CN106910881A - Metatitanic acid lithium coats the preparation method of nickel cobalt lithium aluminate cathode material - Google Patents
Metatitanic acid lithium coats the preparation method of nickel cobalt lithium aluminate cathode material Download PDFInfo
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- CN106910881A CN106910881A CN201710195762.5A CN201710195762A CN106910881A CN 106910881 A CN106910881 A CN 106910881A CN 201710195762 A CN201710195762 A CN 201710195762A CN 106910881 A CN106910881 A CN 106910881A
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- nickel cobalt
- metatitanic acid
- lithium
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- lithium aluminate
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to anode material for lithium-ion batteries technical field, the preparation method that a kind of metatitanic acid lithium coats nickel cobalt lithium aluminate cathode material is particularly disclosed.The metatitanic acid lithium coats the preparation method of nickel cobalt lithium aluminate cathode material, it is characterized by:By in titanium dioxide and nickel cobalt aluminic acid powder for lithium simultaneously addition coating unit, by fully dispersed, absorption and restructuring, solid powder is obtained;Solid powder is put into Muffle furnace to heat up, is calcined in air atmosphere, be then naturally cooling to room temperature, obtain the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.The present invention is coated using metatitanic acid lithium to surface, and metatitanic acid lithium is used as Li+Conductor material, Li can be better achieved+Insertion and abjection, improve material cycle performance and high rate performance;Simultaneously using metatitanic acid lithium cladding, to reduce NCA to moisture sensitivity, the directly contact of electrode material and organic electrolyte is reduced, further improve the structural stability of NCA, improve the security of material.
Description
(One)Technical field
The present invention relates to anode material for lithium-ion batteries technical field, more particularly to a kind of metatitanic acid lithium cladding nickel cobalt lithium aluminate is just
The preparation method of pole material.
(Two)Background technology
In recent years, with the continuous progress of science and technology, for civilian, military domain power-supply system continuous upgrading, people
It is also proposed requirement higher for lithium ion battery.Particularly, Large Copacity, high-energy-density, extended-life lithium ion battery
Demand is very urgent, meanwhile, the requirement to product use environment is also increasingly harsher.The anode material for lithium-ion batteries master of main flow
To include LiCoO2、LiNi1/3Mn1/3Co1/3O2、LiMn2O4、LiFePO4、LiNiO2, in the occasion that battery volume is restricted,
Using similar LiNiO2Nickelic system material prepare cell specific energy highest.Common LiNiO2Although material
Specific energy is high, but its cycle performance and security performance are poor, therefore, researcher carries out various metals by the type material
The bulk phase-doped of element improves its performance, Co element dopings is more generally used at present, with solid phase method, sol-gel
The LiNi of the synthesis such as method, coprecipitation0.8Co0.2O2, system material specific energy higher is not only ensure that, while making cyclicity
Can and security performance have and lifted by a relatively large margin, additionally, the doping vario-property of Al can equally reach stabilizing material structure, improve it
The effect of normal temperature, high temperature cyclic performance and heat endurance.The LiNi for synthesizing on this basis0.8Co0.15Al0.05O2Material is (referred to as
NCA materials), the advantage of Co, Al element doping is combined, in the contrast with other system materials, embody high in Large Copacity
The advantage that specific energy field of batteries becomes apparent.
NCA materials mainly have at following 2 points in use there are still some problems:(1) in charging process, due to
Ni2+And Li+Radius closely, part Ni2+Li can be occupied+Room, occur ion mixing, cause the irreversible appearance of material
Amount loss;(2) (Ni when in high oxidation state of the Ni in material3+Or Ni4+) there is very strong unstability, can be led under high temperature
Cause material structure change, and easily with electrolyte occur side reaction, cause capacity attenuation.
(Three)The content of the invention
The present invention is in order to make up the deficiencies in the prior art, there is provided a kind of safe, good cycling stability metatitanic acid lithium bag
Cover the preparation method of nickel cobalt lithium aluminate cathode material.
The present invention is achieved through the following technical solutions:
A kind of metatitanic acid lithium coats the preparation method of nickel cobalt lithium aluminate cathode material, comprises the following steps:
(1)Titanium dioxide and nickel cobalt aluminic acid powder for lithium to add coating unit simultaneously in, by fully dispersed, absorption and recombinate,
Titanium dioxide is set to be evenly coated at nickel cobalt lithium aluminate powder surface, sample crosses 400 eye mesh screens, obtains solid powder;
(2)Solid powder is put into Muffle furnace and is warming up to 300-700 DEG C with the programming rate of 2-10 DEG C/min, in air atmosphere
Roasting, is then naturally cooling to room temperature, obtains the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
The present invention uses simple method for coating, and titanium dioxide is uniformly dispersed in into positive electrode surface first, passes through
Calcining makes the residual alkali reaction production metatitanic acid lithium of titanium dioxide and positive electrode surface, not only in the Surface coating of positive electrode
One layer of metatitanic acid lithium, while reducing the residual alkali amount on positive electrode surface, improves the stability and security of material.
More excellent technical scheme of the invention is:
Step(1)In, titanium dioxide is anatase titanium dioxide, and nickel cobalt lithium aluminate is LiNi0.8Co0.15Al0.05O2;Titanium dioxide
It is 0.001-0.03 with the mass ratio of nickel cobalt lithium aluminate:1, preferred mass ratio is 0.005-0.01:1.
Step(2)In, sintering temperature is 300-700 DEG C, and the time is 3-8h;Preferably, sintering temperature is 400-600
DEG C, the time is 4-6h.
The problem that the present invention exists for NCA materials in the prior art, is usually synthesized by the unit such as adulterate Mg, Mn
LiNi1-x-y-zCoxAlyMzO2Quaternary material and Surface coating is carried out to ternary material improve come the performance to material.Table
Bread covers the directly contact area that can reduce electrode material and electrolyte, reduces corrosion of the HF in electrolyte to material and makees
With being to carry out solve problem from " material outer " so as to suppress the generation of side reaction.
The present invention is coated using metatitanic acid lithium to surface, and metatitanic acid lithium is used as Li+Conductor material, can be preferably
Realize Li+Insertion and abjection, improve material cycle performance and high rate performance;Simultaneously using metatitanic acid lithium cladding, to reduce
NCA reduces the directly contact of electrode material and organic electrolyte to moisture sensitivity, further improves the structural stability of NCA,
Improve the security of material.
(Four)Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is nickel cobalt aluminium ternary material and compound 1% mass Li2TiO3Circulation of the nickel cobalt aluminium ternary material under 1C multiplying powers
Life diagram;
Fig. 2 is nickel cobalt aluminium ternary material and compound 1% mass Li2TiO3Nickel cobalt aluminium ternary material rate capability figure.
(Five)Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1:
During 0.1g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air gas
600 DEG C being warming up to 5 DEG C/min programming rates to be calcined 5 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh sieves under atmosphere
Net, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Embodiment 2:
During 0.1g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air gas
700 DEG C being warming up to 5 DEG C/min programming rates to be calcined 3 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh sieves under atmosphere
Net, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Embodiment 3:
During 0.1g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air gas
300 DEG C being warming up to 5 DEG C/min programming rates to be calcined 8 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh sieves under atmosphere
Net, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Embodiment 4:
During 0.1g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air gas
500 DEG C being warming up to 5 DEG C/min programming rates to be calcined 5 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh sieves under atmosphere
Net, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Embodiment 5:
During 0.02g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air
600 DEG C being warming up to 2 DEG C/min programming rates to be calcined 5 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh under atmosphere
Screen cloth, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Embodiment 6:
During 0.05g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air
600 DEG C being warming up to 5 DEG C/min programming rates to be calcined 5 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh under atmosphere
Screen cloth, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Embodiment 7:
During 0.2g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air gas
600 DEG C being warming up to 10 DEG C/min programming rates to be calcined 5 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh sieves under atmosphere
Net, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Embodiment 8:
During 0.6g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air gas
600 DEG C being warming up to 5 DEG C/min programming rates to be calcined 5 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh sieves under atmosphere
Net, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Embodiment 9:
During 0.1g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air gas
600 DEG C being warming up to 2 DEG C/min programming rates to be calcined 5 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh sieves under atmosphere
Net, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Embodiment 10:
During 0.1g titanium dioxide added into coating unit, while by 20g LiNi0.8Co0.15Al0.05O2In addition coating unit,
At room temperature by mixture ball milling 1h, sample crosses 400 eye mesh screens, obtains solid powder;Solid powder is put into Muffle furnace, in air gas
600 DEG C being warming up to 10 DEG C/min programming rates to be calcined 5 hours, naturally cooling to room temperature, obtained sample crosses 400 mesh sieves under atmosphere
Net, is obtained the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
Claims (6)
1. a kind of metatitanic acid lithium coats the preparation method of nickel cobalt lithium aluminate cathode material, it is characterized by, comprise the following steps:(1)
By in titanium dioxide and nickel cobalt aluminic acid powder for lithium simultaneously addition coating unit, by fully dispersed, absorption and restructuring, make titanium dioxide
Titanium is evenly coated at nickel cobalt lithium aluminate powder surface, and sample crosses 400 eye mesh screens, obtains solid powder;(2)Solid powder is put into
Muffle furnace is warming up to 300-700 DEG C with the programming rate of 2-10 DEG C/min, is calcined in air atmosphere, is then naturally cooling to room
Temperature, obtains the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.
2. metatitanic acid lithium according to claim 1 coats the preparation method of nickel cobalt lithium aluminate cathode material, it is characterised in that:
Step(1)In, titanium dioxide is anatase titanium dioxide, and nickel cobalt lithium aluminate is LiNi0.8Co0.15Al0.05O2。
3. metatitanic acid lithium according to claim 1 coats the preparation method of nickel cobalt lithium aluminate cathode material, it is characterised in that:
Step(1)In, the mass ratio of titanium dioxide and nickel cobalt lithium aluminate is 0.001-0.03:1.
4. metatitanic acid lithium according to claim 1 coats the preparation method of nickel cobalt lithium aluminate cathode material, it is characterised in that:
Step(2)In, sintering temperature is 300-700 DEG C, and the time is 3-8h.
5. metatitanic acid lithium according to claim 3 coats the preparation method of nickel cobalt lithium aluminate cathode material, it is characterised in that:
Step(1)In, the mass ratio of titanium dioxide and nickel cobalt lithium aluminate is 0.005-0.01:1.
6. metatitanic acid lithium according to claim 4 coats the preparation method of nickel cobalt lithium aluminate cathode material, it is characterised in that:
Step(2)In, sintering temperature is 400-600 DEG C, and the time is 4-6h.
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Cited By (5)
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CN107959004A (en) * | 2017-10-23 | 2018-04-24 | 格林美(无锡)能源材料有限公司 | A kind of anode material of lithium battery and preparation method of nitrogen-doped graphene and lithium molybdate |
EP3499611A3 (en) * | 2017-11-23 | 2019-11-06 | Ecopro Bm Co., Ltd. | Lithium metal complex oxide and manufacturing method of the same |
CN110896674A (en) * | 2018-03-21 | 2020-03-20 | 浙江林奈新能源有限公司 | Nickel-cobalt-aluminum ternary lithium ion battery positive electrode material, preparation method and application thereof, and lithium ion battery |
CN112117451A (en) * | 2020-09-29 | 2020-12-22 | 山东省科学院能源研究所 | Mixed-phase titanium dioxide modified high-nickel ternary cathode material and preparation method and application thereof |
CN113363478A (en) * | 2021-03-30 | 2021-09-07 | 万向一二三股份公司 | Coating agent for coating high-nickel ternary cathode material, preparation method and lithium ion battery |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN107959004A (en) * | 2017-10-23 | 2018-04-24 | 格林美(无锡)能源材料有限公司 | A kind of anode material of lithium battery and preparation method of nitrogen-doped graphene and lithium molybdate |
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CN113363478A (en) * | 2021-03-30 | 2021-09-07 | 万向一二三股份公司 | Coating agent for coating high-nickel ternary cathode material, preparation method and lithium ion battery |
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Application publication date: 20170630 |