CN106684323A - Ternary lithium-ion battery cathode material improved by active oxide multiply and preparation method thereof - Google Patents
Ternary lithium-ion battery cathode material improved by active oxide multiply and preparation method thereof Download PDFInfo
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- CN106684323A CN106684323A CN201611200637.0A CN201611200637A CN106684323A CN 106684323 A CN106684323 A CN 106684323A CN 201611200637 A CN201611200637 A CN 201611200637A CN 106684323 A CN106684323 A CN 106684323A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a ternary lithium-ion battery cathode material improved by active oxide multiply and a preparation method thereof. The ternary cathode material has the chemical formula as follows: LiNi1-a-bCoaMnbO2*cNb2O5, wherein a, b and c are mole numbers, a is greater than 0 and smaller than or equal to 0.4, b is greater than 0 and smaller than or equal to 0.4, c is greater than 0 and smaller than or equal to 0.05, and Nb2O5 is active oxide. The preparation method comprises the following steps: coating the surface of a precursor or a positive electrode material with a niobium source, mixing lithium into the precursor, and sintering at high temperature or performing heat treatment at low temperature to prepare the ternary lithium-ion battery cathode material of which the surface is doped with metal ions Nb5<+> and is coated with the oxide Nb2O5. The active oxide Nb2O5 can improve the ternary cathode material multiply. The ternary lithium-ion battery cathode material provided by the invention is greatly improved in aspects of cycle performance and rate performance of a battery, and has excellent electrochemical performance under a high-temperature and large-rate cycle condition.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, more particularly to a kind of activating oxide is multiple to improve lithium
Ion battery tertiary cathode material and preparation method thereof.
Background technology
With the fast development of electric automobile (electric vehicle) and intelligent grid (smart grid), to height
The market demand of the lithium ion battery of energy density and high power density is increasing, therefore, research and develop chemical property
Excellent lithium ion battery is extremely urgent.At present, compared to traditional cobalt acid lithium material (LiCoO2), due to cheap, ring
Many advantages, such as border close friend, specific capacity height, stable performance, the positive electrode based on ternary material is increasingly becoming the master of research
Want one of direction.However, ternary material yet suffers from many shortcomings, such as relatively low coulombic efficiency, poor cycle performance, with
And there is the thermal instability of potential safety hazard, the serious further development for hindering ternary material.
In recent years, many researcheres improve the chemical property of ternary material by method of modifying, such as ion doping and
Surface coating.But single method of modifying can not effectively solve the above problems, although it is oxide coated can reduce with
The side reaction of electrolyte, but oxide does not have electro-chemical activity and reduces specific discharge capacity and energy density；Meanwhile, metal
Although element doping can improve high rate performance, for the stable circulation performance of material is without too many improvement.
Therefore, it is not enough for prior art, there is provided a kind of high rate performance that can simultaneously improve ternary material, stability with
And the activating oxide of high-temperature behavior multiple to improve ternary cathode material of lithium ion battery and preparation method thereof very necessary.
The content of the invention
It is an object of the invention to provide a kind of activating oxide it is multiple improve ternary cathode material of lithium ion battery and its
Preparation method, the multiple ternary cathode material of lithium ion battery that improves of the activating oxide can improve the high rate performance of ternary material,
Stability and high-temperature behavior.
One of above-mentioned purpose of the present invention is realized by following technological means：
There is provided that a kind of activating oxide is multiple to improve ternary cathode material of lithium ion battery, chemical formula is：LiNi1-a- bCoaMnbO2·cNb2O5, wherein, a, b, c be molal quantity, 0 ＜ a≤0.4,0 ＜ b≤0.4 and 0 ＜ c≤0.05, Nb2O5For activity
Oxide.
Preferably, above-mentioned activating oxide is multiple improves ternary cathode material of lithium ion battery, makes as follows
It is standby to form：
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, according to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, is made into dense
The dispersant solution for 0.001~0.5mol/L is spent, nickel cobalt manganese hydroxide precursor material prepared by above-mentioned steps (1)
Material is put in the dispersant solution, stirs 0.5~5h, is then evaporated in the case where being stirred continuously again, makes niobium source be adsorbed in nickel
Cobalt manganese hydroxide precursor material surface, obtains niobium absorption nickel cobalt manganese hydroxide precursor material；
(3) according to molar ratio computing, it is with the metal ion ratio that lithium source adsorbs nickel cobalt manganese hydroxide precursor material with niobium
Li：(Ni+Co+Mn)=1~1.1:1 ratio, the niobium absorption nickel cobalt manganese hydroxide precursor that Jing steps (2) process is obtained
Material is mixed with lithium source, in being then placed in mixing tank, after mixing 2~20 hours, under oxygen or dry air atmosphere
400~700 DEG C of 2~10h of heat pre-treatment, then 750~950 DEG C of 10~30h of sintering are warmed up to, room temperature is naturally cooled to, prepare
Go out that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a-bCoaMnbO2·cNb2O5。
Another preferred, above-mentioned activating oxide is multiple to improve ternary cathode material of lithium ion battery, by following step
Suddenly it is prepared from：
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, the metal ion ratio with lithium source and nickel cobalt manganese hydroxide precursor material is as Li：(Ni+Co
+ Mn)=1~1.1:1 ratio, lithium source is mixed with nickel cobalt manganese hydroxide precursor material, is then placed in mixing tank
In, after mixing 2-20 hours, 400~700 DEG C of 2~10h of heat pre-treatment, then heat up under oxygen or dry air atmosphere
To 750~950 DEG C of 10~30h of sintering, naturally cool to room temperature and obtain uncoated positive electrode；
According to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, it is made into concentration for 0.001~
The dispersant solution of 0.5mol/L, uncoated positive electrode is put in dispersant solution, stirs 0.5~5h, so
It is evaporated in the case where being stirred continuously again afterwards, makes niobium source be coated on positive electrode surface and obtain lithium ion anode material；
(3) by step (2) process lithium ion anode material under dry air atmosphere in 300~700 DEG C of heat-agglomeratings 1
~5h, naturally cools to room temperature, prepares that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a- bCoaMnbO2·cNb2O5。
It is a further object of the present invention to provide the multiple ternary cathode material of lithium ion battery that improves of above-mentioned activating oxide
Preparation method.
A kind of scheme of the present invention is to be made by the steps to form,
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, according to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, is made into dense
The dispersant solution for 0.001~0.5mol/L is spent, nickel cobalt manganese hydroxide precursor material prepared by above-mentioned steps (1)
Material is put in the dispersant solution, stirs 0.5~5h, is then evaporated in the case where being stirred continuously again, makes niobium source be adsorbed in nickel
Cobalt manganese hydroxide precursor material surface, obtains niobium absorption nickel cobalt manganese hydroxide precursor material；
(3) according to molar ratio computing, it is with the metal ion ratio that lithium source adsorbs nickel cobalt manganese hydroxide precursor material with niobium
Li：(Ni+Co+Mn)=1~1.1:1 ratio, the niobium absorption nickel cobalt manganese hydroxide precursor that Jing steps (2) process is obtained
Material is mixed with lithium source, in being then placed in mixing tank, after mixing 2~20 hours, under oxygen or dry air atmosphere
400~700 DEG C of 2~10h of heat pre-treatment, then 750~950 DEG C of 10~30h of sintering are warmed up to, room temperature is naturally cooled to, prepare
Go out that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a-bCoaMnbO2·cNb2O5。
It is a further object of the present invention to provide the multiple ternary cathode material of lithium ion battery that improves of above-mentioned activating oxide
Preparation method.
Another kind of scheme of the present invention is to be made by the steps to form,
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, the metal ion ratio with lithium source and nickel cobalt manganese hydroxide precursor material is as Li：(Ni+Co
+ Mn)=1~1.1:1 ratio, lithium source is mixed with nickel cobalt manganese hydroxide precursor material, is then placed in mixing tank
In, after mixing 2-20 hours, 400~700 DEG C of 2~10h of heat pre-treatment, then heat up under oxygen or dry air atmosphere
To 750~950 DEG C of 10~30h of sintering, naturally cool to room temperature and obtain uncoated positive electrode；
According to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, it is made into concentration for 0.001~
The dispersant solution of 0.5mol/L, uncoated positive electrode is put in dispersant solution, stirs 0.5~5h, so
It is evaporated in the case where being stirred continuously again afterwards, makes niobium source be coated on positive electrode surface and obtain lithium ion anode material；
(3) by step (2) process lithium ion anode material under dry air atmosphere in 300~700 DEG C of heat-agglomeratings 1
~5h, naturally cools to room temperature；Prepare that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a- bCoaMnbO2·cNb2O5。
Further, above-mentioned drying is any one in forced air drying, spray drying, lyophilization or vacuum drying
Or it is several.
Further, above-mentioned lithium source be lithium fluoride, lithium carbonate, lithium acetate, lithium nitrate, Lithium hydrate in any one or
It is several.
Further, above-mentioned niobium source is any one in niobium pentaoxide, columbium sesquioxide, Columbium pentachloride., niobium oxalate
Plant or several.
Further, above-mentioned dispersant is any one or a few in ethanol, acetone, methanol, propanol.
The present invention is obtaining the lithium ion battery ternary of the multiple improvement of activating oxide just by effective and feasible surface modification
Pole material.Activating oxide Nb2O5Multiple can improve tertiary cathode material：Nb5+Doping changes the microcosmic crystal knot of material surface
Structure, can promote the migration of lithium ion；With element nb2O5Stable in properties the characteristics of, the tertiary cathode material after surface modification subtracts
Few material itself and the directly contact of electrolyte, effectively reduce the generation of material and the side reaction of electrolyte etc..Meanwhile, Nb2O5With
Remaining lithium residue reacts generation Lithium metaniobate, but Lithium metaniobate is used as lithium ion conductor, it is possible to increase material surface lithium ion
Transfer rate, improves the high rate performance of material.Experimental data shows that activating oxide is multiple to improve lithium ion battery tertiary cathode
Material can increase substantially the high rate performance and cycle performance of material, and can improve the high-temperature behavior and safety of material.In addition, should
Preparation method is simple, low cost, simple to operate, and the various aspects of performance of tertiary cathode material is but greatly improved, possess compared with
Big commercialization potential quality.
Description of the drawings
Invention is further described using accompanying drawing, but the content in accompanying drawing does not constitute any restriction to inventing.
Fig. 1 is gained LiNi in the embodiment of the present invention 40.8Co0.1Mn0.1O2·0.01Nb2O5With comparative example
LiNi0.8Co0.1Mn0.1O2XRD figure.
Fig. 2 is LiNi in the embodiment of the present invention 40.8Co0.1Mn0.1O2·0.01Nb2O5With comparative example
LiNi0.8Co0.1Mn0.1O2SEM figure.
Fig. 3 is LiNi in the embodiment of the present invention 40.8Co0.1Mn0.1O2·0.01Nb2O5With comparative example
LiNi0.8Co0.1Mn0.1O2First week charging and discharging curve comparison diagram.
Fig. 4 is LiNi in the embodiment of the present invention 40.8Co0.1Mn0.1O2·0.01Nb2O5With comparative example
LiNi0.8Co0.1Mn0.1O2High rate performance curve comparison diagram.
Fig. 5 is LiNi in the embodiment of the present invention 40.8Co0.1Mn0.1O2·0.01Nb2O5With comparative example
LiNi0.8Co0.1Mn0.1O21C cycle performance curve comparison diagrams at 25 DEG C.
Fig. 6 is LiNi in the embodiment of the present invention 40.8Co0.1Mn0.1O2·0.01Nb2O5With comparative example
LiNi0.8Co0.1Mn0.1O21C cycle performance curve comparison diagrams at 55 DEG C of high temperature.
Specific embodiment
With the following Examples the invention will be further described.
Embodiment 1.
There is provided that a kind of activating oxide is multiple to improve ternary cathode material of lithium ion battery, chemical formula is LiNi1-a- bCoaMnbO2·cNb2O5, wherein, a, b, c be molal quantity, 0 ＜ a≤0.4,0 ＜ b≤0.4 and 0 ＜ c≤0.05, Nb2O5For activity
Oxide.
The activating oxide is multiple to improve ternary cathode material of lithium ion battery, is made by the steps and forms：
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, according to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, is made into dense
The dispersant solution for 0.001~0.5mol/L is spent, nickel cobalt manganese hydroxide precursor material prepared by above-mentioned steps (1)
Material is put in the dispersant solution, stirs 0.5~5h, is then evaporated in the case where being stirred continuously again, makes niobium source be adsorbed in nickel
Cobalt manganese hydroxide precursor material surface, obtains niobium absorption nickel cobalt manganese hydroxide precursor material；
(3) according to molar ratio computing, it is with the metal ion ratio that lithium source adsorbs nickel cobalt manganese hydroxide precursor material with niobium
Li：(Ni+Co+Mn)=1~1.1:1 ratio, the niobium absorption nickel cobalt manganese hydroxide precursor that Jing steps (2) process is obtained
Material is mixed with lithium source, in being then placed in mixing tank, after mixing 2~20 hours, under oxygen or dry air atmosphere
400~700 DEG C of 2~10h of heat pre-treatment, then 750~950 DEG C of 10~30h of sintering are warmed up to, room temperature is naturally cooled to, prepare
Go out that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a-bCoaMnbO2·cNb2O5。
Above-mentioned activating oxide is multiple to improve ternary cathode material of lithium ion battery, it is also possible to be made by the steps
Form：
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, the metal ion ratio with lithium source and nickel cobalt manganese hydroxide precursor material is as Li：(Ni+Co
+ Mn)=1~1.1:1 ratio, lithium source is mixed with nickel cobalt manganese hydroxide precursor material, is then placed in mixing tank
In, after mixing 2-20 hours, 400~700 DEG C of 2~10h of heat pre-treatment, then heat up under oxygen or dry air atmosphere
To 750~950 DEG C of 10~30h of sintering, naturally cool to room temperature and obtain uncoated positive electrode；
According to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, it is made into concentration for 0.001~
The dispersant solution of 0.5mol/L, uncoated positive electrode is put in dispersant solution, stirs 0.5~5h, so
It is evaporated in the case where being stirred continuously again afterwards, makes niobium source be coated on positive electrode surface and obtain lithium ion anode material；
(3) by step (2) process lithium ion anode material under dry air atmosphere in 300~700 DEG C of heat-agglomeratings 1
~5h, naturally cools to room temperature, prepares that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a- bCoaMnbO2·cNb2O5。
The present invention is obtaining the lithium ion battery ternary of the multiple improvement of activating oxide just by effective and feasible surface modification
Pole material.Activating oxide Nb2O5Multiple can improve tertiary cathode material：Nb5+Doping changes the microcosmic crystal knot of material surface
Structure, can promote the migration of lithium ion；With element nb2O5Stable in properties the characteristics of, the tertiary cathode material after surface modification subtracts
Few material itself and the directly contact of electrolyte, effectively reduce the generation of material and the side reaction of electrolyte etc..Meanwhile, Nb2O5With
Remaining lithium residue reacts generation Lithium metaniobate, but Lithium metaniobate is used as lithium ion conductor, it is possible to increase material surface lithium ion
Transfer rate, improves the high rate performance of material.Experimental data shows that activating oxide is multiple to improve lithium ion battery tertiary cathode
Material can increase substantially the high rate performance and cycle performance of material, and can improve the high-temperature behavior and safety of material.In addition, should
Preparation method is simple, low cost, simple to operate, and the various aspects of performance of tertiary cathode material is but greatly improved, possess compared with
Big commercialization potential quality.
Embodiment 2.
There is provided a kind of activating oxide the multiple preparation method for improving ternary cathode material of lithium ion battery, by following step
Suddenly it is prepared from,
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, according to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, is made into dense
The dispersant solution for 0.001~0.5mol/L is spent, nickel cobalt manganese hydroxide precursor material prepared by above-mentioned steps (1)
Material is put in the dispersant solution, stirs 0.5~5h, is then evaporated in the case where being stirred continuously again, makes niobium source be adsorbed in nickel
Cobalt manganese hydroxide precursor material surface, obtains niobium absorption nickel cobalt manganese hydroxide precursor material；
(3) according to molar ratio computing, it is with the metal ion ratio that lithium source adsorbs nickel cobalt manganese hydroxide precursor material with niobium
Li：(Ni+Co+Mn)=1~1.1:1 ratio, the niobium absorption nickel cobalt manganese hydroxide precursor that Jing steps (2) process is obtained
Material is mixed with lithium source, in being then placed in mixing tank, after mixing 2~20 hours, under oxygen or dry air atmosphere
400~700 DEG C of 2~10h of heat pre-treatment, then 750~950 DEG C of 10~30h of sintering are warmed up to, room temperature is naturally cooled to, prepare
Go out that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a-bCoaMnbO2·cNb2O5。
The multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide of the present invention, by effective and feasible
Surface modification, obtain the ternary cathode material of lithium ion battery of the multiple improvement of activating oxide.Experimental data shows, active oxygen
The multiple ternary cathode material of lithium ion battery that improves of compound can increase substantially the high rate performance and cycle performance of material, and can change
The high-temperature behavior and safety of kind material.Additionally, the preparation method is simple, low cost, simple to operate, three are but greatly improved
The various aspects of performance of first positive electrode, possesses larger commercialization potential quality.
Embodiment 3.
There is provided a kind of activating oxide the multiple preparation method for improving ternary cathode material of lithium ion battery, by following step
Suddenly it is prepared from,
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, the metal ion ratio with lithium source and nickel cobalt manganese hydroxide precursor material is as Li：(Ni+Co
+ Mn)=1~1.1:1 ratio, lithium source is mixed with nickel cobalt manganese hydroxide precursor material, is then placed in mixing tank
In, after mixing 2-20 hours, 400~700 DEG C of 2~10h of heat pre-treatment, then heat up under oxygen or dry air atmosphere
To 750~950 DEG C of 10~30h of sintering, naturally cool to room temperature and obtain uncoated positive electrode；
According to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, it is made into concentration for 0.001~
The dispersant solution of 0.5mol/L, uncoated positive electrode is put in dispersant solution, stirs 0.5~5h, so
It is evaporated in the case where being stirred continuously again afterwards, makes niobium source be coated on positive electrode surface and obtain lithium ion anode material；
(3) by step (2) process lithium ion anode material under dry air atmosphere in 300~700 DEG C of heat-agglomeratings 1
~5h, naturally cools to room temperature, prepares that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a- bCoaMnbO2·cNb2O5。
The multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide of the present invention, by effective and feasible
Surface modification, obtain the ternary cathode material of lithium ion battery of the multiple improvement of activating oxide.Experimental data shows, active oxygen
The multiple ternary cathode material of lithium ion battery that improves of compound can increase substantially the high rate performance and cycle performance of material, and can change
The high-temperature behavior and safety of kind material.Additionally, the preparation method is simple, low cost, simple to operate, three are but greatly improved
The various aspects of performance of first positive electrode, possesses larger commercialization potential quality.
Embodiment 4.
With reference to instantiation, illustrating that a kind of activating oxide of the present invention is multiple improves ternary cathode material of lithium ion battery
Preparation method, be prepared from especially by following steps.
(1) nickel cobalt manganese hydroxide Ni is prepared using conventional liquid-phase coprecipitation0.8Co0.1Mn0.1(OH)2Presoma material
Material.
(2) (mol ratio is Nb to weigh the niobium oxalate of 0.004mol：(Ni+Co+Mn)=0.02:1), dehydrated alcohol is added,
The aaerosol solution that concentration is 0.01mol/L is made into, by 0.2mol Ni0.8Co0.1Mn0.1(OH)2Nickel cobalt manganese hydroxide precursor
Material is put in above-mentioned solution, stirs 2h, is then evaporated in forced air drying, niobium source is adsorbed in before nickel cobalt manganese hydroxide
Body material surface is driven, niobium absorption nickel cobalt manganese hydroxide precursor material is obtained.
(3) niobium obtained in (2) absorption nickel cobalt manganese hydroxide precursor material powder is put into 0.21mol LiOH
Mixed in mixing tank, after 10 hours, batch mixing uniformly obtains required presoma to batch mixing.Presoma is put in tube furnace,
Lower 500 DEG C of heat pre-treatments 5h of oxygen atmosphere, are then warmed up to 800 DEG C of sintering 16h, naturally cool to room temperature, you can lived
LiNi after the property multiple improvement of oxide0.8Co0.1Mn0.1O2·0.01Nb2O5, laboratory referred to as 811.Spread out by x-ray powder
It is that, with good layer structure, degree of crystallinity is high to penetrate the product obtained by (XRD) analysis shows.It can be seen that material from SEM figures
It is that high compact is spherical, particle diameter is about 12-18 microns.
(4) at 25 DEG C, during carrying out charge and discharge cycles in 2.8-4.3V voltage ranges under different multiplying,
LiNi0.8Co0.1Mn0.1O2·0.01Nb2O5(811) excellent properties are shown, with differences such as 0.1C, 0.2C, 0.5C, 1C, 2C, 5C
When multiplying power carries out charge-discharge test, its specific discharge capacity can reach respectively 204.2mAh/g, 194.3mAh/g, 184.4mAh/g,
176.2mAh/g, 166.8mAh/g, 158.6mAh/g.Discharge and recharge is carried out to it with the multiplying power of 1C, remaining specific volume after the circle of circulation 200
Amount can still reach 161.1mAh/g.At 55 DEG C, discharge and recharge is carried out to it with the multiplying power of 1C, its specific discharge capacity is respectively
192.2mAh/g, remaining specific capacity is 179.5mAh/g after the circle of circulation 100.
In order to verify the technique effect of the present invention, there is provided comparative example 1.
Comparative example 1：
(1) nickel cobalt manganese hydroxide Ni is prepared using conventional liquid-phase coprecipitation0.8Co0.1Mn0.1(OH)2Presoma material
Material.
(2) 0.2mol Ni are weighed0.8Co0.1Mn0.1(OH)2Persursor material is mixed with 0.201mol LiOH, then
Addition alcohol solvent used as dispersant, in being put into mixing tank, after 10 hours in 100 DEG C of calorstats dry, and batch mixing is uniform by batch mixing
Obtain required presoma.Presoma is put in tube furnace, 500 DEG C of heat pre-treatments 5h, are then warmed up under oxygen atmosphere
800 DEG C of sintering 16h, naturally cool to room temperature.Product obtained by X-ray powder diffraction (XRD) analysis shows is with good layer
Shape structure, degree of crystallinity is high.It can be seen that LiNi from SEM figures0.8Co0.1Mn0.1O2Positive electrode is that high compact is spherical, particle diameter
About 12-18 microns.
(3) at 25 DEG C, when carrying out charge and discharge cycles between 2.8-4.3V with the multiplying power of 0.1C, tertiary cathode material with
When the big multiplying power such as 0.1C, 0.2C, 0.5C, 1C, 2C, 5C carries out charge-discharge test, its specific discharge capacity can reach respectively
199.1mAh/g, 187.4mAh/g, 172.8mAh/g, 157.2mAh/g, 133.9mAh/g, 103.2mAh/g.With the multiplying power of 1C
Discharge and recharge is carried out to it, remaining specific capacity can still reach 137.4mAh/g after the circle of circulation 200.At 55 DEG C, with the multiplying power of 1C
Discharge and recharge is carried out to it, its specific discharge capacity is respectively 195.6mAh/g, and remaining specific capacity is 152.6mAh/ after the circle of circulation 100
g。
Fig. 1 to Fig. 6 shows the LiNi prepared by the embodiment of the present invention 40.8Co0.1Mn0.1O2·0.01Nb2O5With comparative example
In unmodified material LiNi0.8Co0.1Mn0.1O2Between characteristic relation.Fig. 1 is gained in embodiment 4
LiNi0.8Co0.1Mn0.1O2·0.01Nb2O5With unmodified material LiNi in comparative example0.8Co0.1Mn0.1O2XRD figure.Penetrated by X
Line powder diffraction analysis show LiNi0.8Co0.1Mn0.1O2·0.01Nb2O5With good layer structure, it is mixed with and modified does not have
Have and produce other any dephasigns, degree of crystallinity is high.
Fig. 2 is gained LiNi in embodiment 40.8Co0.1Mn0.1O2·0.01Nb2O5SEM figure.It can be seen that bag in SEM figures
It is that high compact is spherical to cover doping vario-property material, and particle diameter is about 12-18 microns.
Fig. 3 is gained LiNi in embodiment 40.8Co0.1Mn0.1O2·0.01Nb2O5With of unmodified material in comparative example
One week charging and discharging curve comparison diagram.Fig. 4 is gained LiNi in embodiment 40.8Co0.1Mn0.1O2·0.01Nb2O5With in comparative example not
Material modified high rate performance curve comparison diagram.Fig. 5 is gained LiNi in embodiment 40.8Co0.1Mn0.1O2·0.01Nb2O5With with
The cycle performance curve comparison diagram at 25 DEG C of unmodified material in comparative example.Fig. 6 is obtained by applying in example 4
LiNi0.8Co0.1Mn0.1O2·0.01Nb2O5With the cycle performance curve ratio under high temperature (55 DEG C) of unmodified material in comparative example
Relatively scheme.
From the point of view of contrast and experiment, the multiple ternary cathode material of lithium ion battery that improves of activating oxide can be carried significantly
The high rate performance and cycle performance of high material, and the high-temperature behavior and safety of material can be improved.
The present invention is obtaining the lithium ion battery ternary of the multiple improvement of activating oxide just by effective and feasible surface modification
Pole material.Activating oxide Nb2O5Multiple can improve tertiary cathode material：Nb5+Doping changes the microcosmic crystal knot of material surface
Structure, can promote the migration of lithium ion；With element nb2O5Stable in properties the characteristics of, the tertiary cathode material after surface modification subtracts
Few material itself and the directly contact of electrolyte, effectively reduce the generation of material and the side reaction of electrolyte etc..Meanwhile, Nb2O5With
Remaining lithium residue reacts generation Lithium metaniobate, but Lithium metaniobate is used as lithium ion conductor, it is possible to increase material surface lithium ion
Transfer rate, improves the high rate performance of material.Additionally, the preparation method is simple, low cost, simple to operate, but significantly carry
The high various aspects of performance of tertiary cathode material, possesses larger commercialization potential quality.
Embodiment 5.
With reference to instantiation, illustrating that a kind of activating oxide of the present invention is multiple improves ternary cathode material of lithium ion battery
Preparation method, be prepared from especially by following steps.
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using conventional liquid-phase coprecipitation0.8Co0.1Mn0.1
(OH)2。
(2) 0.2mol Ni are weighed0.8Co0.1Mn0.1(OH)2Nickel cobalt manganese hydroxide precursor material and 0.204mol
LiOH is put in mixing tank and is mixed, and after 20 hours, batch mixing is uniform, in placing into tube furnace, 400 under oxygen atmosphere for batch mixing
DEG C heat pre-treatment 10h, is then warmed up to 750 DEG C of sintering 30h, naturally cools to room temperature and obtains uncoated positive electrode.
Weigh the NbCl of 0.002mol5(mol ratio is Nb：(Ni+Co+Mn)=0.01:1), absolute methanol is added, is made into
Concentration is the aaerosol solution of 0.03mol/L, and the uncoated positive electrode for sintering is put in above-mentioned solution, stirs 0.5h,
Then it is evaporated in lyophilization, makes niobium source be coated on positive electrode surface and obtain lithium ion anode material.
(3) by gained lithium ion anode material powder under dry air atmosphere 500 DEG C of heat-agglomerating 1h, naturally cool to
Room temperature, you can obtain the LiNi after the multiple improvement of activating oxide0.8Co0.1Mn0.1O2·0.005Nb2O5(811).X-ray powder
Product obtained by diffraction (XRD) analysis shows is that, with good layer structure, degree of crystallinity is high.It can be seen that material from SEM figures
Material is that high compact is spherical, and particle diameter is about 13-19 microns.
At 25 DEG C, during carrying out charge and discharge cycles in 2.8-4.3V voltage ranges under different multiplying,
LiNi0.8Co0.1Mn0.1O2·0.005Nb2O5(811) excellent properties are shown.With 0.1C, 0.2C, 0.5C, 1C, 2C, 5C etc. no
When carrying out charge-discharge test with multiplying power, its specific discharge capacity can reach respectively 204.6mAh/g, 197.1mAh/g, 184.8mAh/
G, 178.0mAh/g, 167.3mAh/g, 159.6mAh/g.Discharge and recharge is carried out to it with the multiplying power of 1C, remaining ratio after the circle of circulation 200
Capacity can still reach 158.3mAh/g.At 55 DEG C, discharge and recharge is carried out to it with the multiplying power of 1C, its specific discharge capacity is respectively
194.2mAh/g, remaining specific capacity is 174.1mAh/g after the circle of circulation 100.
The multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide of the present invention, by effective and feasible
Surface modification, obtain the ternary cathode material of lithium ion battery of the multiple improvement of activating oxide.Experimental data shows, active oxygen
The multiple ternary cathode material of lithium ion battery that improves of compound can increase substantially the high rate performance and cycle performance of material, and can change
The high-temperature behavior and safety of kind material.Additionally, the preparation method is simple, low cost, simple to operate, three are but greatly improved
The various aspects of performance of first positive electrode, possesses larger commercialization potential quality.
Embodiment 6.
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using conventional liquid-phase coprecipitation0.7Co0.2Mn0.1
(OH)2。
(2) Nb of 0.004mol is weighed2O5(mol ratio is Nb：(Ni+Co+Mn)=0.04:1), anhydrous propyl alcohol is added, is matched somebody with somebody
It is the aaerosol solution of 0.001mol/L into concentration, weighs 0.2mol Ni0.7Co0.2Mn0.1(OH)2Nickel cobalt manganese hydroxide precursor
Material is put in above-mentioned solution, stirs 5h, is then evaporated under vacuum drying, niobium source is adsorbed in before nickel cobalt manganese hydroxide
Body material surface is driven, niobium absorption nickel cobalt manganese hydroxide precursor material is obtained.
(3) niobium obtained in (2) absorption nickel cobalt manganese hydroxide precursor material powder is put into 0.203mol LiOH
Mixed in mixing tank, batch mixing is after 2 hours, and batch mixing is uniform, in placing into tube furnace, 700 DEG C of heating are pre- under oxygen atmosphere
2h is processed, 950 DEG C of sintering 10h are then warmed up to, room temperature is naturally cooled to.After the multiple improvement of activating oxide is obtained
LiNi0.7Co0.2Mn0.1O2·0.02Nb2O5.Product obtained by X-ray powder diffraction (XRD) analysis shows is with good stratiform
Structure, degree of crystallinity is high.It can be seen that material is that high compact is spherical from SEM figures, particle diameter is about 13-20 microns.
At 25 DEG C, during carrying out charge and discharge cycles in 2.8-4.3V voltage ranges under different multiplying,
LiNi0.7Co0.2Mn0.1O2·0.02Nb2O5Show excellent properties.With different multiplyings such as 0.1C, 0.2C, 0.5C, 1C, 2C, 5C
When carrying out charge-discharge test, its specific discharge capacity can reach respectively 191.6mAh/g, 182.3mAh/g, 173.1mAh/g,
169.5mAh/g, 161.8mAh/g, 150.4mAh/g.Discharge and recharge is carried out to it with the multiplying power of 1C, remaining specific volume after the circle of circulation 200
Amount can still reach 149.1mAh/g.At 55 DEG C, discharge and recharge is carried out to it with the multiplying power of 1C, its specific discharge capacity is respectively
174.2mAh/g, remaining specific capacity is 158.4mAh/g after the circle of circulation 100.
The multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide of the present invention, by effective and feasible
Surface modification, obtain the ternary cathode material of lithium ion battery of the multiple improvement of activating oxide.Experimental data shows, active oxygen
The multiple ternary cathode material of lithium ion battery that improves of compound can increase substantially the high rate performance and cycle performance of material, and can change
The high-temperature behavior and safety of kind material.Additionally, the preparation method is simple, low cost, simple to operate, three are but greatly improved
The various aspects of performance of first positive electrode, possesses larger commercialization potential quality.
Embodiment 7.
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using conventional liquid-phase coprecipitation0.6Co0.2Mn0.2
(OH)2。
(2) 0.2mol Ni are weighed0.6Co0.2Mn0.2(OH)2Nickel cobalt manganese hydroxide precursor material and 0.102mol
Li2CO3It is put in mixing tank and is mixed, batch mixing is after 9 hours, then compound is put in tube furnace, 700 under oxygen atmosphere
DEG C heat pre-treatment 4h, is then warmed up to 850 DEG C of sintering 16h, naturally cools to room temperature and obtains uncoated positive electrode.
Weigh the Nb of 0.0006mol2O3(mol ratio is Nb：(Ni+Co+Mn)=0.006:1), anhydrous propanone is added, is made into
Concentration is the aaerosol solution of 0.02mol/L, and the positive electrode for sintering is put in above-mentioned solution, stirs 3h, then in spray
Mist is evaporated in being dried, and makes niobium source be coated on positive electrode surface and obtains lithium ion anode material.
(3) by gained lithium ion anode material powder under dry air atmosphere 300 DEG C of heat-agglomerating 2h, naturally cool to
Room temperature, you can obtain the LiNi after the multiple improvement of activating oxide0.6Co0.2Mn0.2O2·0.003Nb2O5.X-ray powder diffraction
(XRD) product obtained by analysis shows is that, with good layer structure, degree of crystallinity is high.It can be seen that material is from SEM figures
High compact is spherical, and particle diameter is about 12-20 microns.
At 25 DEG C, during carrying out charge and discharge cycles in 2.8-4.3V voltage ranges under different multiplying,
LiNi0.6Co0.2Mn0.2O2·0.003Nb2O5(622) excellent properties are shown.With 0.1C, 0.2C, 0.5C, 1C, 2C, 5C etc. no
When carrying out charge-discharge test with multiplying power, its specific discharge capacity can reach respectively 181.5mAh/g, 173.3mAh/g, 168.1mAh/
G, 163.5mAh/g, 157.8mAh/g, 148.4mAh/g.Discharge and recharge is carried out to it with the multiplying power of 1C, remaining ratio after the circle of circulation 200
Capacity can still reach 150.1mAh/g.At 55 DEG C, discharge and recharge is carried out to it with the multiplying power of 1C, its specific discharge capacity is respectively
170.0mAh/g, remaining specific capacity is 158.0mAh/g after the circle of circulation 100.
The multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide of the present invention, by effective and feasible
Surface modification, obtain the ternary cathode material of lithium ion battery of the multiple improvement of activating oxide.Experimental data shows, active oxygen
The multiple ternary cathode material of lithium ion battery that improves of compound can increase substantially the high rate performance and cycle performance of material, and can change
The high-temperature behavior and safety of kind material.Additionally, the preparation method is simple, low cost, simple to operate, three are but greatly improved
The various aspects of performance of first positive electrode, possesses larger commercialization potential quality.
Embodiment 8.
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using conventional liquid-phase coprecipitation0.5Co0.2Mn0.3
(OH)2。
(2) (mol ratio is Nb to weigh the niobium oxalate of 0.0012mol：(Ni+Co+Mn)=0.006:1), anhydrous second is added
Alcohol, is made into the aaerosol solution that concentration is 0.003mol/L, by 0.2mol Ni0.5Co0.2Mn0.3CO3Nickel cobalt manganese hydroxide forerunner
Body material is put in above-mentioned solution, stirs 1h, is then evaporated under forced air drying, makes niobium source be adsorbed in nickel cobalt manganese hydroxide
Persursor material surface, obtains niobium absorption nickel cobalt manganese hydroxide precursor material.
(3) by niobium absorption nickel cobalt manganese hydroxide precursor material powder and 0.208mol CH3COOLi is put into mixing tank
In mixed, batch mixing is after 8 hours, and batch mixing is uniform, then compound is put in tube furnace, 500 DEG C under dry air atmosphere
Heat pre-treatment 3h, is then warmed up to 870 DEG C of sintering 8h, naturally cools to room temperature.The multiple improvement of activating oxide is obtained
LiNi afterwards0.5Co0.2Mn0.3O2·0.003Nb2O5.Product obtained by X-ray powder diffraction (XRD) analysis shows is with good
Good layer structure, degree of crystallinity is high.It can be seen that material is that high compact is spherical from SEM figures, particle diameter is about 10-20 microns.
At 25 DEG C, during carrying out charge and discharge cycles in 2.8-4.3V voltage ranges under different multiplying,
LiNi0.5Co0.2Mn0.3O2·0.003Nb2O5(523) excellent properties are shown.With 0.1C, 0.2C, 0.5C, 1C, 2C, 5C etc. no
When carrying out charge-discharge test with multiplying power, its specific discharge capacity can reach respectively 175.3mAh/g, 170.1mAh/g, 165.6mAh/
G, 155.8mAh/g, 149.7mAh/g, 138.9mAh/g.Discharge and recharge is carried out to it with the multiplying power of 1C, remaining ratio after the circle of circulation 200
Capacity can still reach 142.1mAh/g.At 55 DEG C, discharge and recharge is carried out to it with the multiplying power of 1C, its specific discharge capacity is respectively
166.4mAh/g, remaining specific capacity is 147.0mAh/g after the circle of circulation 100.
The multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide of the present invention, by effective and feasible
Surface modification, obtain the ternary cathode material of lithium ion battery of the multiple improvement of activating oxide.Experimental data shows, active oxygen
The multiple ternary cathode material of lithium ion battery that improves of compound can increase substantially the high rate performance and cycle performance of material, and can change
The high-temperature behavior and safety of kind material.Additionally, the preparation method is simple, low cost, simple to operate, three are but greatly improved
The various aspects of performance of first positive electrode, possesses larger commercialization potential quality.
Embodiment 9.
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using conventional liquid-phase coprecipitation1/3Co1/3Mn1/3
(OH)2。
(2) 0.2mol Ni are weighed1/3Co1/3Mn1/3(OH)2Nickel cobalt manganese hydroxide precursor material and 0.208mol
LiNO3It is put in mixing tank and is mixed, batch mixing is put in tube furnace after 8 hours after batch mixing is uniform, under dry air atmosphere
500 DEG C of heat pre-treatments 5h, are then warmed up to 900 DEG C of sintering 16h, naturally cool to room temperature and obtain uncoated positive electrode.Claim
Take the Nb of 0.0005mol2O5(mol ratio is Nb：(Ni+Co+Mn)=0.005:1), dehydrated alcohol is added, being made into concentration is
The solution of 0.01mol/L, the uncoated positive electrode for sintering is put in above-mentioned solution, stirs 2h, then lyophilization
Under be evaporated, make niobium source be coated on positive electrode surface and obtain lithium ion anode material.
(3) by lithium ion anode material powder under dry air atmosphere 450 DEG C of heat-agglomerating 1.5h, naturally cool to room
Temperature, you can obtain the LiNi after the multiple improvement of activating oxide0.33Co0.33Mn0.33O2·0.0025Nb2O5.X-ray powder diffraction
(XRD) product obtained by analysis shows is that, with good layer structure, degree of crystallinity is high.It can be seen that material is from SEM figures
High compact is spherical, and particle diameter is about 14-18 microns.
At 25 DEG C, during carrying out charge and discharge cycles in 2.8-4.3V voltage ranges under different multiplying,
LiNi0.33Co0.33Mn0.33O2·0.0025Nb2O5Show excellent chemical property.At 25 DEG C, with 0.1C, 0.2C,
When the different multiplyings such as 0.5C, 1C, 2C, 5C carry out charge-discharge test, its specific discharge capacity can reach respectively 165.6mAh/g,
154.4mAh/g, 149.8mAh/g, 144.2mAh/g, 139.9mAh/g, 135.2mAh/g.Charge and discharge is carried out to it with the multiplying power of 1C
Electricity, remaining specific capacity can still reach 140.1mAh/g after the circle of circulation 200.At 55 DEG C, charge and discharge is carried out to it with the multiplying power of 1C
Electricity, its specific discharge capacity is respectively 150.7mAh/g, and remaining specific capacity is 145.6mAh/g after the circle of circulation 100.
The multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide of the present invention, by effective and feasible
Surface modification, obtain the ternary cathode material of lithium ion battery of the multiple improvement of activating oxide.Experimental data shows, active oxygen
The multiple ternary cathode material of lithium ion battery that improves of compound can increase substantially the high rate performance and cycle performance of material, and can change
The high-temperature behavior and safety of kind material.Additionally, the preparation method is simple, low cost, simple to operate, three are but greatly improved
The various aspects of performance of first positive electrode, possesses larger commercialization potential quality.
Finally it should be noted that above example is only to illustrate technical scheme rather than the present invention is protected
The restriction of scope, although being explained in detail to the present invention with reference to preferred embodiment, one of ordinary skill in the art should manage
Solution, technical scheme can be modified or equivalent, without deviating from technical solution of the present invention essence and
Scope.
Claims (9)
1. a kind of activating oxide is multiple improves ternary cathode material of lithium ion battery, it is characterised in that：Chemical formula is：
LiNi1-a-bCoaMnbO2·cNb2O5, wherein, a, b, c be molal quantity, 0 ＜ a≤0.4,0 ＜ b≤0.4 and 0 ＜ c≤0.05,
Nb2O5For activating oxide.
2. activating oxide according to claim 1 is multiple improves ternary cathode material of lithium ion battery, it is characterised in that：
It is made by the steps and forms：
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, according to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, and being made into concentration is
The dispersant solution of 0.001~0.5mol/L, nickel cobalt manganese hydroxide precursor material prepared by above-mentioned steps (1) is put
In entering the dispersant solution, 0.5~5h is stirred, be then evaporated in the case where being stirred continuously again, make niobium source be adsorbed in nickel cobalt manganese
Hydroxide precursor material surface, obtains niobium absorption nickel cobalt manganese hydroxide precursor material；
(3) according to molar ratio computing, the metal ion ratio of nickel cobalt manganese hydroxide precursor material is adsorbed as Li with lithium source and niobium：
(Ni+Co+Mn)=1~1.1:1 ratio, the niobium absorption nickel cobalt manganese hydroxide precursor material that Jing steps (2) process is obtained
Material is mixed with lithium source, in being then placed in mixing tank, after mixing 2~20 hours, 400 under oxygen or dry air atmosphere
~700 DEG C of 2~10h of heat pre-treatment, then 750~950 DEG C of 10~30h of sintering are warmed up to, room temperature is naturally cooled to, prepare work
Oxide is multiple improves ternary cathode material of lithium ion battery LiNi for property1-a-bCoaMnbO2·cNb2O5。
3. activating oxide according to claim 1 is multiple improves ternary cathode material of lithium ion battery, it is characterised in that：
It is made by the steps and forms：
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, the metal ion ratio with lithium source and nickel cobalt manganese hydroxide precursor material is as Li：(Ni+Co+Mn)
=1~1.1:1 ratio, lithium source is mixed with nickel cobalt manganese hydroxide precursor material, in being then placed in mixing tank, is mixed
After closing 2-20 hours, 400~700 DEG C of 2~10h of heat pre-treatment, are then warmed up to 750 under oxygen or dry air atmosphere
~950 DEG C of 10~30h of sintering, naturally cool to room temperature and obtain uncoated positive electrode；
According to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, is made into concentration for 0.001~0.5mol/
The dispersant solution of L, uncoated positive electrode is put in dispersant solution, 0.5~5h is stirred, then again not
It is evaporated under disconnected stirring, makes niobium source be coated on positive electrode surface and obtain lithium ion anode material；
(3) by step (2) process lithium ion anode material under dry air atmosphere in 300~700 DEG C of heat-agglomeratings 1~
5h, naturally cools to room temperature, prepares that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a- bCoaMnbO2·cNb2O5。
4. the multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide as claimed in claim 1, its
It is characterised by：It is made by the steps and forms,
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, according to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, and being made into concentration is
The dispersant solution of 0.001~0.5mol/L, nickel cobalt manganese hydroxide precursor material prepared by above-mentioned steps (1) is put
In entering the dispersant solution, 0.5~5h is stirred, be then evaporated in the case where being stirred continuously again, make niobium source be adsorbed in nickel cobalt manganese
Hydroxide precursor material surface, obtains niobium absorption nickel cobalt manganese hydroxide precursor material；
(3) according to molar ratio computing, the metal ion ratio of nickel cobalt manganese hydroxide precursor material is adsorbed as Li with lithium source and niobium：
(Ni+Co+Mn)=1~1.1:1 ratio, the niobium absorption nickel cobalt manganese hydroxide precursor material that Jing steps (2) process is obtained
Material is mixed with lithium source, in being then placed in mixing tank, after mixing 2~20 hours, 400 under oxygen or dry air atmosphere
~700 DEG C of 2~10h of heat pre-treatment, then 750~950 DEG C of 10~30h of sintering are warmed up to, room temperature is naturally cooled to, prepare work
Oxide is multiple improves ternary cathode material of lithium ion battery LiNi for property1-a-bCoaMnbO2·cNb2O5。
5. the multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide as claimed in claim 1, its
It is characterised by：It is made by the steps and forms,
(1) nickel cobalt manganese hydroxide precursor material Ni is prepared using liquid-phase coprecipitation1-a-bCoaMnb(OH)2；
(2) with molar ratio computing, the metal ion ratio with lithium source and nickel cobalt manganese hydroxide precursor material is as Li：(Ni+Co+Mn)
=1~1.1:1 ratio, lithium source is mixed with nickel cobalt manganese hydroxide precursor material, in being then placed in mixing tank, is mixed
After closing 2-20 hours, 400~700 DEG C of 2~10h of heat pre-treatment, are then warmed up to 750 under oxygen or dry air atmosphere
~950 DEG C of 10~30h of sintering, naturally cool to room temperature and obtain uncoated positive electrode；
According to Nb：(Ni+Co+Mn)=2c:1 ratio weighs niobium source, adds dispersant, is made into concentration for 0.001~0.5mol/
The dispersant solution of L, uncoated positive electrode is put in dispersant solution, 0.5~5h is stirred, then again not
It is evaporated under disconnected stirring, makes niobium source be coated on positive electrode surface and obtain lithium ion anode material；
(3) by step (2) process lithium ion anode material under dry air atmosphere in 300~700 DEG C of heat-agglomeratings 1~
5h, naturally cools to room temperature；Prepare that activating oxide is multiple to improve ternary cathode material of lithium ion battery LiNi1-a- bCoaMnbO2·cNb2O5。
6. the multiple preparation side for improving ternary cathode material of lithium ion battery of activating oxide according to claim 3 or 4
Method, it is characterised in that：The drying be forced air drying, sprays drying, lyophilization or be vacuum dried in any one or
It is several.
7. the multiple preparation side for improving ternary cathode material of lithium ion battery of activating oxide according to claim 3 or 4
Method, it is characterised in that：The lithium source is any one in lithium fluoride, lithium carbonate, lithium acetate, lithium nitrate, Lithium hydrate or several
Kind.
8. the multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide according to claim 7,
It is characterized in that：Described niobium source is any one in niobium pentaoxide, columbium sesquioxide, Columbium pentachloride., niobium oxalate or several
Kind.
9. the multiple preparation method for improving ternary cathode material of lithium ion battery of activating oxide according to claim 8,
It is characterized in that：The dispersant is any one or a few in ethanol, acetone, methanol, propanol.
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