CN106299320A - Modified nickel cobalt lithium manganate ternary material and preparation method thereof - Google Patents
Modified nickel cobalt lithium manganate ternary material and preparation method thereof Download PDFInfo
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- CN106299320A CN106299320A CN201610979031.5A CN201610979031A CN106299320A CN 106299320 A CN106299320 A CN 106299320A CN 201610979031 A CN201610979031 A CN 201610979031A CN 106299320 A CN106299320 A CN 106299320A
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- lithium manganate
- nickel
- cobalt
- ternary material
- cobalt lithium
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- 239000000463 material Substances 0.000 title claims abstract description 200
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical class [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 26
- 239000010936 titanium Substances 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 20
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 20
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 19
- 230000004048 modification Effects 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 claims description 13
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 claims description 13
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000010406 cathode material Substances 0.000 claims description 7
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000011572 manganese Substances 0.000 abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052748 manganese Inorganic materials 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 8
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 4
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 20
- 238000005253 cladding Methods 0.000 description 10
- 238000011065 in-situ storage Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- UAAWQXWGRFRTRQ-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Co+2].[Li+].[Ni+2].[Ni+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Co+2].[Li+].[Ni+2].[Ni+2] UAAWQXWGRFRTRQ-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a modified nickel cobalt lithium manganate ternary material, which comprises a nickel cobalt lithium manganate material and a titanium dioxide layer compounded on the surface of the nickel cobalt lithium manganate material. According to the invention, a layer of titanium dioxide is creatively compounded on the surface of the nickel cobalt lithium manganate ternary material, so that the change of the surface microstructure of the NCM ternary material in the first charging process is effectively reduced, and the first cycle efficiency is increased; and because titanium dioxide is used as a shell layer to form a core-shell structure with the NCM material, only lithium ions can pass through the titanium dioxide layer, and nickel ions and manganese ions cannot pass through the titanium dioxide layer, the dissolution of Ni and Mn in the NCM ternary material in the circulating process is reduced, and the circulating performance of the ternary material is optimized.
Description
Technical field
The present invention relates to technical field of lithium ion battery electrode, relate to the cobalt nickel lithium manganate ternary material of a kind of modification
And preparation method thereof, nickelic cobalt nickel lithium manganate ternary material being specifically related to a kind of modification and preparation method thereof.
Background technology
Lithium ion battery has that running voltage is high, specific energy high, has extended cycle life, electric discharge lightweight, white less, memoryless effect
Should be with cost performance ratio, oneself becomes the field rechargeable type power supplys such as high power electric vehicle, artificial satellite, Aero-Space
Main selection object.Therefore lithium ion battery and associated materials thereof become the study hotspot of scientific research personnel.Positive electrode is lithium
One of ion battery critical material, decides the performance of lithium ion battery.And at present limiting lithium ion electrokinetic cell energy density,
The maximum bottleneck of power density, cycle life and safety is positive electrode technology.
In current power lithium-ion battery positive electrode, cobalt nickel lithium manganate ternary material (NCM), i.e. nickle cobalt lithium manganate
Ternary layered positive electrode, its chemical formula is LiNi1-x-yCoxMnyO2, due to the cooperative effect of tri-kinds of elements of Ni, Co and Mn, tool
There are specific discharge capacity height, energy density height, cost relatively low and advantages of environment protection, become world market power lithium in recent years
The great positive electrode of ion battery application increment.The most Ni-based ternary material, or claim nickelic ternary material
(LiNi1-x-yCoxMnyO2(1-x-y >=0.5)) combine LiCoO2, LiNiO2And LiMnO2Three kinds of anode material for lithium-ion batteries
Advantage, its performance is better than any of the above one-component positive electrode, there is obvious cooperative effect.In this system, material
Chemical property and physical property are different along with the change of these three transition metal ratio.Introduce Ni, be favorably improved
The capacity of material, but Ni2+During too high levels, with Li+Mixing cause cycle performance to deteriorate.By introducing Co, it is possible to reduce
Cation mixing occupy-place, the layer structure of effective stabilizing material, reduce resistance value, improve electrical conductivity, but when the increasing of Co ratio
Greatly to a and c being caused during certain limit to reduce and c/a increase, capacity step-down.Introduce Mn, be possible not only to reduce material cost, and
And the safety and stability of material can also be improved.
Cycle performance excellence, specific energy just because of NCM ternary material are high, and relative low toxicity, good rate capability are considered
It is most potential pure electric vehicle and energy storage lithium ion battery battery positive electrode.But nickel-cobalt lithium manganate cathode material, especially
It is nickelic tertiary cathode material, there is also defect, due to the change during initial charge of the material surface micro structure, makes
The battery first charge-discharge efficiency becoming ternary material to be positive electrode is the highest, and first effect is generally less than 90%.In cyclic process
With the HF in organic bath, side reaction can occur, cause the dissolving of Ni and Mn, thus have impact on its electrical property, become NCM tri-
The yoke that unit's material develops further.
Therefore, a kind of cobalt nickel lithium manganate ternary material with more preferable electrical property how is obtained, it has also become each in field
Production firm's problem demanding prompt solution.
Summary of the invention
In view of this, the technical problem to be solved in the present invention be to provide the cobalt nickel lithium manganate ternary material of a kind of modification and
Its preparation method, the composite modified cobalt nickel lithium manganate ternary material that the present invention provides, the most composite modified nickelic nickel cobalt
LiMn2O4 ternary material, has higher cycle performance and stability.Meanwhile, the preparation method technique that the present invention provides is simple,
Mild condition, it is adaptable to large-scale production and application.
The invention provides the cobalt nickel lithium manganate ternary material of a kind of modification, including nickel-cobalt lithium manganate material and be compounded in
The titanium dioxide layer on described nickel-cobalt lithium manganate material surface；
Shown in the chemical formula of described nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, x ＞ 0, y ＞ 0,1 ＞ 1-x-y ＞ 0.
Preferably, described nickel-cobalt lithium manganate material is nickelic tertiary cathode material；
Shown in the chemical formula such as formula (II) of described nickelic tertiary cathode material,
LiNi1-x-yCoxMnyO2(II)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
Preferably, described 0.1≤x≤0.2 and/or 0.1≤y≤0.3.
Preferably, described titanium dioxide is (0.1～2) with the mass ratio of described nickel-cobalt lithium manganate material: 1；
The particle diameter D of described nickel-cobalt lithium manganate material50It is 12～14 μm.
Present invention also offers the preparation method of the cobalt nickel lithium manganate ternary material of a kind of modification, comprise the following steps:
1) nickel-cobalt lithium manganate material is put in water after dispersion, process and obtain the nickel-cobalt lithium manganate material that surface is aqueous；
Shown in the chemical formula of described nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, x ＞ 0, y ＞ 0,1 ＞ 1-x-y ＞ 0；
2) after nickel-cobalt lithium manganate material, titanium source and organic solvent mixing that the surface that above-mentioned steps obtained is aqueous, hydrolysis
Reaction, obtains nickle cobalt lithium manganate composite；
3), after nickle cobalt lithium manganate composite calcining above-mentioned steps obtained, the nickle cobalt lithium manganate ternary material of modification is obtained
Material.
Preferably, described titanium source includes tetraethyl titanate and/or butyl titanate；
Described organic solvent includes one or more in ethanol, n-butyl alcohol, ethylene glycol, isopropanol and acetone.
Preferably, described nickel-cobalt lithium manganate material is (20～40) with the mass ratio of described water: (15～25)；
Described titanium source is 1:(200～400 with the mass ratio of described nickel-cobalt lithium manganate material)；
Described titanium source and the mass ratio 1:(1000～2000 of described organic solvent).
Preferably, the described scattered time is 30～60min；
Described process includes filtering and/or being dried；
Concretely comprising the following steps of described mixing: after first titanium source and organic solvent dispersion being mixed, then the nickel cobalt aqueous with surface
Lithium manganate material mixes.
Preferably, the time of described hydrolysis is 3～5h；
Described hydrolysis also includes again filtering and drying steps after completing；
Described dry temperature is 100～130 DEG C, and the described dry time is 2～4h.
Preferably, described calcining is for calcine under vacuum；
The temperature of described calcining is 400～700 DEG C, and the time of described calcining is 1～5h.
The invention provides the cobalt nickel lithium manganate ternary material of a kind of modification, including nickel-cobalt lithium manganate material and be compounded in
The titanium dioxide layer on described nickel-cobalt lithium manganate material surface；Shown in the chemical formula of described nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, x ＞ 0, y ＞ 0,1 ＞ 1-x-y ＞ 0.Compared with prior art, the present invention is directed to due to
NCM material surface microstructure change, the battery first charge-discharge efficiency causing ternary material to be positive electrode is the highest, and is following
With the HF in organic bath, side reaction can occur during ring, cause the defect of the dissolving of Ni and Mn.The invention
The layer of titanium dioxide in cobalt nickel lithium manganate ternary material surface recombination, is effectively reduced NCM ternary material at initial charge
During the change of surface micro-structure, add first week efficiency；And owing to have employed titanium dioxide as shell, with NCM material
Material formation nucleocapsid structure, only lithium ion can pass through titanium dioxide layer, nickel ion and manganese ion and can not pass through, and decreases and is circulated throughout
The dissolving of Ni and Mn in NCM ternary material in journey, optimizes the cycle performance of ternary material.Test result indicate that, by this
The battery that the modified cobalt nickel lithium manganate ternary material of bright preparation is prepared as positive electrode, first week efficiency be about 0.83～
0.86；After circulating 50 times, within a gram specific capacity loss only has 13%, compare uncoated NCM material and improve more than 22%.
Accompanying drawing explanation
Fig. 1 is the nickelic ternary material of coated by titanium dioxide of the embodiment of the present invention 1 preparation and uncoated nickelic ternary material
Li[Ni0.6Co0.2Mn0.2]O2Gram specific capacity cycle performance comparison diagram.
Detailed description of the invention
In order to further appreciate that the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but
Should be appreciated that these describe simply as further illustrating the features and advantages of the present invention rather than to patent requirements of the present invention
Limit.
The all raw materials of the present invention, are not particularly limited its source, that commercially buy or according to people in the art
Prepared by the conventional method known to Yuan.
The all raw materials of the present invention, are not particularly limited its purity, present invention preferably employs analytical pure or lithium ion battery
The purity that field is conventional.
The invention provides the cobalt nickel lithium manganate ternary material of a kind of modification, including nickel-cobalt lithium manganate material and be compounded in
The titanium dioxide layer on described nickel-cobalt lithium manganate material surface；
Shown in the chemical formula of described nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, x ＞ 0, y ＞ 0,1 ＞ 1-x-y ＞ 0.
Described nickel-cobalt lithium manganate material is not particularly limited by the present invention, with well known to those skilled in the art for making
The NCM ternary material of lithium ion cell positive, the present invention is preferably cobalt nickel lithium manganate ternary material, described nickle cobalt lithium manganate
The chemical formula of ternary material preferably as shown in formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, x ＞ 0, y ＞ 0,1 ＞ 1-x-y ＞ 0；
The present invention is the performance improving ternary material as positive electrode, and described nickel-cobalt lithium manganate material is the most nickelic
Nickle cobalt lithium manganate tertiary cathode material (or claiming rich nickel cobalt nickel lithium manganate ternary material, Ni-based ternary material), described nickelic ternary
Shown in the chemical formula of positive electrode such as formula (II),
LiNi1-x-yCoxMnyO2(II)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
Further, the span of described x is preferably 0.1≤x≤0.2, more preferably 0.12≤x≤0.18, more preferably
It it is 0.14≤x≤0.16；The span of described y is preferably 0.1≤y≤0.3, more preferably 0.13≤y≤0.27, more preferably
0.16≤y≤0.24, most preferably 0.19≤y≤0.21；The span of described 1-x-y is preferably 0.5≤1-x-y≤0.9, more
Preferably 0.6≤1-x-y≤0.9, most preferably 0.7≤1-x-y≤0.8.
Other conditions of described nickel-cobalt lithium manganate material are not particularly limited by the present invention, with well known to those skilled in the art
The normal condition of NCM ternary material, those skilled in the art can be according to practical condition, combining case and product
Performance selects, and the present invention is the performance being further ensured that trielement composite material, the particle diameter D of described nickel-cobalt lithium manganate material50
It is preferably 12～14 μm, more preferably 12.3～13.7 μm, most preferably 12.5～13.5 μm.The present invention is to described titanium dioxide
Being not particularly limited, with titanic oxide material well known to those skilled in the art, the present invention does not has spy to its concrete property
Not limiting, those skilled in the art can select according to practical condition, combining case and properties of product.
Described being combined is not particularly limited by the present invention, with composite definitions well known to those skilled in the art, this
Bright preferably cladding, half cladding, stacking or generation, be more preferably coated with or half cladding, most preferably cladding.The present invention is to described
Cladding is not particularly limited, and defines with cladding well known to those skilled in the art, and the present invention is preferably full cladding.The present invention
The mass ratio of described titanium dioxide with described nickel-cobalt lithium manganate material is not particularly limited, and those skilled in the art can basis
Practical condition, cladding situation and properties of product select, titanium dioxide of the present invention and described nickle cobalt lithium manganate
The mass ratio of material is preferably (0.1%～2%): 1, more preferably (0.4%～1.7%): 1, more preferably (0.7%～
1.4%): 1, most preferably (0.9%～1.2%): 1.
The present invention is layer of titanium dioxide in cobalt nickel lithium manganate ternary material surface recombination, in particular for nickelic nickel cobalt manganese
Acid lithium ternary material, is effectively reduced the change of surface micro-structure during initial charge of NCM ternary material, adds head
All efficiency；And owing to have employed titanium dioxide as shell, forming nucleocapsid structure, only lithium ion with NCM material can pass through
Titanium dioxide layer, nickel ion and manganese ion can not pass through, Ni's and Mn decreased in cyclic process in NCM ternary material is molten
Solve, optimize the cycle performance of ternary material.
The invention provides the preparation method of the cobalt nickel lithium manganate ternary material of a kind of modification, comprise the following steps:
1) nickel-cobalt lithium manganate material is put in water after dispersion, process and obtain the nickel-cobalt lithium manganate material that surface is aqueous；
Shown in the chemical formula of described nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, x ＞ 0, y ＞ 0,1 ＞ 1-x-y ＞ 0；
2) after nickel-cobalt lithium manganate material, titanium source and organic solvent mixing that the surface that above-mentioned steps obtained is aqueous, hydrolysis
Reaction, obtains nickle cobalt lithium manganate composite；
3), after nickle cobalt lithium manganate composite calcining above-mentioned steps obtained, the nickle cobalt lithium manganate ternary material of modification is obtained
Material.
The present invention is to optimum principles such as the selection of described raw material and ratios, as without the most dated, with aforementioned modified nickel cobalt
All consistent in LiMn2O4 ternary material, this is no longer going to repeat them.
First nickel-cobalt lithium manganate material is put in water after dispersion by the present invention, processes and obtains the nickle cobalt lithium manganate that surface is aqueous
Material；Shown in the chemical formula of described nickel-cobalt lithium manganate material such as formula (I).
The source of described nickel-cobalt lithium manganate material is not particularly limited by the present invention, and those skilled in the art can be according to often
Rule method is prepared or commercially；The present invention does not has spy to the concrete element ratio of described nickel-cobalt lithium manganate material
Do not limit, with the element ratio of nickel-cobalt lithium manganate material well known to those skilled in the art.The present invention is preferred processing condition,
Enhancing product performance further, described nickel-cobalt lithium manganate material is preferably nickelic nickel-cobalt lithium manganate material；Described nickle cobalt lithium manganate
The particle diameter distribution of material, D50 is preferably 12～14 μm, more preferably 12.5～13.5 μm, most preferably 12.8～13.2 μm.
Described dispersion is not particularly limited by the present invention, with dispersing mode well known to those skilled in the art and condition is
Can, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement, of the present invention
Disperseing the most dispersed, the described scattered time is preferably 30～60min, more preferably 35～55min, and most preferably 40
～50min.The consumption of described water is not particularly limited by the present invention, those skilled in the art can according to practical condition,
Product situation and performance requirement are adjusted, and the present invention is preferably so that the abundant moistening in nickel-cobalt lithium manganate material surface, more
The mass ratio being preferably described nickel-cobalt lithium manganate material and described water is (20～40): (15～25), more preferably (25～35):
(15～25), more preferably (25～35): (17～23), most preferably (28～32): (19～21).The present invention is to described process
It is not particularly limited, to remove unnecessary water, facilitates later processing operation, can select through processing, it is also possible to without
Crossing process, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement, the present invention
Described process is preferably to be filtered or is dried.Described filtration or dry mode and condition are not particularly limited by the present invention, with this
The mode filtering or being dried known to skilled person and condition, those skilled in the art can be according to actual production feelings
Condition, product situation and performance requirement are adjusted, filter footpath preferably 1～5 μm of filtration of the present invention, more preferably 2～4 μ
M, most preferably 3 μm；Described filter type is preferably filter paper filtering, and more preferably double-layer filter paper filters.
Nickel-cobalt lithium manganate material, titanium source and the organic solvent mixing that surface that then above-mentioned steps is obtained by the present invention is aqueous
After, hydrolysis, obtain nickle cobalt lithium manganate composite.
Described titanium source is not particularly limited by the present invention, with the titanium source reacted for this type of well known to those skilled in the art
, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement, institute of the present invention
State titanium source and be preferably tetraethyl titanate and/or butyl titanate, more preferably tetraethyl titanate or butyl titanate, most preferably
Tetraethyl titanate.Described organic solvent is not particularly limited by the present invention, with well known to those skilled in the art anti-for this type of
The organic solvent answered, those skilled in the art can be carried out according to practical condition, product situation and performance requirement
Adjusting, organic solvent of the present invention preferably includes one or more in ethanol, n-butyl alcohol, ethylene glycol, isopropanol and acetone,
More preferably ethanol, n-butyl alcohol, isopropanol or acetone, most preferably ethanol.The present invention is the most special to the consumption in described titanium source
Limiting, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement, institute of the present invention
The mass ratio stating titanium source and described nickel-cobalt lithium manganate material is preferably 1:(200～400), more preferably 1:(250～350),
It is preferably 1:(270～330).The consumption of described organic solvent is not particularly limited by the present invention, and those skilled in the art are permissible
It is adjusted according to practical condition, product situation and performance requirement, titanium source of the present invention and described organic solvent
Mass ratio is preferably 1:(1000～2000), more preferably 1:(1200～1800), most preferably 1:(1400～1600).
Mode and the parameter of described mixing are not particularly limited by the present invention, with mixing well known to those skilled in the art
Mode and parameter, those skilled in the art can adjust according to practical condition, product situation and performance requirement
Whole, the present invention is to improve the effect of late phase reaction, it is ensured that fully dispersed, and the concrete steps of described mixing are preferably: first by titanium source
After mixing with organic solvent dispersion, then the nickel-cobalt lithium manganate material aqueous with surface mixes；I.e. it is initially formed organic dispersion in titanium source
Liquid, then the nickel-cobalt lithium manganate material aqueous with surface mix.The condition of described hydrolysis is not particularly limited by the present invention, with
The condition of hydrolysis well known to those skilled in the art, those skilled in the art can be according to practical condition, product
Product situation and performance requirement are adjusted, the time of hydrolysis of the present invention be preferably 3～5h, more preferably 3.5～
4.5h, most preferably 3.7～4.3h.
The present invention is to remove unnecessary solvent, facilitates later processing operation, after hydrolysis completes, can select warp
Later process, it is also possible to without post processing, those skilled in the art can be according to practical condition, product situation and property
Can require to be adjusted, hydrolysis of the present invention the most also includes again filtering and drying steps after completing.The present invention couple
The described concrete technology again filtering and being dried and condition are not particularly limited, with filtration well known to those skilled in the art and dry
Dry concrete technology and condition, those skilled in the art can want according to practical condition, product situation and performance
Asking and be adjusted, dry temperature of the present invention is preferably 100～130 DEG C, more preferably 105～125 DEG C, most preferably
110～120 DEG C；The described dry time is preferably 2～4h, more preferably 2.5～3.5h, most preferably 2.7～3.3h.
Above-mentioned steps of the present invention provides a kind of at NCM ternary material, the most nickelic ternary material in-stiu coating dioxy
The method changing titanium, is first dispersed in water nickelic ternary material so that it is surface fully absorbs water, then by the sample after above-mentioned process
Put in the organic solution being dissolved with titanium source, allow titanium source carry out in-situ hydrolysis reaction on NCM ternary material surface, in nickelic ternary
The uniformly reaction of material generates metatitanic acid, after question response completes, has obtained the NCM ternary material that metatitanic acid is uniformly coated with
Material.
The nickle cobalt lithium manganate composite that above-mentioned steps is finally obtained by the present invention, i.e. the NCM ternary material of metatitanic acid cladding
After material calcining, obtain the cobalt nickel lithium manganate ternary material of modification.
The condition of described calcining is not particularly limited by the present invention, multiple with nickle cobalt lithium manganate well known to those skilled in the art
Condensation material calcining concrete technology and condition, those skilled in the art can according to practical condition, product situation with
And performance requirement is adjusted, the temperature of calcining of the present invention is preferably 400～700 DEG C, more preferably 450～650 DEG C,
It is preferably 500～600 DEG C；The time of described calcining is preferably 1～5h, more preferably 2～4h, most preferably 2.5～3.5h；Institute
The heating rate stating calcining is preferably 5～10 DEG C/min, more preferably 6～9 DEG C/min, most preferably 7～8 DEG C/min；Described
Calcining is more preferably calcined in the condition of vacuum.The concrete force value of described vacuum is not particularly limited, with ability by the present invention
The normal pressures value of the nickle cobalt lithium manganate composite vacuum calcining known to field technique personnel, those skilled in the art are permissible
It is adjusted according to practical condition, product situation and performance requirement.
Above-mentioned steps of the present invention has prepared the cobalt nickel lithium manganate ternary material of modification, and the present invention utilizes NCM ternary material
Material, the feature that the most nickelic ternary material surface is hygroscopic, use titanium source to hydrolyze at nickelic ternary material surface in situ, due to
Titanium source is to react at nickelic ternary material surface in situ, generates metatitanic acid, and then sintering forms titanium dioxide (TiO2) clad,
Making coated by titanium dioxide layer be combined in nickelic ternary material surface densely, covered effect is good, finally dries after sintering at material
Material surface forms the coated by titanium dioxide layer of densification, effectively solves existing cladding scheme and causes shell at positive electrode table
The defect that face is fine and close not.It is simple that the above-mentioned preparation method of the present invention also has flow process, it is simple to the advantages such as industrial applications, and directly
Carry out in the reaction of nickelic ternary material surface in situ, be coated on ternary material surface, shape the titanium dioxide even compact of gained
Become a protective layer, reduce ternary material as during anode material for lithium-ion batteries during initial charge surface micro-structure
Change, increase first week efficiency, and being dissolved in electrolyte of Ni and Mn that can reduce in ternary material in cyclic process.
The present invention is layer of titanium dioxide in cobalt nickel lithium manganate ternary material surface recombination, is effectively reduced NCM ternary
Material is the change of surface micro-structure during initial charge, adds first all efficiency；And make owing to have employed titanium dioxide
For shell, can pass through titanium dioxide layer, nickel ion and manganese ion with NCM material formation nucleocapsid structure, only lithium ion can not lead to
Cross, the dissolving of Ni and Mn decreased in cyclic process in NCM ternary material, optimize the cycle performance of ternary material；And
Being to react at nickelic ternary material surface in situ owing to have employed titanium source, sintering forms coated by titanium dioxide layer so that clad
Being combined in nickelic ternary material surface densely, covered effect is good, and technique is simple, mild condition, it is adaptable to give birth on a large scale
Produce application.Test result indicate that, the modified cobalt nickel lithium manganate ternary material present invention prepared is prepared as positive electrode
Battery, first all efficiency values are about 0.83～0.86；After circulating 50 times, within a gram specific capacity loss only has 13%, compare uncoated
NCM material improve more than 22%.
In order to further illustrate the present invention, below in conjunction with the nickle cobalt lithium manganate of a kind of modification that the present invention is provided by embodiment
Ternary material and preparation method thereof is described in detail, but it is to be understood that these embodiments are with technical solution of the present invention
Implement under premised on, give detailed embodiment and concrete operating process, simply for further illustrating the present invention
Feature and advantage rather than limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following enforcement
Example.
Embodiment 1
First by 4g D50Nickelic ternary material Li [Ni0.6Co0.2Mn0.2] O2 of=12～14 μm is dispersed in 2ml water
In, magnetic agitation, after 30 minutes, makes the abundant moistening in nickelic ternary material surface, carries out filtering with the filter paper of two-layer aperture 3 μm
The nickelic ternary material aqueous to surface.
Then 0.114g tetraethyl titanate is dispersed in 250mL ethanol solution, adds above-mentioned surface aqueous
Nickelic ternary material, stir 4h, allow tetraethyl titanate nickelic ternary material surface occur in-situ hydrolysis reaction, nickelic three
The uniformly reaction of unit's material generates metatitanic acid, after question response completes, filters with the filter paper of two-layer aperture 3 μm, will
Product puts into 120 DEG C of baking 2h in baking oven, obtains the nickelic ternary material that metatitanic acid is uniformly coated with.
Material used in above-mentioned steps is counted in mass ratio, tetraethyl titanate: nickelic ternary material: water: ethanol=1:35:
18:1750.
The nickelic ternary material being finally uniformly coated with by above-mentioned metatitanic acid is warming up to 450 with 5 DEG C of heating rates per minute
DEG C, and calcining at constant temperature 5 hours, make metatitanic acid fully be pyrolyzed formation titanium dioxide, the coated by titanium dioxide obtained after furnace cooling
Modified nickelic ternary material, i.e. Li [Ni0.6Co0.2Mn0.2]O2/TiO2.Wherein, the quality of titanium dioxide is about nickelic ternary material
The 1% of material quality.
By conventional Li [Ni0.6Co0.2Mn0.2]O2And the Li of the coated by titanium dioxide prepared by the embodiment of the present invention 1
[Ni0.6Co0.2Mn0.2]O2Mix homogeneously with mass ratio 90:10:10 with conductive black and binding agent PVDF respectively, be coated in aluminium foil
On, it is cut into anode pole piece, 100 DEG C of vacuum drying 20h after drying.Lithium metal is negative pole, and electrolyte is that LiPF6 is dissolved in mass ratio
For in the organic solvent of ethylene carbonate (EC)/dimethyl carbonate (the DMC)/Ethyl methyl carbonate (EMC) of 1:1:1, concentration is
1mol/L, is assembled into button cell.
The button cell preparing above-mentioned steps is at 25 DEG C, in the range of 3～4.3V, with 0.2C discharge and recharge, test material
Cycle performance, first all efficiency is 0.86.
See the nickelic ternary material of coated by titanium dioxide that Fig. 1, Fig. 1 are the embodiment of the present invention 1 preparation nickelic with uncoated
Ternary material Li [Ni0.6Co0.2Mn0.2]O2Gram specific capacity cycle performance comparison diagram.As shown in Figure 1, circulate 50 times, uncoated
Li [Ni0.6Co0.2Mn0.2]O2Gram specific capacity drops to 114mAh/g from 160mAh/g；And the bag of the embodiment of the present invention 1 preparation
Cover the Li [Ni of modification0.6Co0.2Mn0.2]O2Gram specific capacity then from 160mAh/g to 139mAh/g, cycle performance has had significantly
Improve.
Embodiment 2
By 4g D50The nickelic ternary material Li [Ni of=12～14um0.6Co0.2Mn0.2]O2Being dispersed in 2ml water, magnetic force stirs
After mixing 30 minutes, carry out being filtrated to get the nickelic ternary material that surface is aqueous with the filter paper of two-layer aperture 3 μm.
0.0114g tetraethyl titanate is dispersed in 25ml ethanol solution, adds the height that above-mentioned surface is aqueous
Nickel ternary material, stirs 5h, filters with the filter paper of two-layer aperture 3 μm, product is put into 120 DEG C of baking 2h in baking oven, obtains
The nickelic ternary material that metatitanic acid is uniformly coated with.
Material tetraethyl titanate in mass ratio used in above-mentioned steps: nickelic ternary material: water: ethanol=1:350:
175:1750.
Gains are warming up to 500 DEG C with 10 DEG C of heating rates per minute, and calcining at constant temperature 5 hours, make metatitanic acid fill
Divide pyrolysis to form titanium dioxide, after furnace cooling, obtain the nickelic ternary material of coated by titanium dioxide.Wherein, the matter of titanium dioxide
Amount is about the 0.1% of nickelic ternary material quality.
Nickelic ternary material to the coated by titanium dioxide of embodiment 2 preparation, prepares button cell according to above-mentioned steps, so
After at 25 DEG C, in the range of 3～4.3V, with 0.2C discharge and recharge, the cycle performance of test material, first week efficiency be 0.83.
Embodiment 3
By 4g D50The nickelic ternary material Li [Ni of=12～14um0.6Co0.2Mn0.2]O2Being dispersed in 2ml water, magnetic force stirs
After mixing 30 minutes, carry out being filtrated to get the nickelic ternary material that surface is aqueous with the filter paper of two-layer aperture 3 μm.
0.344g butyl titanate is dispersed in 650ml ethanol solution, adds the height that above-mentioned surface is aqueous
Nickel ternary material, stirs 3h, filters with the filter paper of two-layer aperture 3 μm, product is put into 120 DEG C of baking 2h in baking oven, obtains
The nickelic ternary material that metatitanic acid is uniformly coated with.
The butyl titanate in mass ratio of material used by above-mentioned steps: nickelic ternary material: water: ethanol=1:12:6:1500.
Gains are warming up to 450 DEG C with 5 DEG C of heating rates per minute, and calcining at constant temperature 6 hours, make metatitanic acid abundant
Pyrolysis forms titanium dioxide, obtains the nickelic ternary material of required coated by titanium dioxide after furnace cooling.Wherein, titanium dioxide
Quality be about the 2% of nickelic ternary material quality.
Nickelic ternary material to the coated by titanium dioxide of embodiment 3 preparation, prepares button cell according to above-mentioned steps, so
After at 25 DEG C, in the range of 3～4.3V, with 0.2C discharge and recharge, the cycle performance of test material, first week efficiency be 0.85.
Above cobalt nickel lithium manganate ternary material of a kind of modification that the present invention provides and preparation method thereof is carried out in detail
Introduction, principle and the embodiment of the present invention are set forth by specific case used herein, saying of above example
Bright method and the core concept thereof being only intended to help to understand the present invention, including best mode, and also makes appointing of this area
What technical staff can put into practice the present invention, including manufacturing and using any device or system, and the method implementing any combination.
It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to right
The present invention carries out some improvement and modification, and these improve and modify in the protection domain also falling into the claims in the present invention.This
The scope of bright patent protection is defined by the claims, and those skilled in the art can be included it is conceivable that other implement
Example.If these other embodiments have the structural element being not different from claim character express, if or they bags
Include the equivalent structural elements without essence difference of the character express with claim, then these other embodiments also should be included in power
In the range of profit requires.
Claims (10)
1. a modified cobalt nickel lithium manganate ternary material, it is characterised in that include nickel-cobalt lithium manganate material and be compounded in institute
State the titanium dioxide layer on nickel-cobalt lithium manganate material surface；
Shown in the chemical formula of described nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, x ＞ 0, y ＞ 0,1 ＞ 1-x-y ＞ 0.
Cobalt nickel lithium manganate ternary material the most according to claim 1, it is characterised in that described nickel-cobalt lithium manganate material is high
Nickel tertiary cathode material；
Shown in the chemical formula such as formula (II) of described nickelic tertiary cathode material,
LiNi1-x-yCoxMnyO2(II)；Wherein, (1-x-y) >=0.5, x ＞ 0, y ＞ 0.
Cobalt nickel lithium manganate ternary material the most according to claim 2, it is characterised in that
Described 0.1≤x≤0.2 and/or 0.1≤y≤0.3.
Cobalt nickel lithium manganate ternary material the most according to claim 1, it is characterised in that described titanium dioxide and described nickel cobalt
The mass ratio of lithium manganate material is (0.1%～2%): 1；
The particle diameter D of described nickel-cobalt lithium manganate material50It is 12～14 μm.
5. the preparation method of a modified cobalt nickel lithium manganate ternary material, it is characterised in that comprise the following steps:
1) nickel-cobalt lithium manganate material is put in water after dispersion, process and obtain the nickel-cobalt lithium manganate material that surface is aqueous；
Shown in the chemical formula of described nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, x ＞ 0, y ＞ 0,1 ＞ 1-x-y ＞ 0；
2) after nickel-cobalt lithium manganate material, titanium source and organic solvent mixing that the surface that above-mentioned steps obtained is aqueous, hydrolysis,
Obtain nickle cobalt lithium manganate composite；
3), after nickle cobalt lithium manganate composite calcining above-mentioned steps obtained, the cobalt nickel lithium manganate ternary material of modification is obtained.
Preparation method the most according to claim 5, it is characterised in that described titanium source includes tetraethyl titanate and/or metatitanic acid
Four butyl esters；
Described organic solvent includes one or more in ethanol, n-butyl alcohol, ethylene glycol, isopropanol and acetone.
Preparation method the most according to claim 5, it is characterised in that described nickel-cobalt lithium manganate material and the quality of described water
Than being (20～40): (15～25)；
Described titanium source is 1:(200～400 with the mass ratio of described nickel-cobalt lithium manganate material)；
Described titanium source and the mass ratio 1:(1000～2000 of described organic solvent).
Preparation method the most according to claim 5, it is characterised in that the described scattered time is 30～60min；
Described process includes filtering and/or being dried；
Concretely comprising the following steps of described mixing: after first titanium source and organic solvent dispersion being mixed, then the nickel cobalt mangaic acid aqueous with surface
Lithium material mixes.
Preparation method the most according to claim 5, it is characterised in that the time of described hydrolysis is 3～5h；
Described hydrolysis also includes again filtering and drying steps after completing；
Described dry temperature is 100～130 DEG C, and the described dry time is 2～4h.
Preparation method the most according to claim 5, it is characterised in that described calcining is for calcine under vacuum；
The temperature of described calcining is 400～700 DEG C, and the time of described calcining is 1～5h.
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| CN108232137A (en) * | 2017-12-19 | 2018-06-29 | 珠海格力电器股份有限公司 | Modified L TO/L iMXMn2-XO4Lithium ion battery anode material and preparation method thereof |
| CN108682795B (en) * | 2018-03-28 | 2021-01-08 | 合肥国轩高科动力能源有限公司 | Surface pickling coating TiO of ternary anode material of lithium ion battery2Method (2) |
| CN108682795A (en) * | 2018-03-28 | 2018-10-19 | 合肥国轩高科动力能源有限公司 | Surface pickling coating TiO of ternary anode material of lithium ion battery2Method (2) |
| CN108777295A (en) * | 2018-05-29 | 2018-11-09 | 中航锂电（洛阳）有限公司 | A kind of nickel cobalt lithium manganate and preparation method thereof, lithium ion battery |
| CN109713250A (en) * | 2018-11-19 | 2019-05-03 | 北京泰丰先行新能源科技有限公司 | A kind of preparation method of the core-shell structure presoma of anode material of lithium battery |
| CN109742334A (en) * | 2018-12-03 | 2019-05-10 | 中国电子科技集团公司第十八研究所 | Lithium battery anode material coated with protective layer |
| CN109742388A (en) * | 2018-12-03 | 2019-05-10 | 中国电子科技集团公司第十八研究所 | Coating method of lithium battery positive electrode material |
| CN111342012A (en) * | 2020-03-03 | 2020-06-26 | 沁新集团(天津)新能源技术研究院有限公司 | Mesoporous spherical titanium dioxide coated ternary material, preparation method thereof, lithium ion battery anode and lithium ion battery |
| CN111342012B (en) * | 2020-03-03 | 2021-08-20 | 沁新集团(天津)新能源技术研究院有限公司 | Mesoporous spherical titanium dioxide coated ternary material, preparation method thereof, lithium ion battery anode and lithium ion battery |
| CN111517378A (en) * | 2020-04-29 | 2020-08-11 | 蜂巢能源科技有限公司 | High-nickel anode material and preparation method and application thereof |
| CN113178560A (en) * | 2021-05-11 | 2021-07-27 | 湖北亿纬动力有限公司 | Metal oxide coated NCM ternary electrode material, preparation method thereof and lithium ion battery |
| CN113206238A (en) * | 2021-05-12 | 2021-08-03 | 湖北亿纬动力有限公司 | NCM ternary cathode material, preparation method thereof and lithium ion battery |
| CN113328082A (en) * | 2021-06-25 | 2021-08-31 | 珠海冠宇电池股份有限公司 | Positive electrode lithium supplement material and lithium ion battery comprising same |
| CN113611834A (en) * | 2021-07-30 | 2021-11-05 | 蜂巢能源科技有限公司 | Three-layer core-shell structured positive electrode material, preparation method and battery |
| CN113611834B (en) * | 2021-07-30 | 2023-01-24 | 蜂巢能源科技有限公司 | Three-layer core-shell structured positive electrode material, preparation method and battery |
| WO2023092886A1 (en) * | 2021-11-25 | 2023-06-01 | 微宏动力系统（湖州）有限公司 | Modified positive electrode material and preparation method therefor, and lithium ion battery |
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