CN105742606A - Preparation method for coating type nickel doped lithium-manganese-aluminum-cobalt positive electrode material - Google Patents
Preparation method for coating type nickel doped lithium-manganese-aluminum-cobalt positive electrode material Download PDFInfo
- Publication number
- CN105742606A CN105742606A CN201610230064.XA CN201610230064A CN105742606A CN 105742606 A CN105742606 A CN 105742606A CN 201610230064 A CN201610230064 A CN 201610230064A CN 105742606 A CN105742606 A CN 105742606A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- aluminum
- cobalt
- solution
- doped lithium
- 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.)
- Granted
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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method for a coating type nickel doped lithium-manganese-aluminum-cobalt positive electrode material. The chemical formula of the nickel doped lithium-manganese-aluminum-cobalt positive electrode material is LiMn<1-x-y-z>Al<x>Co<y>Ni<z>O<2-a>Fa, wherein x is 0.27-0.3, y is 0.2-0.25, z is 0.04-0.07, and a is 0.03-0.05; and the preparation method comprises the following steps of (1) preparing the nickel doped lithium-manganese-aluminum-cobalt; (2) preparing a positive electrode active material coating liquid; and (3) coating. The positive electrode material prepared by the method is relatively high in conductivity, cycling performance and specific capacity, and relatively long in service life.
Description
Art
The present invention relates to technical field of lithium batteries, be specifically related to the system of a kind of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode
Preparation Method.
Background technology
Developing rapidly of auto industry, has promoted progress and the development of the industries such as global machinery, the energy, traffic, but fuel oil
Automobile is while promoting the well-being of mankind, and exhaust emissions also causes severe contamination to human residential environment.Environmental protection and energy starved
Requirement has driven electric automobile (EV) and the development of electrokinetic cell.The subject matter that electric motor car at present exists is price, driving
The aspect such as mileage, power performance, and these problems are all closely related with battery technology, the research of battery technology and battery material is opened
Send out and its development will be played a decisive role, thus find exploitation high-energy-density, low price, safe and reliable positive electrode to dynamic
The exploitation of power power supply lithium ion battery has very important significance.
In recent years, the ternary lithium ion anode material development in lithium ion anode material is very swift and violent, due to nickel cobalt
The cooperative effect of manganese, nickel-cobalt-manganese ternary anode material for lithium-ion batteries combines LiNiO2、LiCoO2、LiMnO2Three kinds of stratiform knots
The advantage of structure material, its chemical property is better than above LiNiO2、LiCoO2、LiMnO2In any one-component positive electrode, tool
There are height ratio capacity, cost lower-security preferably can wait feature it is considered to be preferably replace LiCoO2Positive electrode.So
And such lithium-rich anode material there is also initial stage specific capacity and declines rapidly and the problem of high rate performance difference.
Summary of the invention
The present invention provides the preparation method of a kind of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode, uses the method to prepare
Positive electrode, has preferable electric conductivity and cycle performance, has higher specific capacity and longer service life.
To achieve these goals, the present invention provides the preparation side of a kind of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode
Method, the chemical formula of this nickel elements doped lithium manganese aluminum cobalt positive electrode is LiMn1-x-y-zAlxCoyNizO2-aFa, wherein x=0.27-0.3, y=
0.2-0.25, z=0.04-0.07, a=0.03-0.05, the method comprises the steps:
(1) nickel elements doped lithium manganese aluminum cobalt is prepared
By Mn: the mol ratio of Al: Co:Ni=1-x-y-z: x: y:z, manganese chloride, aluminum chloride, cobalt nitrate and nitric acid niobium are dissolved in heat
Making metallic ion mixed liquor in water, in mixed liquor, the total concentration of four metal ion species is 2-3mol/L, prepares mass fraction
For KOH solution and the ammonia spirit of 15-20% of 25-35%, being dissolved in the NaOH solution of 3-5mol/L by hydrogen peroxide, preparation contains
0.5-1mol/L H2O2NaOH solution；
With deionized water for end liquid, temperature rises to 60-70 DEG C, opens stirring, controls speed of agitator in 100-150r/min, addition
Ammonia, regulates end liquid pH value, and PH controls at 10-11, with constant flow pump by above-mentioned metallic ion mixed liquor, ammonia spirit and KOH
Solution adds in the reactor of high-speed stirred parallel, and the pH of regulation reaction solution is 12-14, and regulation temperature is 60-70 DEG C, basicity
Maintaining 25-35g/L, digestion time is 20-24h；
After to be aged, add above-mentioned containing H under conditions of stirring2O2NaOH solution, control reaction solution pH be 10-11,
Adjusting synthesis reaction temperature and be 45-60 DEG C, basicity maintains 20-30g/L, and digestion time is 10-12h, reacts after terminating through washing
Wash, at 80-90 DEG C, be dried 3-4h after sucking filtration, obtain precursor Mn1-x-y-zAlxCoyNizOOH；
By precursor Mn1-x-y-zAlxCoyNizOOH, lithium oxalate, lithium fluoride 1-a:1:a in molar ratio weigh, levigate in mortar respectively
Rear mix homogeneously, adds suitable quantity of water and ethylene glycol, continues to grind, until mixture is the cement paste of uniform and smooth；
In 120-150 DEG C, cement paste mixture is dried 10-15h, and then after 500-600 DEG C of pre-burning 6-8h, cooling is ground, then
Calcine 15-18h at 900-1000 DEG C, obtain nickel elements doped lithium manganese aluminum cobalt；
(2) positive electrode active materials covering liquid is prepared
In alcohols solvent, add phosphate compounds, obtain phosphate ester solution；
Adding aluminium salt in this phosphate ester solution, this aluminium salt is dissolved in this alcohols solvent, and reacts with this phosphate compounds
To homogeneous settled solution, reaction temperature is 40-80 DEG C, and the response time is 2-5 hour；
Adding acidity regulator and regulate the pH value of this homogeneous settled solution to 6-7, acidity regulator can be ammonia, bicarbonate
One or more in ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine, the total addition of this acidity regulator is according to N:
Al mol ratio is that 1:1-6:1 weighs and obtains this positive electrode active materials covering liquid；
(3) cladding
Described nickel elements doped lithium manganese aluminum cobalt is mixed homogeneously with this positive electrode active materials covering liquid, obtains a solidliquid mixture；And
This solidliquid mixture is dried and is sintered, and this is dried can be that room temperature dries or heating, drying naturally, as long as removing this mixing
Solvent in thing, the temperature of described heating, drying is preferably 60-100 DEG C.Described sintering is carried out in atmosphere, makes this cladding
Organic group in predecessor is removed, and generates this clad.This sintering temperature is 450-750 DEG C, and sintering time is 5-8 hour,
Obtaining anode composite material, this anode composite material includes positive electrode active materials and is coated on the bag of this surface of positive electrode active material
Coating.
Preferably, during this alcohols solvent is methanol, ethanol, propanol, n-butyl alcohol and isopropanol one or more
Double solvents, this phosphate compounds formula can be AnP(O)(OH)m, wherein A is the carbon corresponding with this alcohol solvent molecules
At least one in oxygen groups, i.e. methoxyl group, ethyoxyl, propoxyl group, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；
Phosphate compounds is 1:5-1:25 with the mass ratio of alcohols solvent.
Preferably, one or more during aluminium salt is aluminum chloride, aluminum nitrate, aluminum isopropylate. and aluctyl..This alcohol is molten
Property the total addition of aluminium salt be preferably 1:10-1:20 with alcohols solvent mass ratio.
The nickel elements doped lithium manganese aluminum cobalt composite positive pole nickel of the present invention, then with solid phase high temperature method adulterate in the material F unit
Element, to increase the activity of positive electrode.Positive electrode active materials covering liquid in the present invention is a homogeneous settled solution, can relatively hold
Change places and be respectively formed clad at ferrosilicon silicate of lithium particle surface, make each ferrosilicon silicate of lithium particle surface be wrapped by layer bag completely
Cover, improve its electric conductivity and cyclical stability further.Therefore the nickel elements doped lithium manganese aluminum cobalt that prepared by this present invention is for lithium
During ion battery, there is higher electric discharge reversible capacity and longer service life first.
Detailed description of the invention
Embodiment one
By Mn: the mol ratio of Al: Co:Ni=0.49: 0.27: 0.2:0.04, by manganese chloride, aluminum chloride, cobalt nitrate and nitric acid niobium
Being dissolved in hot water and make metallic ion mixed liquor, in mixed liquor, the total concentration of four metal ion species is 2mol/L, prepares quality
Mark is KOH solution and the ammonia spirit of 15% of 25%, is dissolved in the NaOH solution of 3mol/L by hydrogen peroxide, and preparation contains
0.5mol/L H2O2NaOH solution.
With deionized water for end liquid, temperature rises to 60 DEG C, opens stirring, controls speed of agitator at 100r/min, addition ammonia
Water, regulates end liquid pH value, and PH controls at 10-11, with constant flow pump by molten to above-mentioned metallic ion mixed liquor, ammonia spirit and KOH
Liquid adds in the reactor of high-speed stirred parallel, and the pH of regulation reaction solution is 12-14, and regulation temperature is 60 DEG C, and basicity maintains
At 25g/L, digestion time is 24h.
After to be aged, add above-mentioned containing H under conditions of stirring2O2NaOH solution, control reaction solution pH be 10-
11, adjusting synthesis reaction temperature is 45 DEG C, and basicity maintains 20g/L, and digestion time is 12h, reacts after terminating through washing, sucking filtration
After at 80 DEG C be dried 4h, obtain precursor Mn0.49Al0.27Co0.2Ni0.04OOH。
By precursor Mn0.49Al0.27Co0.2Ni0.04OOH, lithium oxalate, lithium fluoride 0.97:1:0.03 in molar ratio weighs,
Levigate rear mix homogeneously in mortar respectively, adds suitable quantity of water and ethylene glycol, continues to grind, until mixture is uniform and smooth
Cement paste；In 120 DEG C, cement paste mixture is dried 15h, and then after 500 DEG C of pre-burning 8h, cooling is ground, then at 900 DEG C
Calcining 18h, obtains product and i.e. obtains nickel elements doped lithium manganese aluminum cobalt LiMn0.49Al0.27Co0.2Ni0.04O1.97F0.03。
In alcohols solvent, add phosphate compounds, obtain phosphate ester solution.Preferably, this alcohols solvent is first
One or more double solvents in alcohol, ethanol, propanol, n-butyl alcohol and isopropanol, this phosphate compounds formula
Can be AnP(O)(OH)m, wherein A is the carbon oxygen groups corresponding with this alcohol solvent molecules, i.e. methoxyl group, ethyoxyl, the third oxygen
At least one in base, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；Phosphate compounds and alcohols solvent
Mass ratio is 1:5.
Adding aluminium salt in this phosphate ester solution, this aluminium salt is dissolved in this alcohols solvent, and anti-with this phosphate compounds
Should obtain homogeneous settled solution, reaction temperature is 40 DEG C, and the response time is 2 hours；Preferably, aluminium salt is aluminum chloride, nitric acid
One or more in aluminum, aluminum isopropylate. and aluctyl..The total addition of this alcohol-soluble aluminium salt and alcohols solvent mass ratio
It is preferably 1:10.
Adding acidity regulator and regulate the pH value of this homogeneous settled solution to 6-7, acidity regulator can be ammonia, carbon
One or more in acid hydrogen ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine, the total addition of this acidity regulator is pressed
It is that 1:1 weighs and obtains this positive electrode active materials covering liquid according to N:Al mol ratio.
Described nickel elements doped lithium manganese aluminum cobalt is mixed homogeneously with this positive electrode active materials covering liquid, obtains a solidliquid mixture；
And this solidliquid mixture is dried and sinters, this is dried can be that room temperature dries or heating, drying naturally, as long as removing this mixing
Solvent in thing, the temperature of described heating, drying is preferably 60 DEG C.Described sintering is carried out in atmosphere, makes this cladding forerunner
Organic group in thing is removed, and generates this clad.This sintering temperature is 450 DEG C, and sintering time is 5 hours, obtains positive pole multiple
Condensation material, this anode composite material includes positive electrode active materials and is coated on the clad of this surface of positive electrode active material.
Embodiment two
By Mn: the mol ratio of Al: Co:Ni=0.38: 0.3: 0.25:0.07, by manganese chloride, aluminum chloride, cobalt nitrate and nitric acid niobium
Being dissolved in hot water and make metallic ion mixed liquor, in mixed liquor, the total concentration of four metal ion species is 3mol/L, prepares quality
Mark is KOH solution and the ammonia spirit of 20% of 35%, is dissolved in the NaOH solution of 5mol/L by hydrogen peroxide, and preparation contains
1mol/L H2O2NaOH solution.
With deionized water for end liquid, temperature rises to 70 DEG C, opens stirring, controls speed of agitator at 150r/min, addition ammonia
Water, regulates end liquid pH value, and PH controls at 10-11, with constant flow pump by molten to above-mentioned metallic ion mixed liquor, ammonia spirit and KOH
Liquid adds in the reactor of high-speed stirred parallel, and the pH of regulation reaction solution is 12-14, and regulation temperature is 70 DEG C, and basicity maintains
At 35g/L, digestion time is 20h.
After to be aged, add above-mentioned containing H under conditions of stirring2O2NaOH solution, control reaction solution pH be 10-
11, adjusting synthesis reaction temperature is 60 DEG C, and basicity maintains 30g/L, and digestion time is 10h, reacts after terminating through washing, sucking filtration
After at 90 DEG C be dried 3h, obtain precursor Mn0.38Al0.3Co0.25Ni0.07OOH。
By precursor Mn0.38Al0.3Co0.25Ni0.07OOH, lithium oxalate, lithium fluoride .095:1:0.05 in molar ratio weighs, point
Levigate rear mix homogeneously in mortar, does not adds suitable quantity of water and ethylene glycol, continues to grind, until mixture is uniform and smooth
Cement paste；In 150 DEG C, cement paste mixture is dried 10h, and then after 600 DEG C of pre-burning 6h, cooling is ground, then forges at 1000 DEG C
Burn 18h, obtain nickel elements doped lithium manganese aluminum cobalt LiMn0.38Al0.3Co0.25Ni0.07O1.95F0.05。
In alcohols solvent, add phosphate compounds, obtain phosphate ester solution.This alcohols solvent is isopropanol, this phosphorus
Acid esters compound formula can be AnP(O)(OH)m, wherein A is the carbon oxygen groups corresponding with this alcohol solvent molecules, i.e. methoxy
At least one in base, ethyoxyl, propoxyl group, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；Phosphoric acid ester chemical combination
Thing is 1:25 with the mass ratio of alcohols solvent.
Adding aluminium salt in this phosphate ester solution, this aluminium salt is dissolved in this alcohols solvent, and anti-with this phosphate compounds
Should obtain homogeneous settled solution, reaction temperature is 80 DEG C, and the response time is 5 hours；Preferably, aluminium salt is aluminum chloride, nitric acid
One or more in aluminum, aluminum isopropylate. and aluctyl..The total addition of this alcohol-soluble aluminium salt and alcohols solvent mass ratio
It is preferably 1:20.
Adding acidity regulator and regulate the pH value of this homogeneous settled solution to 6-7, acidity regulator can be ammonia, carbon
One or more in acid hydrogen ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine, the total addition of this acidity regulator is pressed
It is that 6:1 weighs and obtains this positive electrode active materials covering liquid according to N:Al mol ratio.
Described nickel elements doped lithium manganese aluminum cobalt is mixed homogeneously with this positive electrode active materials covering liquid, obtains a solidliquid mixture；
And this solidliquid mixture is dried and sinters, this is dried can be that room temperature dries or heating, drying naturally, as long as removing this mixing
Solvent in thing, the temperature of described heating, drying is preferably 100 DEG C.Described sintering is carried out in atmosphere, before making this cladding
Drive the organic group in thing to remove, generate this clad.This sintering temperature is 750 DEG C, and sintering time is 8 hours, obtains positive pole
Composite, this anode composite material includes positive electrode active materials and is coated on the clad of this surface of positive electrode active material.
Comparative example
With Quilonorm (SKB), manganese acetate, cobalt acetate and oxalic acid for initiation material, by 0.3270g manganese acetate, 4.4836g cobalt acetate,
2.5305g Quilonorm (SKB) is dissolved in dehydrated alcohol, obtains the metal salt solution of ethanol；Again by the oxalic acid than stoichiometric proportion excess 20%
4.8021g be dissolved in dehydrated alcohol；The ethanol solution of oxalic acid is added in the metal salt solution of ethanol, after stirring 1h sucking filtration and in
It is ground into powder after 100 DEG C of dry 3h and loads crucible；It is warmed up to 900 DEG C with the programming rate of 4 DEG C/min in batch-type furnace
Lower heating 12h, and anneal at room temperature, i.e. can get Li1.033Mn0.067Co0.9O2Powder body material.
Above-described embodiment one, two and comparative example products therefrom are used NMP as solvent, by active substance: SP: PVDF
Be configured to slurry that solid content be 70% at=90: 5: 5 is evenly applied on Al paper tinsel, makes positive pole.Negative pole selects diameter 14mm's
Metal lithium sheet, 1mol LiFP6 (EC:DMC:EMC=1:1:1, v/v) selected by electrolyte, with negative electrode casing shell fragment pad lithium
Battery is packaged by the order of sheet electrolyte barrier film positive plate pad anode cover, and whole process is all being filled with argon
The glove box of gas completes.It is at 25 DEG C, to carry out electric performance test, the after tested material of this embodiment one and two in test temperature
Compared with the product of comparative example, first charge-discharge reversible capacity improves 32-35%, brings up to more than 45% service life.
Claims (3)
1. a preparation method for cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode, the change of this nickel elements doped lithium manganese aluminum cobalt positive electrode
Formula is LiMn1-x-y-zAlxCoyNizO2-aFa, wherein x=0.27-0.3, y=0.2-0.25, z=0.04-0.07, a=0.03-
0.05, the method comprises the steps:
(1) nickel elements doped lithium manganese aluminum cobalt is prepared
By Mn: the mol ratio of Al: Co:Ni=1-x-y-z: x: y:z, manganese chloride, aluminum chloride, cobalt nitrate and nitric acid niobium are dissolved in heat
Making metallic ion mixed liquor in water, in mixed liquor, the total concentration of four metal ion species is 2-3mol/L, prepares mass fraction
For KOH solution and the ammonia spirit of 15-20% of 25-35%, being dissolved in the NaOH solution of 3-5mol/L by hydrogen peroxide, preparation contains
0.5-1mol/L H2O2NaOH solution；
With deionized water for end liquid, temperature rises to 60-70 DEG C, opens stirring, controls speed of agitator in 100-150r/min, addition
Ammonia, regulates end liquid pH value, and PH controls at 10-11, with constant flow pump by above-mentioned metallic ion mixed liquor, ammonia spirit and KOH
Solution adds in the reactor of high-speed stirred parallel, and the pH of regulation reaction solution is 12-14, and regulation temperature is 60-70 DEG C, basicity
Maintaining 25-35g/L, digestion time is 20-24h；
After to be aged, add above-mentioned containing H under conditions of stirring2O2NaOH solution, control reaction solution pH be 10-11, adjust
Being integrated into reaction temperature and be 45-60 DEG C, basicity maintains 20-30g/L, and digestion time is 10-12h, reaction terminate after through washing,
At 80-90 DEG C, it is dried 3-4h after sucking filtration, obtains precursor Mn1-x-y-zAlxCoyNizOOH；
By precursor Mn1-x-y-zAlxCoyNizOOH, lithium oxalate, lithium fluoride 1-a:1:a in molar ratio weighs, and grinds respectively in mortar
Mix homogeneously after thin, adds suitable quantity of water and ethylene glycol, continues to grind, until mixture is the cement paste of uniform and smooth；
In 120-150 DEG C, cement paste mixture is dried 10-15h, and then after 500-600 DEG C of pre-burning 6-8h, cooling is ground, then
Calcine 15-18h at 900-1000 DEG C, obtain nickel elements doped lithium manganese aluminum cobalt；
(2) positive electrode active materials covering liquid is prepared
In alcohols solvent, add phosphate compounds, obtain phosphate ester solution；
Adding aluminium salt in this phosphate ester solution, this aluminium salt is dissolved in this alcohols solvent, and reacts with this phosphate compounds
To homogeneous settled solution, reaction temperature is 40-80 DEG C, and the response time is 2-5 hour；
Adding acidity regulator and regulate the pH value of this homogeneous settled solution to 6-7, acidity regulator can be ammonia, bicarbonate
One or more in ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine, the total addition of this acidity regulator is according to N:
Al mol ratio is that 1:1-6:1 weighs and obtains this positive electrode active materials covering liquid；
(3) cladding
Described nickel elements doped lithium manganese aluminum cobalt is mixed homogeneously with this positive electrode active materials covering liquid, obtains a solidliquid mixture；And
This solidliquid mixture is dried and is sintered, and this is dried can be that room temperature dries or heating, drying naturally, as long as removing in this mixture
Solvent, the temperature of described heating, drying is preferably 60-100 DEG C;Described sintering is carried out in atmosphere, makes this cladding forerunner
Organic group in thing is removed, and generates this clad;This sintering temperature is 450-750 DEG C, and sintering time is 5-8 hour, obtains
Anode composite material, this anode composite material includes positive electrode active materials and is coated on the cladding of this surface of positive electrode active material
Layer.
2. the method for claim 1, it is characterised in that this alcohols solvent is methanol, ethanol, propanol, n-butyl alcohol and different
One or more double solvents in propanol, this phosphate compounds formula can be AnP(O)(OH)m, wherein A is
In the carbon oxygen groups corresponding with this alcohol solvent molecules, i.e. methoxyl group, ethyoxyl, propoxyl group, butoxy and isopropoxy extremely
Few one, n=1-3, m=0-2, m+n=3；Phosphate compounds is 1:5-1:25 with the mass ratio of alcohols solvent.
3. method as claimed in claim 2, it is characterised in that aluminium salt is in aluminum chloride, aluminum nitrate, aluminum isopropylate. and aluctyl.
One or more, the total addition of this alcohol-soluble aluminium salt and alcohols solvent mass ratio are preferably 1:10-1:20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610230064.XA CN105742606B (en) | 2016-04-13 | 2016-04-13 | A kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610230064.XA CN105742606B (en) | 2016-04-13 | 2016-04-13 | A kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105742606A true CN105742606A (en) | 2016-07-06 |
| CN105742606B CN105742606B (en) | 2019-08-27 |
Family
ID=56254276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610230064.XA Active CN105742606B (en) | 2016-04-13 | 2016-04-13 | A kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105742606B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532038A (en) * | 2017-01-18 | 2017-03-22 | 宁波金和锂电材料有限公司 | Lithium nickel and cobalt aluminate anode material and preparation method and lithium ion battery thereof |
| CN106972165A (en) * | 2017-05-16 | 2017-07-21 | 苏州思创源博电子科技有限公司 | A kind of preparation method of cladded type lithium manganese aluminum cobalt positive electrode |
| CN107170973A (en) * | 2017-05-23 | 2017-09-15 | 苏州思创源博电子科技有限公司 | A kind of tungsten coats the preparation method of lithium manganese aluminum cobalt positive electrode |
| CN114744188A (en) * | 2022-06-13 | 2022-07-12 | 河南科隆新能源股份有限公司 | Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102447105A (en) * | 2010-10-14 | 2012-05-09 | 清华大学 | Lithium nickel oxide composite material and preparation method thereof and lithium ion battery |
| CN102956895A (en) * | 2012-11-15 | 2013-03-06 | 北大先行科技产业有限公司 | Surface composite coated anode material, preparation method thereof and lithium ion battery |
| CN103326015A (en) * | 2013-06-25 | 2013-09-25 | 蒋涛 | Preparation method of niobium-doped lithium manganese aluminum cobalt composite positive pole material |
-
2016
- 2016-04-13 CN CN201610230064.XA patent/CN105742606B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102447105A (en) * | 2010-10-14 | 2012-05-09 | 清华大学 | Lithium nickel oxide composite material and preparation method thereof and lithium ion battery |
| CN102956895A (en) * | 2012-11-15 | 2013-03-06 | 北大先行科技产业有限公司 | Surface composite coated anode material, preparation method thereof and lithium ion battery |
| CN103326015A (en) * | 2013-06-25 | 2013-09-25 | 蒋涛 | Preparation method of niobium-doped lithium manganese aluminum cobalt composite positive pole material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532038A (en) * | 2017-01-18 | 2017-03-22 | 宁波金和锂电材料有限公司 | Lithium nickel and cobalt aluminate anode material and preparation method and lithium ion battery thereof |
| CN106972165A (en) * | 2017-05-16 | 2017-07-21 | 苏州思创源博电子科技有限公司 | A kind of preparation method of cladded type lithium manganese aluminum cobalt positive electrode |
| CN107170973A (en) * | 2017-05-23 | 2017-09-15 | 苏州思创源博电子科技有限公司 | A kind of tungsten coats the preparation method of lithium manganese aluminum cobalt positive electrode |
| CN114744188A (en) * | 2022-06-13 | 2022-07-12 | 河南科隆新能源股份有限公司 | Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105742606B (en) | 2019-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742605B (en) | A kind of preparation method of cladded type lithium manganate composite anode material | |
| CN101350405B (en) | Positive electrode active materials for lithium secondary battery, method for preparing the same and lithium secondary battery | |
| CN105895872B (en) | A kind of preparation method of cladded type ferrosilicon silicate of lithium composite material | |
| CN105742606B (en) | A kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode | |
| CN103956477A (en) | Preparation method of cathode material of lithium-rich ternary compound lithium ion battery | |
| CN105024067B (en) | Lithium ion battery, composite doped modified positive active material thereof and preparation method | |
| CN106784726B (en) | Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof | |
| CN103682290B (en) | Modified material for lithium-rich manganese-based positive electrode of lithium ion battery | |
| CN105720256B (en) | A kind of preparation method of lithium iron phosphate positive material | |
| CN105958052A (en) | Preparation method of metal element doped manganese-based lithium ion battery positive electrode material | |
| CN105680018A (en) | Ternary positive electrode material and preparation method therefor and lithium ion battery | |
| CN105655573A (en) | General preparing method for manganese-based lithium-ion battery electrode material of one-dimensional micro-nano structure with adjustable length-diameter ratio | |
| CN105932248A (en) | Modified lithium ion battery lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN105470454A (en) | Modified lithium ion battery positive electrode material and preparation method therefor | |
| CN107394164A (en) | Tertiary cathode material and preparation method thereof | |
| CN104900857A (en) | Preparation method of trace Mo-doped lamellar lithium-enriched ternary positive electrode material | |
| CN104393260A (en) | Preparation method of silicate coated material rich in lithium and manganese | |
| CN103435104A (en) | Preparation method for lithium ion battery negative electrode material-nano zinc ferrite | |
| CN102479944B (en) | Preparation method and application of lithium iron phosphate composite material | |
| CN103326015B (en) | Preparation method of niobium-doped lithium manganese aluminum cobalt composite positive pole material | |
| CN108358249B (en) | A kind of preparation method of anode material for lithium-ion batteries nickel molybdate | |
| CN110120503B (en) | Composite cathode material and preparation method and application thereof | |
| CN104009221B (en) | Method for preparing positive electrode material rich in lithium via sol-gel self-propagating combustion method | |
| CN102938457B (en) | The preparation method of the coated lithium-rich manganese-based layered cathode material of a kind of NAF | |
| CN105720257A (en) | Preparation method for lithium cobalt oxide positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220614 Address after: No.568, Section 2, Tengfei Road, Wangcheng economic and Technological Development Zone, Changsha, Hunan 410000 Patentee after: HUNAN MT NEW MATERIAL TECHNOLOGY CO.,LTD. Address before: 312500 7, Da Gu Nian Cun, mirror ridge town, Xinchang County, Shaoxing, Zhejiang. Patentee before: Yang Zhongying |