CN106898757A - A kind of lithium battery composite positive pole based on Graphene and preparation method thereof - Google Patents

A kind of lithium battery composite positive pole based on Graphene and preparation method thereof Download PDF

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CN106898757A
CN106898757A CN201710281528.4A CN201710281528A CN106898757A CN 106898757 A CN106898757 A CN 106898757A CN 201710281528 A CN201710281528 A CN 201710281528A CN 106898757 A CN106898757 A CN 106898757A
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parts
mixture
graphene
lithium battery
positive pole
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李宝玉
陈枫
王慧娟
李良学
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In Guosheng Battery Technology (beijing) Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of lithium battery composite positive pole based on Graphene, it is made up of the following raw material according to weight portion：75 79 parts of cobalt carbonate, 92 97 parts of nickel sulfate, 60 65 parts of manganese acetate, 104 108 parts of lithium oxalate, 6 10 parts of citric acid, 13 18 parts of Graphene, 25 parts of phosphoamide, 58 parts of nano silica fume.The invention also discloses the preparation method of the lithium battery composite positive pole based on Graphene.Lithium battery composite positive pole based on Graphene prepared by the present invention, with specific discharge capacity and good cyclical stability higher, there is wide market prospects.

Description

A kind of lithium battery composite positive pole based on Graphene and preparation method thereof
Technical field
The present invention relates to anode material of lithium battery technical field, specifically a kind of lithium battery anode composite based on Graphene Material and preparation method thereof.
Background technology
China has become sale of automobile market the biggest in the world, and the continuous growth and pollutant emission of consumption of petroleum are not It is disconnected to increase, have become the bottleneck of auto industry sustainable development.Development hybrid electric vehicle, pure electric automobile, fuel-cell vehicle The task of top priority is turned into etc. energy-conservation and new-energy automobile.At present, energy-conservation and new-energy automobile also fail to large-scale promotion, main to go back It is that electrokinetic cell has a series of, for example, energy density is relatively low, bulking value is big, and service life is short, relatively costly, Operating temperature range is narrow, and the charging interval is long etc..In order to improve these adverse effects, people start with from material technology, are moved The further investigation of power battery.In order to solve the problems such as service life, energy density, self discharge or quality of battery, go out Various types of batteries are showed.Lithium ion battery makes it in electricity because its capacity is high, the advantages of have extended cycle life, have a safety feature Electrical automobile field is gathered around to have broad application prospects, it has also become the study hotspot widely paid close attention in recent years.And positive electrode be lithium from The important component of sub- battery, is always the emphasis of people's research and development, and the quality of positive electrode determines final lithium ion battery Performance and price.
Graphene is a kind of graphite material of monoatomic layer thickness, with unique two-dimensional structure and excellent electricity, power Learn and thermal property.It is a kind of electrode material of lithium battery with applications well prospect.Being obtained using Graphene has spy The electrode material of different pattern and microstructure, can be effectively improved every chemical property of material.Graphite in anode composite material The continuous three-dimensional conductive network that alkene is formed can effectively improve the electronics and ion transport capability of composite, in addition compared to tradition Conductive agent, another feature for adding Graphene is to reach more preferably chemical property with less addition.Therefore base is prepared In the positive composite material of lithium battery of Graphene be the study hotspot in lithium battery positive electrode field now.It is existing to be based on The positive composite material of lithium battery of Graphene is in terms of specific discharge capacity and cyclical stability there is still a need for improving.
The content of the invention
It is an object of the invention to provide a kind of lithium battery composite positive pole based on Graphene and preparation method thereof, with Solve the problems, such as to be proposed in above-mentioned background technology.
To achieve the above object, the present invention provides following technical scheme：
A kind of lithium battery composite positive pole based on Graphene, is made up of the following raw material according to weight portion：Cobalt carbonate 75-79 parts, nickel sulfate 92-97 parts, manganese acetate 60-65 parts, lithium oxalate 104-108 parts, citric acid 6-10 parts, Graphene 13-18 Part, phosphoamide 2-5 parts, nano silica fume 5-8 parts.
As further scheme of the invention：It is made up of the following raw material according to weight portion：Cobalt carbonate 76-78 parts, sulfuric acid Nickel 93-96 parts, manganese acetate 61-64 parts, lithium oxalate 105-107 parts, citric acid 7-9 parts, Graphene 14-17 parts, phosphoamide 3-4 Part, nano silica fume 6-7 parts.
As further scheme of the invention：It is made up of the following raw material according to weight portion：77 parts of cobalt carbonate, nickel sulfate 94 parts, 62 parts of manganese acetate, 106 parts of lithium oxalate, 8 parts of citric acid, 15 parts of Graphene, 3 parts of phosphoamide, 7 parts of nano silica fume.
The preparation method of the lithium battery composite positive pole based on Graphene, step is as follows：
1) cobalt carbonate, nickel sulfate, manganese acetate, lithium oxalate and citric acid are weighed, in input to ball mill, in rotating speed 700- Ball milling 10-15h under the rotating speed of 800rpm, obtains the first mixture；
2) by the first mixture input baking oven, 2-5h is dried at 110-115 DEG C, is cooled down, cross 200-400 mesh sieves, obtained Obtain the second mixture；
3) then the second mixture is cooled to 400-450 in the atmosphere of nitrogen, calcination processing 5-8h at 700-730 DEG C DEG C, 2-3h is incubated, then cool to room temperature with the furnace, obtain the 3rd mixture；
4) the 3rd mixture is crushed, crosses 200-400 mesh sieves, obtain the 4th mixture, it is standby；
5) Graphene is weighed, the 15-20 times of ethylene glycol of weight is added, phosphoamide and the 4th mixture, ultrasound is then put into Ripple processes 2-3h, obtains the 5th mixture；
6) the 5th mixture is carried out into vacuum dehydrating at lower temperature, obtains the 6th mixture；
7) then the 6th mixture is cooled to 270-300 in the atmosphere of nitrogen, sintering processes 3-6h at 870-890 DEG C DEG C, 2-3h is incubated, then cool to room temperature with the furnace, obtain the 7th mixture；
8) the 7th mixture is crushed, crosses 200-400 mesh sieves, be subsequently adding the 6-10 times of ethylene glycol of weight, added and receive Rice silica flour, magnetic agitation 1-2h, ultrasonication 1-2h obtain the 8th mixture；
9) the 8th mixture is adopted and is washed with deionized 3-5 times, 7-10h is vacuum dried at 150-170 DEG C, you can.
As further scheme of the invention：Step 5) in, ultrasonication power is 800W.
As further scheme of the invention：Step 8) in, ultrasonication power is 1000W.
Compared with prior art, the beneficial effects of the invention are as follows：
Lithium battery composite positive pole based on Graphene prepared by the present invention, with specific discharge capacity higher and well Cyclical stability, have wide market prospects；Lithium battery composite positive pole based on Graphene prepared by the present invention can Large-scale industrial production, it is easy to promote.
Specific embodiment
Technical scheme is described in more detail with reference to specific embodiment.
Embodiment 1
A kind of lithium battery composite positive pole based on Graphene, is made up of the following raw material according to weight portion：Cobalt carbonate 75 parts, 92 parts of nickel sulfate, 60 parts of manganese acetate, 104 parts of lithium oxalate, 6 parts of citric acid, 13 parts of Graphene, 2 parts of phosphoamide, nano-silicon 5 parts of powder.
In the present embodiment, the preparation method of the lithium battery composite positive pole based on Graphene, step is as follows：
1) cobalt carbonate, nickel sulfate, manganese acetate, lithium oxalate and citric acid are weighed, in input to ball mill, in rotating speed 700rpm Rotating speed under ball milling 10h, obtain the first mixture；
2) by the first mixture input baking oven, 2h is dried at 110 DEG C, is cooled down, cross 200 mesh sieves, obtained second and mix Thing；
3) then the second mixture is cooled to 400 DEG C in the atmosphere of nitrogen, calcination processing 5h at 700 DEG C, is incubated 2h, Cool to room temperature with the furnace again, obtain the 3rd mixture；
4) the 3rd mixture is crushed, crosses 200 mesh sieves, obtain the 4th mixture, it is standby；
5) Graphene is weighed, 15 times of ethylene glycol of weight are added, phosphoamide and the 4th mixture is then put into, at ultrasonic wave Reason 2h, obtains the 5th mixture, wherein, ultrasonication power is 800W；
6) the 5th mixture is carried out into vacuum dehydrating at lower temperature, obtains the 6th mixture；
7) then the 6th mixture is cooled to 270 DEG C in the atmosphere of nitrogen, sintering processes 3h at 870 DEG C, is incubated 2h, Cool to room temperature with the furnace again, obtain the 7th mixture；
8) the 7th mixture is crushed, crosses 200 mesh sieves, be subsequently adding 6 times of ethylene glycol of weight, add nano silica fume, Magnetic agitation 1h, ultrasonication 1h, obtain the 8th mixture, wherein, ultrasonication power is 1000W；
9) the 8th mixture is adopted and is washed with deionized 3 times, 7h is vacuum dried at 150 DEG C, you can.
Embodiment 2
A kind of lithium battery composite positive pole based on Graphene, is made up of the following raw material according to weight portion：Cobalt carbonate 76 parts, 93 parts of nickel sulfate, 61 parts of manganese acetate, 107 parts of lithium oxalate, 9 parts of citric acid, 17 parts of Graphene, 3 parts of phosphoamide, nano-silicon 7 parts of powder.
In the present embodiment, the preparation method of the lithium battery composite positive pole based on Graphene, step is as follows：
1) cobalt carbonate, nickel sulfate, manganese acetate, lithium oxalate and citric acid are weighed, in input to ball mill, in rotating speed 750rpm Rotating speed under ball milling 11h, obtain the first mixture；
2) by the first mixture input baking oven, 3h is dried at 110 DEG C, is cooled down, cross 200 mesh sieves, obtained second and mix Thing；
3) then the second mixture is cooled to 420 DEG C in the atmosphere of nitrogen, calcination processing 6h at 710 DEG C, is incubated 2h, Cool to room temperature with the furnace again, obtain the 3rd mixture；
4) the 3rd mixture is crushed, crosses 200 mesh sieves, obtain the 4th mixture, it is standby；
5) Graphene is weighed, 16 times of ethylene glycol of weight are added, phosphoamide and the 4th mixture is then put into, at ultrasonic wave Reason 2h, obtains the 5th mixture, wherein, ultrasonication power is 800W；
6) the 5th mixture is carried out into vacuum dehydrating at lower temperature, obtains the 6th mixture；
7) then the 6th mixture is cooled to 270 DEG C in the atmosphere of nitrogen, sintering processes 4h at 870 DEG C, is incubated 2h, Cool to room temperature with the furnace again, obtain the 7th mixture；
8) the 7th mixture is crushed, crosses 200 mesh sieves, be subsequently adding 7 times of ethylene glycol of weight, add nano silica fume, Magnetic agitation 1h, ultrasonication 1h, obtain the 8th mixture, wherein, ultrasonication power is 1000W；
9) the 8th mixture is adopted and is washed with deionized 3 times, 8h is vacuum dried at 150 DEG C, you can.
Embodiment 3
A kind of lithium battery composite positive pole based on Graphene, is made up of the following raw material according to weight portion：Cobalt carbonate 77 parts, 94 parts of nickel sulfate, 62 parts of manganese acetate, 106 parts of lithium oxalate, 8 parts of citric acid, 15 parts of Graphene, 3 parts of phosphoamide, nano-silicon 7 parts of powder.
In the present embodiment, the preparation method of the lithium battery composite positive pole based on Graphene, step is as follows：
1) cobalt carbonate, nickel sulfate, manganese acetate, lithium oxalate and citric acid are weighed, in input to ball mill, in rotating speed 750rpm Rotating speed under ball milling 13h, obtain the first mixture；
2) by the first mixture input baking oven, 3h is dried at 112 DEG C, is cooled down, cross 300 mesh sieves, obtained second and mix Thing；
3) by the second mixture in the atmosphere of nitrogen, calcination processing 7h at 720 DEG C, 420 DEG C, insulation are then cooled to 2.5h, then cool to room temperature with the furnace, obtain the 3rd mixture；
4) the 3rd mixture is crushed, crosses 300 mesh sieves, obtain the 4th mixture, it is standby；
5) Graphene is weighed, 18 times of ethylene glycol of weight are added, phosphoamide and the 4th mixture is then put into, at ultrasonic wave Reason 2.5h, obtains the 5th mixture, wherein, ultrasonication power is 800W；
6) the 5th mixture is carried out into vacuum dehydrating at lower temperature, obtains the 6th mixture；
7) by the 6th mixture in the atmosphere of nitrogen, sintering processes 5h at 880 DEG C, 290 DEG C, insulation are then cooled to 2.5h, then cool to room temperature with the furnace, obtain the 7th mixture；
8) the 7th mixture is crushed, crosses 300 mesh sieves, be subsequently adding 8 times of ethylene glycol of weight, add nano silica fume, Magnetic agitation 1.5h, ultrasonication 1.5h, obtain the 8th mixture, wherein, ultrasonication power is 1000W；
9) the 8th mixture is adopted and is washed with deionized 4 times, 9h is vacuum dried at 160 DEG C, you can.
Embodiment 4
A kind of lithium battery composite positive pole based on Graphene, is made up of the following raw material according to weight portion：Cobalt carbonate 78 parts, 96 parts of nickel sulfate, 64 parts of manganese acetate, 105 parts of lithium oxalate, 7 parts of citric acid, 14 parts of Graphene, 4 parts of phosphoamide, nano-silicon 6 parts of powder.
In the present embodiment, the preparation method of the lithium battery composite positive pole based on Graphene, step is as follows：
1) cobalt carbonate, nickel sulfate, manganese acetate, lithium oxalate and citric acid are weighed, in input to ball mill, in rotating speed 800rpm Rotating speed under ball milling 14h, obtain the first mixture；
2) by the first mixture input baking oven, 4h is dried at 113 DEG C, is cooled down, cross 400 mesh sieves, obtained second and mix Thing；
3) then the second mixture is cooled to 430 DEG C in the atmosphere of nitrogen, calcination processing 7h at 720 DEG C, is incubated 3h, Cool to room temperature with the furnace again, obtain the 3rd mixture；
4) the 3rd mixture is crushed, crosses 400 mesh sieves, obtain the 4th mixture, it is standby；
5) Graphene is weighed, 19 times of ethylene glycol of weight are added, phosphoamide and the 4th mixture is then put into, at ultrasonic wave Reason 3h, obtains the 5th mixture, wherein, ultrasonication power is 800W；
6) the 5th mixture is carried out into vacuum dehydrating at lower temperature, obtains the 6th mixture；
7) by the 6th mixture in the atmosphere of nitrogen, sintering processes 5h at 890 DEG C, 300 DEG C, insulation are then cooled to 2.5h, then cool to room temperature with the furnace, obtain the 7th mixture；
8) the 7th mixture is crushed, crosses 400 mesh sieves, be subsequently adding 8 times of ethylene glycol of weight, add nano silica fume, Magnetic agitation 2h, ultrasonication 1.5h, obtain the 8th mixture, wherein, ultrasonication power is 1000W；
9) the 8th mixture is adopted and is washed with deionized 5 times, 9h is vacuum dried at 165 DEG C, you can.
Embodiment 5
A kind of lithium battery composite positive pole based on Graphene, is made up of the following raw material according to weight portion：Cobalt carbonate 79 parts, 97 parts of nickel sulfate, 65 parts of manganese acetate, 108 parts of lithium oxalate, 10 parts of citric acid, 18 parts of Graphene, 5 parts of phosphoamide, nano-silicon 8 parts of powder.
In the present embodiment, the preparation method of the lithium battery composite positive pole based on Graphene, step is as follows：
1) cobalt carbonate, nickel sulfate, manganese acetate, lithium oxalate and citric acid are weighed, in input to ball mill, in rotating speed 800rpm Rotating speed under ball milling 15h, obtain the first mixture；
2) by the first mixture input baking oven, 5h is dried at 115 DEG C, is cooled down, cross 400 mesh sieves, obtained second and mix Thing；
3) then the second mixture is cooled to 450 DEG C in the atmosphere of nitrogen, calcination processing 8h at 730 DEG C, is incubated 3h, Cool to room temperature with the furnace again, obtain the 3rd mixture；
4) the 3rd mixture is crushed, crosses 400 mesh sieves, obtain the 4th mixture, it is standby；
5) Graphene is weighed, 20 times of ethylene glycol of weight are added, phosphoamide and the 4th mixture is then put into, at ultrasonic wave Reason 3h, obtains the 5th mixture, wherein, ultrasonication power is 800W；
6) the 5th mixture is carried out into vacuum dehydrating at lower temperature, obtains the 6th mixture；
7) then the 6th mixture is cooled to 300 DEG C in the atmosphere of nitrogen, sintering processes 6h at 890 DEG C, is incubated 3h, Cool to room temperature with the furnace again, obtain the 7th mixture；
8) the 7th mixture is crushed, crosses 400 mesh sieves, be subsequently adding 10 times of ethylene glycol of weight, add nano silica fume, Magnetic agitation 2h, ultrasonication 2h, obtain the 8th mixture, wherein, ultrasonication power is 1000W；
9) the 8th mixture is adopted and is washed with deionized 5 times, 10h is vacuum dried at 170 DEG C, you can.
Comparative example
Compared with Example 3, without nano silica fume, other are same as Example 3.
The positive electrode prepared using embodiment 1-5 and comparative example is made lithium battery anode, and is assembled into battery, in 2- Tested under the conditions of the discharge and recharge of 4.8V, 200mA/g, the first discharge specific capacity of embodiment 1-5 is 218.327- 289.534mAh/g, the specific discharge capacity after 50 times circulate is 247.534-292.173mAh/g.Wherein, embodiment 3 First discharge specific capacity is 275.851mAh/g, and the specific discharge capacity after 50 times circulate is 292.173mAh/g.Comparative example First discharge specific capacity be 192.536mAh/g, by 50 times circulate after specific discharge capacity be 259.374mAh/g.Therefore It can be seen that the positive electrode prepared by the present invention has a good specific discharge capacity and cyclical stability, and embodiment 3 property Comparative example can be better than.
Lithium battery composite positive pole based on Graphene prepared by the present invention, with specific discharge capacity higher and well Cyclical stability, have wide market prospects；Lithium battery composite positive pole based on Graphene prepared by the present invention can Large-scale industrial production, it is easy to promote.
Better embodiment of the invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party Formula, in the ken that one skilled in the relevant art possesses, can also be on the premise of present inventive concept not be departed from Various changes can be made.

Claims (6)

1. a kind of lithium battery composite positive pole based on Graphene, it is characterised in that by the following raw material system according to weight portion Into：Cobalt carbonate 75-79 parts, nickel sulfate 92-97 parts, manganese acetate 60-65 parts, lithium oxalate 104-108 parts, citric acid 6-10 parts, stone Black alkene 13-18 parts, phosphoamide 2-5 parts, nano silica fume 5-8 parts.
2. the lithium battery composite positive pole based on Graphene according to claim 1, it is characterised in that by it is following according to The raw material of weight portion is made：Cobalt carbonate 76-78 parts, nickel sulfate 93-96 parts, manganese acetate 61-64 parts, lithium oxalate 105-107 parts, lemon 7-9 parts, Graphene 14-17 parts, phosphoamide 3-4 parts, nano silica fume 6-7 parts of lemon acid.
3. the lithium battery composite positive pole based on Graphene according to claim 2, it is characterised in that by it is following according to The raw material of weight portion is made：77 parts of cobalt carbonate, 94 parts of nickel sulfate, 62 parts of manganese acetate, 106 parts of lithium oxalate, 8 parts of citric acid, graphite 15 parts of alkene, 3 parts of phosphoamide, 7 parts of nano silica fume.
4. the preparation method of a kind of lithium battery composite positive pole based on Graphene as described in claim 1-3 is any, its It is characterised by, step is as follows：
1) cobalt carbonate, nickel sulfate, manganese acetate, lithium oxalate and citric acid are weighed, in input to ball mill, in rotating speed 700-800rpm Rotating speed under ball milling 10-15h, obtain the first mixture；
2) in the first mixture being put into baking oven, 2-5h is dried at 110-115 DEG C, is cooled down, cross 200-400 mesh sieves, obtain the Two mixtures；
3) then the second mixture is cooled to 400-450 DEG C in the atmosphere of nitrogen, calcination processing 5-8h at 700-730 DEG C, is protected Warm 2-3h, then cool to room temperature with the furnace, obtain the 3rd mixture；
4) the 3rd mixture is crushed, crosses 200-400 mesh sieves, obtain the 4th mixture, it is standby；
5) Graphene is weighed, the 15-20 times of ethylene glycol of weight is added, phosphoamide and the 4th mixture is then put into, at ultrasonic wave Reason 2-3h, obtains the 5th mixture；
6) the 5th mixture is carried out into vacuum dehydrating at lower temperature, obtains the 6th mixture；
7) then the 6th mixture is cooled to 270-300 DEG C in the atmosphere of nitrogen, sintering processes 3-6h at 870-890 DEG C, is protected Warm 2-3h, then cool to room temperature with the furnace, obtain the 7th mixture；
8) the 7th mixture is crushed, crosses 200-400 mesh sieves, be subsequently adding the 6-10 times of ethylene glycol of weight, add nano-silicon Powder, magnetic agitation 1-2h, ultrasonication 1-2h obtain the 8th mixture；
9) the 8th mixture is adopted and is washed with deionized 3-5 times, 7-10h is vacuum dried at 150-170 DEG C, you can.
5. the preparation method of the lithium battery composite positive pole based on Graphene according to claim 4, it is characterised in that Step 5) in, ultrasonication power is 800W.
6. the preparation method of the lithium battery composite positive pole based on Graphene according to claim 4, it is characterised in that Step 8) in, ultrasonication power is 1000W.
CN201710281528.4A 2017-04-26 2017-04-26 A kind of lithium battery composite positive pole based on Graphene and preparation method thereof Pending CN106898757A (en)

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CN106207134A (en) * 2016-09-05 2016-12-07 中南大学 A kind of surface coating method of ball-shaped lithium-ion battery material

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Application publication date: 20170627