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Method for preparing graphene modified high-nickel series positive electrode material through spray drying process and positive electrode material prepared by same

A technology of graphene modification and spray drying, which is applied in the direction of spray evaporation, battery electrodes, electrical components, etc., can solve the problems of mechanical and electrical properties of pole pieces, poor processing performance, corrosion of Al foil, etc., to reduce the interface Effects of side reactions, improvement of processability, and high electronic conductivity

Inactive Publication Date: 2018-09-14
宁夏汉尧石墨烯储能材料科技有限公司
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] First, the lithium-ion diffusion coefficient and electronic conductivity of high-nickel materials are low, which makes the rate performance of the material not very ideal;
[0007] Second, compared with lithium cobalt oxide materials, the residual alkali on the surface of high-nickel materials is high, especially LiOH is very high, which will lead to poor processing performance of materials in the battery manufacturing process, mainly manifested in two aspects: 1) LiOH It will attack the adjacent C-F and C-H bonds of PVDF, causing bimolecular elimination reaction to occur, and when the internal double bonds increase, the cohesive force will increase, resulting in an increase in the viscosity of the slurry, and even the slurry is in a gel state
Moreover, when the double bonds in PVDF increase, the cohesive force increases, resulting in an increase in the brittleness of the pole piece, and it is particularly easy to break during the winding and unwinding process of the pole piece rolling, slitting, etc.
2) LiOH will corrode the Al foil and change the surface properties of the Al foil, which will affect the mechanical and electrical properties of the pole piece, and the battery safety will also be affected
[0010] 1. The technical introduction of the preparation of ternary and high-nickel precursors by spray drying method is simple, and there is no existing technology to refer to for the preparation of graphene-modified high-nickel materials by spray drying method; 2. The drying process of some technologies takes a long time, which makes High-nickel strong oxidizing surface is prone to a series of side reactions in contact with graphene or air; 3. The existing technology does not have a graphene coating layer, which makes high-nickel materials have a series of side reactions with the electrolyte during charging and discharging

Method used

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  • Method for preparing graphene modified high-nickel series positive electrode material through spray drying process and positive electrode material prepared by same

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] A method for preparing a graphene-modified high-nickel series cathode material by a spray-drying method, comprising the following steps:

[0044] 1) The median particle size (D 50 )=10μm battery-grade nickel-cobalt-manganese hydroxide high-nickel precursor (the molar content of nickel is 80%) and lithium hydroxide according to the molar ratio of lithium ions and total metal ions (Li:Metal) is 1.05:1 at high speed Mix evenly, take 3kg of the mixed material and put it into a refractory saggar, under an oxygen atmosphere, the oxygen purity is controlled at 99.5% (V / V), and calcined in a roller kiln at 700°C for 25 hours to obtain a high-nickel primary The roasted material is then mechanically pulverized and classified at a frequency of 22 Hz to obtain the primary pulverized material of nickel oxide, cobalt, manganese and lithium;

[0045] 2) Add 1g of polyvinylpyrrolidone (PVP) to 1100g of ethanol and stir evenly to form solution I, then add 100g of polyvinylidene fluorid...

Embodiment 2

[0049] A method for preparing a graphene-modified high-nickel series cathode material by a spray-drying method, comprising the following steps:

[0050] 1) will D 50 =15μm battery-grade nickel-cobalt-manganese hydroxide high-nickel precursor (the molar content of nickel is 85%) and lithium carbonate are mixed at a high speed according to the Li:Metal molar ratio of 1.03:1, and the mixed material is packed in 3kg Put it into a refractory sagger, when the oxygen purity is controlled at 99.5%, calcined in a roller kiln at 800°C for 22 hours to obtain a high-nickel primary roasted material, and then mechanically pulverize and classify at a frequency of 18Hz to obtain a nickel-cobalt-manganese-lithium primary crushed material ;

[0051] 2) Add 1g of PVP to 1100g of ethanol and stir evenly to form solution I, then add 100g of PVDF to solution I and disperse evenly to form solution II, and finally add 80g of D 50 Graphene with a diameter of 5 μm is added to the solution II to dispe...

Embodiment 3

[0055] A method for preparing a graphene-modified high-nickel series cathode material by a spray-drying method, comprising the following steps:

[0056] 1) will D 50 =10 μm battery-grade nickel-cobalt-manganese hydroxide high-nickel precursor (the molar content of nickel is 80%) and lithium hydroxide are uniformly mixed at a high speed according to the Li:Metal molar ratio of 1.05:1, and the mixed material takes 3kg Put it into a refractory sagger, and when the oxygen purity is controlled at 99.5%, calcinate in a roller kiln at 700°C for 25 hours to obtain a high-nickel primary roasted material, and then mechanically pulverize and classify at a frequency of 20Hz to obtain primary pulverization of nickel oxide, cobalt, manganese, and lithium material;

[0057] 2) First add 1g of polyethylene glycol octylphenyl ether into 1100g of deionized water and stir to form solution I, then add 75g of polyvinyl alcohol (PVA) to solution I to disperse evenly to form solution II, and finall...

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Abstract

The invention discloses a method for preparing a graphene modified high-nickel series positive electrode material through a spray drying process and the positive electrode material prepared by the same. The method includes following steps: 1), well mixing high-nickel precursor with lithium carbonate or lithium hydroxide according to a certain molar ratio, calcining in an oxygen atmosphere roller way kiln, and smashing to obtain a high-nickel primary smashed material; 2), adding a dispersant, a binder and graphene into a solvent, and stirring and dispersing well to form graphene electroconductive paste with certain solid content, wherein the graphene electroconductive paste is a uniform emulsion in dispersion state; 3), stirring and mixing an oxygen-containing compound source with the high-nickel primary smashed material, adding the graphene electroconductive paste, stirring to obtain graphene mixed paste; 4), utilizing a spray dryer for drying, calcining in the oxygen roller way kiln,smashing, and screening to obtain a final graphene modified high-nickel product. The graphene modified high-nickel positive electrode material produced by adopting the method has the advantages of lowresidual alkali and excellent rate performance and circulating performance and is suitable for industrial production.

Description

technical field [0001] The invention belongs to the field of preparation of electrode materials for lithium-ion secondary batteries, and relates to a method for preparing a graphene-modified high-nickel positive electrode material by a spray drying method and the positive electrode material prepared by the method. Background technique [0002] Spray drying is a drying method for processing solutions, emulsions, suspensions and slurry materials into powdery, granular, hollow ball or granular dry products. It mainly uses an atomizer to disperse the material liquid into fine particles. The process of spraying droplets and rapidly evaporating the solvent in a hot drying medium to form a dry powder product. Generally, the spray drying stage is divided into atomization of material liquid, contact and mixing of mist group and hot drying medium, evaporation and drying of mist droplets, and separation of dry product and drying medium. Compared with traditional drying methods, spray ...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/485H01M4/505H01M4/525H01M4/62H01M10/0525B01D1/18
CPCB01D1/18H01M4/366H01M4/485H01M4/505H01M4/525H01M4/625H01M10/0525Y02E60/10
Inventor 靳佳周大桥李来强张宁
Owner 宁夏汉尧石墨烯储能材料科技有限公司
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