CN106299273A - A kind of preparation method of titanium cladding nickel cobalt manganese lithium ion power battery cathode material - Google Patents
A kind of preparation method of titanium cladding nickel cobalt manganese lithium ion power battery cathode material Download PDFInfo
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- CN106299273A CN106299273A CN201610709536.XA CN201610709536A CN106299273A CN 106299273 A CN106299273 A CN 106299273A CN 201610709536 A CN201610709536 A CN 201610709536A CN 106299273 A CN106299273 A CN 106299273A
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- nickel cobalt
- cobalt manganese
- lithium ion
- titanium
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- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000010936 titanium Substances 0.000 title claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 28
- 239000010406 cathode material Substances 0.000 title claims abstract description 23
- 238000005253 cladding Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004137 mechanical activation Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 11
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 10
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 7
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims abstract description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 20
- 239000010405 anode material Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 abstract description 5
- 235000019441 ethanol Nutrition 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013905 LiNi0.3Co0.4Mn0.3O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 description 1
- GFBBLVIVJHUGIF-UHFFFAOYSA-N [Mn].[Ni].[Co].[Ni] Chemical compound [Mn].[Ni].[Co].[Ni] GFBBLVIVJHUGIF-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
-
- 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 discloses the preparation method of a kind of titanium cladding nickel cobalt manganese lithium ion power battery cathode material, including: stoichiometrically by solid-state Mn (NO3)2、CoCO3With Ni (NO3)2·6H2O mixes, ball milling；Then with solid-state Li2CO3Mixing, the wind-force utilizing the centrifugal force of the cylinder of high speed rotating and fan is mutual, Circulation, mix homogeneously；It is subsequently added into dispersant, utilizes planetary ball mill to carry out mechanical activation；It is dried；Pre-burning；Roasting；And TiCl4, dehydrated alcohol, oxalic acid, hexamethylene, triethylamine mixing and stirring, hydro-thermal reaction processes, cooling, and adds excess ethyl alcohol and be precipitated, washing, and vacuum drying obtains.The titanium of the inventive method is evenly coated so that the stable electrochemical property of this positive electrode, and safety is high, and cycle performance is excellent.
Description
Technical field
The present invention relates to technical field of lithium ion, specifically a kind of titanium cladding nickel cobalt manganese lithium ion power battery cathode
The preparation method of material.
Background technology
In recent years, under the support of national policy, electric automobile industry has obtained rapid development.High-energy-density, longevity
Life, the novel anode material of low cost and battery thereof are particularly important.Lithium ion battery is high with its running voltage, specific energy
Greatly, have extended cycle life, pollute the advantage such as little and show one's talent in numerous electrochmical power sources.
At present, positive electrode lithium-ion-power cell used is generally nickel cobalt manganese lithium anode material, this positive pole material
Expect to have preferably to react reversibility, stronger large current discharging capability, and preferably cyclical stability and security performance；But
The recycling performance of traditional nickel cobalt manganese lithium anode material can not meet the demand in market, along with researchers are to material
Further investigation, find positive electrode surface property on its chemical property particularly on high-temperature behavior and the impact of cycle performance
Very big, the positive electrode being particularly due in pond is understood directly and the concurrent biochemical reaction of electrolyte contacts, causes positive electrode table
Face structure collapses, lithium ion embedding de-performance such as is substantially reduced at the problem.Therefore, the coating modification to positive pole material surface becomes research
Focus.
The coating of positive electrode current material includes that carbon cladding, metal-oxide are (such as ZnO, Al2O3Deng), phosphate (as
AlPO4Deng) and anion (such as F-etc.).Though these covering materials have intercepted nickel ion doped material and have contacted with the direct of electrolyte,
But exist and reduce specific capacity, corrosion material surface and increase the problems such as resistance.
Summary of the invention
It is an object of the invention to provide the titanium cladding nickel cobalt manganese lithium ion power battery cathode that a kind of cycle performance is excellent
The preparation method of material.
For achieving the above object, the present invention provides following technical scheme:
The preparation method of a kind of titanium cladding nickel cobalt manganese lithium ion power battery cathode material, comprises the following steps:
(1) stoichiometrically by solid-state Mn (NO3)2、CoCO3With Ni (NO3)2·6H2O mixes, 420～480r/min
Rotating speed under ball milling 2～4h, obtain compound；
(2) again by above-mentioned compound and solid-state Li2CO3Mixing, puts into the vertical rotary cylinder inner chamber of high speed rotating from top to bottom
In, the mixture in inner chamber is thrown away under centrifugal action by the cylinder of high speed rotating from the through hole of downside sidewall；It is arranged at rolling
The mixture thrown away is blowed the cover on the upside of cylinder by fan on the downside of Tong from bottom to top, and mixture is thrown after clashing into cover again
Enter in drum cavity；So circulation, mixture being uniformly mixed；Dispersion is added in the mixture of above-mentioned mix homogeneously
Agent, utilizes planetary ball mill to carry out mechanical activation under the rotating speed of 300～350r/min, and the time of mechanical activation is 1～2h；Machine
Ball material mass ratio during tool activation is (3～5): 1；
(4) it is dried in then the slurry after activation being placed in the drying baker of 85～88 DEG C, obtains presoma；
(5) presoma being carried out pre-burning, calcined temperature is 650～680 DEG C, and the time is 1.5～2h；
(6) it is ground after pre-burning, then roasting, the temperature of roasting is 850～880 DEG C, and the time is 4～5h, it is thus achieved that nickel cobalt
Manganese anode material of lithium battery；
(7) by nickel cobalt manganese anode material of lithium battery and TiCl4, dehydrated alcohol, oxalic acid, hexamethylene, triethylamine mix and blend
Uniformly, it is transferred to water heating kettle, reacts 14～18h at 170～175 DEG C, after reaction terminates, naturally cool to room temperature, and added
Amount ethanol, the precipitate with deionized water obtained wash 3～5 times, at 70～78 DEG C be vacuum dried, obtain titanium cladding nickel cobalt manganese lithium from
Sub-power battery anode material.
As the further scheme of the present invention: the structural formula of described nickel cobalt manganese lithium ion power battery cathode material is
LiNixCoyMnzO2, wherein x+y+z=1,0 ＜ x ＜ 1,0 ＜ y ＜ 1,0 ＜ z ＜ 1.
As the further scheme of the present invention: 0.4 ＜ x ＜ 0.5,0.2 ＜ y ＜ 0.3,0.2 ＜ z ＜ 0.3.
As the further scheme of the present invention: x=0.45, y=0.27, z=0.28.
As the further scheme of the present invention: described nickel cobalt manganese anode material of lithium battery: TiCl4: dehydrated alcohol: grass
Acid: hexamethylene: the mass ratio of triethylamine is 100:(0.8～1.2): (80～120): (2～5): (40～55): (25～35).
As the further scheme of the present invention: described nickel cobalt manganese anode material of lithium battery: TiCl4: dehydrated alcohol: grass
Acid: hexamethylene: the mass ratio of triethylamine is 100:1:100:3:48:28.
Compared with prior art, the invention has the beneficial effects as follows:
First with ball mill, material being carried out ball milling so that material particle size is uniform, recycling centrifugal force and fan make
The material of mixing realizes random shuttling movement, thus reaches batch mixing uniformly without the purpose at dead angle；Mixture clashes into cover, can
Make to produce between mixture the adhesive effect of appropriateness, thus when ensureing follow-up sintering, lithium ion is uniformly embedded in presoma；Will
Mixture carries out mechanical activation, makes granular precursor be evenly distributed further, uniform particle sizes；Electrification is obtained by pre-burning and roasting
Learn the nickel cobalt nickel manganese anode material of lithium battery of function admirable；Dehydrated alcohol and oxalic acid is used to carry out esterification under hydrothermal conditions
The water generated promotes TiCl4Hydrolysis, hydrolysis rate is slow, and titanium particle diameter is easily controllable, and oxalic acid is also wrapped in titanium as dispersant
Surface so that it is be difficult to reunite；Titanium is evenly coated so that the electrochemistry of titanium cladding nickel cobalt manganese lithium ion power battery cathode material
Can be stable, safety is high, and cycle performance is excellent.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, the preparation method of a kind of titanium cladding nickel cobalt manganese lithium ion power battery cathode material, including
Following steps:
(1) according to structural formula LiNi0.8Co0.1Mn0.1O2Stoichiometric proportion, by solid-state Mn (NO3)2、CoCO3And Ni
(NO3)2·6H2O mixes, and under the rotating speed of 420r/min, ball milling 4h, obtains compound；
(2) again by above-mentioned compound and solid-state Li2CO3Mixing, puts into the vertical rotary cylinder inner chamber of high speed rotating from top to bottom
In, the mixture in inner chamber is thrown away under centrifugal action by the cylinder of high speed rotating from the through hole of downside sidewall；It is arranged at rolling
The mixture thrown away is blowed the cover on the upside of cylinder by fan on the downside of Tong from bottom to top, and mixture is thrown after clashing into cover again
Enter in drum cavity；So circulation, mixture being uniformly mixed；Dispersion is added in the mixture of above-mentioned mix homogeneously
Agent, utilizes planetary ball mill to carry out mechanical activation under the rotating speed of 350r/min, and the time of mechanical activation is 1h；During mechanical activation
Ball material mass ratio be 3:1；
(4) it is dried in then the slurry after activation being placed in the drying baker of 85 DEG C, obtains presoma；
(5) presoma being carried out pre-burning, calcined temperature is 650 DEG C, and the time is 2h；
(6) it is ground after pre-burning, then roasting, the temperature of roasting is 880 DEG C, and the time is 4h, it is thus achieved that nickel cobalt manganese lithium battery
Positive electrode；
(7) by nickel cobalt manganese anode material of lithium battery and TiCl4, dehydrated alcohol, oxalic acid, hexamethylene, triethylamine is according to quality
Ratio 100:0.8:80:2:40:25 mixing and stirring, is transferred to water heating kettle, reacts 18h at 170 DEG C, after reaction terminates, natural
Being cooled to room temperature, and add excess ethyl alcohol, the precipitate with deionized water obtained is washed 3 times, is vacuum dried, obtains titanium bag at 70 DEG C
Cover nickel cobalt manganese lithium ion power battery cathode material.
Embodiment 2
In the embodiment of the present invention, the preparation method of a kind of titanium cladding nickel cobalt manganese lithium ion power battery cathode material, including
Following steps:
(1) according to structural formula LiNi0.3Co0.4Mn0.3O2Stoichiometric proportion, by solid-state Mn (NO3)2、CoCO3And Ni
(NO3)2·6H2O mixes, and under the rotating speed of 480r/min, ball milling 2h, obtains compound；
(2) again by above-mentioned compound and solid-state Li2CO3Mixing, puts into the vertical rotary cylinder inner chamber of high speed rotating from top to bottom
In, the mixture in inner chamber is thrown away under centrifugal action by the cylinder of high speed rotating from the through hole of downside sidewall；It is arranged at rolling
The mixture thrown away is blowed the cover on the upside of cylinder by fan on the downside of Tong from bottom to top, and mixture is thrown after clashing into cover again
Enter in drum cavity；So circulation, mixture being uniformly mixed；Dispersion is added in the mixture of above-mentioned mix homogeneously
Agent, utilizes planetary ball mill to carry out mechanical activation under the rotating speed of 300r/min, and the time of mechanical activation is 2h；During mechanical activation
Ball material mass ratio be 3:1；
(4) it is dried in then the slurry after activation being placed in the drying baker of 88 DEG C, obtains presoma；
(5) presoma being carried out pre-burning, calcined temperature is 680 DEG C, and the time is 1.5h；
(6) it is ground after pre-burning, then roasting, the temperature of roasting is 850 DEG C, and the time is 5h, it is thus achieved that nickel cobalt manganese lithium battery
Positive electrode；
(7) by nickel cobalt manganese anode material of lithium battery and TiCl4, dehydrated alcohol, oxalic acid, hexamethylene, triethylamine is according to quality
Ratio 100:1.2:120:5:55:35 mixing and stirring, is transferred to water heating kettle, reacts 14h at 175 DEG C, after reaction terminates, natural
Being cooled to room temperature, and add excess ethyl alcohol, the precipitate with deionized water obtained is washed 5 times, is vacuum dried, obtains titanium bag at 78 DEG C
Cover nickel cobalt manganese lithium ion power battery cathode material.
Embodiment 3
In the embodiment of the present invention, the preparation method of a kind of titanium cladding nickel cobalt manganese lithium ion power battery cathode material, including
Following steps:
(1) according to structural formula LiNi0.45Co0.27Mn0.28O2Stoichiometric proportion, by solid-state Mn (NO3)2、CoCO3And Ni
(NO3)2·6H2O mixes, and under the rotating speed of 450r/min, ball milling 3h, obtains compound；
(2) again by above-mentioned compound and solid-state Li2CO3Mixing, puts into the vertical rotary cylinder inner chamber of high speed rotating from top to bottom
In, the mixture in inner chamber is thrown away under centrifugal action by the cylinder of high speed rotating from the through hole of downside sidewall；It is arranged at rolling
The mixture thrown away is blowed the cover on the upside of cylinder by fan on the downside of Tong from bottom to top, and mixture is thrown after clashing into cover again
Enter in drum cavity；So circulation, mixture being uniformly mixed；Dispersion is added in the mixture of above-mentioned mix homogeneously
Agent, utilizes planetary ball mill to carry out mechanical activation under the rotating speed of 350r/min, and the time of mechanical activation is 1.5h；Mechanical activation
Time ball material mass ratio be 4:1；
(4) it is dried in then the slurry after activation being placed in the drying baker of 85 DEG C, obtains presoma；
(5) presoma being carried out pre-burning, calcined temperature is 660 DEG C, and the time is 2h；
(6) it is ground after pre-burning, then roasting, the temperature of roasting is 880 DEG C, and the time is 4h, it is thus achieved that nickel cobalt manganese lithium battery
Positive electrode；
(7) by nickel cobalt manganese anode material of lithium battery and TiCl4, dehydrated alcohol, oxalic acid, hexamethylene, triethylamine is according to quality
Ratio 100:1:100:3:48:28 mixing and stirring, is transferred to water heating kettle, reacts 16h at 172 DEG C, after reaction terminates, the coldest
But to room temperature, and adding excess ethyl alcohol, the precipitate with deionized water obtained is washed 5 times, is vacuum dried at 75 DEG C, obtains titanium cladding
Nickel cobalt manganese lithium ion power battery cathode material.
According to the method described in above-described embodiment 1～3, by prepared titanium cladding nickel cobalt manganese lithium ion power battery cathode material
20Ah lithium-ion-power cell A～C made by material, meanwhile, according to the first six step of method described in above-described embodiment 1～3, and will system
The nickel cobalt manganese lithium ion power battery cathode material obtained makes 20Ah lithium-ion-power cell D～F, tests its 1C electric discharge specific volume
Amount, 300 weeks capability retentions of circulation and 85 DEG C of high temperature storage capacity restoration rates, test result is as shown in table 1.
The performance test results of each Battery pack of table 1
| Project | Battery capacity first | 300 weeks capability retentions | 85 DEG C of high temperature storage capacity restoration rates |
| A | 22.3Ah | 87.5% | 96.6% |
| B | 22.9Ah | 90..4% | 97.5% |
| C | 24.1Ah | 94.5% | 98.3% |
| D | 21.8Ah | 83.4% | 90.0% |
| E | 22.1Ah | 84.1% | 91.2% |
| F | 22.7Ah | 86.4 | 93.6% |
As shown in Table 1: compared with the nickel cobalt manganese lithium ion power battery cathode material not carrying out titanium cladding, titanium cladding nickel
The stable electrochemical property of cobalt manganese lithium ion power battery cathode material, safety is high, and cycle performance is excellent.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of the spirit or essential attributes of the present invention, it is possible to realize the present invention in other specific forms.Therefore, no matter
From the point of view of which point, all should regard embodiment as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all by fall in the implication of equivalency and scope of claim
Change is included in the present invention.
Although moreover, it will be appreciated that this specification is been described by according to embodiment, but the most each embodiment only wraps
Containing an independent technical scheme, this narrating mode of description is only that for clarity sake those skilled in the art should
Description can also be formed those skilled in the art through appropriately combined as an entirety, the technical scheme in each embodiment
May be appreciated other embodiments.
Claims (6)
1. the preparation method of a titanium cladding nickel cobalt manganese lithium ion power battery cathode material, it is characterised in that include following step
Rapid:
(1) stoichiometrically by solid-state Mn (NO3)2、CoCO3With Ni (NO3)2·6H2O mix, 420～480r/min turn
The lower ball milling 2～4h of speed, obtains compound；
(2) again by above-mentioned compound and solid-state Li2CO3Mixing, puts in the vertical rotary cylinder inner chamber of high speed rotating from top to bottom, high
Mixture in inner chamber is thrown away under centrifugal action by the cylinder that speed rotates from the through hole of downside sidewall；It is arranged on the downside of cylinder
Fan the mixture thrown away is blowed from bottom to top the cover on the upside of cylinder, mixture puts into cylinder after clashing into cover again
In inner chamber；So circulation, mixture being uniformly mixed；In the mixture of above-mentioned mix homogeneously, add dispersant, utilize
Planetary ball mill carries out mechanical activation under the rotating speed of 300～350r/min, and the time of mechanical activation is 1～2h；Mechanical activation
Time ball material mass ratio be (3～5): 1；
(4) it is dried in then the slurry after activation being placed in the drying baker of 85～88 DEG C, obtains presoma；
(5) presoma being carried out pre-burning, calcined temperature is 650～680 DEG C, and the time is 1.5～2h；
(6) it is ground after pre-burning, then roasting, the temperature of roasting is 850～880 DEG C, and the time is 4～5h, it is thus achieved that nickel cobalt manganese lithium
Cell positive material；
(7) by nickel cobalt manganese anode material of lithium battery and TiCl4, dehydrated alcohol, oxalic acid, hexamethylene, triethylamine mixing and stirring,
It is transferred to water heating kettle, at 170～175 DEG C, reacts 14～18h, after reaction terminates, naturally cool to room temperature, and add excess second
Alcohol, the precipitate with deionized water obtained is washed 3～5 times, is vacuum dried at 70～78 DEG C, obtains titanium cladding nickel cobalt manganese lithium ion and moves
Power cell positive material.
The preparation method of titanium the most according to claim 1 cladding nickel cobalt manganese lithium ion power battery cathode material, its feature
Being, the structural formula of described nickel cobalt manganese lithium ion power battery cathode material is LiNixCoyMnzO2, wherein x+y+z=1,0
＜ x ＜ 1,0 ＜ y ＜ 1,0 ＜ z ＜ 1.
The preparation method of titanium the most according to claim 2 cladding nickel cobalt manganese lithium ion power battery cathode material, its feature
It is, 0.4 ＜ x ＜ 0.5,0.2 ＜ y ＜ 0.3,0.2 ＜ z ＜ 0.3.
The preparation method of titanium the most according to claim 3 cladding nickel cobalt manganese lithium ion power battery cathode material, its feature
It is, x=0.45, y=0.27, z=0.28.
The preparation method of titanium the most according to claim 1 cladding nickel cobalt manganese lithium ion power battery cathode material, its feature
It is, described nickel cobalt manganese anode material of lithium battery: TiCl4: dehydrated alcohol: oxalic acid: hexamethylene: the mass ratio of triethylamine is
100:(0.8～1.2): (80～120): (2～5): (40～55): (25～35).
The preparation method of titanium the most according to claim 5 cladding nickel cobalt manganese lithium ion power battery cathode material, its feature
It is, described nickel cobalt manganese anode material of lithium battery: TiCl4: dehydrated alcohol: oxalic acid: hexamethylene: the mass ratio of triethylamine is
100:1:100:3:48:28.
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| CN105789613A (en) * | 2016-04-22 | 2016-07-20 | 柳州凯通新材料科技有限公司 | Method for preparing precursor of cobalt-nickel-manganese-lithium battery cathode material |
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