CN109546123A - Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material and preparation method - Google Patents
Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material and preparation method Download PDFInfo
- Publication number
- CN109546123A CN109546123A CN201811408690.9A CN201811408690A CN109546123A CN 109546123 A CN109546123 A CN 109546123A CN 201811408690 A CN201811408690 A CN 201811408690A CN 109546123 A CN109546123 A CN 109546123A
- Authority
- CN
- China
- Prior art keywords
- nickel cobalt
- cobalt manganese
- shell structure
- nickel
- core
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material and preparation method, the positive electrode are formed by vanadic anhydride clad coated core-shell structure gradient nickel cobalt manganese anode material；Its chemical formula is V2O5@LiNixCoyMn(1‑x‑y)O2, wherein 0.5≤x≤0.85,0.05≤y≤0.4,1-x-y > 0；The core-shell structure gradient nickel cobalt manganese anode material mixes lithium sintering gained by core-shell structure gradient nickel cobalt manganese positive electrode material precursor.The preparation method is that: (1) positive electrode material precursor is aged, is filtered, washed, it is dry；(2) lithium source is added, grinding after pre-burning, is sintered；(3) it is mixed in alcoholic solution with vanadium source, ultrasound, heating reaction；(4) under an oxygen-containing atmosphere, it is heat-treated,.Battery discharge specific capacity height, circulation and the good rate capability of positive electrode assembling of the present invention；The method of the present invention is simple, it is at low cost, be suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of nickel cobalt manganese anode material and preparation methods, and in particular to a kind of vanadic anhydride coated core-shell
Structure gradient nickel cobalt manganese anode material and preparation method.
Background technique
Into 21st century, extensive energy shortages is got worse with the problem of environmental pollution in world wide, is forced
It is sought that enough substituting traditional fossil energy, and the green power supply of new energy (solar energy, wind energy and nuclear energy etc.) can be stored
System.Lithium ion battery rely on its excellent energy density, high rate performance and long life, be widely applied to mobile phone,
In the equipment such as digital camera and pocket pc, and its application target is just from small type mobile devices to Large Electric vehicle vehicle
With battery string (Vehicular batteries of pure electric vehicle, hybrid electric vehicle and plug-in hybrid electric vehicles etc.) and energy storage system etc.
Aspect transformation.Whether lithium ion battery can be applied in large-sized power battery and energy storage cells, key be energy density,
The five aspect factor such as power density, service life, safety and price.Wherein, when solving these problems, battery assembler should be optimized
Skill and battery management system, again from the building block of lithium-ion battery system (positive electrode, negative electrode material, diaphragm and electrolysis
Liquid etc.) aspect strengthened.In lithium-ion battery system, positive electrode restricts the development of battery overall performance, and ternary
Material, because it has many advantages, such as that voltage is high, specific capacity is high, low in cost, is as one of anode material for lithium-ion batteries
Generally acknowledged most promising one of anode material for lithium-ion batteries.
CN102637871A discloses a kind of lithium ion activating oxide V2O5The side of coated lithium ion battery positive electrode
Method is to form solution by the way that vanadium source to be dissolved in medium, adds anode material for lithium-ion batteries or its presoma, drying is simultaneously
Low-temperature sintering is carried out, its modified anode material for lithium-ion batteries is obtained.But this method is needed using spray drying process,
Preparation process is more complex, and under 2C multiplying power, and initial discharge only has the specific capacity of 170mAh/g, and the performance under high magnification is not yet
It is good.
CN106654201A discloses a kind of complex ternary material and preparation method thereof, is that vanadium source is added to oxalic acid solution
In, phosphorus source, lithium source is then added, is subsequently added into ternary material and stirs evenly, then dropwise addition ethylene glycol, ethylenediamine, low-temperature heat,
Presoma is obtained, then by high temperature sintering, there must be the ternary material of clad.Although clad slows down ternary material to electrolyte
Catalysis reaction, alleviate the moment aggregation of heat, and can inhibit the generation of battery precarious position.But the sintering temperature of this method
Degree is 800~860 DEG C, and temperature is high, and energy consumption is big, and discharge capacity is only 169mHh/g to 1C for the first time, and capacity is lower.
CN107230771A discloses a kind of method of vanadium phosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium, is
By the way that vanadium source, phosphate and reducing agent to be mixed in deionized water according to a certain percentage, and hydro-thermal reaction is carried out, then pass through
It is filtered, washed, dries, obtain vanadium phosphate, then preparation gained vanadium phosphate is mixed and is sintered according to a certain percentage with ternary material, obtains
Target product.Although this method can effectively improve the capacity and cycle performance of lithium ion battery, this method is firstly the need of conjunction
At coating, complex procedures, the process for synthesizing coating needs 20~48h, expends overlong time, efficiency is lower, is unfavorable for producing
Industry metaplasia produces, and the capacity of 20 circle of circulation electric discharge keeps being only 91.92% under 0.1C multiplying power, and cycle performance is bad.
What CN103700825A disclosed a kind of tertiary cathode material is mixed with method, be by ternary material precursor,
It is sintered after lithium carbonate, vanadic anhydride mixing, is blended into lithium fluoride and carries out double sintering, be dissolved in alcohol later, and be added
Isopropanol, it is dry, it is finally putting into Muffle furnace inside holding.Although this method can be improved the efficiency of material, and then improve battery
Cyclicity and high-temperature stability, still, this method needs to be sintered three times, not only complex procedures, but also is unfavorable for energy conservation, unfavorable
In industrialization production, and the specific capacity under 0.2C multiplying power after 100 circle of circulation electric discharge only has 176mAh/g, and cycle performance is bad.
It would therefore be highly desirable to find a kind of ternary material while obtaining high specific discharge capacity, optimize its multiplying power and cyclicity
Energy.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of assembled
Battery discharge specific capacity is high, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material of circulation and good rate capability
Material.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide a kind of work
The system of skill vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material that is simple, at low cost, being suitable for industrialized production
Preparation Method.
The technical solution adopted by the present invention to solve the technical problems is as follows: vanadic anhydride coated core-shell structure gradient nickel
Cobalt manganese anode material is formed by vanadic anhydride clad coated core-shell structure gradient nickel cobalt manganese anode material；Five oxidation
The chemical formula of two vanadium coated core-shell structure gradient nickel cobalt manganese anode materials is V2O5@ LiNixCoyMn(1-x-y)O2, wherein 0.5≤x
≤ 0.85,0.05≤y≤0.4,1-x-y > 0；The core-shell structure gradient nickel cobalt manganese anode material is by core-shell structure gradient nickel cobalt
Manganese anode material presoma mixes lithium sintering gained.Using the basic material of full concentration gradient, the circulation and again of material can be improved
Rate performance, kernel are to be precipitated as nickle cobalt lithium manganate made from presoma with the hydroxide of nickel cobalt manganese, and structure is comparatively dense, can protect
Hinder the compacted density of material, shell is that have micropore using nickel cobalt manganese carbonate as nickle cobalt lithium manganate made from presoma, be conducive to lithium
Deintercalation of ion during discharge and recharge reaction, and prevent material from generating due to the variation of volume during discharge and recharge reaction
Structure change；And the clad of vanadic anhydride can provide lithium ion tunnel in charge and discharge process, improve ionic conduction
Rate, clad can provide one layer of protection shell, inhibit the material structure variation in charge and discharge process, meanwhile, surface V2O5Cladding
Layer all has preferable stability in air and electrolyte, can preferably completely cut off CO in air2/H2O and electrolyte, substantially
Improve the air storge quality of material and the cyclical stability of material electrochemical.
Preferably, the vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material is 3~12 μm of average grain diameter
Spheric granules.
Preferably, the coating thickness of the vanadic anhydride is 3~10nm, and the mass percent of vanadic anhydride is 1
More preferable 2~5%)~7%(.Clad is blocked up or covering amount excessively will lead to material initial capacity loss it is excessive, and coat
The excessively thin or covering amount of layer is very few can not play ideal modified effect because coating substance not enough.
Preferably, nickel content is gradually decreased from center to the shell layer surface of core-shell structure gradient nickel cobalt manganese anode material, manganese,
The content of cobalt and vanadium is uniformly distributed at the center of core-shell structure particles with shell.Due to core-shell structure gradient nickel cobalt manganese anode material
Material has micropore or tiny gap, and vanadium source can be permeated along these micropores or gap to the internal diameter of particle in encapsulation process,
Occur to spread and generate vanadic anhydride in sintering process to reside in gap.
Preferably, the kernel of the core-shell structure gradient nickel cobalt manganese anode material is precipitated as with the hydroxide of nickel cobalt manganese
Presoma mixes lithium and is sintered resulting nickle cobalt lithium manganate, and shell is to mix lithium as presoma using nickel cobalt manganese carbonate to be sintered resulting nickel cobalt
LiMn2O4.
Preferably, the diameter of the kernel be 2.5~9.0 μm, shell with a thickness of 0.3~3.0 μm.
Preferably, the preparation method of the core-shell structure gradient nickel cobalt manganese positive electrode material precursor, comprising the following steps:
1) low nickel content nickel cobalt manganese solution is pumped into the container equipped with high nickel content nickel cobalt or nickel cobalt manganese solution, and stirred, with
The high nickel content nickel cobalt for being constantly pumped into low nickel content nickel cobalt manganese solution or nickel cobalt manganese solution are pumped into equipped with ammonia spirit by this simultaneously
Reaction kettle in, and simultaneously with ammonium hydroxide adjust reaction system ammonia concn, with hydroxide precipitant solution adjust reactant
The pH value of system, stirring carry out coprecipitation reaction and obtain presoma nuclear material until mean particle size grows to 2.5~9.0 μm, after
It is continuous to carry out aforesaid operations, hydroxide precipitant solution is only replaced with into carbonate deposition agent solution and is used to adjust reaction system
PH value, stirring carries out coprecipitation reaction, until low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel cobalt manganese solution are complete
Finish, obtains the solution containing presoma nucleocapsid layer material；
2) the solution stirring obtained by step (1) containing presoma nucleocapsid layer material is aged, filters, washs, it is dry, obtain core
Shell structure gradient nickel cobalt manganese positive electrode material precursor.
Preferably, in step 1), the charging rate of the low nickel content nickel cobalt manganese solution is 20~60mL/h, described continuous
The charging rate of the high nickel content nickel cobalt or nickel cobalt manganese solution that are pumped into low nickel content nickel cobalt manganese solution is 50~100mL/h.
Preferably, in step 1), in the low nickel content nickel cobalt manganese solution, the concentration of metal ion is 1~3mol/L, Ni
The molar percentage of the total metal ion of Zhan is that the molar percentage of the total metal ion of 40~70%, Co Zhan is that 10~40%, Mn Zhan is total
The molar percentage of metal ion is 20~50%, and Ni, Co, Mn ion summation are 100%.
Preferably, in step 1), in the high nickel content nickel cobalt or nickel cobalt manganese solution, the concentration of metal ion is 1~
The molar percentage of the total metal ion of 3mol/L, Ni Zhan be the molar percentage of the total metal ion of 60~90%, Co Zhan be 10~
The molar percentage of the total metal ion of 40%, Mn Zhan is 0~30%, and Ni, Co, Mn ion summation are 100%.
Preferably, in step 1), in same reaction system, the nickel content of low nickel content nickel cobalt manganese solution contains lower than nickelic
Measure the nickel content of nickel cobalt or nickel cobalt manganese solution.
Preferably, in step 1), ammonia spirit, low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel in reaction kettle
The volume ratio of cobalt manganese solution is the more preferable 0.5~2.5:0.8 of 0.1~10:0.8~1.2:1(~1.2:1).
Preferably, in step 1), the molar concentration of the ammonia spirit is 0.3~0.5mol/L.
Preferably, in step 1), reaction system ammonia concn is adjusted with ammonium hydroxide and is maintained at 0.3~0.5mol/L.
Preferably, in step 1), the mass concentration of the ammonium hydroxide for adjusting reaction system ammonia concn is 25~28%.
Preferably, in step 1), pH value of reaction system is adjusted with hydroxide precipitant solution and is maintained at 10.5~11.5.
Preferably, in step 1), the molar concentration of the hydroxide precipitant solution is 5~10mol/L.
Preferably, in step 1), the hydroxide precipitating reagent is in sodium hydroxide, potassium hydroxide or lithium hydroxide etc.
It is one or more of.
Preferably, in step 1), pH value of reaction system is adjusted with carbonate deposition agent solution and is maintained at 8.5~10.5.
Preferably, in step 1), the molar concentration of the carbonate deposition agent solution is 0.5~1.5mol/L.
Preferably, in step 1), the carbonate deposition agent is sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate or carbonic acid
One or more of hydrogen potassium etc..
Preferably, in step 1), the co-precipitation for generating presoma nuclear material and generating presoma nucleocapsid layer material is anti-
Ying Zhong, the speed of stirring are 600~1200r/min, and temperature is 50~70 DEG C.
Preferably, in step 1), the low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel cobalt manganese solution are can
The mixed solution of insoluble nickel salt and soluble cobalt or soluble nickel salt, soluble cobalt and soluble manganese salt.
Preferably, the soluble nickel salt is one or more of nickel sulfate, nickel nitrate, nickel acetate or nickel chloride etc..
Preferably, the soluble cobalt is one or more of cobaltous sulfate, cobalt nitrate, cobalt acetate or cobalt chloride etc..
Preferably, the soluble manganese salt is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride etc..
Preferably, in step 2, the speed of the stirring is 400~800r/min.
Preferably, in step 2, the temperature of the ageing is 50~80 DEG C, and the time is 5~15h.
Preferably, in step 2, the temperature of the drying is 50~100 DEG C, and the time is 5~15h.
Core-shell structure gradient nickel cobalt manganese positive electrode material precursor of the present invention can also be obtained by other prior art preparations.
It is as follows that the present invention further solves technical solution used by its technical problem: vanadic anhydride coated core-shell structure
The preparation method of gradient nickel cobalt manganese anode material, comprising the following steps:
(1) core-shell structure gradient nickel cobalt manganese positive electrode material precursor is aged, is filtered, washed, it is dry, nucleocapsid knot must be aged
Structure gradient nickel cobalt manganese positive electrode material precursor；
(2) in the ageing core-shell structure gradient nickel cobalt manganese positive electrode material precursor obtained by step (1), lithium source, grinding, pre-burning is added
Afterwards, it is sintered, obtains core-shell structure gradient nickel cobalt manganese anode material；
(3) core-shell structure gradient nickel cobalt manganese anode material obtained by step (2) is mixed in alcoholic solution with vanadium source, ultrasound, heating
It is stirred to react to being evaporated, obtains mixed-powder；
(4) under an oxygen-containing atmosphere by mixed-powder obtained by step (3), it is heat-treated, obtains vanadic anhydride coated core-shell structure
Gradient nickel cobalt manganese anode material.
Preferably, in step (1), the temperature of the ageing is 50~80 DEG C, and revolving speed is 600~1200r/min, and the time is
5~15h.Particle, which is more advantageous to, by ageing grows more uniform.If Aging Temperature is excessively high or overlong time, there is side reaction
Occur, if Aging Temperature is too low or the time is too short, will be difficult to reach ageing purpose.
Preferably, in step (1), the temperature of the drying is 50~100 DEG C, and the time is 5~15h.The mesh of the drying
Be that removal solvent has side reaction, if drying temperature is too low, will lead to if drying temperature is excessively high or overlong time
Drying time is too long and influences efficiency, if drying time is too short, material can be made to contain residual solvents.
Preferably, in step (2), in the lithium source in elemental lithium and core-shell structure gradient nickel cobalt manganese positive electrode material precursor
The molar ratio of the sum of nickel, cobalt, manganese element molal quantity is 1.01~1.07:1.If elemental lithium additional amount is too low, elemental lithium can not
Foot, it is too low so as to cause specific discharge capacity；If elemental lithium additional amount is excessively high, active material ratio reduces, and also results in electric discharge
Specific capacity reduces.
Preferably, in step (2), the lithium source be lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate or lithium acetate and it
One or more of hydrate etc..
Preferably, in step (2), the revolving speed of the grinding is 600~1000r/min, and the time is 5~10min.Grinding turns
The fast too low or time is too short, mixing can be made uneven, if grinding revolving speed is excessively high or overlong time, and can destroy the nucleocapsid of material
Structure.
Preferably, in step (2), the temperature of the pre-burning is 350~550 DEG C, and the time is 3~6h.Pre-burning is to go
Except remaining moisture in nickel cobalt manganese positive electrode material precursor, dehydration is realized, while melting lithium source, make material mixed on a microscopic level
Close more evenly.If calcined temperature is too low or the time is too short, it is uneven to will lead to mixing, if calcined temperature is excessively high or time mistake
It is long, then it will lead to energy waste.
Preferably, in step (2), the temperature of the sintering is 650~950 DEG C, the time is 8~for 24 hours.In sintering process
In, Li2The crystal grain boundary of O and metal oxide reacts, and increasingly generates the nickel-cobalt lithium manganate material of stratiform.If the temperature of sintering
Low or overlong time is spent, then will lead to material reaction not exclusively, crystal form is imperfect, so that the performance of material is influenced, if burning
The temperature of knot is excessively high or overlong time, then will lead to the generation of side reaction, to influence the performance of material.
Preferably, in step (3), nickel in vanadium and core-shell structure gradient nickel cobalt manganese anode material in the vanadium source, cobalt,
The molar ratio of the sum of manganese element molal quantity is the more preferable 0.015~0.055:1 of 0.01~0.10:1().If as cladding raw material
Vanadium source dosage it is excessive, then can reduce the initial capacity of material, if as cladding raw material vanadium source dosage it is too low, will be difficult to
Reach expected modified effect.
Preferably, in step (3), the vanadium source is one in vanadium acetylacetonate, vanadyl acetylacetonate or ammonium metavanadate etc.
Kind is several.The vanadium source is all soluble in alcoholic solution, can uniformly mix with base material.
Preferably, in step (3), the alcoholic solution and core-shell structure gradient nickel cobalt manganese anode material and vanadium source gross mass
Volume mass ratio (mL/g) is the more preferable 36~56:1 of 10~60:1().Ultrasonic disperse is carried out using alcoholic solution, can will not only be made
For the vanadium source dissolution for coating raw material, vanadium source also may make uniformly to mix with base material.If the dosage of alcoholic solution is too low,
It will lead to that mixing is uneven, if the dosage of alcoholic solution is excessively high, unnecessary waste can be generated.
Preferably, in step (3), the alcoholic solution is one or more of dehydrated alcohol, ethylene glycol or methanol etc..
Preferably, in step (3), the frequency of the ultrasonic disperse is 30~40kHz, and the time is 4~8h.If supersonic frequency
The too low or time is too short, then it is not complete enough to will lead to dispersion, if supersonic frequency is excessively high or overlong time, will affect material nucleocapsid
The integrality of structure.
Preferably, in step (3), the temperature of heating stirring reaction is 40~60 DEG C, the speed of stirring is 100~
200r/min.Heating reaction is the dissolubility in order to improve the vanadium source as cladding raw material, further enhances the equal of its mixing
Even property.If the temperature of heating stirring reaction is too low, the raw material crystallization of dissolution can be made, if temperature is excessively high, can be easy to produce
Side reaction.If the speed stirred in reaction process is excessively slow, mixing can be made uneven, it, can shadow if the excessive velocities of stirring
Ring the integrality of Core-shell structure material.
Preferably, in step (4), the temperature of the heat treatment is 300~600 DEG C, and the time is 4~8h.Heat treatment process
Middle vanadium source can decompose reaction, in substrate ternary material Surface Creation vanadic anhydride.If heat treatment temperature it is too low or when
Between it is too short, then be difficult to generate target material, if heat treatment temperature is excessively high or overlong time, the nucleocapsid and packet of material can be destroyed
Structure is covered, and side reaction occurs.
Preferably, in step (4), the oxygen-containing atmosphere is one of air atmosphere, oxygen atmosphere or ozone atmosphere etc.
Or it is several.
Beneficial effects of the present invention are as follows:
(1) core-shell structure gradient nickel cobalt manganese anode material of the present invention by 3~10nm thickness vanadic anhydride clad coated core-shell
Structure gradient nickel cobalt manganese anode material forms, and average grain diameter is 4~12 μm；The core-shell structure gradient nickel cobalt manganese anode material
Kernel is to be precipitated as presoma with the hydroxide of nickel cobalt manganese to mix the resulting nickle cobalt lithium manganate of lithium sintering, and diameter is 2.5~9.0 μ
M, shell are to mix lithium as presoma using nickel cobalt manganese carbonate to be sintered resulting nickle cobalt lithium manganate, shell with a thickness of 1~3 μm；Nickel
Content is gradually decreased from center to the shell layer surface of core-shell structure gradient nickel cobalt manganese anode material, and the content of manganese, cobalt and vanadium exists
The center of core-shell structure particles is uniformly distributed with shell；Kernel is fine and close, and shell has microcellular structure, lithium ion can be made in deintercalation
Cheng Gengwei is unobstructed, to promote the ionic conductivity of material, optimizes material property；
(2) positive electrode of the present invention is assembled into battery, in 0.1C(20mA/g) current density under, discharge capacity can be high for the first time
Up to 195mAh/g, in 10C(2000mA/g) current density under, specific discharge capacity may be up to 151mAh/g, and specific discharge capacity is high；
In 1C(200mA/g) under current density, after 100 circle of circulation, specific discharge capacity remains at 165mAh/g, and capacity retention ratio is
89.2%, show excellent circulation and high rate performance；
(3) the method for the present invention simple process, it is at low cost, be suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the XRD diagram of 1 vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material of the embodiment of the present invention；
Fig. 2 is the SEM figure of 1 vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material of the embodiment of the present invention；
Fig. 3 is the TEM figure of 1 vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material of the embodiment of the present invention；
Fig. 4 is that the focused ion beam of 1 vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material of the embodiment of the present invention is surveyed
Attempt；
Fig. 5 is that the line of tetra- kinds of elements of Ni, Co, Mn, V of Fig. 4 grain section sweeps EDS figure；
Fig. 6 is the head of 1 vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material institute of embodiment of the present invention assembled battery
Enclose charging and discharging curve figure；
Fig. 7 is putting for 1 vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material institute's assembled battery of the embodiment of the present invention
Electricity circulation figure；
Fig. 8 is putting for 1 vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material institute's assembled battery of the embodiment of the present invention
Electric multiplying power figure；
Fig. 9 is the head of 2 vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material institutes of embodiment of the present invention assembled battery
Enclose charging and discharging curve figure；
Figure 10 is the head of 3 vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material institutes of embodiment of the present invention assembled battery
Enclose charging and discharging curve figure；
Figure 11 is the discharge cycles figure of 1 core-shell structure gradient nickel cobalt manganese anode material institute of comparative example of the present invention assembled battery.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Chemical reagent used in the embodiment of the present invention is obtained by routine business approach unless otherwise specified.
Core-shell structure gradient nickel cobalt manganese positive electrode material precursor reference example 1
1) by the 2L low nickel content nickel cobalt manganese solution (mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, wherein Ni, Co, Mn are accounted for
The molar percentage of total metal ion is followed successively by 70%, 10%, 20%, concentration of metal ions 2mol/L) with charging rate 40mL/
H is pumped into equipped with the 2L high nickel content nickel and cobalt solution (mixed solution of nickel sulfate and cobaltous sulfate, wherein the total metal ion of Ni, Co Zhan
Molar percentage be followed successively by 90%, 10%, concentration of metal ions 2mol/L) container in, and stir, at the same time, will not
The disconnected high nickel content nickel and cobalt solution for being pumped into low nickel content nickel cobalt manganese solution is pumped into charging rate 80mL/h equipped with 2L, mole dense
Degree is the ammonia spirit of 0.45mol/L, and volume is in the reaction kettle of 5L, and adjusts reaction with the ammonium hydroxide of mass concentration 25% simultaneously
The ammonia concn of system is maintained at 0.45mol/L, is maintained at the pH value that the sodium hydroxide solution of 10mol/L adjusts reaction system
11.4, at 1000r/min, 60 DEG C, stirring carries out coprecipitation reaction and obtains presoma until mean particle size grows to 3.5 μm
Nuclear material continues aforesaid operations, is only used to adjust reaction for the sodium carbonate liquor that sodium hydroxide solution replaces with 1mol/L
The pH value of system is maintained at 9.5, and at 1000r/min, 60 DEG C, stirring carries out coprecipitation reaction, until low nickel content nickel cobalt manganese is molten
Liquid and the charging of high nickel content nickel and cobalt solution finish, and obtain the solution containing presoma nucleocapsid layer material；
2) by the solution containing presoma nucleocapsid layer material obtained by step 1), at 600r/min, 60 DEG C, stirring is aged
10h, filtering, deionized water washing, at 80 DEG C, dry 10h obtains core-shell structure gradient nickel cobalt manganese positive electrode material precursor
Ni0.75Co0.12Mn0.13(OH)2。
Core-shell structure gradient nickel cobalt manganese positive electrode material precursor reference example 2
1) by the 1.6L low nickel content nickel cobalt manganese solution (mixed solution of nickel nitrate, cobalt nitrate and manganese nitrate, wherein Ni, Co, Mn
The molar percentage of the total metal ion of Zhan is followed successively by 40%, 30%, 30%, concentration of metal ions 2.5mol/L) with charging rate
30mL/h, be pumped into equipped with 2L high nickel content nickel cobalt manganese solution (mixed solution of nickel nitrate, cobalt nitrate and manganese nitrate, wherein Ni,
The molar percentage of the total metal ion of Co, Mn Zhan is followed successively by 80%, 10%, 10%, concentration of metal ions 2.5mol/L) container
In, and stir, at the same time, the high nickel content nickel cobalt manganese solution of low nickel content nickel cobalt manganese solution will be pumped into constantly with charging rate
60mL/h is pumped into equipped with 1.8L, the ammonia spirit that molar concentration is 0.4mol/L, and volume is and to use simultaneously in the reaction kettle of 5L
The ammonia concn that the ammonium hydroxide of mass concentration 25% adjusts reaction system is maintained at 0.45mol/L, with the sodium hydroxide solution of 5mol/L
The pH value for adjusting reaction system is maintained at 11.0, and at 800r/min, 55 DEG C, stirring carries out coprecipitation reaction, until particle is average
Particle size growth obtains presoma nuclear material to 4 μm, continues aforesaid operations, sodium hydroxide solution is only replaced with 0.8mol/L
Sodium carbonate liquor adjust reaction system pH value be maintained at 9, at 800r/min, 55 DEG C, stirring carry out coprecipitation reaction, until
Low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt manganese solution finish, and obtain the solution containing presoma nucleocapsid layer material；
2) by the solution containing presoma nucleocapsid layer material obtained by step (1), at 500r/min, 70 DEG C, stirring is aged
12h, filtering, deionized water washing, at 60 DEG C, dry 8h obtains core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma
Ni0.6Co0.2Mn0.2(OH)2。
Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material embodiment 1
Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material is by vanadic anhydride clad coated core-shell structure ladder
Degree nickel cobalt manganese anode material forms；The chemical formula of the vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material is
V2O5@ LiNi0.75Co0.12Mn0.13O2；The core-shell structure gradient nickel cobalt manganese anode material is by 1 gained core-shell structure ladder of reference example
Spend nickel cobalt manganese positive electrode material precursor Ni0.75Co0.12Mn0.13(OH)2Mixed lithium sintering gained；The vanadic anhydride coated core-shell
The spheric granules that structure gradient nickel cobalt manganese anode material is 4 μm of average grain diameter；The coating thickness of the vanadic anhydride is
5nm, the mass percent of vanadic anhydride are 3%；Nickel content is from the center of core-shell structure gradient nickel cobalt manganese anode material to shell
Surface gradually decreases, and the content of manganese, cobalt and vanadium is uniformly distributed at the center of core-shell structure particles and shell；The core-shell structure
The kernel of gradient nickel cobalt manganese anode material is to be precipitated as presoma with the hydroxide of nickel cobalt manganese to mix the resulting nickel cobalt manganese of lithium sintering
Sour lithium, shell are to mix lithium as presoma using nickel cobalt manganese carbonate to be sintered resulting nickle cobalt lithium manganate；The diameter of the kernel is 3.5
μm, shell with a thickness of 0.5 μm.
The preparation method embodiment 1 of vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material
(1) by 1 gained core-shell structure gradient nickel cobalt manganese positive electrode material precursor of 1g(0.01038mol) reference example
Ni0.75Co0.12Mn0.13(OH)2, at 60 DEG C, revolving speed 800r/min, ageing 10h is carried out, is filtered, deionized water washing, 80
At DEG C, dry 10h must be aged core-shell structure gradient nickel cobalt manganese positive electrode material precursor；
(2) in the ageing core-shell structure gradient nickel cobalt manganese positive electrode material precursor obtained by step (1), 0.458g is added
(0.0109mol) hydronium(ion) lithia (molar ratio of elemental lithium and the sum of nickel, cobalt, manganese element molal quantity is 1.05:1),
Under 800r/min, 8min is ground, at 450 DEG C, after pre-burning 4h, then at 750 DEG C, 12h is sintered, obtains core-shell structure gradient nickel cobalt
Manganese anode material；
(3) by 1g core-shell structure gradient nickel cobalt manganese anode material obtained by step (2) and 0.087g(0.00033mol) acetylacetone,2,4-pentanedione
Vanadyl mixes in 50mL ethanol solution, and at 35kHz, ultrasonic 6h, under 50 DEG C, the revolving speed of 150r/min, heating is stirred
Reaction is mixed to being evaporated, obtains mixed-powder；
(4) in air atmosphere by mixed-powder obtained by step (3), at 500 DEG C, heat treatment 6h is carried out, vanadic anhydride is obtained
Coated core-shell structure gradient nickel cobalt manganese anode material V2O5@ LiNi0.75Co0.12Mn0.13O2。
As shown in Figure 1, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material obtained by the embodiment of the present invention
V2O5@ LiNi0.75Co0.12Mn0.13O2For pure phase nickel-cobalt-manganternary ternary anode material, do not change after coating vanadic anhydride
Become its crystal structure.
As shown in Fig. 2, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material obtained by the embodiment of the present invention
V2O5@ LiNi0.75Co0.12Mn0.13O2For 4 μm of spheric granules of partial size, pattern is uniform.
As shown in figure 3, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material obtained by the embodiment of the present invention
V2O5@ LiNi0.75Co0.12Mn0.13O2Particle outer layer has more uniform clad, with a thickness of 5nm.
As shown in Figure 4,5, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material obtained by the embodiment of the present invention
V2O5@ LiNi0.75Co0.12Mn0.13O2The diameter of kernel is 3.5 μm, shell with a thickness of 0.5 μm, nickel content is from core-shell structure ladder
Center to the shell layer surface of degree nickel cobalt manganese anode material gradually decreases, and the content of manganese, cobalt and vanadium is in core-shell structure particles
The heart is uniformly distributed with shell.
Battery assembly: vanadic anhydride coated core-shell structure gradient nickel cobalt manganese obtained by the 0.16 g embodiment of the present invention is being weighed just
Pole material V2O5@ LiNi0.75Co0.12Mn0.13O2, addition 0.02g acetylene black makees conductive agent and 0.02g Kynoar bonds
Agent, N-Methyl pyrrolidone is as dispersing agent, after mixing, is applied on aluminium foil, negative electrode tab is made, in vacuum glove box,
It is anode with metal lithium sheet, using the composite membrane of pe, pp as diaphragm, 1mol/L lithium hexafluoro phosphate/DMC:EC(volume ratio 1:1) it is electricity
Liquid is solved, the button cell of CR2025 is assembled into.
As shown in fig. 6, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material obtained by the embodiment of the present invention
V2O5@ LiNi0.75Co0.12Mn0.13O2In 0.1C(20mA/g) first discharge specific capacity under multiplying power is 195mAh/g.
As shown in fig. 7, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material obtained by the embodiment of the present invention
V2O5@ LiNi0.75Co0.12Mn0.13O2In 1C(mA/g) under multiplying power, after 100 circle of circulation, specific discharge capacity remains at 165mAh/
G, capacity retention ratio 89.2% illustrate that cycle performance is excellent.
As shown in figure 8, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material obtained by the embodiment of the present invention
V2O5@ LiNi0.75Co0.12Mn0.13O2In 0.1C(20mA/g) first discharge specific capacity under multiplying power is 192mAh/g, circulation 10
After circle, specific discharge capacity remains at 194mAh/g, capacity retention ratio 101%；Switch to 0.5C(100mA/g) after multiplying power
First discharge specific capacity is 188mAh/g, and after 10 circle of circulation, specific discharge capacity remains at 188mAh/g, and capacity retention ratio is
100%；Switching to 1C(200mA/g) first discharge specific capacity after multiplying power is 180mAh/g, after 10 circle of circulation, specific discharge capacity
Remain at 179.5mAh/g, capacity retention ratio 99.7%；Switch to 2C(400mA/g) first discharge specific capacity after multiplying power
For 172.5mAh/g, after circulation 10 is enclosed, specific discharge capacity remains at 171mAh/g, capacity retention ratio 99.1%；Switch to 5C
First discharge specific capacity after (1000mA/g) multiplying power is 167.5mAh/g, and after circulation 10 is enclosed, specific discharge capacity is remained at
164mAh/g, capacity retention ratio 97.9%；Switch to 10C(2000mA/g) high current density after first discharge specific capacity
For 151mAh/g, after circulation 10 is enclosed, specific discharge capacity remains at 146mAh/g, and capacity retention ratio 96.7% illustrates forthright again
It can be excellent.
Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material embodiment 2
Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material is by vanadic anhydride clad coated core-shell structure ladder
Degree nickel cobalt manganese anode material forms；The chemical formula of the vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material is
V2O5@ LiNi0.6Co0.2Mn0.2O2；The core-shell structure gradient nickel cobalt manganese anode material is by 2 gained core-shell structure gradient of reference example
Nickel cobalt manganese positive electrode material precursor Ni0.6Co0.2Mn0.2(OH)2Mixed lithium sintering gained；The vanadic anhydride coated core-shell structure
The spheric granules that gradient nickel cobalt manganese anode material is 4.6 μm of average grain diameter；The coating thickness of the vanadic anhydride is 3nm,
The mass percent of vanadic anhydride is 2%；Nickel content is from the center of core-shell structure gradient nickel cobalt manganese anode material to shell layer surface
It gradually decreases, the content of manganese, cobalt and vanadium is uniformly distributed at the center of core-shell structure particles and shell；The core-shell structure gradient
The kernel of nickel cobalt manganese anode material is to be precipitated as presoma with the hydroxide of nickel cobalt manganese to mix the resulting nickle cobalt lithium manganate of lithium sintering,
Shell is to mix lithium as presoma using nickel cobalt manganese carbonate to be sintered resulting nickle cobalt lithium manganate；The diameter of the kernel is 4 μm, shell
With a thickness of 0.6 μm.
The preparation method embodiment 2 of vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material
(1) by 2 gained core-shell structure gradient nickel cobalt manganese positive electrode material precursor of 1g(0.01065mol) reference example
Ni0.6Co0.2Mn0.2(OH)2, at 50 DEG C, revolving speed 1000r/min, ageing 12h is carried out, is filtered, deionized water washing, 100
At DEG C, dry 8h must be aged core-shell structure gradient nickel cobalt manganese positive electrode material precursor；
(2) in the ageing core-shell structure gradient nickel cobalt manganese positive electrode material precursor obtained by step (1), 1.163g is added
(0.0114mol) two is hydrated lithium acetate (molar ratio of elemental lithium and the sum of nickel, cobalt, manganese element molal quantity is 1.07:1),
Under 700r/min, 10min is ground, at 400 DEG C, after pre-burning 5h, then at 800 DEG C, 8h is sintered, obtains core-shell structure gradient nickel cobalt
Manganese anode material；
(3) by 1g core-shell structure gradient nickel cobalt manganese anode material obtained by step (2) and 0.074g(0.00021mol) acetylacetone,2,4-pentanedione
Vanadium mixes in 60mL ethanol solution, at 30kHz, ultrasonic 8h, and under 40 DEG C, the revolving speed of 200r/min, heating stirring
Reaction obtains mixed-powder to being evaporated；
(4) in air atmosphere by mixed-powder obtained by step (3), at 550 DEG C, heat treatment 8h is carried out, vanadic anhydride is obtained
Coated core-shell structure gradient nickel cobalt manganese anode material V2O5@ LiNi0.6Co0.2Mn0.2O2。
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.6Co0.2Mn0.2O2For pure phase nickel-cobalt-manganternary ternary anode material, its crystal is not changed after coating vanadic anhydride
Structure.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.6Co0.2Mn0.2O2For 4.6 μm of spheric granules of partial size, pattern is uniform.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.6Co0.2Mn0.2O2Particle outer layer has more uniform clad, with a thickness of 3nm.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.6Co0.2Mn0.2O2, the diameter of kernel is 4 μm, shell with a thickness of 0.6 μm, nickel content is from core-shell structure gradient nickel cobalt manganese
The center of positive electrode to shell layer surface gradually decreases, center and shell of the content of manganese, cobalt and vanadium in core-shell structure particles
It is uniformly distributed.
Battery assembly: with embodiment 1.
As shown in figure 9, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material obtained by the embodiment of the present invention
V2O5@ LiNi0.6Co0.2Mn0.2O2In 0.1C(20mA/g) first discharge specific capacity under multiplying power is 193mAh/g.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.6Co0.2Mn0.2O2In 1C(mA/g) under multiplying power, after 100 circle of circulation, specific discharge capacity remains at 158mAh/g, capacity
Conservation rate is 88.3%, illustrates that cycle performance is excellent.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.6Co0.2Mn0.2O2In 10C(2000mA/g) under high current density, first discharge specific capacity 144.5mAh/g, circulation 10
After circle, specific discharge capacity remains at 142.5mAh/g, and capacity retention ratio 98.6% illustrates that high rate performance is excellent.
Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material embodiment 3
Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material is by vanadic anhydride clad coated core-shell structure ladder
Degree nickel cobalt manganese anode material forms；The chemical formula of the vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material is
V2O5@ LiNi0.75Co0.12Mn0.13O2；The core-shell structure gradient nickel cobalt manganese anode material is by 1 gained core-shell structure ladder of reference example
Spend nickel cobalt manganese positive electrode material precursor Ni0.75Co0.12Mn0.13(OH)2Mixed lithium sintering gained；The vanadic anhydride coated core-shell
The spheric granules that structure gradient nickel cobalt manganese anode material is 3.9 μm of average grain diameter；The coating thickness of the vanadic anhydride is
8nm, the mass percent of vanadic anhydride are 3.5%；Nickel content is from the center of core-shell structure gradient nickel cobalt manganese anode material to shell
Layer surface gradually decreases, and the content of manganese, cobalt and vanadium is uniformly distributed at the center of core-shell structure particles and shell；The nucleocapsid knot
The kernel of structure gradient nickel cobalt manganese anode material is to be precipitated as presoma with the hydroxide of nickel cobalt manganese to mix the resulting nickel cobalt of lithium sintering
LiMn2O4, shell are to mix lithium as presoma using nickel cobalt manganese carbonate to be sintered resulting nickle cobalt lithium manganate；The diameter of the kernel is
3.5 μm, shell with a thickness of 0.4 μm.
The preparation method embodiment 3 of vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material
(1) by 1 gained core-shell structure gradient nickel cobalt manganese positive electrode material precursor of 1g(0.01029mol) reference example
Ni0.75Co0.12Mn0.13(OH)2, at 70 DEG C, revolving speed 600r/min, ageing 8h is carried out, is filtered, deionized water washing, at 60 DEG C
Under, dry 12h must be aged core-shell structure gradient nickel cobalt manganese positive electrode material precursor；
(2) in the ageing core-shell structure gradient nickel cobalt manganese positive electrode material precursor obtained by step (1), 0.399g is added
(0.0054mol) lithium carbonate (molar ratio of elemental lithium and the sum of nickel, cobalt, manganese element molal quantity is 1.05:1), in 900r/min
Under, 5min is ground, at 500 DEG C, after pre-burning 3h, then at 700 DEG C, 16h is sintered, obtains core-shell structure gradient nickel cobalt manganese anode material
Material；
(3) by 1g core-shell structure gradient nickel cobalt manganese anode material obtained by step (2) and 0.0432g(0.00037mol) metavanadic acid
Ammonium mixes in 40mL ethylene glycol solution, and at 40kHz, ultrasonic 4h, under 60 DEG C, the revolving speed of 100r/min, heating stirring is anti-
Mixed-powder should be obtained to being evaporated；
(4) mixed-powder obtained by step (3) at 450 DEG C, is carried out heat treatment 4h, obtains vanadic anhydride under oxygen atmosphere
Coated core-shell structure gradient nickel cobalt manganese anode material V2O5@ LiNi0.75Co0.12Mn0.13O2。
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.75Co0.12Mn0.13O2For pure phase nickel-cobalt-manganternary ternary anode material, its crystalline substance is not changed after coating vanadic anhydride
Body structure.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.75Co0.12Mn0.13O2For 3.9 μm of spheric granules of partial size, pattern is uniform.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.75Co0.12Mn0.13O2Particle outer layer has more uniform clad, with a thickness of 8nm.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.75Co0.12Mn0.13O2, the diameter of kernel is 3.5 μm, shell with a thickness of 0.4 μm, nickel content is from core-shell structure gradient nickel
The center of cobalt manganese anode material to shell layer surface gradually decreases, the content of manganese, cobalt and vanadium core-shell structure particles center with
Shell is uniformly distributed.
Battery assembly: with embodiment 1.
As shown in Figure 10, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material obtained by the embodiment of the present invention
V2O5@ LiNi0.75Co0.12Mn0.13O2In 0.1C(20mA/g) first discharge specific capacity under multiplying power is 192mAh/g.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.75Co0.12Mn0.13O2In 1C(mA/g) under multiplying power, after 100 circle of circulation, specific discharge capacity remains at 155mAh/g, holds
Measuring conservation rate is 86.7%, illustrates that cycle performance is excellent.
Through detecting, vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material V obtained by the embodiment of the present invention2O5@
LiNi0.75Co0.12Mn0.13O2In 10C(2000mA/g) under high current density, first discharge specific capacity 142.8mAh/g, circulation
After 10 circles, specific discharge capacity remains at 140.5mAh/g, and capacity retention ratio 98.4% illustrates that high rate performance is excellent.
Comparative example 1
The difference of this comparative example and embodiment 1 is only that: being removed step (3), (4), is obtained core-shell structure gradient nickel cobalt manganese anode material
Material, remaining same embodiment 1.
Through detecting, core-shell structure gradient nickel cobalt manganese anode material LiNi obtained by this comparative example0.75Co0.12Mn0.13O2?
0.1C(20mA/g) under current density, first discharge specific capacity 199mAh/g.
As shown in figure 11, core-shell structure gradient nickel cobalt manganese anode material LiNi obtained by this comparative example0.75Co0.12Mn0.13O2?
1C(mA/g) under multiplying power, after 100 circle of circulation, specific discharge capacity is only 142mAh/g, and capacity retention ratio is only 78%.
Through detecting, core-shell structure gradient nickel cobalt manganese anode material LiNi obtained by this comparative example0.75Co0.12Mn0.13O2In 10C
Under (2000mA/g) high current density, first discharge specific capacity 141mAh/g, capacity retention ratio is only 70.8%.
From the foregoing, it will be observed that the not no cladding of vanadic anhydride, to the cycle performance of core-shell structure gradient nickel cobalt manganese anode material
Raising with high rate performance is affected.
Claims (10)
1. a kind of vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material, it is characterised in that: by vanadic anhydride packet
Coating coated core-shell structure gradient nickel cobalt manganese anode material forms；The vanadic anhydride coated core-shell structure gradient nickel cobalt manganese is just
The chemical formula of pole material is V2O5@ LiNixCoyMn(1-x-y)O2, wherein 0.5≤x≤0.85,0.05≤y≤0.4,1-x-y >
0；The core-shell structure gradient nickel cobalt manganese anode material mixes lithium by core-shell structure gradient nickel cobalt manganese positive electrode material precursor and is sintered institute
?.
2. vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material according to claim 1, it is characterised in that: institute
State the spheric granules that vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material is 3~12 μm of average grain diameter；Described five
The coating thickness of V 2 O is 3~10nm, and the mass percent of vanadic anhydride is 1~7%；Nickel content is from core-shell structure
Center to the shell layer surface of gradient nickel cobalt manganese anode material gradually decreases, and the content of manganese, cobalt and vanadium is in core-shell structure particles
Center is uniformly distributed with shell；The kernel of the core-shell structure gradient nickel cobalt manganese anode material is heavy with the hydroxide of nickel cobalt manganese
Forming sediment is that presoma mixes the resulting nickle cobalt lithium manganate of lithium sintering, and shell is resulting using nickel cobalt manganese carbonate as the mixed lithium sintering of presoma
Nickle cobalt lithium manganate；The diameter of the kernel be 2.5~9.0 μm, shell with a thickness of 0.3~3.0 μm.
3. vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material according to claim 1 or claim 2, feature exist
In: the preparation method of the core-shell structure gradient nickel cobalt manganese positive electrode material precursor, comprising the following steps:
1) low nickel content nickel cobalt manganese solution is pumped into the container equipped with high nickel content nickel cobalt or nickel cobalt manganese solution, and stirred, with
The high nickel content nickel cobalt for being constantly pumped into low nickel content nickel cobalt manganese solution or nickel cobalt manganese solution are pumped into equipped with ammonia spirit by this simultaneously
Reaction kettle in, and simultaneously with ammonium hydroxide adjust reaction system ammonia concn, with hydroxide precipitant solution adjust reactant
The pH value of system, stirring carry out coprecipitation reaction and obtain presoma nuclear material until mean particle size grows to 2.5~9.0 μm, after
It is continuous to carry out aforesaid operations, hydroxide precipitant solution is only replaced with into carbonate deposition agent solution and is used to adjust reaction system
PH value, stirring carries out coprecipitation reaction, until low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel cobalt manganese solution are complete
Finish, obtains the solution containing presoma nucleocapsid layer material；
2) the solution stirring obtained by step (1) containing presoma nucleocapsid layer material is aged, filters, washs, it is dry, obtain core
Shell structure gradient nickel cobalt manganese positive electrode material precursor.
4. vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material according to claim 3, it is characterised in that: step
It is rapid 1) in, the charging rate of the low nickel content nickel cobalt manganese solution is 20~60mL/h, described to be constantly pumped into low nickel content nickel cobalt
The high nickel content nickel cobalt of manganese solution or the charging rate of nickel cobalt manganese solution are 50~100mL/h；The low nickel content nickel cobalt manganese is molten
In liquid, the concentration of metal ion is 1~3mol/L, and the molar percentage of the total metal ion of Ni Zhan is the total metal of 40~70%, Co Zhan
The molar percentage of ion is that the molar percentage of the total metal ion of 10~40%, Mn Zhan is 20~50%, and Ni, Co, Mn ion are total
Be 100%；In the high nickel content nickel cobalt or nickel cobalt manganese solution, the concentration of metal ion is 1~3mol/L, the total metal of Ni Zhan
The molar percentage of ion is that the molar percentage of the total metal ion of 60~90%, Co Zhan is the total metal ion of 10~40%, Mn Zhan
Molar percentage be 0~30%, Ni, Co, Mn ion summation be 100%；In same reaction system, low nickel content nickel cobalt manganese is molten
The nickel content of liquid is lower than high nickel content nickel cobalt or the nickel content of nickel cobalt manganese solution；Ammonia spirit, low nickel content nickel cobalt in reaction kettle
Manganese solution and high nickel content nickel cobalt or the volume ratio of nickel cobalt manganese solution are 0.1~10:0.8~1.2:1；The ammonia spirit rubs
Your concentration is 0.3~0.5mol/L；Reaction system ammonia concn, which is adjusted, with ammonium hydroxide is maintained at 0.3~0.5mol/L；For adjusting
The mass concentration of the ammonium hydroxide of reaction system ammonia concn is 25~28%；Reaction system pH is adjusted with hydroxide precipitant solution
Value is maintained at 10.5~11.5；The molar concentration of the hydroxide precipitant solution is 5~10mol/L；The hydroxide
Precipitating reagent is one or more of sodium hydroxide, potassium hydroxide or lithium hydroxide；It is adjusted and is reacted with carbonate deposition agent solution
System pH is maintained at 8.5~10.5；The molar concentration of the carbonate deposition agent solution is 0.5~1.5mol/L；The carbon
Hydrochlorate precipitating reagent is one or more of sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate or saleratus；Before the generation
In the coprecipitation reaction for driving body nuclear material and generation presoma nucleocapsid layer material, the speed of stirring is 600~1200r/min,
Temperature is 50~70 DEG C；The low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel cobalt manganese solution are soluble nickel salt
With the mixed solution of soluble cobalt or soluble nickel salt, soluble cobalt and soluble manganese salt；The soluble nickel salt is sulphur
One or more of sour nickel, nickel nitrate, nickel acetate or nickel chloride；The soluble cobalt is cobaltous sulfate, cobalt nitrate, cobalt acetate
Or one or more of cobalt chloride；The solubility manganese salt be one of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride or
It is several；In step 2, the speed of the stirring is 400~800r/min；The temperature of the ageing is 50~80 DEG C, the time 5
~15h；The temperature of the drying is 50~100 DEG C, and the time is 5~15h.
5. a kind of system of the vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material as described in one of Claims 1 to 4
Preparation Method, which comprises the following steps:
(1) core-shell structure gradient nickel cobalt manganese positive electrode material precursor is aged, is filtered, washed, it is dry, nucleocapsid knot must be aged
Structure gradient nickel cobalt manganese positive electrode material precursor；
(2) in the ageing core-shell structure gradient nickel cobalt manganese positive electrode material precursor obtained by step (1), lithium source, grinding, pre-burning is added
Afterwards, it is sintered, obtains core-shell structure gradient nickel cobalt manganese anode material；
(3) core-shell structure gradient nickel cobalt manganese anode material obtained by step (2) is mixed in alcoholic solution with vanadium source, ultrasound, heating
It is stirred to react to being evaporated, obtains mixed-powder；
(4) under an oxygen-containing atmosphere by mixed-powder obtained by step (3), it is heat-treated, obtains vanadic anhydride coated core-shell structure
Gradient nickel cobalt manganese anode material.
6. the preparation method of vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material according to claim 5,
Be characterized in that: in step (1), the temperature of the ageing is 50~80 DEG C, and revolving speed is 600~1200r/min, the time is 5~
15h；The temperature of the drying is 50~100 DEG C, and the time is 5~15h.
7. according to the preparation method of the vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material of claim 5 or 6,
It is characterized by: in step (2), nickel in elemental lithium and core-shell structure gradient nickel cobalt manganese positive electrode material precursor in the lithium source,
The molar ratio of the sum of cobalt, manganese element molal quantity is 1.01~1.07:1；The lithium source is lithium hydroxide, lithium nitrate, lithium carbonate, grass
One or more of sour lithium or lithium acetate and their hydrate.
8. the preparation of vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material according to one of claim 5~7
Method, it is characterised in that: in step (2), the revolving speed of the grinding is 600~1000r/min, and the time is 5~10min；It is described
The temperature of pre-burning is 350~550 DEG C, and the time is 3~6h；The temperature of the sintering be 650~950 DEG C, the time be 8~for 24 hours.
9. the preparation of vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material according to one of claim 5~8
Method, it is characterised in that: in step (3), nickel in vanadium and core-shell structure gradient nickel cobalt manganese anode material in the vanadium source,
The molar ratio of the sum of cobalt, manganese element molal quantity is 0.01~0.10:1；The vanadium source be vanadium acetylacetonate, vanadyl acetylacetonate or
One or more of ammonium metavanadate；The body of the alcoholic solution and core-shell structure gradient nickel cobalt manganese anode material and vanadium source gross mass
Product mass ratio is 10~60:1；The alcoholic solution is one or more of dehydrated alcohol, ethylene glycol or methanol；The ultrasound point
Scattered frequency is 30~40kHz, and the time is 4~8h；The temperature of the heating stirring reaction is 40~60 DEG C, and the speed of stirring is
100~200r/min.
10. the preparation of vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material according to one of claim 5~9
Method, it is characterised in that: in step (4), the temperature of the heat treatment is 300~600 DEG C, and the time is 4~8h；It is described oxygenous
Atmosphere is one or more of air atmosphere, oxygen atmosphere or ozone atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811408690.9A CN109546123B (en) | 2018-11-23 | 2018-11-23 | Vanadium pentoxide-coated core-shell structure gradient nickel-cobalt-manganese positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811408690.9A CN109546123B (en) | 2018-11-23 | 2018-11-23 | Vanadium pentoxide-coated core-shell structure gradient nickel-cobalt-manganese positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109546123A true CN109546123A (en) | 2019-03-29 |
| CN109546123B CN109546123B (en) | 2021-09-14 |
Family
ID=65849875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811408690.9A Active CN109546123B (en) | 2018-11-23 | 2018-11-23 | Vanadium pentoxide-coated core-shell structure gradient nickel-cobalt-manganese positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109546123B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109980219A (en) * | 2019-04-19 | 2019-07-05 | 中南大学 | Full gradient nickel cobalt manganese anode material, ruthenium-oxide covering material and preparation method thereof |
| CN110176587A (en) * | 2019-05-28 | 2019-08-27 | 华东理工大学 | A kind of vanadium ion surface doping nickel cobalt aluminium tertiary cathode material, preparation method and applications |
| CN110212189A (en) * | 2019-06-18 | 2019-09-06 | 贵州梅岭电源有限公司 | A kind of lithium-rich manganese base material and its preparation method and application |
| CN111933914A (en) * | 2020-09-03 | 2020-11-13 | 中南大学 | Vanadium pentoxide and rGO co-coated gradient ternary cathode material and preparation method thereof |
| CN112456567A (en) * | 2020-11-18 | 2021-03-09 | 浙江钠创新能源有限公司 | Preparation method of sodium-ion battery positive electrode material with coating structure |
| CN112531155A (en) * | 2019-09-17 | 2021-03-19 | 湖南杉杉新能源有限公司 | Preparation method of positive electrode material precursor and preparation method of positive electrode material |
| CN113422010A (en) * | 2021-06-07 | 2021-09-21 | 杉杉能源（宁夏）有限公司 | Vanadium oxide composite high-nickel ternary cathode material and preparation method and application thereof |
| CN114023939A (en) * | 2021-11-08 | 2022-02-08 | 苏州新中能源科技有限公司 | Titanium and zirconium doped and vanadium coated ternary cathode material and preparation method thereof |
| CN114094060A (en) * | 2021-10-08 | 2022-02-25 | 中南大学 | Preparation method of high-voltage positive electrode material with core-shell structure |
| CN116332249A (en) * | 2023-05-26 | 2023-06-27 | 浙江帕瓦新能源股份有限公司 | Vanadate coated modified precursor material and preparation method and application thereof |
| CN116588991A (en) * | 2023-07-07 | 2023-08-15 | 南通瑞翔新材料有限公司 | Ultra-high nickel anode material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637871A (en) * | 2012-04-19 | 2012-08-15 | 中南大学 | Preparation method of lithium ion anode material coated with lithium ion activating oxide V2O5 |
| CN102637866A (en) * | 2012-04-25 | 2012-08-15 | 中南大学 | Method for preparing lithium ion battery anode material with concentration gradient |
| KR20170102293A (en) * | 2014-12-31 | 2017-09-08 | 베이징 이스프링 머티리얼 테크놀로지 컴퍼니 리미티드 | Multicomponent materials having a classification structure for lithium ion batteries, a method for manufacturing the same, an anode of a lithium ion battery and a lithium ion battery |
| CN108793268A (en) * | 2018-06-19 | 2018-11-13 | 中南大学 | Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof |
-
2018
- 2018-11-23 CN CN201811408690.9A patent/CN109546123B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637871A (en) * | 2012-04-19 | 2012-08-15 | 中南大学 | Preparation method of lithium ion anode material coated with lithium ion activating oxide V2O5 |
| CN102637866A (en) * | 2012-04-25 | 2012-08-15 | 中南大学 | Method for preparing lithium ion battery anode material with concentration gradient |
| KR20170102293A (en) * | 2014-12-31 | 2017-09-08 | 베이징 이스프링 머티리얼 테크놀로지 컴퍼니 리미티드 | Multicomponent materials having a classification structure for lithium ion batteries, a method for manufacturing the same, an anode of a lithium ion battery and a lithium ion battery |
| CN108793268A (en) * | 2018-06-19 | 2018-11-13 | 中南大学 | Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109980219A (en) * | 2019-04-19 | 2019-07-05 | 中南大学 | Full gradient nickel cobalt manganese anode material, ruthenium-oxide covering material and preparation method thereof |
| US20200335784A1 (en) * | 2019-04-19 | 2020-10-22 | Central South University | Full-gradient nickel cobalt manganese positive electrode material, ruthenium oxide coated material and preparation method thereof |
| CN110176587A (en) * | 2019-05-28 | 2019-08-27 | 华东理工大学 | A kind of vanadium ion surface doping nickel cobalt aluminium tertiary cathode material, preparation method and applications |
| CN110212189A (en) * | 2019-06-18 | 2019-09-06 | 贵州梅岭电源有限公司 | A kind of lithium-rich manganese base material and its preparation method and application |
| CN112531155A (en) * | 2019-09-17 | 2021-03-19 | 湖南杉杉新能源有限公司 | Preparation method of positive electrode material precursor and preparation method of positive electrode material |
| CN112531155B (en) * | 2019-09-17 | 2022-05-31 | 巴斯夫杉杉电池材料(宁乡)有限公司 | Preparation method of positive electrode material precursor and preparation method of positive electrode material |
| CN111933914A (en) * | 2020-09-03 | 2020-11-13 | 中南大学 | Vanadium pentoxide and rGO co-coated gradient ternary cathode material and preparation method thereof |
| CN112456567A (en) * | 2020-11-18 | 2021-03-09 | 浙江钠创新能源有限公司 | Preparation method of sodium-ion battery positive electrode material with coating structure |
| CN113422010A (en) * | 2021-06-07 | 2021-09-21 | 杉杉能源（宁夏）有限公司 | Vanadium oxide composite high-nickel ternary cathode material and preparation method and application thereof |
| CN114094060A (en) * | 2021-10-08 | 2022-02-25 | 中南大学 | Preparation method of high-voltage positive electrode material with core-shell structure |
| CN114023939A (en) * | 2021-11-08 | 2022-02-08 | 苏州新中能源科技有限公司 | Titanium and zirconium doped and vanadium coated ternary cathode material and preparation method thereof |
| CN116332249A (en) * | 2023-05-26 | 2023-06-27 | 浙江帕瓦新能源股份有限公司 | Vanadate coated modified precursor material and preparation method and application thereof |
| CN116332249B (en) * | 2023-05-26 | 2023-07-28 | 浙江帕瓦新能源股份有限公司 | Vanadate coated modified precursor material and preparation method and application thereof |
| CN116588991A (en) * | 2023-07-07 | 2023-08-15 | 南通瑞翔新材料有限公司 | Ultra-high nickel anode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109546123B (en) | 2021-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109980219B (en) | Full-gradient nickel-cobalt-manganese positive electrode material, ruthenium oxide coating material and preparation method thereof | |
| CN109546123A (en) | Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material and preparation method | |
| CN108878818B (en) | Core-shell structure nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof | |
| CN108793268B (en) | Core-shell structure gradient nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof | |
| CN109273701B (en) | High-nickel core-shell structure gradient nickel-cobalt-manganese ternary cathode material and preparation method thereof | |
| CN107445214B (en) | A kind of lithium ion battery nickel-cobalt-manganternary ternary anode material and preparation method thereof | |
| CN111785960B (en) | Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| CN108899539A (en) | A kind of nickelic ternary lithium ion anode material and preparation method thereof | |
| CN102208611B (en) | A kind of induced crystallization synthetic method of lithium ion secondary battery positive electrode dusty material | |
| CN107785551B (en) | Lithium-rich layered oxide material with gradient phase structure proportion and preparation method thereof | |
| CN101771145B (en) | Method for preparing multielement cathode materials for lithium ion batteries | |
| CN102244236A (en) | Method for preparing lithium-enriched cathodic material of lithium ion battery | |
| CN104852038A (en) | Preparation method of high-capacity quickly-chargeable/dischargeable lithium ion battery ternary anode material | |
| CN106784790B (en) | A kind of preparation method of nickle cobalt lithium manganate tertiary cathode material | |
| CN110226251A (en) | Nickel hydroxide active material presoma and preparation method thereof, nickel hydroxide active material and lithium secondary battery | |
| CN102569773B (en) | Anode material for lithium-ion secondary battery and preparation method thereof | |
| CN103094554B (en) | Modified lithium manganate anode material and preparation method thereof | |
| CN103413926B (en) | Preparation method of lithium nickel cobalt manganese oxide precursor | |
| CN106602004A (en) | High-safety power lithium ion secondary battery composite positive material and preparation method thereof | |
| CN109256557A (en) | Nickelic layered oxide lithium electricity positive electrode of a kind of perofskite type oxide cladding and preparation method thereof | |
| CN108448109A (en) | A kind of stratiform lithium-rich manganese-based anode material and preparation method thereof | |
| CN102983326A (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN110233261B (en) | Preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| CN108539193A (en) | Include the nucleocapsid NCM tertiary cathode materials and preparation method thereof of carbon nanotube |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 |