CN105742606B - A kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode - Google Patents
A kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode Download PDFInfo
- Publication number
- CN105742606B CN105742606B CN201610230064.XA CN201610230064A CN105742606B CN 105742606 B CN105742606 B CN 105742606B CN 201610230064 A CN201610230064 A CN 201610230064A CN 105742606 B CN105742606 B CN 105742606B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- lithium manganese
- doped lithium
- solution
- elements doped
- 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.)
- Active
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
Abstract
The present invention relates to a kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode, the chemical formula of the 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, this method comprises the following steps: (1) preparing nickel elements doped lithium manganese aluminum cobalt.(2) positive electrode active materials covering liquid is prepared.(3) it coats.The positive electrode of method preparation, has preferable electric conductivity and cycle performance, specific capacity with higher and longer service life.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of system of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode
Preparation Method.
Background technique
The rapid development of auto industry has pushed the progress and development of the industries such as global machinery, the energy, traffic, but fuel oil
For automobile while promoting the well-being of mankind, exhaust emissions also causes serious pollution to human residential environment.Environmental protection and energy shortage
It is required that having driven the development of electric car (EV) and power battery.Main problem existing for electric vehicle is price, driving at present
Mileage, power performance etc., and these problems are all closely related with battery technology, the research of battery technology and battery material is opened
Hair, which will develop it, to play a decisive role, thus finds exploitation high-energy-density, cheap, 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 synergistic effect of manganese, nickel-cobalt-manganese ternary anode material for lithium-ion batteries combine LiNiO2、LiCoO2、LiMnO2Three kinds of stratiform knots
The advantages of structure material, chemical property are better than the above LiNiO2、LiCoO2、LiMnO2In any one-component positive electrode, tool
There is the features such as height ratio capacity, cost is relatively low security performance are preferable, it is considered to be preferably substitution LiCoO2Positive electrode.So
And there is also initial stage specific capacities to decline rapid and high rate performance difference problem for such lithium-rich anode material.
Summary of the invention
The present invention provides a kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode, is prepared using this method
Positive electrode has preferable electric conductivity and cycle performance, specific capacity with higher and longer service life.
To achieve the goals above, the present invention provides a kind of preparation side of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode
Method, the chemical formula of the nickel elements doped lithium manganese aluminum cobalt positive electrode are 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, this method comprises the following steps:
(1) nickel elements doped lithium manganese aluminum cobalt is prepared
It is by Mn: Al: Co:Ni=1-x-y-z: x: y:z molar ratio, manganese chloride, aluminium chloride, cobalt nitrate and nitric acid niobium is molten
Metallic ion mixed liquor is made in hot water, the total concentration of four metal ion species is 2-3mol/L in mixed liquor, prepares quality
Score is the KOH solution of 25-35% and the ammonia spirit of 15-20%, and hydrogen peroxide is dissolved in the NaOH solution of 3-5mol/L, is matched
Make H containing 0.5-1mol/L2O2NaOH solution；
Using deionized water as bottom liquid, temperature rises to 60-70 DEG C, opens stirring, control speed of agitator in 100-150r/min,
Ammonium hydroxide is added, adjusts bottom liquid pH value, PH control in 10-11, with constant flow pump by above-mentioned metallic ion mixed liquor, ammonia spirit and
KOH solution is added parallel in the reaction kettle of high-speed stirred, and the pH for adjusting reaction solution is 12-14, and adjusting temperature is 60-70 DEG C,
Basicity maintains 25-35g/L, digestion time 20-24h；
After to be aged, it is added under stirring conditions above-mentioned containing H2O2NaOH solution, control reaction solution pH be 10-
11, adjustment synthesis reaction temperature is 45-60 DEG C, and basicity maintains 20-30g/L, and digestion time 10-12h is passed through after reaction
Washing dries 3-4h after filtering at 80-90 DEG C, obtains precursor Mn1-x-y-zAlxCoyNizOOH；
By precursor Mn1-x-y-zAlxCoyNizOOH, lithium oxalate, 1-a:1:a is weighed lithium fluoride in molar ratio, respectively in mortar
It is uniformly mixed after levigate, adds suitable quantity of water and ethylene glycol, continue to grind, until mixture is in the cement paste of uniform and smooth；
By cement paste mixture in 120-150 DEG C of baking 10-15h, the then cooling grinding after 500-600 DEG C of pre-burning 6-8h,
15-18h is calcined at 900-1000 DEG C again, obtains nickel elements doped lithium manganese aluminum cobalt；
(2) positive electrode active materials covering liquid is prepared
Phosphate compounds are added in alcohols solvent, obtain phosphate ester solution；
Aluminium salt is added in the phosphate ester solution, which is dissolved in the alcohols solvent, and anti-with the phosphate compounds
Homogeneous clear solution should be obtained, reaction temperature is 40-80 DEG C, and the reaction time is 2-5 hours；
Addition acidity regulator adjusts the pH value of the homogeneous clear solution to 6-7, and acidity regulator can be ammonium hydroxide, carbon
One of sour hydrogen ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine or more than one, the total additional amount of the acidity regulator is pressed
It is that 1:1-6:1 weighs to obtain the positive electrode active materials covering liquid according to N:Al molar ratio；
(3) it coats
The nickel elements doped lithium manganese aluminum cobalt is uniformly mixed with the positive electrode active materials covering liquid, obtains a solidliquid mixture；
And
It by solidliquid mixture drying and is sintered, which can be room temperature naturally dry or heating, drying, as long as removal should
Solvent in mixture, the temperature of the heating, drying are preferably 60-100 DEG C.The sintering carries out in air, makes this
The organic group removal in predecessor is coated, the clad is generated.The sintering temperature is 450-750 DEG C, and sintering time is that 5-8 is small
When, anode composite material is obtained, which includes positive electrode active materials and be coated on the surface of positive electrode active material
Clad.
Preferably, the alcohols solvent be one of methanol, ethyl alcohol, propyl alcohol, n-butanol and isopropanol or more than one
Double solvents, the phosphate compounds general formula can be AnP(O)(OH)m, wherein A is carbon corresponding with the alcohol solvent molecules
At least one of oxygen groups, i.e. methoxyl group, ethyoxyl, propoxyl group, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；
The mass ratio of phosphate compounds and alcohols solvent is 1:5-1:25.
Preferably, aluminium salt be one of aluminium chloride, aluminum nitrate, aluminium isopropoxide and aluctyl or more than one.The alcohol is molten
Property the total additional amount of aluminium salt and alcohols solvent mass ratio be preferably 1:10-1:20.
Then nickel elements doped lithium manganese aluminum cobalt composite positive pole nickel of the invention adulterates F member with solid phase high temperature method in the material
Element, to increase the activity of positive electrode.Positive electrode active materials covering liquid in the present invention is a homogeneous clear solution, can relatively be held
It changes places and is respectively formed clad in ferrosilicon silicate of lithium particle surface, each ferrosilicon silicate of lithium particle surface is made to be wrapped by layer packet completely
It covers, further increases its electric conductivity and cyclical stability.Therefore the nickel elements doped lithium manganese aluminum cobalt prepared by the present invention is being used for lithium
When ion battery, reversible capacity and the longer service life with higher of discharging for the first time.
Specific embodiment
Embodiment one
By Mn: Al: Co:Ni=0.49: 0.27: 0.2:0.04 molar ratio, by manganese chloride, aluminium chloride, cobalt nitrate and nitre
Sour niobium, which is dissolved in hot water, is made metallic ion mixed liquor, and the total concentration of four metal ion species is 2mol/L in mixed liquor, prepares
Mass fraction is 25% KOH solution and 15% ammonia spirit, hydrogen peroxide is dissolved in the NaOH solution of 3mol/L, preparation contains
0.5mol/L H2O2NaOH solution.
Using deionized water as bottom liquid, temperature rises to 60 DEG C, opens stirring, and ammonia is added in 100r/min in control speed of agitator
Water, adjusts bottom liquid pH value, and PH control is molten by above-mentioned metallic ion mixed liquor, ammonia spirit and KOH with constant flow pump in 10-11
Liquid is added parallel in the reaction kettle of high-speed stirred, and the pH for adjusting reaction solution is 12-14, and adjusting temperature is 60 DEG C, and basicity maintains
In 25g/L, digestion time is for 24 hours.
After to be aged, it is added under stirring conditions above-mentioned containing H2O2NaOH solution, control reaction solution pH be 10-
11, adjustment synthesis reaction temperature is 45 DEG C, and basicity maintains 20g/L, digestion time 12h, washed after reaction, suction filtration
The dry 4h at 80 DEG C afterwards, obtains precursor Mn0.49Al0.27Co0.2Ni0.04OOH。
By precursor Mn0.49Al0.27Co0.2Ni0.040.97:1:0.03 is weighed in molar ratio for OOH, lithium oxalate, lithium fluoride,
It is levigate rear uniformly mixed in mortar respectively, suitable quantity of water and ethylene glycol are added, continues to grind, until mixture is in uniform and smooth
Cement paste；By cement paste mixture in 120 DEG C of baking 15h, the then cooling grinding after 500 DEG C of pre-burning 8h, then at 900 DEG C
18h is calcined, obtains product up to nickel elements doped lithium manganese aluminum cobalt LiMn0.49Al0.27Co0.2Ni0.04O1.97F0.03。
Phosphate compounds are added in alcohols solvent, obtain phosphate ester solution.Preferably, which is first
One of alcohol, ethyl alcohol, propyl alcohol, n-butanol and isopropanol or more than one double solvents, the phosphate compounds general formula
It can be AnP(O)(OH)m, wherein A is carbon oxygen groups corresponding with the alcohol solvent molecules, i.e. methoxyl group, ethyoxyl, the third oxygen
At least one of base, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；Phosphate compounds and alcohols solvent
Mass ratio is 1:5.
Aluminium salt is added in the phosphate ester solution, which is dissolved in the alcohols solvent, and anti-with the phosphate compounds
Homogeneous clear solution should be obtained, reaction temperature is 40 DEG C, and the reaction time is 2 hours；Preferably, aluminium salt is aluminium chloride, nitric acid
One of aluminium, aluminium isopropoxide and aluctyl or more than one.The total additional amount of the alcohol-soluble aluminium salt and alcohols solvent mass ratio
Preferably 1:10.
Addition acidity regulator adjusts the pH value of the homogeneous clear solution to 6-7, and acidity regulator can be ammonium hydroxide, carbon
One of sour hydrogen ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine or more than one, the total additional amount of the acidity regulator is pressed
It is that 1:1 weighs to obtain the positive electrode active materials covering liquid according to N:Al molar ratio.
The nickel elements doped lithium manganese aluminum cobalt is uniformly mixed with the positive electrode active materials covering liquid, obtains a solidliquid mixture；
And by solidliquid mixture drying and be sintered, which can be room temperature naturally dry or heating, drying, as long as removing the mixing
Solvent in object, the temperature of the heating, drying are preferably 60 DEG C.The sintering carries out in air, makes cladding forerunner
Organic group removal in object, generates the clad.The sintering temperature is 450 DEG C, and sintering time is 5 hours, and it is multiple to obtain anode
Condensation material, the anode composite material include positive electrode active materials and the clad for being coated on the surface of positive electrode active material.
Embodiment two
By Mn: Al: Co:Ni=0.38: 0.3: 0.25:0.07 molar ratio, by manganese chloride, aluminium chloride, cobalt nitrate and nitre
Sour niobium, which is dissolved in hot water, is made metallic ion mixed liquor, and the total concentration of four metal ion species is 3mol/L in mixed liquor, prepares
Mass fraction is 35% KOH solution and 20% ammonia spirit, hydrogen peroxide is dissolved in the NaOH solution of 5mol/L, preparation contains
1mol/L H2O2NaOH solution.
Using deionized water as bottom liquid, temperature rises to 70 DEG C, opens stirring, and ammonia is added in 150r/min in control speed of agitator
Water, adjusts bottom liquid pH value, and PH control is molten by above-mentioned metallic ion mixed liquor, ammonia spirit and KOH with constant flow pump in 10-11
Liquid is added parallel in the reaction kettle of high-speed stirred, and the pH for adjusting reaction solution is 12-14, and adjusting temperature is 70 DEG C, and basicity maintains
In 35g/L, digestion time 20h.
After to be aged, it is added under stirring conditions above-mentioned containing H2O2NaOH solution, control reaction solution pH be 10-
11, adjustment synthesis reaction temperature is 60 DEG C, and basicity maintains 30g/L, digestion time 10h, washed after reaction, suction filtration
The dry 3h at 90 DEG C afterwards, obtains precursor Mn0.38Al0.3Co0.25Ni0.07OOH。
By precursor Mn0.38Al0.3Co0.25Ni0.07.095:1:0.05 is weighed in molar ratio for OOH, lithium oxalate, lithium fluoride, point
It is levigate rear uniformly mixed not in mortar, suitable quantity of water and ethylene glycol are added, continues to grind, until mixture is in uniform and smooth
Cement paste；By cement paste mixture in 150 DEG C of baking 10h, the then cooling grinding after 600 DEG C of pre-burning 6h, then forged at 1000 DEG C
18h is burnt, to get nickel elements doped lithium manganese aluminum cobalt LiMn0.38Al0.3Co0.25Ni0.07O1.95F0.05。
Phosphate compounds are added in alcohols solvent, obtain phosphate ester solution.The alcohols solvent is isopropanol, the phosphorus
Acid esters compound general formula can be AnP(O)(OH)m, wherein A is carbon oxygen groups corresponding with the alcohol solvent molecules, i.e. methoxy
At least one of base, ethyoxyl, propoxyl group, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；Phosphoric acid ester chemical combination
The mass ratio of object and alcohols solvent is 1:25.
Aluminium salt is added in the phosphate ester solution, which is dissolved in the alcohols solvent, and anti-with the phosphate compounds
Homogeneous clear solution should be obtained, reaction temperature is 80 DEG C, and the reaction time is 5 hours；Preferably, aluminium salt is aluminium chloride, nitric acid
One of aluminium, aluminium isopropoxide and aluctyl or more than one.The total additional amount of the alcohol-soluble aluminium salt and alcohols solvent mass ratio
Preferably 1:20.
Addition acidity regulator adjusts the pH value of the homogeneous clear solution to 6-7, and acidity regulator can be ammonium hydroxide, carbon
One of sour hydrogen ammonium, ammonium carbonate, ammonium acetate, pyridine and triethylamine or more than one, the total additional amount of the acidity regulator is pressed
It is that 6:1 weighs to obtain the positive electrode active materials covering liquid according to N:Al molar ratio.
The nickel elements doped lithium manganese aluminum cobalt is uniformly mixed with the positive electrode active materials covering liquid, obtains a solidliquid mixture；
And by solidliquid mixture drying and be sintered, which can be room temperature naturally dry or heating, drying, as long as removing the mixing
Solvent in object, the temperature of the heating, drying are preferably 100 DEG C.The sintering carries out in air, before making the cladding
The organic group removal in object is driven, the clad is generated.The sintering temperature is 750 DEG C, and sintering time is 8 hours, obtains anode
Composite material, the anode composite material include positive electrode active materials and the clad for being coated on the surface of positive electrode active material.
Comparative example
With lithium acetate, manganese acetate, cobalt acetate and oxalic acid are starting material, by 0.3270g manganese acetate, 4.4836g cobalt acetate,
2.5305g lithium acetate is dissolved in dehydrated alcohol, obtains the metal salt solution of ethyl alcohol；Again by the oxalic acid more excessive by 20% than stoichiometric ratio
4.8021g being dissolved in dehydrated alcohol；Will oxalic acid ethanol solution be added ethyl alcohol metal salt solution in, stir 1h after filter and in
It is ground into powder after 100 DEG C of dry 3h and is packed into crucible；In being warming up to 900 DEG C in batch-type furnace with the heating rate of 4 DEG C/min
Lower heating 12h, and anneal at room temperature, Li can be obtained1.033Mn0.067Co0.9O2Powder body material.
Using above-described embodiment one, two and comparative example products therefrom using NMP as solvent, by active material: SP: PVDF
Be configured to slurry that solid content be 70% at=90: 5: 5 is evenly applied on Al foil, and anode is made.Cathode selects diameter 14mm's
Metal lithium sheet, electrolyte selects 1mol LiFP6 (EC:DMC:EMC=1:1:1, v/v), with negative electrode casing-elastic slice-gasket-lithium
Battery is packaged by piece-electrolyte-diaphragm-positive plate-gasket-anode cover sequence, and whole process is all filled with argon
It is completed in the glove box of gas.Electric performance test is carried out at being 25 DEG C in test temperature, after tested the material of the embodiment one and two
Compared with the product of comparative example, first charge-discharge reversible capacity improves 32-35%, and service life is increased to 45% or more.
Claims (1)
1. a kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode, the nickel elements doped lithium manganese aluminum cobalt positive electrode
Chemical 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, described method includes following steps:
(1) nickel elements doped lithium manganese aluminum cobalt is prepared
By Mn: Al: Co:Ni=1-x-y-z: x: y:z molar ratio, manganese chloride, aluminium chloride, cobalt nitrate and nickel nitrate are dissolved in heat
Metallic ion mixed liquor is made in water, the total concentration of four metal ion species is 2-3mol/L in mixed liquor, prepares mass fraction
For the KOH solution of 25-35% and the ammonia spirit of 15-20%, hydrogen peroxide is dissolved in the NaOH solution of 3-5mol/L, preparation contains
0.5-1mol/L H2O2NaOH solution；
Using deionized water as bottom liquid, temperature rises to 60-70 DEG C, opens stirring, and control speed of agitator is added in 100-150r/min
Ammonium hydroxide adjusts bottom liquid pH value, and PH control is in 10-11, with constant flow pump by above-mentioned metallic ion mixed liquor, ammonia spirit and KOH
Solution is added parallel in the reaction kettle of high-speed stirred, and the pH for adjusting reaction solution is 12-14, and adjusting temperature is 60-70 DEG C, basicity
Maintain 25-35g/L, digestion time 20-24h；
After to be aged, it is added contains H under stirring conditions2O2NaOH solution, control reaction solution pH be 10-11, adjustment close
It is 45-60 DEG C at reaction temperature, basicity maintains 20-30g/L, digestion time 10-12h, washed after reaction, suction filtration
The dry 3-4h at 80-90 DEG C afterwards, obtains precursor Mn1-x-y-zAlxCoyNizOOH；
By precursor Mn1-x-y-zAlxCoyNiz1-a:1:a is weighed in molar ratio for OOH, lithium oxalate, lithium fluoride, is ground in mortar respectively
It is uniformly mixed after thin, adds suitable quantity of water and ethylene glycol, continue to grind, until mixture is in the cement paste of uniform and smooth；
By cement paste mixture in 120-150 DEG C of baking 10-15h, the then cooling grinding after 500-600 DEG C of pre-burning 6-8h, then
15-18h is calcined at 900-1000 DEG C, obtains nickel elements doped lithium manganese aluminum cobalt；
(2) positive electrode active materials covering liquid is prepared
Phosphate compounds are added in alcohols solvent, obtain phosphate ester solution；
Be added aluminium salt in the phosphate ester solution, the aluminium salt is dissolved in the alcohols solvent, and with the phosphoric acid ester chemical combination
Object reacts to obtain homogeneous clear solution, and reaction temperature is 40-80 DEG C, and the reaction time is 2-5 hours；
Addition acidity regulator adjusts the pH value of homogeneous clear solution to 6-7, and acidity regulator is ammonium hydroxide, ammonium hydrogen carbonate, carbon
One or more of sour ammonium, ammonium acetate, pyridine and triethylamine, the total additional amount of the acidity regulator are according to N:Al molar ratio
1:1-6:1 weighs to obtain the positive electrode active materials covering liquid；
(3) it coats
The nickel elements doped lithium manganese aluminum cobalt is uniformly mixed with the positive electrode active materials covering liquid, obtains a solidliquid mixture；With
And
It by the solidliquid mixture drying and is sintered, the drying can be room temperature naturally dry or heating, drying, as long as removal institute
The solvent in mixture is stated, the temperature of the heating, drying is 60-100 DEG C, and the sintering carries out in air, makes to coat
Organic group removal in predecessor generates clad, and the sintering temperature is 450-750 DEG C, and sintering time is 5-8 hours,
Obtain anode composite material, the anode composite material includes positive electrode active materials and is coated on the surface of positive electrode active material
Clad；
The alcohols solvent is the solvent of one or more of methanol, ethyl alcohol, propyl alcohol, n-butanol and isopropanol, the phosphate
Class compound formula is AnP(O)(OH)m, wherein A is carbon oxygen groups corresponding with the alcohol solvent molecules, i.e. methoxyl group, second
At least one of oxygroup, propoxyl group, butoxy and isopropoxy, n=1-3, m=0-2, m+n=3；Phosphate compounds and alcohol
The mass ratio of class solvent is 1:5-1:25；
Aluminium salt is one or more of aluminium chloride, aluminum nitrate, aluminium isopropoxide and aluctyl, the total additional amount of aluminium salt and alcohols solvent
Mass ratio is 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 CN105742606A (en) | 2016-07-06 |
| CN105742606B true 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) |
Families Citing this family (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 |
| CN114744188B (en) * | 2022-06-13 | 2022-09-09 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105742606A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742605B (en) | A kind of preparation method of cladded type lithium manganate composite anode material | |
| CN102005563B (en) | Lithium ion battery high-voltage anode material preparation and surface coating method | |
| CN103413931B (en) | Boron doped lithium-enriched cathodic material of lithium ion battery and preparation method thereof | |
| CN101350405B (en) | Positive electrode active materials for lithium secondary battery, method for preparing the same and lithium secondary battery | |
| CN105742606B (en) | A kind of preparation method of cladded type nickel elements doped lithium manganese aluminum cobalt positive electrode | |
| CN105895872B (en) | A kind of preparation method of cladded type ferrosilicon silicate of lithium composite material | |
| CN106450282A (en) | Large monocrystal lithium nickel manganate anode material and preparation method thereof | |
| CN103682322B (en) | A kind of rich lithium Fe-Mn base lithium ion cell positive material and preparation method thereof | |
| CN104953172A (en) | Sodium-ion battery cathode materials, preparation method of sodium-ion battery cathode materials, and sodium-ion batteries | |
| CN102332577A (en) | Lithium ion battery and anode material thereof | |
| CN106784726B (en) | Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof | |
| CN105024067B (en) | Lithium ion battery, composite doped modified positive active material thereof and preparation method | |
| CN105720256B (en) | A kind of preparation method of lithium iron phosphate positive material | |
| CN105680018A (en) | Ternary positive electrode material and preparation method therefor and lithium ion battery | |
| CN105655554A (en) | Hydrothermal modification method of lithium-rich manganese-based positive material | |
| CN107394164A (en) | Tertiary cathode material and preparation method thereof | |
| CN101853934A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN109037649A (en) | It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof | |
| CN105932248A (en) | Modified lithium ion battery lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN108539193A (en) | Include the nucleocapsid NCM tertiary cathode materials and preparation method thereof of carbon nanotube | |
| CN104393260A (en) | Preparation method of silicate coated material rich in lithium and manganese | |
| CN103035904A (en) | Modified lithium manganate material, and preparation method and application thereof | |
| CN102479944B (en) | Preparation method and application of lithium iron phosphate composite material | |
| CN108400320A (en) | A method of in spinel nickel manganate cathode material for lithium surface sulfide | |
| CN103259008B (en) | Ternary composite positive electrode material of lithium ion battery and preparation method thereof |
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 |