CN109888261A - A kind of rich nickel ternary composite electrode material of modification and preparation method thereof - Google Patents
A kind of rich nickel ternary composite electrode material of modification and preparation method thereof Download PDFInfo
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- CN109888261A CN109888261A CN201910289498.0A CN201910289498A CN109888261A CN 109888261 A CN109888261 A CN 109888261A CN 201910289498 A CN201910289498 A CN 201910289498A CN 109888261 A CN109888261 A CN 109888261A
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Abstract
The present invention provides a kind of rich nickel ternary composite electrode materials of modification, the decorative layer of rich nickel ternary electrode material and outside lithiumation object including doping oxide, rich nickel ternary electrode material is made of LiO, NiO, CoO, MnO and doping oxide, additionally provide preparation method, it will be sintered after LiO, NiO, CoO, MnO and the dry-mixed ball milling of doping oxide, it is sintered again with after the dry-mixed ball milling of lithium compound, obtains modified rich nickel ternary composite electrode material.The present invention can prevent metal ion in rich nickel ternary electrode material from dissolving after lithium compound is modified, battery is solved in high current density cyclic process, material property rapid decay caused by being corroded because of electrolyte, lithium, nickel are reset in the oxide-doped inhibition material of niobium or molybdenum, improve cycle performance and high rate performance, it is poor to solve stability, the fast problem of capacity attenuation, lithium compound has excellent lithium ion conductivity, lithium ion is improved in the diffusion rate of positive electrode, improves cycle performance of lithium ion battery and high rate performance.
Description
Technical field
The invention belongs to electrode material technical fields, and in particular to a kind of rich nickel ternary composite electrode material of modification and its
Preparation method.
Background technique
Lithium ion battery has operating voltage is high, energy density is high, pollutes small, memory-less effect etc. relative to conventional batteries
Advantage is widely applied in fields such as electronic product, mobile tools.With the pay attention to day by day of people's environmental pollution, with
Lithium ion is started to be advocated by people, be paid close attention to by the environmentally protective electric car of power or auxiliary power.
Ternary anode material for lithium-ion batteries is a kind of Olivine-type Cathode Material in Li-ion Batteries developed in recent years and cobalt acid
Lithium material compares, and reduces production cost, and improving security performance and comparing with lithium manganate material has higher capacity and phosphorus
Sour iron lithium, which is compared, has better cryogenic property, and the status in positive electrode gradually shows, and has energy density high, continuous
The advantages that mileage that navigates is relatively long, therefore domestic vehicle enterprise passenger car turns to ternary material one after another, and rich nickel tertiary cathode material phase
To common ternary material, there is more height ratio capacity, nickel is main redox reaction element, and therefore, improving nickel content can be with
Effectively improve the specific capacity of battery.From the point of view of battery energy density and electric vehicle course continuation mileage, nickeliferous ternary system is with the obvious advantage,
The battery of especially rich nickel ternary material production.And Co content is lower in rich nickel ternary material, it means that it has more
Good cost and energy density advantage.But with the raising of nickel content, the cycle performance dramatic decrease of material, stability is poor,
Capacity attenuation is fast, and disadvantage mentioned above restricts the commercial applications of this material.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of rich nickel of modification
Ternary composite electrode material and preparation method thereof, rich nickel ternary electrode material can prevent after lithium compound is modified in the invention
The dissolution of metal ion in rich nickel ternary electrode material, solves battery in high current density cyclic process, and electrolyte corrodes
Positive electrode, solves that rich nickel ternary electrode stability of material is poor, and capacity attenuation is fast at the problem of causing material property rapid decay
The problem of, and lithium compound has excellent lithium ion conductivity, effectively improves lithium ion in the diffusion speed of positive electrode
Rate improves cycle performance of lithium ion battery and high rate performance.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of rich nickel ternary composite electrode of modification
Material, the decorative layer of rich nickel ternary electrode material and rich nickel ternary electrode outer material side including doping oxide, the modification
Layer with a thickness of 0.5nm~50nm, the decorative layer is made of lithiumation object, decorative layer in the richness nickel ternary composite electrode material
Mass percent be 1%~5%, the doping oxide of the richness nickel ternary electrode material is Nb2O3Or MoO3, the richness nickel
The molar ratio of LiO, NiO, CoO, MnO and doping oxide is (1.0~1.1): (0.7~0.9) in ternary electrode material:
(0.05~0.15): (0.05~0.15): (0~0.01).
Preferably, the molar ratio of LiO, NiO, CoO, MnO and doping oxide is in the rich nickel ternary electrode material
1.04: 0.8: 0.1: 0.1:0.005.
Preferably, the mass percent of decorative layer is 2% in the rich nickel ternary composite electrode material.
Preferably, the lithiumation object is Li2SiO3、Li2ZrO3、Li2GeO3And LiAlO2One of or more than one.
The present invention also provides the preparation method of the rich nickel ternary composite electrode material of the above-mentioned modification stated, this method includes
Following steps:
Step 1: carrying out dry-mixed ball milling after LiO, NiO, CoO, MnO and doping oxide are mixed, electrode material is obtained;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The system of the sintering are as follows: temperature is risen to 500 DEG C from room temperature with the heating rate of 3 DEG C/min, 4h is kept the temperature, then with 5
DEG C/after the heating rate of min rises to 700 DEG C~900 DEG C, sintering 12~for 24 hours, last natually cooled to room temperature;
Step 3: after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object,
Obtain presoma;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel ternary is obtained
Combination electrode material;The system of the sintering are as follows: temperature is risen to 400 DEG C~500 DEG C from room temperature with the heating rate of 3 DEG C/min
Afterwards, 5~10h, last natually cooled to room temperature are sintered.
Preferably, the ratio of grinding media to material of dry-mixed ball milling described in step 1 and step 5 is 1:5, and the revolving speed of dry-mixed ball milling is
50r/min~150r/min, the time of dry-mixed ball milling are 5h~15h.
Preferably, the revolving speed of dry-mixed ball milling described in step 1 and step 3 is 100r/min, and the time of dry-mixed ball milling is equal
For 10h.
Preferably, the temperature of sintering described in step 4 is 500 DEG C, sintering time 5h.
Preferably, the rate that is passed through of oxygen atmosphere described in step 2 and step 4 is 0.01L/min~0.2L/min.
Compared with the prior art, the present invention has the following advantages:
1, doping oxide of the invention, lithium compound carry out modification to rich nickel ternary electrode material, improve heat
Stability and cycle performance, niobium or molybdenum doping inhibit lithium in material, nickel to reset in doping oxide, reduce the mixed of cation
Scheduling degree is conducive to the cycle performance and high rate performance that improve material, while it is coated on rich nickel ternary electrode by lithium compound
Material surface can not only prevent battery electrolyte in high current density cyclic process from corroding positive electrode, can prevent rich nickel
Ternary electrode material because metal ion dissolution caused by material property rapid decay, resist electrolyte and positive electrode invaded
Erosion, and lithium compound has excellent lithium ion conductivity, effectively improves lithium ion in the diffusion rate of positive electrode, has
Solves rich nickel conducive to the transmission of lithium ion so as to which the cyclical stability and high rate performance of lithium ion battery is greatly improved
Ternary electrode stability of material is poor, the fast problem of capacity attenuation, and lithium compound selects one or more compounds, and lithiumation is closed
Synergistic effect between object can preferably improve the stability and cycle performance of material.
2, the thickness of the decorative layer of the lithium compound of electrode material of the invention is only 0.5nm~50nm, and decorative layer is too thick
Although the surface impedance of material can be reduced, the dissolution of metal ion in material is prevented, enhances the stability of combination electrode material,
But too thick decorative layer can also weaken its chemical property to a certain extent.
3, the present invention is with doping oxide (Nb2O3Or MoO3), LiO, NiO, CoO, MnO and lithium compound be raw material, pass through
Doping oxide adulterates in situ and lithiumation object secondary modification, is sintered through oxygen atmosphere high temperature, completes lithium compound to rich nickel three
The modification of first electrode material, simple process is at low cost, is suitble to large-scale production, and the present invention selects the oxidation of Li, Ni, Co and Mn
Object is raw material, avoids the generation of impurity during the reaction, and the content of Ni is high in Ni, Co and Mn ternary material, and preparation is modified
Rich nickel ternary composite electrode material energy density it is big.
Invention is further described in detail with reference to the accompanying drawings and examples.
Detailed description of the invention
Fig. 1 is the rich nickel ternary composite electrode scanning of materials electron microscope of the modification of the embodiment of the present invention 1.
Fig. 2 is the rich nickel ternary composite electrode material X diffracting spectrum of the modification of the embodiment of the present invention 1.
Specific embodiment
Embodiment 1
The rich nickel ternary composite electrode material of the modification of the present embodiment, the rich nickel ternary electrode material including doping oxide
With the decorative layer of rich nickel ternary electrode outer material side, the decorative layer with a thickness of 0.5nm~50nm, the decorative layer is by lithiumation
Object Li2SiO3It is made, the mass percent of decorative layer is 2% in the richness nickel ternary composite electrode material, the richness nickel ternary electricity
The doping oxide of pole material is Nb2O3, LiO, NiO, CoO, MnO and Nb in the richness nickel ternary electrode material2O3Molar ratio
It is 1.04: 0.8: 0.1: 0.1:0.005.
The present embodiment additionally provides the method for preparing the rich nickel ternary composite electrode material of above-mentioned modification, and this method includes
Following steps:
Step 1: by LiO, NiO, CoO, MnO and Nb2O3Dry-mixed ball milling is carried out after mixing, obtains electrode material;It is described dry
The ratio of grinding media to material of bastard mill is 1:5, and the revolving speed of dry-mixed ball milling is 100r/min, and the time of dry-mixed ball milling is 10h;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The rate that is passed through of the oxygen atmosphere is 0.1L/min;The system of the sintering are as follows: will with the heating rate of 3 DEG C/min
Temperature rises to 500 DEG C from room temperature, keeps the temperature 4h, after then rising to 800 DEG C with the heating rate of 5 DEG C/min, is sintered 18h, finally certainly
So cool down to room temperature;
Step 3: after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object,
Obtain presoma;The ratio of grinding media to material of the dry-mixed ball milling be 1:5, the revolving speed of dry-mixed ball milling is 100r/min, dry-mixed ball milling when
Between be 10h;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel ternary is obtained
Combination electrode material;The rate that is passed through of the oxygen atmosphere is 0.1L/min;The system of the sintering are as follows: with the liter of 3 DEG C/min
After temperature is risen to 500 DEG C from room temperature by warm rate, it is sintered 5h, last natually cooled to room temperature.
Fig. 1 is rich nickel ternary composite electrode scanning of materials electron microscope manufactured in the present embodiment, and figure is 2 manufactured in the present embodiment
The X diffracting spectrum of rich nickel ternary composite electrode material, a are the corresponding standard card of rich nickel ternary material, and b is rich nickel ternary material
Material, c are the rich nickel ternary material of lithium zirconate niobium oxide modification, and analysis can obtain, and all spectrograms all show typical stratiform knot
Structure can go out the anode synthesized by each diffraction maximum.The splitting degree at (006) of synthetic sample/(102) and (108)/(110) peak is said
The layer structure of bright sample is good.
Under 1C discharge-rate, first discharge specific capacity reaches richness nickel ternary composite electrode material manufactured in the present embodiment
155mAh/g, capacity retention ratio reaches 85.5% after recycling 100 times.
Comparative example 1
The rich nickel ternary electrode material of this comparative example, the richness nickel ternary electrode material is by LiO, NiO, CoO and MnO system
At the molar ratio of LiO, NiO, CoO and MnO are 1.04: 0.8: 0.1: 0.1 in the richness nickel ternary electrode material.
This comparative example additionally provides the method for preparing above-mentioned rich nickel ternary electrode material, method includes the following steps:
Step 1: carrying out dry-mixed ball milling after LiO, NiO, CoO and MnO are mixed, electrode material is obtained;The dry-mixed ball milling
Ratio of grinding media to material be 1:5, the revolving speed of dry-mixed ball milling is 100r/min, and time of dry-mixed ball milling is 10h;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The rate that is passed through of the oxygen atmosphere is 0.1L/min;The system of the sintering are as follows: will with the heating rate of 3 DEG C/min
Temperature rises to 500 DEG C from room temperature, keeps the temperature 4h, after then rising to 800 DEG C with the heating rate of 5 DEG C/min, is sintered 18h, finally certainly
Room temperature so is cooled down to, obtains rich nickel ternary electrode material.
Under 1C discharge-rate, first discharge specific capacity reaches the rich nickel ternary composite electrode material of this comparative example preparation
150mAh/g, capacity retention ratio is 75% after recycling 100 times, and compared with Example 1, performance is poor, illustrates the doping of embodiment 1
Oxide Nb2O3, lithium compound Li2SiO3Thermal stability can be improved and follow by carrying out modification to rich nickel ternary electrode material
Ring performance.
The present embodiment doping oxide Nb2O3, lithium compound Li2SiO3Modification is carried out to rich nickel ternary electrode material to change
Property, thermal stability and cycle performance are improved, niobium doping inhibits lithium in material, nickel to reset in doping oxide, reduces sun
The mixing degree of ion is conducive to the cycle performance and high rate performance that improve material, while it is coated on rich nickel by lithium compound
Ternary electrode material surface can not only prevent battery electrolyte in high current density cyclic process from corroding positive electrode, can
Prevent rich nickel ternary electrode material because metal ion dissolution caused by material property rapid decay, resist electrolyte to positive material
The erosion of material, and lithium compound has excellent lithium ion conductivity, effectively improves lithium ion in the diffusion of positive electrode
Rate is conducive to the transmission of lithium ion, so as to which the cyclical stability and high rate performance of lithium ion battery is greatly improved, solves
Rich nickel ternary electrode stability of material is poor, capacity attenuation fast problem, and lithium compound selects one or more compounds,
Synergistic effect between lithium compound can preferably improve the stability and cycle performance of material.
The thickness of the decorative layer of the lithium compound of the electrode material of the present embodiment is only 0.5nm~50nm, and decorative layer is too thick
Although the surface impedance of material can be reduced, the dissolution of metal ion in material is prevented, enhances the stability of combination electrode material,
But too thick decorative layer can also weaken its chemical property to a certain extent.
The present embodiment is with doping oxide Nb2O3, LiO, NiO, CoO, MnO and lithium compound be raw material, pass through doping oxidation
Object adulterates in situ and lithiumation object secondary modification, is sintered through oxygen atmosphere high temperature, completes lithium compound to rich nickel ternary electrode material
The modification of material, simple process is at low cost, is suitble to large-scale production, and the present invention selects the oxide of Li, Ni, Co and Mn for raw material,
The generation of impurity during the reaction is avoided, the content of Ni is high in Ni, Co and Mn ternary material, prepares modified rich nickel ternary
The energy density of combination electrode material is big.
Embodiment 2
The rich nickel ternary composite electrode material of the modification of the present embodiment, the rich nickel ternary electrode material including doping oxide
With the decorative layer of rich nickel ternary electrode outer material side, the decorative layer with a thickness of 0.5nm~50nm, the decorative layer is by lithiumation
Object Li2ZrO3And Li2GeO3It is made in mass ratio of 1:1, the quality percentage of decorative layer in the richness nickel ternary composite electrode material
Number is 1%, and the doping oxide of the richness nickel ternary electrode material is Nb2O3, LiO, NiO in the richness nickel ternary electrode material,
CoO, MnO and Nb2O3Molar ratio be 1.0: 0.7: 0.05: 0.05:0.005.
The present embodiment additionally provides the method for preparing the rich nickel ternary composite electrode material of above-mentioned modification, and this method includes
Following steps:
Step 1: by LiO, NiO, CoO, MnO and Nb2O3Dry-mixed ball milling is carried out after mixing, obtains electrode material;It is described dry
The ratio of grinding media to material of bastard mill is 1:5, and the revolving speed of dry-mixed ball milling is 50r/min, and the time of dry-mixed ball milling is 15h;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The rate that is passed through of the oxygen atmosphere is 0.01L/min;The system of the sintering are as follows: will with the heating rate of 3 DEG C/min
Temperature rises to 500 DEG C from room temperature, keeps the temperature 4h, after then rising to 700 DEG C with the heating rate of 5 DEG C/min, is sintered for 24 hours, finally certainly
So cool down to room temperature;
Step 3: after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object,
Obtain presoma;The ratio of grinding media to material of the dry-mixed ball milling is 1:5, and the revolving speed of dry-mixed ball milling is 50r/min, the time of dry-mixed ball milling
For 15h;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel ternary is obtained
Combination electrode material;The rate that is passed through of the oxygen atmosphere is 0.01L/min;The system of the sintering are as follows: with the liter of 3 DEG C/min
After temperature is risen to 400 DEG C from room temperature by warm rate, it is sintered 10h, last natually cooled to room temperature.
Under 1C discharge-rate, first discharge specific capacity reaches richness nickel ternary composite electrode material manufactured in the present embodiment
148mAh/g, capacity retention ratio reaches 80% after recycling 100 times.
Embodiment 3
The rich nickel ternary composite electrode material of the modification of the present embodiment, the rich nickel ternary electrode material including doping oxide
With the decorative layer of rich nickel ternary electrode outer material side, the decorative layer with a thickness of 0.5nm~50nm, the decorative layer is by lithiumation
Object Li2ZrO3、Li2GeO3And LiAlO2It is made according to mass ratio of 1:1:1, is repaired described in the richness nickel ternary composite electrode material
The mass percent for adoring layer is 2%, and the doping oxide of the richness nickel ternary electrode material is MoO3, the richness nickel ternary electrode
LiO, NiO, CoO, MnO and MoO in material3Molar ratio be 1.1: 0.9: 0.15: 0.15:0.01.
The present embodiment additionally provides the method for preparing the rich nickel ternary composite electrode material of above-mentioned modification, and this method includes
Following steps:
Step 1: by LiO, NiO, CoO, MnO and MoO3Dry-mixed ball milling is carried out after mixing, obtains electrode material;It is described dry
The ratio of grinding media to material of bastard mill is 1:5, and the revolving speed of dry-mixed ball milling is 150r/min, and the time of dry-mixed ball milling is 5h;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The rate that is passed through of the oxygen atmosphere is 0.2L/min;The system of the sintering are as follows: will with the heating rate of 3 DEG C/min
Temperature rises to 500 DEG C from room temperature, keeps the temperature 4h, after then rising to 900 DEG C with the heating rate of 5 DEG C/min, is sintered 12h, finally certainly
So cool down to room temperature;
Step 3: after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object,
Obtain presoma;The ratio of grinding media to material of the dry-mixed ball milling be 1:5, the revolving speed of dry-mixed ball milling is 150r/min, dry-mixed ball milling when
Between be 5h;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel ternary is obtained
Combination electrode material;The rate that is passed through of the oxygen atmosphere is 0.2L/min;The system of the sintering are as follows: with the liter of 3 DEG C/min
After temperature is risen to 450 DEG C from room temperature by warm rate, it is sintered 7.5h, last natually cooled to room temperature.
Under 1C discharge-rate, first discharge specific capacity reaches richness nickel ternary composite electrode material manufactured in the present embodiment
154mAh/g, capacity retention ratio reaches 85% after recycling 100 times.
Embodiment 4
The rich nickel ternary composite electrode material of the modification of the present embodiment, the rich nickel ternary electrode material including doping oxide
With the decorative layer of rich nickel ternary electrode outer material side, the decorative layer with a thickness of 0.5nm~50nm, the decorative layer is by lithiumation
Object Li2ZrO3、Li2GeO3And LiAlO2It is made in mass ratio of 1:1:1, decorative layer in the richness nickel ternary composite electrode material
Mass percent is 1%, and the doping oxide of the richness nickel ternary electrode material is MoO3, in the richness nickel ternary electrode material
LiO, NiO, CoO, MnO and MoO3Molar ratio be 1.1: 0.7: 0.05: 0.05:0.002.
The present embodiment additionally provides the method for preparing the rich nickel ternary composite electrode material of above-mentioned modification, and this method includes
Following steps:
Step 1: by LiO, NiO, CoO, MnO and MoO3Dry-mixed ball milling is carried out after mixing, obtains electrode material;It is described dry
The ratio of grinding media to material of bastard mill is 1:5, and the revolving speed of dry-mixed ball milling is 100r/min, and the time of dry-mixed ball milling is 10h;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The rate that is passed through of the oxygen atmosphere is 0.15L/min;The system of the sintering are as follows: will with the heating rate of 3 DEG C/min
Temperature rises to 500 DEG C from room temperature, keeps the temperature 4h, after then rising to 800 DEG C with the heating rate of 5 DEG C/min, is sintered for 24 hours, finally certainly
So cool down to room temperature;
Step 3: after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object,
Obtain presoma;The ratio of grinding media to material of the dry-mixed ball milling be 1:5, the revolving speed of dry-mixed ball milling is 100r/min, dry-mixed ball milling when
Between be 10h;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel ternary is obtained
Combination electrode material;The rate that is passed through of the oxygen atmosphere is 0.15L/min;The system of the sintering are as follows: with the liter of 3 DEG C/min
After temperature is risen to 450 DEG C from room temperature by warm rate, it is sintered 10h, last natually cooled to room temperature.
Under 1C discharge-rate, first discharge specific capacity reaches richness nickel ternary composite electrode material manufactured in the present embodiment
151mAh/g, capacity retention ratio reaches 82% after recycling 100 times.
Embodiment 5
The rich nickel ternary composite electrode material of the modification of the present embodiment, the rich nickel ternary electrode material including doping oxide
With the decorative layer of rich nickel ternary electrode outer material side, the decorative layer with a thickness of 0.5nm~50nm, the decorative layer is by lithiumation
Object Li2GeO3It is made, the mass percent of decorative layer is 3% in the richness nickel ternary composite electrode material, the richness nickel ternary electricity
The doping oxide of pole material is Nb2O3, LiO, NiO, CoO, MnO and Nb in the richness nickel ternary electrode material2O3Molar ratio
It is 1.0: 0.7: 0.15: 0.15:0.01.
The present embodiment additionally provides the method for preparing the rich nickel ternary composite electrode material of above-mentioned modification, and this method includes
Following steps:
Step 1: by LiO, NiO, CoO, MnO and Nb2O3Dry-mixed ball milling is carried out after mixing, obtains electrode material;It is described dry
The ratio of grinding media to material of bastard mill is 1:5, and the revolving speed of dry-mixed ball milling is 80r/min, and the time of dry-mixed ball milling is 8h;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The rate that is passed through of the oxygen atmosphere is 0.2L/min;The system of the sintering are as follows: will with the heating rate of 3 DEG C/min
Temperature rises to 500 DEG C from room temperature, keeps the temperature 4h, after then rising to 800 DEG C with the heating rate of 5 DEG C/min, is sintered 18h, finally certainly
So cool down to room temperature;
Step 3: after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object,
Obtain presoma;The ratio of grinding media to material of the dry-mixed ball milling is 1:5, and the revolving speed of dry-mixed ball milling is 80r/min, the time of dry-mixed ball milling
For 8h;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel ternary is obtained
Combination electrode material;The rate that is passed through of the oxygen atmosphere is 0.2L/min;The system of the sintering are as follows: with the liter of 3 DEG C/min
After temperature is risen to 400 DEG C from room temperature by warm rate, it is sintered 10h, last natually cooled to room temperature.
Under 1C discharge-rate, first discharge specific capacity reaches richness nickel ternary composite electrode material manufactured in the present embodiment
151mAh/g, capacity retention ratio reaches 82% after recycling 100 times.
Embodiment 6
The rich nickel ternary composite electrode material of the modification of the present embodiment, the rich nickel ternary electrode material including doping oxide
With the decorative layer of rich nickel ternary electrode outer material side, the decorative layer with a thickness of 0.5nm~50nm, the decorative layer is by lithiumation
Object Li2GeO3And LiAlO2It is made in mass ratio of 1:2, the quality percentage of decorative layer in the richness nickel ternary composite electrode material
Number is 4%, and the doping oxide of the richness nickel ternary electrode material is Nb2O3, LiO, NiO in the richness nickel ternary electrode material,
CoO, MnO and Nb2O3Molar ratio be 1.0: 0.9: 0.05: 0.15:0.008.
The present embodiment additionally provides the method for preparing the rich nickel ternary composite electrode material of above-mentioned modification, and this method includes
Following steps:
Step 1: by LiO, NiO, CoO, MnO and Nb2O3Dry-mixed ball milling is carried out after mixing, obtains electrode material;It is described dry
The ratio of grinding media to material of bastard mill is 1:5, and the revolving speed of dry-mixed ball milling is 150r/min, and the time of dry-mixed ball milling is 5h;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The rate that is passed through of the oxygen atmosphere is 0.02L/min;The system of the sintering are as follows: will with the heating rate of 3 DEG C/min
Temperature rises to 500 DEG C from room temperature, keeps the temperature 4h, after then rising to 850 DEG C with the heating rate of 5 DEG C/min, is sintered 18h, finally certainly
So cool down to room temperature;
Step 3: after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object,
Obtain presoma;The ratio of grinding media to material of the dry-mixed ball milling be 1:5, the revolving speed of dry-mixed ball milling is 150r/min, dry-mixed ball milling when
Between be 5h;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel ternary is obtained
Combination electrode material;The rate that is passed through of the oxygen atmosphere is 0.02L/min;The system of the sintering are as follows: with the liter of 3 DEG C/min
After temperature is risen to 450 DEG C from room temperature by warm rate, it is sintered 7.5h, last natually cooled to room temperature.
Under 1C discharge-rate, first discharge specific capacity reaches richness nickel ternary composite electrode material manufactured in the present embodiment
153mAh/g, capacity retention ratio reaches 85% after recycling 100 times.
Embodiment 7
The rich nickel ternary composite electrode material of the modification of the present embodiment, including mix rich nickel ternary electrode material and rich nickel ternary
Decorative layer on the outside of electrode material, the decorative layer with a thickness of 0.5nm~50nm, the decorative layer is by lithiumation object Li2ZrO3With
Li2GeO3It is made in mass ratio of 1:4, the mass percent of decorative layer is 2% in the richness nickel ternary composite electrode material, institute
The molar ratio for stating LiO, NiO, CoO and MnO in rich nickel ternary electrode material is 1.05: 0.8: 0.05: 0.15.
The present embodiment additionally provides the method for preparing the rich nickel ternary composite electrode material of above-mentioned modification, and this method includes
Following steps:
Step 1: carrying out dry-mixed ball milling after LiO, NiO, CoO and MnO are mixed, electrode material is obtained;The dry-mixed ball milling
Ratio of grinding media to material be 1:5, the revolving speed of dry-mixed ball milling is 50r/min, and time of dry-mixed ball milling is 15h;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The rate that is passed through of the oxygen atmosphere is 0.18L/min;The system of the sintering are as follows: will with the heating rate of 3 DEG C/min
Temperature rises to 500 DEG C from room temperature, keeps the temperature 4h, after then rising to 850 DEG C with the heating rate of 5 DEG C/min, is sintered 18h, finally certainly
So cool down to room temperature;
Step 3: after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object,
Obtain presoma;The ratio of grinding media to material of the dry-mixed ball milling is 1:5, and the revolving speed of dry-mixed ball milling is 50r/min, the time of dry-mixed ball milling
For 15h;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel ternary is obtained
Combination electrode material;The rate that is passed through of the oxygen atmosphere is 0.18L/min;The system of the sintering are as follows: with the liter of 3 DEG C/min
After temperature is risen to 500 DEG C from room temperature by warm rate, it is sintered 5h, last natually cooled to room temperature.
Under 1C discharge-rate, first discharge specific capacity reaches richness nickel ternary composite electrode material manufactured in the present embodiment
148.5mAh/g, capacity retention ratio reaches 78% after recycling 100 times.
Embodiment 8
The rich nickel ternary composite electrode material of the modification of the present embodiment, the rich nickel ternary electrode material including doping oxide
With the decorative layer of rich nickel ternary electrode outer material side, the decorative layer with a thickness of 0.5nm~50nm, the decorative layer is by lithiumation
Object LiAlO2It is made, the mass percent of decorative layer is 5% in the richness nickel ternary composite electrode material, the richness nickel ternary electricity
The doping oxide of pole material is MoO3, LiO, NiO, CoO, MnO and MoO in the richness nickel ternary electrode material3Molar ratio be
1.0: 0.8: 0.05: 0.1:0.007.
The present embodiment additionally provides the method for preparing the rich nickel ternary composite electrode material of above-mentioned modification, and this method includes
Following steps:
Step 1: by LiO, NiO, CoO, MnO and MoO3Dry-mixed ball milling is carried out after mixing, obtains electrode material;It is described dry
The ratio of grinding media to material of bastard mill is 1:5, and the revolving speed of dry-mixed ball milling is 100r/min, and the time of dry-mixed ball milling is 10h;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode is obtained
Material;The rate that is passed through of the oxygen atmosphere is 0.06L/min;The system of the sintering are as follows: will with the heating rate of 3 DEG C/min
Temperature rises to 500 DEG C from room temperature, keeps the temperature 4h, after then rising to 800 DEG C with the heating rate of 5 DEG C/min, is sintered for 24 hours, finally certainly
So cool down to room temperature;
Step 3: after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object,
Obtain presoma;The ratio of grinding media to material of the dry-mixed ball milling be 1:5, the revolving speed of dry-mixed ball milling is 100r/min, dry-mixed ball milling when
Between be 10h;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel ternary is obtained
Combination electrode material;The rate that is passed through of the oxygen atmosphere is 0.06L/min;The system of the sintering are as follows: with the liter of 3 DEG C/min
After temperature is risen to 5000 DEG C from room temperature by warm rate, it is sintered 5h, last natually cooled to room temperature.
Under 1C discharge-rate, first discharge specific capacity reaches richness nickel ternary composite electrode material manufactured in the present embodiment
156mAh/g, capacity retention ratio reaches 80% after recycling 100 times.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (9)
1. a kind of rich nickel ternary composite electrode material of modification, which is characterized in that the rich nickel ternary electrode including doping oxide
The decorative layer of material and rich nickel ternary electrode outer material side, the decorative layer with a thickness of 0.5nm~50nm, the decorative layer by
Lithiumation object is made, and the mass percent of decorative layer is 1%~5% in the richness nickel ternary composite electrode material, the richness nickel three
The doping oxide of first electrode material is Nb2O3Or MoO3, LiO, NiO, CoO, MnO and mix in the richness nickel ternary electrode material
The molar ratio of miscellaneous oxide is (1.0~1.1): (0.7~0.9): (0.05~0.15): (0.05~0.15): (0~0.01).
2. a kind of rich nickel ternary composite electrode material of modification according to claim 1, which is characterized in that the richness nickel three
The molar ratio of LiO, NiO, CoO, MnO and doping oxide is 1.04: 0.8: 0.1: 0.1:0.005 in first electrode material.
3. a kind of rich nickel ternary composite electrode material of modification according to claim 1, which is characterized in that the richness nickel three
The mass percent of decorative layer is 2% in first combination electrode material.
4. a kind of rich nickel ternary composite electrode material of modification according to claim 1, which is characterized in that the lithiumation object
For Li2SiO3、Li2ZrO3、Li2GeO3And LiAlO2One of or more than one.
5. a kind of side for the rich nickel ternary composite electrode material for preparing the modification as described in claim 1-4 any claim
Method, which is characterized in that method includes the following steps:
Step 1: carrying out dry-mixed ball milling after LiO, NiO, CoO, MnO and doping oxide are mixed, electrode material is obtained;
Step 2: electrode material obtained in step 1 is sintered in oxygen atmosphere, rich nickel ternary electrode material is obtained;
The system of the sintering are as follows: temperature is risen to 500 DEG C from room temperature with the heating rate of 3 DEG C/min, keeps the temperature 4h, then with 5 DEG C/
After the heating rate of min rises to 700 DEG C~900 DEG C, sintering 12~for 24 hours, last natually cooled to room temperature;
Step 3: being obtained after carrying out dry-mixed ball milling after richness nickel ternary electrode material obtained in step 2 is mixed with lithiumation object
Presoma;
Step 4: presoma obtained in step 3 is sintered in oxygen atmosphere, modified rich nickel tri compound is obtained
Electrode material;The system of the sintering are as follows: after temperature is risen to 400 DEG C~500 DEG C from room temperature with the heating rate of 3 DEG C/min,
It is sintered 5~10h, last natually cooled to room temperature.
6. according to the method described in claim 5, it is characterized in that, the ratio of grinding media to material of dry-mixed ball milling described in step 1 and step 5 is equal
For 1:5, the revolving speed of dry-mixed ball milling is 50r/min~150r/min, and the time of dry-mixed ball milling is 5h~15h.
7. the method according to requiring 6, which is characterized in that the revolving speed of dry-mixed ball milling described in step 1 and step 3 is
100r/min, the time of dry-mixed ball milling are 10h.
8. according to the method described in claim 5, it is characterized in that, the temperature of sintering described in step 4 is 500 DEG C, when sintering
Between be 5h.
9. according to the method described in claim 5, it is characterized in that, oxygen atmosphere described in step 2 and step 4 is passed through speed
Rate is 0.01L/min~0.2L/min.
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