-10, stir until viscous, add pure water under stirring to make a solution with a metal Mn+Ni ion concentration of 100g / l, add a sedimentation aid hydroxyl Methyl cellulose until the precipitation is complete, filter, and dry the precipitate to obtain a nickel-manganese precursor;

[0034] (3) Three-dimensional oblique mixing: use a three-dimensional oblique mixer to disperse and mix the nickel-manganese precursor and lithium carbonate salt obtained in step (2) for 2 hours under the medium of polyurethane balls, metal (Mn+Ni): Li moles The ratio is 0...

Embodiment 2

[0041] (1) Preparation of manganese salt and nickel salt materials: mix manganese nitrate and nickel nitrate materials with a Mn:Ni molar ratio of 3:1;

[0042] (2) The sol-gel method prepares the nickel-manganese precursor: the mixture obtained in step (1) is added in the chelating agent polyethylene glycol-4000, and the quality of the chelating agent is 100% of the metal Mn+Ni quality, with ammonium bicarbonate Adjust the pH to 8-10, stir until viscous, add pure water under stirring to make a solution with a metal Mn+Ni ion concentration of 120g / l, add a sedimentation aid hydroxyl that is 5% of the metal Mn+Ni Methyl cellulose until the precipitation is complete, filter, and dry the precipitate to obtain a nickel-manganese precursor;

[0043] (3) Three-dimensional oblique mixing: use a three-dimensional oblique mixer to disperse and mix the nickel-manganese precursor and lithium carbonate salt obtained in step (2) for 4 hours under the medium of zirconia balls, metal (Mn+Ni)...

Embodiment 3

[0050] (1) Preparation of manganese salt and nickel salt materials: mix manganese chloride and nickel chloride materials with a Mn:Ni molar ratio of 3:1;

[0051] (2) Sol-gel method to prepare nickel-manganese precursor: the mixture of step (1) gained is added chelating agent polyethylene glycol-2000, and the quality of chelating agent is 80% of metal Mn+Ni quality, adjusts with ammonium bicarbonate When the pH is 8-10, stir until viscous, add pure water under stirring to make a solution with a metal Mn+Ni ion concentration of 150g / l, and add a settling aid hydroxyformide whose mass is 4% of the mass of the metal Mn+Ni Base cellulose until the precipitation is complete, filter, and dry the precipitate to obtain the nickel-manganese precursor;

[0052] (3) Three-dimensional oblique mixing: use a three-dimensional oblique mixer to disperse and mix the nickel-manganese precursor and lithium carbonate salt obtained in step (2) for 3 hours under the medium of polyurethane balls, me...

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Abstract

The invention discloses a preparation method of an oxide-cladding lithium ion battery positive material. The preparation method comprises the following steps: mixing manganese salt and nickel salt materials, preparing a nickel-manganese precursor by virtue of a sol-gel method, mixing the nickel-manganese precursor with lithium salt by adopting a three-dimensional oblique mixer, pre-sintering, sintering at high temperature, cladding in a wet method by selecting metal-containing oxide, sintering at low temperature, crushing by virtue of air flow, and grading to obtain a lithium nickel manganese oxide finished product. By adopting metal oxide and cladding the lithium nickel manganese oxide material by virtue of a special wet-method cladding process, the cycling performance and high-temperature performance of the lithium nickel manganese oxide can be improved.

Description

technical field [0001] The invention relates to the technical field of battery materials, in particular to a preparation method of lithium nickel manganese oxide, an oxide-coated positive electrode material of a lithium ion battery. Background technique [0002] Lithium-ion power battery is currently recognized as the most potential vehicle battery at home and abroad. It is mainly composed of positive electrode materials, negative electrode materials, separators, electrolytes, etc. Among them, positive electrode materials are an important part of lithium-ion batteries and also determine the quality of lithium-ion batteries. Therefore, in terms of resources, environmental protection and safety performance, finding the ideal electrode active material for lithium-ion batteries is still the primary problem to be solved by international energy materials workers. [0003] Lithium cobalt oxide (LiCoO 2 ), lithium manganate (LiMn 2 o 4 ) and lithium iron phosphate (LiFePO 4 ); L...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/505H01M4/525H01M4/1391H01M4/36
CPCH01M4/1391H01M4/362H01M4/366H01M4/505H01M4/525Y02E60/10
Inventor 王春飞闫冠杰李运姣王习志李林辉伍锡乐唐跃波曾文明黎兆明
Owner DAXIN MANGANESE MINE BRANCH OF CITIC DAMENG MINING IND
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