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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
electrode material
nickel ternary
rich nickel
dry
ball milling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910289498.0A
Other languages
Chinese (zh)
Other versions
CN109888261B (en
Inventor
何蕊
刘振法
张利辉
魏爱佳
白薛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Energy Research Institute of Hebei Academy of Sciences
Original Assignee
Energy Research Institute of Hebei Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Energy Research Institute of Hebei Academy of Sciences filed Critical Energy Research Institute of Hebei Academy of Sciences
Priority to CN201910289498.0A priority Critical patent/CN109888261B/en
Publication of CN109888261A publication Critical patent/CN109888261A/en
Application granted granted Critical
Publication of CN109888261B publication Critical patent/CN109888261B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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

A kind of rich nickel ternary composite electrode material of modification and preparation method thereof
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.
CN201910289498.0A 2019-04-11 2019-04-11 Modified nickel-rich ternary composite electrode material and preparation method thereof Active CN109888261B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910289498.0A CN109888261B (en) 2019-04-11 2019-04-11 Modified nickel-rich ternary composite electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910289498.0A CN109888261B (en) 2019-04-11 2019-04-11 Modified nickel-rich ternary composite electrode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109888261A true CN109888261A (en) 2019-06-14
CN109888261B CN109888261B (en) 2021-03-09

Family

ID=66936952

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910289498.0A Active CN109888261B (en) 2019-04-11 2019-04-11 Modified nickel-rich ternary composite electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109888261B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110854384A (en) * 2019-11-26 2020-02-28 河北省科学院能源研究所 Preparation method of surface-modified nickel-based electrode material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102738451A (en) * 2012-07-13 2012-10-17 河南师范大学 Modified positive electrode material of lithium ion battery and preparation method of modified positive electrode material
CN104300135A (en) * 2014-09-18 2015-01-21 秦皇岛中科远达电池材料有限公司 Nickel-rich concentration gradient type lithium nickel cobalt aluminum oxide positive pole material, preparation method thereof and lithium ion battery
CN104362295A (en) * 2014-11-13 2015-02-18 四川浩普瑞新能源材料有限公司 Nickel-based anode material for lithium ion battery and preparation method of nickel-based anode material
CN107492636A (en) * 2017-07-10 2017-12-19 河南大学 A kind of preparation method of lithium ion battery composite cathode material
CN108011098A (en) * 2017-11-29 2018-05-08 欣旺达电子股份有限公司 Tertiary cathode material and preparation method thereof
CN108023077A (en) * 2017-11-30 2018-05-11 宁波容百新能源科技股份有限公司 A kind of nickelic positive electrode of fast-ionic conductor coating modification and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102738451A (en) * 2012-07-13 2012-10-17 河南师范大学 Modified positive electrode material of lithium ion battery and preparation method of modified positive electrode material
CN104300135A (en) * 2014-09-18 2015-01-21 秦皇岛中科远达电池材料有限公司 Nickel-rich concentration gradient type lithium nickel cobalt aluminum oxide positive pole material, preparation method thereof and lithium ion battery
CN104362295A (en) * 2014-11-13 2015-02-18 四川浩普瑞新能源材料有限公司 Nickel-based anode material for lithium ion battery and preparation method of nickel-based anode material
CN107492636A (en) * 2017-07-10 2017-12-19 河南大学 A kind of preparation method of lithium ion battery composite cathode material
CN108011098A (en) * 2017-11-29 2018-05-08 欣旺达电子股份有限公司 Tertiary cathode material and preparation method thereof
CN108023077A (en) * 2017-11-30 2018-05-11 宁波容百新能源科技股份有限公司 A kind of nickelic positive electrode of fast-ionic conductor coating modification and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110854384A (en) * 2019-11-26 2020-02-28 河北省科学院能源研究所 Preparation method of surface-modified nickel-based electrode material
CN110854384B (en) * 2019-11-26 2021-04-02 河北省科学院能源研究所 Preparation method of surface-modified nickel-based electrode material

Also Published As

Publication number Publication date
CN109888261B (en) 2021-03-09

Similar Documents

Publication Publication Date Title
CN100502106C (en) Secondary cell anode material and its preparing method
CN103794773B (en) A kind of method of producing high power capacity 523 type tertiary cathode material
CN108847477B (en) Nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof
CN107437619A (en) A kind of anode for lithium battery material and preparation method thereof
CN111106331B (en) Layered-spinel phase composite positive electrode material and preparation method thereof
CN101964416A (en) Preparation method of lithium ion battery anode material lithium manganate and automobile lithium ion battery
CN103384003B (en) Preparation method and application of high-capacity high-temperature-resistant lithium manganate
CN102237516A (en) Preparation method of lithium ion power battery positive electrode material
CN108807950A (en) The rich nickel ternary composite electrode material and preparation method thereof of fluoride modification
CN108232182A (en) A kind of modified nickel-cobalt lithium manganate cathode material and preparation method thereof
CN105958054A (en) Method for lanthanum phosphate coated lithium ion battery cathode material nickel cobalt lithium manganate
CN107579213B (en) Multiphase sodium ion battery electrode material structure design and performance regulation and control technology
CN103715422B (en) Electrolysis prepares the method for the nickelic system positive electrode of lithium ion battery
CN113517424A (en) Cobalt-free positive electrode material of high-voltage lithium ion battery and preparation method thereof
CN110061225A (en) A kind of monocrystalline high capacity nickel-cobalt lithium manganate cathode material and preparation method thereof
CN102315437B (en) High specific capacity lithium-rich composite anode material of power lithium ion battery and synthetic method thereof
CN112635722B (en) Composite positive electrode material of lithium ion battery and preparation method
CN114695876A (en) Method for in-situ solid-phase coating of lithium ion conductor by using ternary cathode material NCM
CN103066263B (en) Lithium ion battery positive material and preparation method thereof
CN109888261A (en) A kind of rich nickel ternary composite electrode material of modification and preparation method thereof
CN115806281B (en) Lithium iron manganese phosphate composite material, preparation method thereof and battery
CN115806319A (en) Layered high-entropy oxide, preparation method and application thereof
CN115939396A (en) Ternary blended positive electrode material, preparation method thereof and battery
CN109037639A (en) A kind of preparation method coating nickel element adulterated lithium manganate composite material
CN109037669A (en) Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant