A kind of preparation method of fluorine ion doped nickel manganese oxide lithium

A technology of lithium nickel manganate and fluoride ion is applied in the field of preparation of fluoride ion doped lithium nickel manganate, which can solve the problems of cycle performance, poor thermal stability and high temperature performance, poor battery safety and thermal stability, It is difficult to realize the replacement of lithium cobalt oxide and other problems, and achieve the effect of good market promotion value, accelerated migration rate, and improved high temperature performance and cycle performance

Active Publication Date: 2018-09-25
DAXIN MANGANESE MINE BRANCH OF CITIC DAMENG MINING IND
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  • Application Information

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

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  • A kind of preparation method of fluorine ion doped nickel manganese oxide lithium

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Experimental program
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Effect test

Embodiment 1

[0035] (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;

[0036] (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;

[0037] (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

[0044] (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;

[0045] (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;

[0046] (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

[0053] (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;

[0054] (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;

[0055] (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 fluorine ion-doped lithium nickel manganese oxide. The preparation method comprises the following steps: mixing manganese salt and nickel salt materials to prepare a nickel manganese precursor through a sol-gel method; mixing the nickel manganese precursor with lithium salt by adopting a three-dimensional inclined mixer; carrying out pre-sintering and high-temperature sintering, and then doping F for mixing; and finally carrying out low-temperature sintering, fluid energy milling and grading to obtain a lithium nickel manganese oxide finished product. According to the preparation method, the battery material lithium nickel manganese oxide is modified through the doped negative F ions, and the structure change for the doped and modified material crystal is little, so that the diffusion rate of lithium ions in the modified material is quickened, the conductivity is improved, and the high temperature performance and cycle performance of the lithium nickel manganese oxide are effectively improved.

Description

technical field [0001] The invention relates to the technical field of battery materials, in particular to a preparation method of fluoride ion-doped lithium nickel manganese oxide. 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 ); Lithium cobaltate is currently widely used as a posi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/505H01M4/525H01M4/62H01M10/0525
CPCH01M4/505H01M4/525H01M4/624H01M10/0525Y02E60/10
Inventor 李华成明宪权黄冠汉闫冠杰王春飞李春流苏琳圆李海亮吴贤图
Owner DAXIN MANGANESE MINE BRANCH OF CITIC DAMENG MINING IND
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