CN107768642A - A kind of lithium ion battery ternary material of surface double cladding and preparation method thereof - Google Patents
A kind of lithium ion battery ternary material of surface double cladding and preparation method thereof Download PDFInfo
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- CN107768642A CN107768642A CN201710979117.2A CN201710979117A CN107768642A CN 107768642 A CN107768642 A CN 107768642A CN 201710979117 A CN201710979117 A CN 201710979117A CN 107768642 A CN107768642 A CN 107768642A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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
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Abstract
The invention discloses a kind of lithium ion battery ternary material of surface double-coating, including nickel-cobalt-manganese ternary material, there are lithium-rich oxide cladding layers in the Surface coating of the nickel-cobalt-manganese ternary material, and there is aluminum fluoride clad in the Surface coating of the lithium-rich oxide cladding layers, the lithium ion battery ternary material clad of the surface double-coating is difficult for drop-off, chemical stability is good, and capacity is high.The invention also discloses a kind of preparation method of the lithium ion battery ternary material, organic complexing agent assisting sol gel method is first used in the Surface coating lithium-rich oxide of ternary material, form rich lithium clad, again aluminum fluoride is coated with liquid phase method in lithium-rich oxide surface, obtain the lithium ion battery ternary material of double-coating, the preparation method technique is simple, and operation possibility is high, and element utilization rate is high.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium ion battery ternary of surface double cladding
Material and preparation method thereof.
Background technology
Due to environmental pollution and fossil fuel resource increasingly deficient outstanding problem, the change of increasingly depleted is substituted with green energy resource
The stone energy turns into various countries new energy development direction.Since the nineties in last century, commercial li-ion battery came out, lithium ion battery
Industry develops rapidly in a short time, and it is multiple to be widely used to communication, energy storage, 3C electronic products and electric automobile etc. at present
Field.Current commercial lithium battery material mainly has cobalt acid lithium, LiMn2O4, LiFePO4, ternary material etc..Wherein ternary material
It is good with higher specific capacity and energy density and power density, operating voltage height and stability, so as to turn into Business Studies
Active material.However, when charging to high voltage, Ni caused by ternary material surface4+Ion can occur serious with electrolyte
Side reaction, the big calorimetric of simultaneous and the release of oxygen, so as to cause poor circulation and heat endurance to reduce.It is in addition, new
The LiOH or Li of the material surface residual of synthesis2O easily with the H in air2O and CO2Reaction forms LiOH and Li2CO3, cause height
Temperature expands and then causes the decline of chemical property and storge quality.Therefore need to be modified ternary material.
Cladding is that current researcher uses a kind of more surface modifying methods, after material is coated, shape
Into protective layer the active material in material can be kept apart with electrolyte, so as to substantially reduce electrode/electrolyte
The side reaction of interface, such as, reduce the precipitation of transition metal, the precipitation for forming thinner surface protection film, reducing oxygen atom
Deng so as to inhibit structure of the material in charge and discharge process to destroy, improving electrochemical stability, extend cycle life.
Existing method for coating is not readily available uniform clad and controllable nanoscale cladding material, material and main body after cladding
Material compatibility is not good enough or is not sufficiently stable, and so as to cause clad easily to come off, covered effect is had a greatly reduced quality.
It is lithium-rich manganese-based with spinelle mangaic acid that Publication No. CN107086298A Chinese invention patent discloses a kind of stratiform
The nucleocapsid isomery material that lithium is formed, because both material mix variances are larger, causes covered effect bad；And lithium-rich
The structural instability of oxide, long-term cycle performance can not meet demands.Publication No. CN104953112A Chinese invention
Patent discloses a kind of AlF3The preparation method of coated porous ball-shaped lithium-ion battery material precursor, the follow-up mixed lithium of this method
High-temperature sintering process can be to AlF3Clad damages, and influences covered effect, and persursor material and AlF3Layer cladding is compatible
Property is poor, causes covered effect to be had a greatly reduced quality.Publication No. CN104218233A Chinese invention patent discloses one kind in nickel cobalt
The mixture Surface coating AlF of LiMn2O4 and cobalt acid lithium3Method, this method will be subsequently dried by spray method, mistake
Journey is cumbersome.
The content of the invention
For the deficiency and defect mentioned in background above technology, it is an object of the invention to provide a kind of covered effect
The lithium ion battery ternary material of the surface double cladding good, chemical stability is good, capacity is high, and a kind of above-mentioned lithium is also provided
The preparation method of ion battery ternary material, the preparation method technique is simple, operation possibility is high, element utilization rate is high.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of lithium ion battery ternary material of surface double-coating, including nickel-cobalt-manganese ternary material, in the nickel cobalt manganese
The Surface coating of ternary material has lithium-rich oxide cladding layers, and on the surface of the lithium-rich oxide cladding layers
It is coated with aluminum fluoride clad.
The present invention coats lithium-rich oxide in lithium ion battery nickel-cobalt-manganese ternary material surface, and in lithium-rich oxygen
Compound cover surface coats aluminum fluoride, forms double-coating structure.Because rich oxidate for lithium and nickel-cobalt-manganese ternary material are
Layer structure, compared to existing clad, between lithium-rich oxide cladding layers and nickel-cobalt-manganese ternary material of the invention
Compatibility is good, and with reference to more close, clad is difficult for drop-off.The present invention on the surface of lithium-rich oxide cladding layers by entering
One step coats aluminum fluoride, forms double-coating structure, and aluminum fluoride plays the work of activation and protection lithium-rich oxide cladding layers
With the high capacity characteristics of lithium-rich oxide can be given full play to, and and can plays very well to lithium-rich oxide cladding layers
Protective effect, avoid lithium-rich oxide cladding layers structure in cyclic process from changing, and then improve compound
The capacity and stability of material.
Preferably, the nickel-cobalt-manganese ternary material is LiNixCoyMn1-x-yO2, wherein 0≤x, y≤1.
Preferably, the lithium-rich oxide is Li [LiaMb]O2, wherein a+b=1, M Ni, Co, Mn, Al, Ti,
One or more in Sn, Ru.
Preferably, the covering amount of the lithium-rich oxide cladding layers is the 1 of the nickel cobalt manganese lithium ternary material quality
~10%,；The covering amount of the aluminum fluoride clad is nickel cobalt manganese lithium ternary material and the total matter of lithium-rich oxide cladding layers
The 0.1%~1% of amount.Covering amount has large effect to covered effect, and covering amount is too high may to cause covering material independent
Particle is formed, covering amount is too low, does not have effect or effect unobvious.
Preferably, the lithium-rich oxide cladding layers form gel by organic complexing agent, lithium source, M sources, by nickel cobalt
Manganese ternary material is immersed in the gel, then is formed through drying and being tempered.
Preferably, the organic complexing agent is selected from citric acid, polyvinylpyrrolidone, tartaric acid, ethylenediamine tetra-acetic acid, benzene
One or both of diphenol and formaldehyde.The M sources are more preferably nickel source and manganese source.
Preferably, the mol ratio of the organic complexing agent and metallic element total in the lithium-rich oxide cladding layers
For 1：(1~5), more preferably 1：(3~4).Organic complexing agent play the role of to the synthetic effect of rich lithium it is important, if network
Mixture amount is very few to be complexed completely with metal ion, and the wasting of resources can be caused if dosage is complexed excessively.
The technical concept total as one, another aspect of the present invention provide a kind of lithium ion of above-mentioned surface double-coating
The preparation method of battery ternary material, comprises the following steps：
(1) organic complexing agent is scattered in solvent, stirred, obtain dispersion liquid；
(2) lithium-rich oxide molecule formula ratio is added into dispersion liquid obtained by step (1) under ultrasound and stirring
Lithium source, nickel source and manganese source, continue stirring until to form gel；
(3) nickel-cobalt-manganese ternary material is immersed in gel obtained by step (2), stirring, obtains mixture, and gained is mixed
Thing is dried and is tempered, and obtaining Surface coating has the ternary material of lithium-rich oxide；
(4) take the mixture obtained by step (3) after tempering to be scattered in solvent, be dispersed with stirring uniformly, then add
Fluorine source and silicon source, stirring, obtain mixture, then gained mixture is dried and is tempered, produce the lithium of surface double-coating from
Sub- battery ternary material.
The present invention forms rich lithium by adding organic complexing agent, and using sol-gal process in nickel-cobalt-manganese ternary material surface
Layered oxide clad, the organic complexing agent added can make metal ion in lithium source, M sources with the level of atomic level with
Nickel-cobalt-manganese ternary material forms cross-linked structure, can make lithium-rich oxide in the homogeneous precipitation of nickel-cobalt-manganese ternary material surface and life
It is long, the clad of even particle size distribution is obtained, substantially increases the uniformity of lithium-rich oxide cladding layers；It is basic herein
On, the present invention further plays work by liquid phase method in one layer of aluminum fluoride of lithium-rich oxide shell layer Surface coating, aluminum fluoride
Change and protect the effect of lithium-rich oxide, both given full play to the high capacity characteristics of lithium-rich oxide, and played guarantor again
The effect of lithium-rich oxide is protected, avoids lithium-rich oxide structure in cyclic process from changing, so as to improve
The capacity and stability of composite.The preparation method of the present invention is effectively improved the uniformity and chemically stable of clad
Property, and present invention process is simple, and operation possibility is high, and element utilization rate is high, significantly improves the electrochemistry of ternary material
Energy.
Above-mentioned preparation method, it is preferred that in the step (2), ultrasonic frequency is 20~50kHz, further preferably
For 30~50kHz, ultrasonic power is 300~600W, more preferably 400~500W, and mixing speed is 300~600r/
Min, more preferably 400~500r/min；In the step (3) and step (4), mixing speed is 300~600r/min,
More preferably 400~500r/min, mixing time are 10~60min, more preferably 20~40min.Supersonic frequency,
Power and mixing speed and time are sufficiently dispersed with large effect to positive electrode, can be follow-up successfully orderly cladding
Lay a good foundation.
Above-mentioned preparation method, it is preferred that in the step (3), the temperature of tempering is 600~800 DEG C, further preferably
For 650~750 DEG C；In the step (5), the temperature of tempering is 300~500 DEG C, more preferably 350~450 DEG C.Tempering
Formation of the temperature to covering material is most important, temperature it is too high with too low all without forming material requested or make obtained material
Can be poor, temperature needed for the formation of rich lithium is higher in step (3), and temperature needed for the formation of aluminum fluoride is relatively in step (5)
It is low.
Above-mentioned preparation method, it is preferred that in the step (1) and step (4), solvent is deionized water, ethanol, second two
One or more in alcohol, methanol and isopropanol.
Above-mentioned preparation method, it is preferred that in the step (2), lithium source is lithium acetate, lithium hydroxide, lithium chloride, sulfuric acid
Any one in lithium and lithium nitrate, nickel source are any one in nickel acetate, nickel chloride, nickel sulfate and nickel nitrate, and manganese source is
Any one in manganese acetate, manganese chloride, manganese sulfate and manganese nitrate；In the step (4), Fluorine source be ammonium fluoride, sodium fluoride and
Any one in potassium fluoride, silicon source are any one in aluminum nitrate, aluminium chloride and aluminum sulfate.
Above-mentioned preparation method, it is preferred that the lithium source, nickel source, manganese source, the concentration of Fluorine source and silicon source be 0.0.1~
0.1mol/L。
Compared with prior art, the advantage of the invention is that：
(1) lithium ion battery ternary material of the invention is double-coating structure, including located in nickel-cobalt-manganese ternary material
The lithium-rich oxide cladding layers on surface, and the aluminum fluoride located at lithium-rich oxide cladding layers surface, the rich lithia
Compound and nickel-cobalt-manganese ternary material are layer structure, are tightly combined, difficult for drop-off；Aluminum fluoride plays to lithium-rich oxide
Activation and protective effect so that lithium ion battery ternary material has high power capacity and good stability.
(2) present invention forms rich lithium layer using organic complexing agent-assisting sol gel method in nickel-cobalt-manganese ternary material surface
Shape oxide cladding layers, organic complexing agent make metal ion form cross-linked structure with nickel-cobalt-manganese ternary material, make lithium-rich oxygen
Compound is layer structure in the homogeneous precipitation of nickel-cobalt-manganese ternary material surface and growth, the uniformity height of gained richness oxidate for lithium,
The lithium-rich oxide cladding layers stability of formation is good.
(3) present invention is forming rich lithium using organic complexing agent-assisting sol gel method in nickel-cobalt-manganese ternary material surface
On the basis of layered oxide clad, aluminum fluoride is further coated in lithium layer shape oxide surface using liquid phase method, to rich lithium
Layered oxide clad plays activation and protective effect, further increases the capacity and cladding of lithium ion battery ternary material
The stability of layer.
(4) preparation method technique of the invention is simple, and operation possibility is high, and element utilization rate is high, and significantly improves
The chemical property of lithium ion battery ternary material.
Brief description of the drawings
Fig. 1 is the flow chart of lithium-rich oxide and aluminum fluoride dual cladding ternary material.
Fig. 2 is that front and rear LiNi is coated in embodiment 10.6Co0.2Mn0.2O2The SEM figures of ternary material.
Fig. 3 is Li in embodiment 11.2Ni0.2Mn0.6O2And dual cladding LiNi0.6Co0.2Mn0.2O2XRD.
Fig. 4 is that front and rear LiNi is coated in embodiment 10.6Co0.2Mn0.2O2Ternary material is under 1C current densities, 25 DEG C and
Cyclic curve figure in 2.0V~4.6V voltage ranges.
Fig. 5 is that front and rear LiNi is coated in embodiment 10.6Co0.2Mn0.2O2Ternary material is under 1C current densities, 50 DEG C and
Cyclic curve figure in 2.0V~4.6V voltage ranges.
Fig. 6 is that front and rear LiNi is coated in embodiment 20.5Co0.2Mn0.3O2Ternary material is under 1C current densities, 50 DEG C and
Cyclic curve figure in 2.0V~4.6V voltage ranges.
Fig. 7 is that front and rear LiNi is coated in embodiment 30.8Co0.1Mn0.1O2Ternary material is under 1C current densities, 50 DEG C and
Cyclic curve figure in 2.0V~4.6V voltage ranges.
Fig. 8 is uncoated LiNi0.6Co0.2Mn0.2O2Li in ternary material, embodiment 11.2Ni0.2Mn0.6O2And AlF3It is dual
Coat LiNi0.6Co0.2Mn0.2O2Li in ternary material and comparative example 11.2Ni0.2Mn0.6O2Individually cladding
LiNi0.6Co0.2Mn0.2O2Ternary material is under 1C current densities, the cyclic curve in 50 DEG C and 2.0V~4.6V voltage ranges
Figure.
Fig. 9 is uncoated LiNi0.6Co0.2Mn0.2O2Li in ternary material, embodiment 11.2Ni0.2Mn0.6O2And AlF3It is dual
Coat LiNi0.6Co0.2Mn0.2O2AlF in ternary material and comparative example 23Individually cladding LiNi0.6Co0.2Mn0.2O2Ternary material
Cyclic curve figure under 1C current densities, in 50 DEG C and 2.0V~4.6V voltage ranges.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
By citric acid, (total metal ion mol ratio with lithium, nickel, manganese is 3:1) it is uniformly dispersed, obtains in deionized water
Dispersion liquid；Into dispersion liquid, cocurrent addition concentration is 0.05mol/L lithium acetate solution, acetic acid under ultrasound and stirring action
Nickel solution and acetic acid manganese solution, be stirred continuously until occur gel (wherein, supersonic frequency 40kHz, ultrasonic power 450W,
Mixing speed is 450r/min；The mol ratio of lithium ion, nickel ion and manganese ion is 6：1：3)；
By LiNi0.6Co0.2Mn0.2O2Ternary material is immersed in above-mentioned gel, persistently stirs 20min, by gained mixture
It is dried and temper, temperature is 700 DEG C, in LiNi0.6Co0.2Mn0.2O2Ternary material surface is formed
Li1.2Ni0.2Mn0.6O2(lithium-rich oxide) clad；Weigh the compound after tempering to be scattered in alcohol solvent, ultrasound
Stirring makes it be uniformly dispersed；0.03mol/L ammonium fluoride solution and aluminum nitrate solution are added in the dispersion liquid, lasting stirring
30min, gained mixture is dried and temper, temperature are 400 DEG C, produces Li1.2Ni0.2Mn0.6O2And AlF3
The LiNi of dual cladding0.6Co0.2Mn0.2O2Ternary material.Wherein, Li1.2Ni0.2Mn0.6O2And AlF3Covering amount be respectively 2%
With 0.2%.
Fig. 1 is the flow chart of lithium-rich oxide and aluminum fluoride dual cladding ternary material.Fig. 2 is that cladding is front and rear
LiNi0.6Co0.2Mn0.2O2The SEM figures of ternary material.As seen from Figure 2, two samples are that Size Distribution is 10~13 μm
Spheric granules, be made up of 0.2~0.5 μm of primary particle.Primary particle before cladding on material surface be it is smooth visible,
And the material after coating can clearly find out that many nano particles are uniformly adhered on surface, and show fuzzy edge.
Fig. 3 is Li1.2Ni0.2Mn0.6O2And dual cladding LiNi0.6Co0.2Mn0.2O2XRD.As seen from Figure 3, two
Individual sample is typical α-NaFeO2Type layered rock salt structure, space group are R3m (LiNiO2, PDF#74-0919).From Fig. 3
As can be seen that (006)/(102) and (108)/(110) diffraction maximum show significantly to divide, show that two samples have been respectively provided with
The layer structure of sequence.Compared with original material, the material after cladding occurs in the range of 20~25 ° of diffraction maximums
Li1.2Ni0.2Mn0.6O2Middle Li2MnO3Characteristic peak (the Li of component2MnO3, PDF#73-0152), show LiNi0.6Co0.2Mn0.2O2Table
Face has coated Li as expected1.2Ni0.2Mn0.6O2.Due to AlF3Covering amount is less, therefore does not detect its characteristic peak.
Fig. 4 is the front and rear LiNi of cladding0.6Co0.2Mn0.2O2Ternary material is under 1C current densities, 25 DEG C and 2.0V~
Cyclic curve figure in 4.6V voltage ranges.As shown in Figure 4, uncoated LiNi0.6Co0.2Mn0.2O2Ternary material circulation 100
After circle, the capacity of material is from 196.8mAhg-1Decay to 166.5mAhg-1, capability retention 84.6%；And dual packet
LiNi after covering0.6Co0.2Mn0.2O2After the circle of ternary material circulation 100, the capacity of material is from 195.1mAhg-1Decay to
179.3mAh·g-1, capability retention 91.9%, hence it is evident that higher than uncoated material.
Fig. 5 is the front and rear LiNi of cladding0.6Co0.2Mn0.2O2Ternary material is under 1C current densities, 50 DEG C and 2.0V~
Cyclic curve figure in 4.6V voltage ranges.As shown in Figure 5, the LiNi after dual cladding0.6Co0.2Mn0.2O2Ternary material is in 1C
After lower circulation 100 times, the capacity of material is from 217.8mAhg-1Decay to 189.6mAhg-1, capability retention 87.1%；
And uncoated LiNi0.6Co0.2Mn0.2O2The discharge capacity of ternary material is from 208.6mAhg-1Decay to rapidly
124.7mAh·g-1, capability retention only has 59.8%.
Embodiment 2：
By polyvinylpyrrolidone, (total metal ion mol ratio with lithium, nickel, manganese is 2:1) disperse in alcohol solvent equal
It is even, obtain dispersion liquid；It is equal 0.04mol/L lithium chloride solutions, chlorination to add concentration in dispersion liquid under ultrasound and stirring action
Nickel solution and manganese chloride solution, be stirred continuously until occur gel (wherein, supersonic frequency 40kHz, ultrasonic power 400W,
Mixing speed is 400r/min；The mol ratio of lithium ion, nickel ion and manganese ion is 3：1：1)；
By LiNi0.5Co0.2Mn0.3O2Ternary material is immersed in above-mentioned gel, persistently stirs 20min, by gained mixture
It is dried and temper, temperature is 750 DEG C, in LiNi0.5Co0.2Mn0.3O2Ternary material surface forms Li1.2
[Ni1/2Mn1/2]0.8O2Clad；Weigh the compound after tempering to be scattered in deionized water, ultrasonic agitation makes it be uniformly dispersed；
0.04mol/L Fluorinse and liquor alumini chloridi are added in the dispersion liquid, persistently stir 30min, gained is mixed
Thing is dried and temper, and temperature is 450 DEG C, produces Li1.2[Ni1/2Mn1/2]0.8O2And AlF3Dual cladding
LiNi0.5Co0.2Mn0.3O2Ternary material.Wherein, Li1.2[Ni1/2Mn1/2]0.8O2And AlF3Covering amount be respectively 5% He
0.5%.
Fig. 6 is the front and rear LiNi of cladding0.5Co0.2Mn0.3O2Ternary material is under 1C current densities, 50 DEG C and 2.0V~
Cyclic curve figure in 4.6V voltage ranges.It will be appreciated from fig. 6 that the LiNi before cladding0.5Co0.2Mn0.3O2Ternary material follows under 1C
After ring 100 times, the capacity of material is from 189.8mAhg-1Decay to 125.4mAhg rapidly-1, capability retention is only
66.1%；And the LiNi after dual cladding0.5Co0.2Mn0.3O2Ternary material circulates 100 discharge capacities from 195.7mAhg-1
Decay to 165.8mAhg-1, capability retention 84.7%, hence it is evident that higher than uncoated ternary material.
Embodiment 3：
By tartaric acid, (total metal ion mol ratio with lithium, nickel, cobalt, manganese is 4:1) it is uniformly dispersed, obtains in alcohol solvent
To dispersion liquid；Into dispersion liquid, cocurrent adds concentration as equal 0.05mol/L lithium chloride solutions, chlorination under ultrasound and stirring action
Nickel solution and manganese chloride solution, be stirred continuously until occur gel (wherein, supersonic frequency 50kHz, ultrasonic power 500W,
Mixing speed is 400r/min；Lithium ion, nickel ion, the mol ratio of cobalt ions and manganese ion are according to Li1.2[Ni1/3Co1/ 3Mn1/3]0.8O2Addition)；
By LiNi0.8Co0.1Mn0.1O2Ternary material is immersed in above-mentioned gel, persistently stirs 20min, by gained mixture
It is dried and temper, temperature is 650 DEG C, in LiNi0.8Co0.1Mn0.1O2Ternary material surface forms Li1.2
[Ni1/3Co1/3Mn1/3]0.8O2Clad；Weigh the compound after tempering to be scattered in deionized water, ultrasonic agitation makes it scattered
Uniformly；0.05mol/L potassium fluoride solution and aluminum sulfate solution are added in dispersion liquid, persistently stir 30min, gained is mixed
Compound is dried and temper, and temperature is 400 DEG C, produces Li1.2[Ni1/3Co1/3Mn1/3]0.8O2And AlF3Dual packet
The LiNi covered0.8Co0.1Mn0.1O2Ternary material.Wherein, Li1.2[Ni1/3Co1/3Mn1/3]0.8O2And AlF3Covering amount be respectively
10% and 1%.
Fig. 7 is the front and rear LiNi of cladding0.8Co0.1Mn0.1O2Ternary material is under 1C current densities, 50 DEG C and 2.0V~
Cyclic curve figure in 4.6V voltage ranges.As shown in Figure 7, the LiNi before cladding0.8Co0.1Mn0.1O2Ternary material follows under 1C
After ring 100 times, the capacity of material is from 229.3mAhg-1Decay to 147.6mAhg rapidly-1, capability retention is only
64.6%；And the LiNi after dual cladding0.8Co0.1Mn0.1O2Ternary material circulates 100 discharge capacities from 241.3mAhg-1
Decay to 206.7mAhg-1, capability retention 85.7%, hence it is evident that higher than uncoated ternary material.
Comparative example 1：
Compared with Example 1, the main distinction is this comparative example, and dual cladding is changed to Li1.2Ni0.2Mn0.6O2Individually bag
Cover, in Li1.2Ni0.2Mn0.6O2Surface does not use AlF3Coated.
Fig. 8 is uncoated LiNi0.6Co0.2Mn0.2O2Li in ternary material, embodiment 11.2Ni0.2Mn0.6O2And AlF3It is dual
Coat LiNi0.6Co0.2Mn0.2O2Li in ternary material and this comparative example1.2Ni0.2Mn0.6O2Individually cladding
LiNi0.6Co0.2Mn0.2O2Ternary material is under 1C current densities, the cyclic curve in 50 DEG C and 2.0V~4.6V voltage ranges
Figure.As shown in Figure 8, from 208.6mAhg after the capacity of uncoated ternary material circulates 100 weeks under 1C-1Decay to
124.7mAh·g-1, capability retention is only 59.8%；Aluminum fluoride and the capacity of rich lithium dual cladding ternary material (embodiment 1)
From 217.8mAhg-1Decay to 189.6mAhg-1, capability retention 87.1%；Rich lithium individually coats ternary material (this
Comparative example) discharge capacity from 211.7mAhg-1Decay to 176.1mAhg-1, capability retention 83.2%, higher than not
The ternary material of cladding, but less than the ternary material of dual cladding.
Comparative example 2：
Compared with Example 1, the main distinction is this comparative example, and dual cladding is changed to AlF3Individually cladding, AlF3Directly wrap
Overlay on LiNi0.6Co0.2Mn0.2O2The surface of ternary material.
Fig. 9 is uncoated LiNi0.6Co0.2Mn0.2O2Li in ternary material, embodiment 11.2Ni0.2Mn0.6O2And AlF3It is dual
Coat LiNi0.6Co0.2Mn0.2O2AlF in ternary material and this comparative example3Individually cladding LiNi0.6Co0.2Mn0.2O2Ternary material
Cyclic curve figure under 1C current densities, in 50 DEG C and 2.0V~4.6V voltage ranges.As shown in Figure 9, uncoated ternary material
The capacity of material circulated under 1C 100 weeks after from 208.6mAhg-1Decay to 124.7mAhg-1, capability retention is only
59.8%；Aluminum fluoride and the capacity of rich lithium dual cladding ternary material (embodiment 1) are from 217.8mAhg-1Decay to
189.6mAh·g-1, capability retention 87.1%；AlF3Individually cladding ternary material (this comparative example) discharge capacity from
203.2mAh·g-1Decay to 166.2mAhg-1, capability retention 83.2%, higher than uncoated ternary material, but it is low
In the ternary material of dual cladding.
Claims (10)
1. a kind of lithium ion battery ternary material of surface double-coating, including nickel-cobalt-manganese ternary material, it is characterised in that：Institute
Stating the Surface coating of nickel-cobalt-manganese ternary material has lithium-rich oxide cladding layers, and is coated in the lithium-rich oxide
The Surface coating of layer has aluminum fluoride clad.
2. the lithium ion battery ternary material of surface double-coating according to claim 1, it is characterised in that：The nickel cobalt
Manganese ternary material is LiNixCoyMn1-x-yO2, wherein 0≤x, y≤1；The lithium-rich oxide is Li [LiaMb]O2, wherein a
One or more in+b=1, M Ni, Co, Mn, Al, Ti, Sn, Ru.
3. the lithium ion battery ternary material of surface double-coating according to claim 1, it is characterised in that：The rich lithium
The covering amount of layered oxide clad is the 1~10% of the nickel cobalt manganese lithium ternary material quality；The aluminum fluoride clad
Covering amount be the 0.1%~1% of nickel cobalt manganese lithium ternary material and lithium-rich oxide cladding layers gross mass.
4. the lithium ion battery ternary material of surface double-coating according to claim 1, it is characterised in that：The rich lithium
Layered oxide clad forms gel by organic complexing agent, lithium source, M sources, and nickel-cobalt-manganese ternary material is immersed in the gel,
Formed again through drying and being tempered；The organic complexing agent is selected from citric acid, polyvinylpyrrolidone, tartaric acid, ethylenediamine tetrem
One or both of acid, benzenediol and formaldehyde.
5. the lithium ion battery ternary material of surface double-coating according to claim 4, it is characterised in that：It is described organic
The mol ratio of complexing agent and metallic element total in the lithium-rich oxide cladding layers is 1：(1~5).
A kind of 6. preparation of such as lithium ion battery ternary material of surface double-coating according to any one of claims 1 to 5
Method, comprise the following steps：
(1) organic complexing agent is scattered in solvent, stirred, obtain dispersion liquid；
(2) added under ultrasound and stirring into dispersion liquid obtained by step (1) lithium-rich oxide molecule formula ratio lithium source,
Nickel source and manganese source, continue stirring until to form gel；
(3) nickel-cobalt-manganese ternary material is immersed in gel obtained by step (2), stirring, obtains mixture, and gained mixture is entered
Row is dried and tempering；
(4) take the mixture obtained by step (3) after tempering to be scattered in solvent, be dispersed with stirring uniformly, then add Fluorine source
And silicon source, stirring, mixture is obtained, then gained mixture is dried and is tempered, produce the lithium-ion electric of surface double-coating
Pond ternary material.
7. preparation method according to claim 6, it is characterised in that：In the step (2), ultrasonic frequency be 20~
50kHz, ultrasonic power are 300~600W, and mixing speed is 300~600r/min；In the step (3) and step (4), stir
It is 300~600r/min to mix speed, and mixing time is 10~60min.
8. preparation method according to claim 6, it is characterised in that：In the step (3), the temperature of tempering for 600~
800℃；In the step (5), the temperature of tempering is 300~500 DEG C.
9. preparation method according to claim 6, it is characterised in that：In the step (1) and step (4), solvent is to go
One or more in ionized water, ethanol, ethylene glycol, methanol and isopropanol；In the step (2), lithium source is lithium acetate, hydrogen-oxygen
Change any one in lithium, lithium chloride, lithium sulfate and lithium nitrate, nickel source is in nickel acetate, nickel chloride, nickel sulfate and nickel nitrate
Any one, manganese source is any one in manganese acetate, manganese chloride, manganese sulfate and manganese nitrate；In the step (4), Fluorine source is
Any one in ammonium fluoride, sodium fluoride and potassium fluoride, silicon source are any one in aluminum nitrate, aluminium chloride and aluminum sulfate.
10. the preparation method according to any one of claim 6~9, it is characterised in that：The lithium source, nickel source, manganese source,
The concentration of Fluorine source and silicon source is 0.0.1~0.1mol/L.
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