CN108242535A - A kind of preparation method of tertiary cathode material lithium ion battery - Google Patents

A kind of preparation method of tertiary cathode material lithium ion battery Download PDF

Info

Publication number
CN108242535A
CN108242535A CN201611212395.7A CN201611212395A CN108242535A CN 108242535 A CN108242535 A CN 108242535A CN 201611212395 A CN201611212395 A CN 201611212395A CN 108242535 A CN108242535 A CN 108242535A
Authority
CN
China
Prior art keywords
lithium ion
ion battery
graphene
oxide
positive electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611212395.7A
Other languages
Chinese (zh)
Inventor
不公告发明人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Xiangzhi Electronic Technology Co Ltd
Original Assignee
Qingdao Xiangzhi Electronic Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao Xiangzhi Electronic Technology Co Ltd filed Critical Qingdao Xiangzhi Electronic Technology Co Ltd
Priority to CN201611212395.7A priority Critical patent/CN108242535A/en
Publication of CN108242535A publication Critical patent/CN108242535A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/02—Single layer graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/04—Specific amount of layers or specific thickness
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a kind of preparation methods of tertiary cathode material lithium ion battery.The preparation method of tertiary cathode material lithium ion battery, presoma wet method is co-precipitated coating technology and high temperature solid-state multi-steps sintering technology is combined, the fusing point of material is reduced using the method for addition fluxing agent simultaneously, presoma and lithium salts is made to be in the environment of a melting, accelerate the diffusion of metal ion, crystal grain is made to start growth and development at a lower temperature；Graphene is the high rate performance for being remarkably improved composite material, not only can guarantee the high-energy density of lithium ion battery prepared by positive electrode, but also can improve its power density, and reduce production cost；The lithium ion battery safety performance that this kind of electrode material is produced is high, and environmentally safe, preparation process of the present invention is simple, and raw material is easy to get, and of low cost, condition is easily-controllable, steady performance.

Description

A kind of preparation method of tertiary cathode material lithium ion battery
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of preparation side of tertiary cathode material lithium ion battery Method.
Background technology
At present, the world faces the problem of sternness such as environmental pollution, energy crisis, scarcity of resources, in order to realize sustainability The society of development must just find the secondary energy sources of pollution-free, renewable economizing type.Lithium ion battery is a kind of novel green Electrochmical power source, compared with traditional nickel-cadmium cell, lithium ion battery has voltage height, capacity height, long lifespan, energy density Greatly, the advantages that light-weight.Due to the series of advantages that it has, in portable electronic device, space technology, electronic vapour Vehicle, national defense industry etc. are many-sided to have very wide application prospect, becomes the research widely paid close attention in recent years and industrialization hot spot.
Current commercialized lithium ion anode material is mainly with LiFePO4 (LiFePO4), ternary material (nickel cobalt aluminium three First material NCM, nickel cobalt aluminium ternary material NCA) and LiMn2O4 (LiMn2O4) etc. based on, wherein lithium manganate battery cycle life Cycle life is worse under short and hot environment, and ternary material is as power battery that there are safety issues.LiFePO4 raw material Price is low, and theoretical capacity is big, has extended cycle life, and is the most promising product that lithium battery is generally acknowledged.
Polynary transiting metal nickel bores manganese composite lithium-inserting oxide LiNi1-x-yCoxAlyO2(also referred to as ternary material), with LiNiO2 And LiCoO2Structure is similar, has a-NaFeO2Layer structure, due to the synergistic effect between transition metal, the electricity of multielement ma-terial Chemical property is better than any single component oxide LiNiO2And LiCoO2；With LiCoO2It compares, the Ni-based ternary of Co and Al doping is just Pole material LiNi1-x-yCoxAlyO2With specific capacity is high, the advantages such as cheap, it is generally considered most possible replacement LiCoO2Positive electrode, therefore as current anode material for lithium-ion batteries research hot spot.Existing market high-volume uses Multielement ma-terial main specifications is 111,424 and 523 specifications.But with popularizing for digital mobile product, market is to high power capacity The demand of lithium ion battery is more and more stronger, and the capacity of existing material is all than relatively low, it is difficult to meet people to lithium ion battery High power capacity, high-energy density etc. increasingly higher demands.
Invention content
The present invention provides a kind of preparation method of tertiary cathode material lithium ion battery, the lithium ion prepared using this method Battery has preferable electric conductivity and cycle performance, has higher specific capacity and higher security performance.
To achieve these goals, the present invention provides a kind of preparation method of tertiary cathode material lithium ion battery, the party Method includes the following steps：
(1) nickel sulfate solution, cobalt sulfate solution and manganese sulfate solution are pressed into Ni：Co：Al molar ratios are 60：20：20 mixing Uniformly, NaOH is then added in into solution or KOH solution neutralizes, by the way that crystallisation is controlled to generate the hydroxide of ternary system Ni0.6Co0.2Al0.2(OH)2Precipitation, after then obtained precipitation is filtered, washed, the dry 4-8h at 100-150 DEG C；
(2) in atmosphere furnace, oxygen or air are passed through, hot place will be carried out at 300-600 DEG C in step (1) products therefrom Natural cooling after reason 10-12 hours, obtains oxide；
It (3) will be in the molar ratio of the metal cation and Li ions during oxide obtained by step (2) and lithium salts are by oxide 1:1-1.15 is mixed, and adds in fluxing agent in mixed process simultaneously, and the quality added in is lithium salts and oxide gross mass 5-10%；After abundant mixing, divide reactant to double sintering in air stream or oxygen stream, first in 700-800 DEG C of air It is sintered under the conditions of stream 6-8 hours, sintering temperature is then risen to 850-950 DEG C, then be sintered 10-12 hours in oxygen stream, burnt Furnace cooling after knot, obtains composite oxides；Obtained composite oxides are crushed, are classified, cross 300 mesh sieve, are obtained To ternary system complex oxide LiNi0.6Co0.2Al0.2O2Basis material；
(4) by graphene or graphene oxide and dispersant, solvent mixing ultrasonic disperse or mechanical agitation, graphene is formed Or graphene oxide dispersion, it adds in above-mentioned basis material to dispersion liquid, ball milling or high-speed stirred are uniformly mixed, and 100 DEG C are true Sky is 12 hours dry, under nitrogen, argon gas or hydrogen-argon-mixed protection, is heated up with 3-10 DEG C/min, 450-800 DEG C of heating 3-8 Hour, natural cooling crushed 200 mesh screens, positive electrode active materials be prepared；
(5) a certain amount of positive electrode active materials and conductive agent are weighed, and positive-active material is ground using agate mortar respectively Material, carbon nanometer cucurbit structural material and conductive agent are to uniform；
Ground positive electrode active materials and conductive agent are added in the N- methylpyrroles of Kynoar (PVDF) bonding agent It in alkanone (NMP) organic solvent, and is stirred, obtains slurry, mixing time 1h-5h；
On the collector that the slurry prepared is equably coated on cleaning and is dried, and it is dried to get to pole piece, Drying time is 5h-12h；
The stainless steel case of battery with distilled water is cleaned, is then cleaned by ultrasonic 10-30min with distilled water, then with anhydrous second Alcohol is cleaned by ultrasonic 10-30min, finally in an oven 70 DEG C -100 DEG C；
In the dry glove box full of inert gas, according to stainless steel casing, pole piece, diaphragm, lithium piece, nickel foam, no The sequence installation for steel lid of becoming rusty.Electrolyte is added dropwise in centre, and electrolyte is made fully to infiltrate pole piece and diaphragm material；
Mounted lithium ion battery is positioned over ventilation lucifugal and goes out dry 12h-24h.
Preferably, in step (4), in gained positive electrode active materials, graphene or graphene oxide, that is, individual layer or 10-20 Layer, for size between 5nm-10 μm, graphene or graphene oxide compound quantity are the mass fraction of nickel cobalt aluminium tertiary cathode material 0.5-1.5%.
Presoma wet method is co-precipitated cladding skill by the preparation method of tertiary cathode material lithium ion battery of the present invention Art and high temperature solid-state multi-steps sintering technology are combined, while the fusing point of the method reduction material using addition fluxing agent, make forerunner Body and lithium salts are in the environment of a melting, accelerate the diffusion of metal ion, crystal grain is made to start to grow at a lower temperature Development；Graphene is the high rate performance for being remarkably improved composite material, both can guarantee lithium ion battery prepared by positive electrode High-energy density, and its power density can be improved, and reduce production cost；The lithium-ion electric that this kind of electrode material is produced Pond security performance is high, and environmentally safe, preparation process of the present invention is simple, and raw material is easy to get, and of low cost, condition is easily-controllable, performance The advantages that stablizing.
Specific embodiment
Embodiment one
Nickel sulfate solution, cobalt sulfate solution and manganese sulfate solution are pressed into Ni：Co：Al molar ratios are 60：20：20 mixing are equal It is even, NaOH is then added in into solution or KOH solution neutralizes, by the way that crystallisation is controlled to generate the hydroxide of ternary system Ni0.6Co0.2Al0.2(OH)2Precipitation, after then obtained precipitation is filtered, washed, the dry 4h at 100 DEG C.
In atmosphere furnace, oxygen or air are passed through, it is naturally cold after products therefrom being carried out at 300 DEG C to heat treatment 10 hours But, oxide is obtained.
By gained oxide and lithium salts by the metal cation and the molar ratio 1 of Li ions in oxide:1 is mixed, Fluxing agent is added in mixed process simultaneously, the quality added in is the 5% of lithium salts and oxide gross mass；It, will after abundant mixing Reactant divides double sintering in air stream or oxygen stream, is sintered first under 700 DEG C of airflow conditions 6 hours, then will Sintering temperature rises to 850 DEG C, then is sintered 10 hours in oxygen stream, and furnace cooling after sintering obtains composite oxides；It will Obtained composite oxides are crushed, are classified, crossing 300 mesh sieve, obtain ternary system complex oxide LiNi0.6Co0.2Al0.2O2 Basis material.
By graphene or graphene oxide and dispersant, solvent mixing ultrasonic disperse or mechanical agitation, formed graphene or Graphene oxide dispersion is added in above-mentioned basis material to dispersion liquid, and ball milling or high-speed stirred are uniformly mixed, 100 DEG C of vacuum It is 12 hours dry, it under nitrogen, argon gas or hydrogen-argon-mixed protection, is heated up with 3 DEG C/min, 450 DEG C are heated 3 hours, naturally cold But, 200 mesh screens are crushed, positive electrode active materials are prepared.
In gained positive electrode active materials, graphene or graphene oxide, that is, individual layer or 10-20 layers, size is between 5nm-10 μ M, graphene or graphene oxide compound quantity are the 0.5% of the mass fraction of nickel cobalt aluminium ternary base anode material.
Weigh a certain amount of positive electrode active materials and conductive agent, and using agate mortar grind respectively positive electrode active materials, Carbon nanometer cucurbit structural material and conductive agent are to uniform；Ground positive electrode active materials and conductive agent are added in into Kynoar (PVDF) it in N-Methyl pyrrolidone (NMP) organic solvent of bonding agent, and is stirred, obtains slurry, mixing time 1h； On the collector that the slurry prepared is equably coated on cleaning and is dried, and it is dried to get to pole piece, drying time For 5hh；The stainless steel case of battery with distilled water is cleaned, is then cleaned by ultrasonic 10min with distilled water, then ultrasonic with absolute ethyl alcohol 10min is cleaned, finally in an oven 70 DEG C；In the dry glove box full of inert gas, according to stainless steel casing, pole piece, Diaphragm, lithium piece, nickel foam, the installation of the sequence of stainless steel cover.Electrolyte is added dropwise in centre, and electrolyte is made fully to infiltrate pole piece and diaphragm Material；Mounted lithium ion battery is positioned over ventilation lucifugal and goes out dry 12h.
Embodiment two
Nickel sulfate solution, cobalt sulfate solution and manganese sulfate solution are pressed into Ni：Co：Al molar ratios are 60：20：20 mixing are equal It is even, NaOH is then added in into solution or KOH solution neutralizes, by the way that crystallisation is controlled to generate the hydroxide of ternary system Ni0.6Co0.2Al0.2(OH)2Precipitation, after then obtained precipitation is filtered, washed, the dry 8h at 150 DEG C.
In atmosphere furnace, oxygen or air are passed through, it is naturally cold after products therefrom being carried out at 600 DEG C to heat treatment 12 hours But, oxide is obtained.
By gained oxide and lithium salts by the metal cation and the molar ratio 1 of Li ions in oxide:1.15 it is mixed It closes, adds in fluxing agent in mixed process simultaneously, the quality added in is the 10% of lithium salts and oxide gross mass；Abundant mixing Afterwards, divide reactant to double sintering in air stream or oxygen stream, be sintered 8 hours first under 800 DEG C of airflow conditions, so Sintering temperature is risen to 950 DEG C afterwards, then is sintered 12 hours in oxygen stream, furnace cooling after sintering obtains combined oxidation Object；Obtained composite oxides are crushed, are classified, cross 300 mesh sieve, obtain ternary system complex oxide LiNi0.6Co0.2Al0.2O2Basis material.
By graphene or graphene oxide and dispersant, solvent mixing ultrasonic disperse or mechanical agitation, formed graphene or Graphene oxide dispersion is added in above-mentioned basis material to dispersion liquid, and ball milling or high-speed stirred are uniformly mixed, 100 DEG C of vacuum It is 12 hours dry, it under nitrogen, argon gas or hydrogen-argon-mixed protection, is heated up with 10 DEG C/min, 800 DEG C are heated 8 hours, naturally cold But, 200 mesh screens are crushed, positive electrode active materials are prepared.
In gained positive electrode active materials, graphene or graphene oxide, that is, individual layer or 10-20 layers, size is between 5nm-10 μ M, graphene or graphene oxide compound quantity are the 1.5% of nickel cobalt aluminium ternary base anode material mass fraction.
Weigh a certain amount of positive electrode active materials and conductive agent, and using agate mortar grind respectively positive electrode active materials, Carbon nanometer cucurbit structural material and conductive agent are to uniform；Ground positive electrode active materials and conductive agent are added in into Kynoar (PVDF) it in N-Methyl pyrrolidone (NMP) organic solvent of bonding agent, and is stirred, obtains slurry, mixing time 5h； On the collector that the slurry prepared is equably coated on cleaning and is dried, and it is dried to get to pole piece, drying time For 12h；The stainless steel case of battery with distilled water is cleaned, is then cleaned by ultrasonic 30min with distilled water, then ultrasonic with absolute ethyl alcohol 30min is cleaned, finally in an oven 100 DEG C；In the dry glove box full of inert gas, according to stainless steel casing, pole piece, Diaphragm, lithium piece, nickel foam, the installation of the sequence of stainless steel cover.Electrolyte is added dropwise in centre, and electrolyte is made fully to infiltrate pole piece and diaphragm Material；Mounted lithium ion battery is positioned over ventilation lucifugal and goes out drying for 24 hours.

Claims (2)

1. a kind of preparation method of tertiary cathode material lithium ion battery, this method comprises the following steps：
(1) nickel sulfate solution, cobalt sulfate solution and manganese sulfate solution are pressed into Ni：Co：Al molar ratios are 60：20：20 are uniformly mixed, Then NaOH is added in into solution or KOH solution neutralizes, by the way that crystallisation is controlled to generate the hydroxide of ternary system Ni0.6Co0.2Al0.2(OH)2Precipitation, after then obtained precipitation is filtered, washed, the dry 4-8h at 100-150 DEG C；
(2) in atmosphere furnace, oxygen or air are passed through, will be heat-treated at 300-600 DEG C in step (1) products therefrom Natural cooling after 10-12 hours, obtains oxide；
It (3) will be in the molar ratio 1 of the metal cation and Li ions during oxide obtained by step (2) and lithium salts are by oxide:1- 1.15 are mixed, and add in fluxing agent in mixed process simultaneously, and the quality added in is lithium salts and the 5- of oxide gross mass 10%；After abundant mixing, divide reactant to double sintering in air stream or oxygen stream, first in 700-800 DEG C of air stream Under the conditions of be sintered 6-8 hours, sintering temperature is then risen to 850-950 DEG C, then be sintered 10-12 hours in oxygen stream, be sintered After furnace cooling, obtain composite oxides；Obtained composite oxides are crushed, are classified, cross 300 mesh sieve, are obtained Ternary system complex oxide LiNi0.6Co0.2Al0.2O2Basis material；
(4) by graphene or graphene oxide and dispersant, solvent mixing ultrasonic disperse or mechanical agitation, graphene or oxygen are formed Graphite alkene dispersion liquid, adds in above-mentioned basis material to dispersion liquid, and ball milling or high-speed stirred are uniformly mixed, and 100 DEG C of vacuum are done It dry 12 hours, under nitrogen, argon gas or hydrogen-argon-mixed protection, being heated up with 3-10 DEG C/min, 450-800 DEG C is heated 3-8 hours, Natural cooling crushed 200 mesh screens, positive electrode active materials be prepared；
(5) a certain amount of positive electrode active materials and conductive agent are weighed, and positive electrode active materials, carbon are ground using agate mortar respectively Nanometer cucurbit structural material and conductive agent are to uniform；
The N-Methyl pyrrolidone that ground positive electrode active materials and conductive agent are added in Kynoar bonding agent is organic molten It in agent, and is stirred, obtains slurry, mixing time 1h-5h；
It on the collector that the slurry prepared is equably coated on cleaning and is dried, and is dried to get to pole piece, dries Time is 5h-12h；
The stainless steel case of battery with distilled water is cleaned, is then cleaned by ultrasonic 10-30min, then surpassed with absolute ethyl alcohol with distilled water Sound cleans 10-30min, finally in an oven 70 DEG C -100 DEG C；
In the dry glove box full of inert gas, according to stainless steel casing, pole piece, diaphragm, lithium piece, nickel foam, stainless steel The sequence installation of lid,
Electrolyte is added dropwise in centre, and electrolyte is made fully to infiltrate pole piece and diaphragm material；
Mounted lithium ion battery is positioned over ventilation lucifugal and goes out dry 12h-24h.
2. the method as described in claim 1, which is characterized in that in step (4), in gained positive electrode active materials, graphene or Graphene oxide, that is, individual layer or 10-20 layers, for size between 5nm-10 μm, graphene or graphene oxide compound quantity are nickel cobalt aluminium The 0.5-1.5% of the mass fraction of tertiary cathode material.
CN201611212395.7A 2016-12-25 2016-12-25 A kind of preparation method of tertiary cathode material lithium ion battery Pending CN108242535A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611212395.7A CN108242535A (en) 2016-12-25 2016-12-25 A kind of preparation method of tertiary cathode material lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611212395.7A CN108242535A (en) 2016-12-25 2016-12-25 A kind of preparation method of tertiary cathode material lithium ion battery

Publications (1)

Publication Number Publication Date
CN108242535A true CN108242535A (en) 2018-07-03

Family

ID=62704481

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611212395.7A Pending CN108242535A (en) 2016-12-25 2016-12-25 A kind of preparation method of tertiary cathode material lithium ion battery

Country Status (1)

Country Link
CN (1) CN108242535A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108933261A (en) * 2018-07-17 2018-12-04 河南电池研究院有限公司 A kind of nickel cobalt lithium aluminate/grapheme composite positive electrode material preparation method of cerium dopping
CN109728261A (en) * 2018-11-30 2019-05-07 宁波容百新能源科技股份有限公司 A kind of tertiary cathode material and preparation method thereof
CN111785965A (en) * 2020-05-22 2020-10-16 浙江兴海能源科技有限公司 Nanoscale graphene material dispersing process
CN112047394A (en) * 2020-09-10 2020-12-08 江西智锂科技有限公司 Method for preparing composite manganese-based lithium battery cathode material by two-step crystallization method
CN112886084A (en) * 2021-01-13 2021-06-01 上海紫剑化工科技有限公司 Method for repairing layered oxide positive electrode material of sodium ion battery

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108933261A (en) * 2018-07-17 2018-12-04 河南电池研究院有限公司 A kind of nickel cobalt lithium aluminate/grapheme composite positive electrode material preparation method of cerium dopping
CN109728261A (en) * 2018-11-30 2019-05-07 宁波容百新能源科技股份有限公司 A kind of tertiary cathode material and preparation method thereof
CN111785965A (en) * 2020-05-22 2020-10-16 浙江兴海能源科技有限公司 Nanoscale graphene material dispersing process
CN111785965B (en) * 2020-05-22 2024-02-13 浙江兴海能源科技有限公司 Nanometer graphene material dispersing process
CN112047394A (en) * 2020-09-10 2020-12-08 江西智锂科技有限公司 Method for preparing composite manganese-based lithium battery cathode material by two-step crystallization method
CN112886084A (en) * 2021-01-13 2021-06-01 上海紫剑化工科技有限公司 Method for repairing layered oxide positive electrode material of sodium ion battery

Similar Documents

Publication Publication Date Title
Tang et al. Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2
CN103456944B (en) A kind of method of modifying of tertiary cathode material
CN108539141B (en) Preparation method of ternary layered positive electrode material for sodium-ion battery
CN101950804B (en) Method for preparing spherical SnS2 anode material of lithium ion battery
CN108242535A (en) A kind of preparation method of tertiary cathode material lithium ion battery
CN101521276A (en) Method for producing lithium ion battery positive material coated with carbon
CN103413924B (en) A kind of La 1-xca xcoO 3coated lithium ion battery LiNi 1/3co 1/3mn 1/3o 2positive electrode and preparation method thereof
CN102427129A (en) Lithium ion battery composite negative electrode material, its preparation method, negative electrode with application of material thereof and lithium ion battery
CN107579237B (en) Preparation method of ternary cathode material and ternary cathode material
CN101955175A (en) Industrial preparation method for lithium iron phosphate
CN106025208A (en) Preparation method for carbon-coated ternary positive electrode material
CN113060775B (en) Cobalt-free positive electrode material and preparation method and application thereof
CN106910887A (en) A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode
CN106654245A (en) Preparation method of cobalt-doped nano tungsten oxide negative electrode material
CN105047905A (en) Surface modification method of nickel-rich cathode material
CN109860533A (en) A kind of anode of magnesium ion battery material of compound core-shell structure and its preparation method and application
CN114203949A (en) Layered manganese-based sodium-ion battery positive electrode material, and preparation method and application thereof
CN102709548A (en) Multi-element cathode material for lithium ion battery and preparation method for multi-element cathode material
CN108923032A (en) With the ternary cathode material of lithium ion battery and preparation method of modified metal oxide
CN111204813B (en) Preparation method of vanadium-doped lithium-rich manganese-based positive electrode material
CN103000879A (en) Preparation method of spinel type lithium-nickel-manganese oxide with one-dimensional porous structure
CN105958053A (en) Preparation method for lithium ion battery from ternary positive electrode material
CN102157727B (en) Preparation method for nano MnO of negative electrode material of lithium ion battery
CN105958027B (en) A kind of manganese base composite positive pole and preparation method thereof
CN101807686A (en) Preparation method of spinel type lithium manganate with high crystallinity used in lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180703

WD01 Invention patent application deemed withdrawn after publication