CN108649195A - A kind of nickelic ternary lithium battery material of polythiophene base and preparation method - Google Patents

A kind of nickelic ternary lithium battery material of polythiophene base and preparation method Download PDF

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CN108649195A
CN108649195A CN201810396629.0A CN201810396629A CN108649195A CN 108649195 A CN108649195 A CN 108649195A CN 201810396629 A CN201810396629 A CN 201810396629A CN 108649195 A CN108649195 A CN 108649195A
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nickelic ternary
nickel
polythiophene
cobalt
lithium battery
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陈庆
曾军堂
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Chengdu New Keli Chemical Science Co Ltd
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Chengdu New Keli Chemical Science 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/62—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
    • 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

Abstract

The present invention proposes a kind of preparation method of the nickelic ternary lithium battery material of polythiophene base, using lithium salts, nickel salt, cobalt salt, manganese salt as raw material, then lye is added, nickel cobalt manganese precipitates, sintering obtains nickelic ternary basic material, then thiophene monomer and dispersion is added, after ultrasonic disperse, strong oxidizer is added during high speed dispersion, thiophene monomer is oxidatively polymerized into polythiophene, and polythiophene complex microsphere is collectively formed with nickel cobalt manganese, the nickelic ternary material of high solidity is obtained after being then spray-dried.The present invention overcomes existing nickelic ternary materials to recycle defect that is unstable, being mixed with reduction density, reduce conductivity, it polymerize the guiding to form microballoon polythiophene by thiophene monomer, nickelic ternary material is set to form microballoon, microstructure change has been firmly fixed, the compacted density for improving nickle cobalt lithium manganate, efficiently solves the high temperature of nickel-cobalt lithium manganate cathode material lithium battery, overcharges, the safety under Condition of Acupuncture.

Description

A kind of nickelic ternary lithium battery material of polythiophene base and preparation method
Technical field
The present invention relates to lithium ion anode material and preparing technical fields, and in particular to a kind of nickelic ternary lithium of polythiophene base Battery material and preparation method.
Background technology
Lithium ion battery is current most promising and application prospect high-energy secondary battery, wherein lithium-ion electric Pond positive electrode is the key factor for determining lithium ion battery development.
The cobalt nickel lithium manganate ternary material of especially rich nickel is due to higher specific capacity, it is considered to be most potential Next-generation lithium ion battery material.But rich nickel ternary material still has the reality that some critical issues hinder the material at present Border is applied, such as lithium nickel mixing, the shortcomings of high temperature circulation stability is poor.Currently, coprecipitation prepares nickel cobalt manganese hydroxide Common method, especially in the sintering process of rich nickel ternary material, since the factors such as lithium nickel mixing cause material surface that can not keep away Exempt from there are a large amount of lithium residue Li2O/LiOH.When nickel-rich positive pole material exposes in air, lithium residue can absorb H2O and CO2 It is converted into LiOH/Li2CO3And it is attached to the surface of nickel-rich positive pole material.Some researches show that these are attached to nickel-rich positive pole material The substance on surface can not only hinder Li+Transmission migration, keep the electrochemistry loss of energy of nickel-rich positive pole material very big.
Therefore, stablize the structure of nickelic ternary, reduce being in direct contact of material and air or electrolyte, reduce material and absorb H2O/CO2Or it is the key that improve rich nickel material chemical property and security performance that side reaction, which occurs, with electrolyte.
Current solution includes mainly that doping treatment and surface cladding and two kinds of means are combined.Such as Chinese invention Number of patent application 201710029243.1 provides a kind of nickelic positive electrode and preparation method thereof and lithium ion battery.This Invention in the presoma of nickelic positive electrode by being added nonmetal doping agent, lithium source is added and obtaining having non-gold after being sintered Belong to the nickelic positive electrode of element doping.Chinese invention patent application number 201710167988.4 is disclosed based on high-nickel material The preparation method of the codoping modified ternary precursor of cobalt magnesium and positive electrode, by nickel cobalt magnesium mixed solution, ammonium hydroxide and sodium hydroxide Mixed solution, sodium hydroxide solution cocurrent are added in reaction kettle, after coprecipitation reaction, first obtain precursor powder, then by forerunner Body powder is uniformly mixed with lithium salts, is calcined in tube furnace, is ground up, sieved to obtain nickelic tertiary cathode material.Pass through the hand of doping Section is modified processing, and the type and concentration of foreign atom are very big on active material properties influence, needs during the test pair Doping and Elemental redistribution are strictly controlled, higher to technological requirement.
Chinese invention patent application number 201410078072.8 discloses a kind of High-nickel-base lithium ion battery anode material and its system Preparation Method, coating layer material are coated on formed core-shell structure outside nickelic base anode material so that the positive electrode has height The high power capacity of nickel-base anode material and the good advantage of the thermal stability of coating layer material.Chinese invention patent application number 201510740732.9 a kind of nickelic tertiary cathode materials of coating modification and preparation method thereof, are with LiNixCo (1-x)/2Mn (1-x)/2O2 materials are matrix, wherein 0.6≤x≤0.9；Matrix is coated with a clad, containing there are many nanometers in clad Metal salt and/or nano-metal-oxide；Cationic metal gross mass therein account for tertiary cathode material quality 0.01%~ 10%.It is modified processing by the means of cladding, coating thickness and Elemental redistribution uniformity coefficient are difficult to effectively control, cladding Layer is big with tertiary cathode material crystal lattice difference, causes coating to fall off during high temperature circulation, modified effect is bad.
Chinese invention patent application number 201610658086.6 discloses a kind of height that aluminium doping is modified altogether with surface modification Nickelic positive electrode material precursor is added in aluminium salt colloidal sol and is mixed into slurry, while stirring by the preparation method of nickel positive electrode Heating evaporation solution obtains dry powder；Dry powder lithium source is mixed again to calcine to get to aluminium doping and surface The nickelic positive electrode that modification is modified altogether.Aluminium salt colloidal sol uniformly mixes nickelic positive electrode material precursor in the present invention, mixes By a step high-temperature roasting after conjunction lithium source.The means being combined by doping vario-property and coating modification can improve nickelic ternary material Cyclical stability, equally face doping vario-property and coating modification there are the problem of, and method and step is cumbersome, increases modification Cost.
Although using doping and cladding at present to promote nickelic cyclical stability, since preparation method limits, altogether Elemental redistribution is uneven in the particle that the precipitation method obtain, and the Elemental redistribution and coating of doping and cladding are difficult to equal control, reduce and live Property density of material and conductivity.It is therefore proposed that a kind of method, which is prepared, can be firmly fixed nickelic ternary microstructure change, The compacted density for improving nickle cobalt lithium manganate, it is significant to the safety and cycle performance that improve the electroactive positive electrode of lithium.
Invention content
Defect that is unstable, being mixed with reduction density, reduce conductivity, this hair are recycled for existing nickelic ternary material It is bright to propose a kind of nickelic ternary lithium battery material of polythiophene base and preparation method, improve the safety of the electroactive positive electrode of lithium And cycle performance, it efficiently solves the high temperature of nickel-cobalt lithium manganate cathode material lithium battery, overcharge, the safety under Condition of Acupuncture.
To solve the above problems, the present invention uses following technical scheme：
A kind of preparation method of the nickelic ternary lithium battery material of polythiophene base first prepares nickelic ternary by coprecipitation, sintering Basic material, then mixed with thiophene monomer, the nickelic ternary material of high compacted density, specific preparation process are obtained after polymerisation It is as follows：
（1）According to stoichiometric ratio LiNixCoyMn1-x-yO2Lithium salts, nickel salt, cobalt salt, manganese salt powder are weighed, wherein 1>X >=0.6, 0.4>y>0,1-x-y>0, high-speed stirred after suitable quantity of water is added, is uniformly mixed, obtains mixed solution；
（2）Precipitating reagent is added into mixed solution, by filtering, presoma is obtained, by the presoma further in 750-900 DEG C, be sintered 1-2 hours under excess oxygen, be ground to Nano grade, obtain nickelic ternary basic material；
（3）By thiophene monomer, dispersant and nickelic ternary basic material 1.2-3 in molar ratio:0.01-0.05:20 mixing, add Enter suitable quantity of water, after ultrasonic disperse, strong oxidizer is added, polymerisation occurs, obtain nickel cobalt manganese polythiophene complex microsphere slurry；
（4）Nickel cobalt manganese polythiophene complex microsphere slurry is finally obtained into the nickelic ternary material of high compacted density by being spray-dried Material.
Preferably, the nickel salt is one kind in nickel chloride, nickelous carbonate, nickel nitrate, nickelous bromide, nickel fluoride, the cobalt salt For one kind in cobalt chloride, cobalt carbonate, cobalt nitrate, cobalt acid sodium, cobaltous bromide, cobaltous fluoride or one kind in lithium hydroxide.
Preferably, the high-speed stirred speed is 200-800rpm.
Preferably, the precipitating reagent is one or more of sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide Combination, pH value 10.2-12.8.
Preferably, in the mixed solution, a concentration of 0.08-0.24mol/L of nickel salt.
Preferably, it is 30-50% that the oxygen-enriched environment, which is oxygen content,.
Preferably, the dispersant is one in neopelex, sodium butylnaphthalenesulfonate and Sodium p-aminobenzene sulfonat Kind or two or more combinations.
Preferably, the strong oxidizer is potassium permanganate, two pyridine silver potassium permanganate, dichlorocyanobenzoquinone and cerous nitrate One kind in ammonium advantageously ensuring that oxidation polymerization is abundant using excessive, but the impurity for crossing polyoxide in order to prevent introduces, preferably Oxidizer be thiophene monomer, dispersant and nickelic ternary basic material gross mass 0.5%.
The nickelic ternary lithium battery material of a kind of polythiophene base being prepared by the above method.
Preferably, the grain size of the nickelic ternary lithium battery material of the polythiophene base is 40-90 microns.
Defect that is unstable, being mixed with reduction density, reduce conductivity, this hair are recycled for existing nickelic ternary material It is bright to propose a kind of nickelic ternary lithium battery material of polythiophene base and preparation method.According to LiNixCoyMn1-x-yO2, prepare nickelic three The precursor liquid of first material, is then added lye, and it is small to be further sintered 1-2 under 750-900 DEG C, excess oxygen for nickel cobalt manganese precipitation When, it is ground to Nano grade, obtains nickelic ternary basic material；Then thiophene monomer and dispersion, ultrasonic disperse is added Afterwards, strong oxidizer is added during high speed dispersion, thiophene monomer is oxidatively polymerized into polythiophene, and is collectively formed with nickel cobalt manganese poly- Thiophene complex microsphere obtains the nickelic ternary material of high solidity after being then spray-dried.Outstanding feature of the present invention exists In polymerizeing the guiding to form microballoon polythiophene by thiophene monomer, so that nickelic ternary material is formed microballoon, be firmly fixed micro- Structure change is seen, the compacted density of nickle cobalt lithium manganate is improved；Polythiophene has good electric conductivity, improves the electroactive anode of lithium The safety of material and cycle performance efficiently solve the high temperature of nickel-cobalt lithium manganate cathode material lithium battery, overcharge, Condition of Acupuncture Under safety.
By the nickelic ternary lithium battery material of a kind of polythiophene base prepared by the present invention and the nickelic ternary for being mixed with processing Electrode material of lithium battery compares, and the present invention has a clear superiority as shown in table 1.
Table 1：
Compacted density g/cm3 0.1C first discharge specific capacities（mAH/g） Discharge capacity after 0.1C is recycled 100 times（mAH/g）
The present invention 3.2-3.9 223.2 202.5
It is mixed with processing 2.2-2.6 184.4 165.2
It is untreated 1.8-2.4 167.3 150.4
A kind of nickelic ternary lithium battery material of polythiophene base of present invention offer and preparation method protrude compared with prior art The characteristics of and excellent effect be：
1, the present invention in nickelic ternary basic material by introducing thiophene monomer and dispersion, after ultrasonic disperse, in height Strong oxidizer is added in fast dispersion process, thiophene monomer is oxidatively polymerized into polythiophene, and polythiophene is collectively formed with nickel cobalt manganese and answers Microballoon is closed, the guiding to form microballoon polythiophene is polymerize by thiophene monomer, so that nickelic ternary material is formed microballoon, is firmly fixed Microstructure change, improves the compacted density of nickle cobalt lithium manganate.
2, the present invention improves the safety of the electroactive positive electrode of lithium by the way that polythiophene medium with good conductivity is added And cycle performance, it efficiently solves the high temperature of nickel-cobalt lithium manganate cathode material lithium battery, overcharge, the safety under Condition of Acupuncture.
3, present invention process is simple and easy to control, the nickelic ternary electrode material of lithium battery LiN preparedixCoyMn1-x-yO2, X >= 0 .6 mass is high, grain size is small, uniform in size, and chemical stability is good, of low cost, suitable for mass production.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）According to stoichiometric ratio LiNixCoyMn1-x-yO2Weigh lithium carbonate, nickel chloride, cobalt chloride, manganese chloride powder, wherein x For 0.8, y 0.1, setting mixing speed is that 200rpm carries out high-speed stirred after suitable quantity of water is added, and is uniformly mixed, obtains mixing molten Liquid, in the mixed solution, a concentration of 0.24mol/L of nickel salt；
（2）The combination of sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide that pH value is 10.2 is added into mixed solution, passes through Fully precipitation filtering, obtains presoma, and the presoma is further burnt under 750 DEG C, the excess oxygen that oxygen content is 50% Knot 2 hours, is ground to 250nm, obtains nickelic ternary basic material；
（3）By thiophene monomer, neopelex and nickelic ternary basic material in molar ratio 1.2:0.01:20 is mixed It closes, addition suitable quantity of water, after ultrasonic disperse, strong oxidizer ammonium ceric nitrate is added, polymerisation occurs, it is multiple to obtain nickel cobalt manganese polythiophene Close microsphere slurries；Oxidizer be thiophene monomer, dispersant and nickelic ternary basic material gross mass 0.5%；
（4）It is close finally to be obtained into the high-pressure solid that grain size is 40 microns by being spray-dried for nickel cobalt manganese polythiophene complex microsphere slurry Spend nickelic ternary material.
Slurry is made in nickelic ternary material prepared by embodiment and is coated in the two-sided of aluminium foil, positive plate is made.MAYZUN MZ-J600 is compacted the maximum compacted density of instrument test positive plate.Use artificial graphite for negative electrode active material, with amount of conductive Agent is stirring evenly and then adding into bonding agent and negative electrode slurry is made, and negative electrode slurry obtained is coated uniformly on to the two sides of copper foil, is made Negative plate.Using conventional commercial electrolyte liquid and diaphragm, box hat electricity is made after positive/negative plate is rolled, assembling, fluid injection and chemical conversion Electrical property is tested in pond, carries out constant current charge-discharge test to battery is made, voltage range records battery between 2.8 ~ 4.6V Discharge capacity is as shown in table 2.The battery is subjected to circulation safe performance detection discovery, is recycled 200 times at 0.1C, 80 DEG C, is appointed So there is good capacity retention ratio.
Embodiment 2
（1）According to stoichiometric ratio LiNixCoyMn1-x-yO2Weigh lithium carbonate, nickel nitrate, cobalt nitrate, manganese nitrate powder, wherein x For 0.8, y 0.1, setting mixing speed is that 800rpm carries out high-speed stirred after suitable quantity of water is added, and is uniformly mixed, obtains mixing molten Liquid, in the mixed solution, a concentration of 0.12mol/L of nickel salt；
（2）The sodium hydroxide solution, the combination in ammonium hydroxide that pH value is 10.8 are added into mixed solution, by fully precipitating, mistake Filter, obtains presoma, and the presoma is further sintered 1 hour under 800 DEG C, the excess oxygen that oxygen content is 45%, is ground It is milled to 350nm, obtains nickelic ternary basic material；
（3）By thiophene monomer, Sodium p-aminobenzene sulfonat and nickelic ternary basic material in molar ratio 3:0.01:20 mixing, are added Suitable quantity of water after ultrasonic disperse, is added two pyridine silver potassium permanganate of strong oxidizer and polymerisation occurs, it is multiple to obtain nickel cobalt manganese polythiophene Close microsphere slurries；
（4）It is close finally to be obtained into the high-pressure solid that grain size is 63 microns by being spray-dried for nickel cobalt manganese polythiophene complex microsphere slurry Spend nickelic ternary material.
Slurry is made in nickelic ternary material prepared by embodiment and is coated in the two-sided of aluminium foil, positive plate is made.MAYZUN MZ-J600 is compacted the maximum compacted density of instrument test positive plate.Use artificial graphite for negative electrode active material, with amount of conductive Agent is stirring evenly and then adding into bonding agent and negative electrode slurry is made, and negative electrode slurry obtained is coated uniformly on to the two sides of copper foil, is made Negative plate.Using conventional commercial electrolyte liquid and diaphragm, box hat electricity is made after positive/negative plate is rolled, assembling, fluid injection and chemical conversion Electrical property is tested in pond, carries out constant current charge-discharge test to battery is made, voltage range records battery between 2.8 ~ 4.6V Discharge capacity is as shown in table 2.The battery is subjected to circulation safe performance detection discovery, is recycled 200 times at 0.1C, 80 DEG C, is appointed So there is good capacity retention ratio.
Embodiment 3
（1）According to stoichiometric ratio LiNixCoyMn1-x-yO2Weigh lithium carbonate, nickel chloride, cobalt acid sodium, sodium manganate powder, wherein x For 0.6, y 0.2, setting mixing speed is that 400rpm carries out high-speed stirred after suitable quantity of water is added, and is uniformly mixed, obtains mixing molten Liquid, in the mixed solution, a concentration of 0.2mol/L of nickel salt；
（2）The combination of sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide that pH value is 12 is added into mixed solution, by heavy It forms sediment and filters, obtain presoma, the presoma is further sintered 1.8 under 880 DEG C, the excess oxygen that oxygen content is 40% Hour, it is ground to 250nm, obtains nickelic ternary basic material；
（3）By thiophene monomer, sodium butylnaphthalenesulfonate and Sodium p-aminobenzene sulfonat and nickelic ternary basic material in molar ratio 1.8: 0.03:20 mix, addition suitable quantity of water, after ultrasonic disperse, strong oxidizer dichlorocyanobenzoquinone are added, polymerisation occurs, obtain Nickel cobalt manganese polythiophene complex microsphere slurry；
（4）It is close finally to be obtained into the high-pressure solid that grain size is 55 microns by being spray-dried for nickel cobalt manganese polythiophene complex microsphere slurry Spend nickelic ternary material.
Slurry is made in nickelic ternary material prepared by embodiment and is coated in the two-sided of aluminium foil, positive plate is made.MAYZUN MZ-J600 is compacted the maximum compacted density of instrument test positive plate.Use artificial graphite for negative electrode active material, with amount of conductive Agent is stirring evenly and then adding into bonding agent and negative electrode slurry is made, and negative electrode slurry obtained is coated uniformly on to the two sides of copper foil, is made Negative plate.Using conventional commercial electrolyte liquid and diaphragm, box hat electricity is made after positive/negative plate is rolled, assembling, fluid injection and chemical conversion Electrical property is tested in pond, carries out constant current charge-discharge test to battery is made, voltage range records battery between 2.8 ~ 4.6V Discharge capacity is as shown in table 2.The battery is subjected to circulation safe performance detection discovery, is recycled 200 times at 0.1C, 80 DEG C, is appointed So there is good capacity retention ratio.
Embodiment 4
（1）According to stoichiometric ratio LiNixCoyMn1-x-yO2Lithium hydroxide, nickelous bromide, cobaltous bromide, manganous bromide powder are weighed, Middle x is 0.6, y 0.2, and setting mixing speed is that 200-800rpm carries out high-speed stirred after suitable quantity of water is added, and is uniformly mixed, obtains To mixed solution, in the mixed solution, a concentration of 0.18mol/L of nickel salt；
（2）The combination of potassium hydroxide solution, ammonium hydroxide that pH value is 11 is added into mixed solution, is filtered by precipitation, before obtaining Body is driven, the presoma is further sintered 1.2 hours under 800 DEG C, the excess oxygen that oxygen content is 35%, is ground to 350nm obtains nickelic ternary basic material；
（3）By thiophene monomer, Sodium p-aminobenzene sulfonat and nickelic ternary basic material in molar ratio 2.5:0.02:20 mixing, add Enter suitable quantity of water, after ultrasonic disperse, strong oxidizer potassium permanganate is added, polymerisation occurs, obtain nickel cobalt manganese polythiophene complex microsphere Slurry；
（4）It is close finally to be obtained into the high-pressure solid that grain size is 76 microns by being spray-dried for nickel cobalt manganese polythiophene complex microsphere slurry Spend nickelic ternary material.
Slurry is made in nickelic ternary material prepared by embodiment and is coated in the two-sided of aluminium foil, positive plate is made.MAYZUN MZ-J600 is compacted the maximum compacted density of instrument test positive plate.Use artificial graphite for negative electrode active material, with amount of conductive Agent is stirring evenly and then adding into bonding agent and negative electrode slurry is made, and negative electrode slurry obtained is coated uniformly on to the two sides of copper foil, is made Negative plate.Using conventional commercial electrolyte liquid and diaphragm, box hat electricity is made after positive/negative plate is rolled, assembling, fluid injection and chemical conversion Electrical property is tested in pond, carries out constant current charge-discharge test to battery is made, voltage range records battery between 2.8 ~ 4.6V Discharge capacity is as shown in table 2.The battery is subjected to circulation safe performance detection discovery, is recycled 200 times at 0.1C, 80 DEG C, is appointed So there is good capacity retention ratio.
Embodiment 5
（1）According to stoichiometric ratio LiNixCoyMn1-x-yO2Weigh lithium carbonate, nickel chloride, cobalt chloride, manganese chloride powder, wherein x For 0.8, y 0.1, setting mixing speed is that 200rpm carries out high-speed stirred after suitable quantity of water is added, and is uniformly mixed, obtains mixing molten Liquid, in the mixed solution, a concentration of 0.24mol/L of nickel salt；
（2）The combination of sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide that pH value is 10.2 is added into mixed solution, passes through Precipitation filtering, obtains presoma, and the presoma is further sintered 2 under 750 DEG C, the excess oxygen that oxygen content is 50% Hour, it is ground to 250nm, obtains nickelic ternary basic material；
（3）By thiophene monomer, neopelex and nickelic ternary basic material in molar ratio 3:0.01:20 mixing, Suitable quantity of water is added, after ultrasonic disperse, strong oxidizer potassium permanganate is added, polymerisation occurs, it is compound micro- to obtain nickel cobalt manganese polythiophene Ball slurry；
（4）It is close finally to be obtained into the high-pressure solid that grain size is 40 microns by being spray-dried for nickel cobalt manganese polythiophene complex microsphere slurry Spend nickelic ternary material.
Slurry is made in nickelic ternary material prepared by embodiment and is coated in the two-sided of aluminium foil, positive plate is made.MAYZUN MZ-J600 is compacted the maximum compacted density of instrument test positive plate.Use artificial graphite for negative electrode active material, with amount of conductive Agent is stirring evenly and then adding into bonding agent and negative electrode slurry is made, and negative electrode slurry obtained is coated uniformly on to the two sides of copper foil, is made Negative plate.Using conventional commercial electrolyte liquid and diaphragm, box hat electricity is made after positive/negative plate is rolled, assembling, fluid injection and chemical conversion Electrical property is tested in pond, carries out constant current charge-discharge test to battery is made, voltage range records battery between 2.8 ~ 4.6V Discharge capacity is as shown in table 2.The battery is subjected to circulation safe performance detection discovery, is recycled 200 times at 0.1C, 80 DEG C, is appointed So there is good capacity retention ratio.
Comparative example 1
（1）According to stoichiometric ratio LiNixCoyMn1-x-yO2Nickel chloride, cobalt chloride, manganese chloride powder are weighed, wherein x is 0.8, y It is 0.1, setting mixing speed is that 200rpm carries out high-speed stirred after suitable quantity of water is added, and is uniformly mixed, obtains mixed solution, described In mixed solution, a concentration of 0.24mol/L of nickel salt；
（2）The combination of sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide that pH value is 10.2 is added into mixed solution, passes through Precipitation filtering, obtain presoma, by the presoma further 750 DEG C, oxygen content be 50% excess oxygen under with carbonic acid Lithium is sintered 2 hours, is ground to 250nm, is obtained nickelic ternary material LiNi0.8Co0.1Mn0.1O2。
It is prepared into battery according to 1 identical method of embodiment, test condition is consistent with embodiment 1-5, obtains test data The results are shown in Table 2.
Comparative example 2
（1）Ratio 0.8 is measured by mol：0.1：0.1 weighs metal salt starting materials, the metal salt starting materials include nickel chloride, cobalt chloride, The metal salt is respectively configured to the solution of 1mol/L by manganese chloride, is added in flask, is heated in 50-80 DEG C of water bath with thermostatic control, simultaneously It is stirred continuously with electric blender, electric stirring mixing speed is 140rpm, the ammonia by the ammonia volumetric concentration of 2mol/L 22% Water is added in mixed solution, reacts 40 minutes, obtains ternary material precursor；
（2）By the ternary precursor material and lithium carbonate according to 1.:1 mixing, mixing is spray-dried under the conditions of 250 DEG C, is obtained To precursor mixture by precursor mixture with the heating rate of 15 DEG C/min, under the conditions of 1200 DEG C, it is sintered 6h, After being cooled to room temperature cooling with 10 DEG C/min cooling rates, nickelic ternary core material is obtained.
（3）Aluminium chloride is dissolved in the titanium chloride solution that deionized water compound concentration is 0.1mol/L, the core is lived Property material be added in above-mentioned salting liquid, the molal quantity of addition is 100 times of aluminium chloride, 2h is sufficiently stirred, in the mistake of stirring The ammonia spirit of a concentration of 2mol/L is added in journey, forms the precipitation of the core active material of cladded aluminium hydroxide, to precipitation Product is filtered, and net is sieved with 100 mesh sieve after gained filter cake is dried at 160 DEG C, and the product after sieving is carried out at 700 DEG C High-temperature process 4h obtains the nickelic ternary material of alumina-coated.It is prepared into battery according to 1 identical method of embodiment, is tested Condition is consistent with embodiment 1-5, and obtaining test data, the results are shown in Table 2.
Table 2：
Sample Tap density g/cm3 0.1C first discharge specific capacities mAH/g 0.1C, 50 capacity retention ratio % of room temperature cycles 0.1C recycles 200 capacity retention ratio % at 80 DEG C
Embodiment 1 3.2 223.2 97.3 94.4
Embodiment 2 3.6 213.3 96.3 95.8
Embodiment 3 3.4 204.3 96.9 94.3
Embodiment 4 3.9 210.9 97.2 95.2
Embodiment 5 3.5 228.4 95.9 94.8
Comparative example 1 2.6 182.9 88.3 65.6
Comparative example 2 2.4 196.3 94.8 71.3

Claims (9)

1. a kind of preparation method of the nickelic ternary lithium battery material of polythiophene base, which is characterized in that specific preparation process is as follows：
（1）According to stoichiometric ratio LiNixCoyMn1-x-yO2Lithium salts, nickel salt, cobalt salt, manganese salt powder are weighed, wherein 1>X >=0.6, 0.4>y>0,1-x-y>0, high-speed stirred after suitable quantity of water is added, is uniformly mixed, obtains mixed solution；
（2）Precipitating reagent is added into mixed solution, by filtering, presoma is obtained, by the presoma further in 750-900 DEG C, be sintered 1-2 hours under excess oxygen, be ground to Nano grade, obtain nickelic ternary basic material；
（3）By thiophene monomer, dispersant and nickelic ternary basic material 1.2-3 in molar ratio:0.01-0.05:20 mixing, add Enter suitable quantity of water, after ultrasonic disperse, strong oxidizer is added, polymerisation occurs, obtain nickel cobalt manganese polythiophene complex microsphere slurry；
（4）Nickel cobalt manganese polythiophene complex microsphere slurry is finally obtained into the nickelic ternary material of high compacted density by being spray-dried Material.
2. a kind of preparation method of the nickelic ternary lithium battery material of polythiophene base according to claim 1, which is characterized in that The nickel salt is nickel chloride, nickelous carbonate, nickel nitrate, nickelous bromide, one kind in nickel fluoride, the cobalt salt be cobalt chloride, cobalt carbonate, One kind in cobalt nitrate, cobalt acid sodium, cobaltous bromide, cobaltous fluoride, the manganese salt are manganese chloride, manganese carbonate, manganese nitrate, sodium manganate, bromine Change one kind in manganese, manganous fluoride, the lithium salts is lithium carbonate.
3. a kind of preparation method of the nickelic ternary lithium battery material of polythiophene base according to claim 1, which is characterized in that The high-speed stirred speed is 200-800rpm.
4. a kind of preparation method of the nickelic ternary lithium battery material of polythiophene base according to claim 1, which is characterized in that The precipitating reagent is the combination of one or more of sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide, and pH value is 10.2-12.8。
5. a kind of preparation method of the nickelic ternary lithium battery material of polythiophene base according to claim 1, which is characterized in that In the mixed solution, a concentration of 0.08-0.24mol/L of nickel salt.
6. a kind of preparation method of the nickelic ternary lithium battery material of polythiophene base according to claim 1, which is characterized in that The oxygen-enriched environment is that oxygen content is 30-50%.
7. a kind of preparation method of the nickelic ternary lithium battery material of polythiophene base according to claim 1, which is characterized in that The dispersant is the group of one or more of neopelex, sodium butylnaphthalenesulfonate and Sodium p-aminobenzene sulfonat It closes.
8. a kind of preparation method of the nickelic ternary lithium battery material of polythiophene base according to claim 1, which is characterized in that The strong oxidizer is one kind in potassium permanganate, two pyridine silver potassium permanganate, dichlorocyanobenzoquinone and ammonium ceric nitrate.
9. the nickelic ternary lithium battery material of a kind of polythiophene base that any one of claim 1-8 the methods are prepared.
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