CN105762348B - A kind of preparation method of complex oxide surface cladding cell positive material - Google Patents
A kind of preparation method of complex oxide surface cladding cell positive material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000005253 cladding Methods 0.000 title claims description 25
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract 2
- 238000005245 sintering Methods 0.000 claims description 22
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 13
- 206010013786 Dry skin Diseases 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 zirconium alkoxide Chemical class 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 230000001603 reducing effect Effects 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 8
- 125000005909 ethyl alcohol group Chemical group 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 210000002700 urine Anatomy 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical class [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical class Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical class Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical class [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to lithium ion battery materials and materialogy field.A kind of preparation method of complex oxide surface clad anode material, includes the following steps successively：(1) various metals source is dissolved in organic solvent, inhibitor is added in organic solvent, under stirring, fertile material well prepared in advance is added thereto, and urea is added, after stirring evenly, it is passed through vapor from feed liquid bottom, at this temperature until stirring to dry；(2) dried sample is sintered under atmosphere of ventilating；(3) sample comminution sintered, sieving are obtained into complex oxide surface and coats cell positive material.The advantages of preparation method is effectively to have completely cut off falling off for contact and cyclic process clad of the cell positive material with electrolyte, prevent part hydrolysis too fast, clad is more advantageous to slowly to generate, with higher thermodynamic stability, stronger resistance to oxidation, reducing property and good electric conductivity.
Description
Technical field
The invention belongs to lithium ion battery materials and materialogy field.
Background of invention
With global energy crisis and ecocrisis, New Energy Industry welcomes rapid development, and development New Energy Industry is necessary
Greatly develop high safety, the long-life, high-energy density power battery and energy-storage battery.Anode material for lithium-ion batteries at present
That commercially produces mainly has cobalt acid lithium, ternary material, LiFePO4, LiMn2O4 etc., for power battery and energy-storage battery
Mainly LiFePO4 and LiMn2O4, LiFePO4 are difficult to control in process of production, and consistency is poor, and LiMn2O4 security performance
Height, resourceful, price is low, is easy to produce in enormous quantities, good product consistency, becomes the master of power battery and energy-storage battery at present
Stream.Though everybody unanimously has an optimistic view of, lithium manganate battery stores process capacities and decays, generation irreversible capacity loss, under hot conditions,
Cycle performance and storge quality are worse, constrain application of the lithium manganate battery in power battery and energy-storage battery.
Dissolving and the Jahn-Teller effects that LiMn2O4 recycles and storage process capacities are decayed mainly due to bivalent manganese,
Current most effective method of modifying mainly passes through doping and surface coating modification two ways.Mangaic acid can be centainly improved by doping
The cycle performance and high-temperature stability of lithium battery, but still the application requirement of power battery and energy-storage battery is not achieved, surface packet
The contact that can directly effectively reduce orthodox material with electrolyte is covered, the speed of manganese dissolving is reduced, may also suppress Jahn-Teller
Effect inhibits phase transformation, so that material is kept good structure in charge and discharge process, thus substantially increase lithium manganate battery
Cycle performance and high-temperature stability.
Invention content
Above-mentioned to solve the problems, such as, the present invention provides a kind of complex oxide surface cladding battery manganese cathode material
Preparation method, this method prepare complex oxide surface cladding manganese cathode material high-temperature stability and cycle life significantly
It improves.
The technical solution adopted in the present invention is as follows：
A kind of preparation method of complex oxide surface clad anode material, includes the following steps successively：(1) by a variety of gold
Category source is dissolved in organic solvent, and inhibitor is added in organic solvent, and under stirring, fertile material well prepared in advance is added
Enter wherein, and urea is added, after stirring evenly, temperature rises to 70~90 DEG C, is passed through vapor from feed liquid bottom, at this temperature
Until stirring to doing, it is put into 80 DEG C~100 DEG C dryings in baking oven；(2) dried sample is burnt under atmosphere of ventilating
Knot, sintering temperature are 350~650 DEG C, and sintering time is 6~15h；(3) sample comminution sintered, sieving are obtained compound
Oxide surface coats cell positive material.
Preferably, the covering amount of the composite oxides of the material is mass ratio 0.1~2%.
Preferably, source metal is aluminium, in the alkoxide or chlorate of titanium, magnesium, lanthanum, niobium, chromium, yttrium, zirconium in the step (1)
At least two；Organic solvent is absolute ethyl alcohol or isopropanol, and the mass ratio of organic solvent and source metal is 30:1~100:1.
Preferably, inhibitor is acetylacetone,2,4-pentanedione in the step (1), acetylacetone,2,4-pentanedione rubs with the metal ion in source metal
You are than being 0.1~0.5.
Preferably, fertile material is the finished product sample after crushing, sieving in the step (1).
Preferably, the amount that urea is added in the step (1) is urea and the metal molar ratio in source metal is 3:1~
6:1。
Preferably, the amount for being passed through vapor in the step (1) is vapor and the metal ion mole in source metal
Than being 10:1~100:1, steam temperature is 70~120 DEG C, and it is 1g/min~20g/min to be passed through speed.
Preferably, ventilation atmosphere is air or oxygen in the step (2).
Preferably, fertile material is LiMn2O4.
Complex oxide surface cladding manganese systems cell positive material prepared by the present invention is verified by manganese dissolution experiment, manganese
Dissolution experiment specific steps：
1. accurate weighing detected materials 1.00g or 2.00g are put into the sample bottle of 10ml；
2. accurately measuring electrolyte 5ml, it is appended to sample bottle；
3. after sample bottle is sealed with double lids, after mixing, being statically placed in 60 DEG C of thermostat 0-5 days；
It is completed at 4.60 DEG C after standing, is gently mixed, is cooled to room temperature, open double lids, draw the liquid filtering on top,
Precise acquisition 1ml carries out sour dissolving, and manganese element content is measured with ICP.
The present invention has the following advantages：
(1) preparation method of the present invention is using Hydrolyze method and the characteristic of homogeneous co-precipitation so that covering material particle is uniform
Slowly be deposited on cell positive material surface, the clad generated in this way evenly, it is fine and close, effectively completely cut off anode
Contact and cyclic process clad of the material with electrolyte fall off.
(2) method for being passed through vapor and be directly added into or titrate ratio that the present invention uses, it is therefore prevented that part hydrolysis is too fast,
Clad is more advantageous to slowly to generate.
(3) composite oxides and simple oxide ratio that the present invention is coated, have higher thermodynamic stability, compared with
Strong resistance to oxidation, reducing property and good electric conductivity, the high-temperature stability by the cell positive material of cladding and cycle longevity
Life all greatly improves.
(4) preparation method of the present invention is not only simple for process, and is easy to industrialize, it may also be used for the surface of other positive electrodes
Cladding, has broad application prospects.
Description of the drawings
Fig. 1 is the normal temperature circulation curve graph of the material and uncoated fertile material prepared by embodiment 1；
Fig. 2 is 55 DEG C of cyclic curve figures of high temperature of the material and uncoated fertile material prepared by embodiment 1；
Fig. 3 is the SEM figures of material after embodiment 3 coats；
Fig. 4 is the electric 50 weeks cycle performance figures of material room temperature button prepared by embodiment 7；
Fig. 5 is the electric 50 weeks cyclic curves of 45 DEG C of buttons of high temperature of the material prepared by embodiment 8 and uncoated fertile material
Figure；
Fig. 6 is that the manganese of the material and uncoated fertile material prepared by embodiment 8 dissolves contrast curve.
Specific implementation mode
Below in conjunction with Figure of description and specific embodiment, the invention will be further described, but protection scope of the present invention
And application range is not limited to following embodiment.
Embodiment 1
A kind of preparation method of complex oxide surface cladding cell positive material, includes the following steps successively：(1) will
45.39g aluminium isopropoxides and six water lanthanum chlorides of 47.10g are dissolved in 3000ml absolute ethyl alcohols, and 4ml levulinics are added in absolute ethyl alcohol
Ketone rapidly joins fertile material 3000g well prepared in advance wherein, and the urea of 85g is added under stirring, stirring
After uniformly, temperature rises to 75 DEG C, and 100 DEG C of vapor is passed through with 5g/min speed from feed liquid bottom, is stopped after being passed through 40min,
At this temperature until stirring to doing, it is put into 100 DEG C of dryings in baking oven.(2) by dried sample in air atmosphere into
Row sintering, sintering temperature are 500 DEG C, sintering time 8h.(3) sample comminution sintered, sieving are obtained into combined oxidation
Object surface coats cell positive material.
Such as Fig. 1, the cell positive material after being coated under room temperature has recycled 2201 weeks capacity retention ratios 80%, and uncoated
Fertile material has recycled 1237 weeks capacity retention ratios 80%, and the positive electrode normal temperature circulation service life is than uncoated parent material after cladding
Material improves 964 weeks.
Such as Fig. 2, the positive electrode after being coated at 55 DEG C of high temperature has recycled 1000 weeks capacity retention ratios 80%, and uncoated
Fertile material has recycled 536 weeks capacity retention ratios 80%, and cycle life is than uncoated at 55 DEG C of positive electrode high temperature after cladding
Fertile material improve 464 weeks.
Embodiment 2
A kind of preparation method of complex oxide surface cladding cell positive material, includes the following steps successively：(1) will
8.90g aluminium isopropoxides and 85.32g butyl titanates are dissolved in 3000ml absolute ethyl alcohols, and 6ml levulinics are added in absolute ethyl alcohol
Ketone rapidly joins LiMn2O4 fertile material 3000g well prepared in advance wherein, and the urine of 55g is added under stirring
Element, after stirring evenly, temperature rises to 70 DEG C, 90 DEG C of vapor is passed through with 5g/min speed from feed liquid bottom, after being passed through 30min
Stop, at this temperature until stirring to doing, is put into 100 DEG C of dryings in baking oven.(2) by dried sample in air atmosphere
Under be sintered, sintering temperature be 450 DEG C, sintering time 8h.(3) sample comminution sintered, sieving are obtained compound
Oxide surface coats lithium manganate cell positive electrode material.
Embodiment 3
A kind of preparation method of complex oxide surface cladding cell positive material, includes the following steps successively：(1) will
31.77g aluminium isopropoxides and 15.81g magnesium chloride hexahydrates are dissolved in 2500ml absolute ethyl alcohols, and 2.5ml acetyl is added in absolute ethyl alcohol
Acetone rapidly joins LiMn2O4 fertile material 3000g well prepared in advance wherein, and the urine of 55g is added under stirring
Element, after stirring evenly, temperature rises to 80 DEG C, and 100 DEG C of vapor is passed through with 5g/min speed from feed liquid bottom, is passed through 30min
After stop, at this temperature until stirring is to dry, be put into 100 DEG C of dryings in baking oven.(2) by dried sample in air gas
It is sintered under atmosphere, sintering temperature is 450 DEG C, sintering time 8h.(3) sample comminution sintered, sieving are answered
It closes oxide surface and coats lithium manganate cell positive electrode material.
Embodiment 4
A kind of preparation method of complex oxide surface cladding cell positive material, includes the following steps successively：(1) will
21.15g chromium chloride hexahydrates and six water yttrium chlorides of 24.06g are dissolved in 2500ml absolute ethyl alcohols, and 3.5ml second is added in absolute ethyl alcohol
Acyl acetone rapidly joins LiMn2O4 fertile material 3000g well prepared in advance wherein, and be added 40g's under stirring
Urea, after stirring evenly, temperature rises to 70 DEG C, and 100 DEG C of vapor is passed through with 5g/min speed from feed liquid bottom, is passed through
Stop after 30min, at this temperature until stirring to doing, is put into 100 DEG C of dryings in baking oven.(2) dried sample is existed
It is sintered under air atmosphere, sintering temperature is 500 DEG C, sintering time 8h.(3) i.e. by the sample comminution sintered, sieving
It obtains complex oxide surface and coats lithium manganate cell positive electrode material.
Embodiment 5
A kind of preparation method of complex oxide surface cladding cell positive material, includes the following steps successively：(1) will
47.56g titanium tetrachlorides and 35.05g zirconium chlorides are dissolved in 3000ml absolute ethyl alcohols, and 8ml acetylacetone,2,4-pentanediones are added in absolute ethyl alcohol,
Under stirring, LiMn2O4 fertile material 3000g well prepared in advance is rapidly joined wherein, and the urea of 75g is added, stirred
After mixing uniformly, temperature rises to 70 DEG C, and 90 DEG C of vapor is passed through with 5g/min speed from feed liquid bottom, is stopped after being passed through 35min,
At this temperature until stirring to doing, it is put into 100 DEG C of dryings in baking oven.(2) by dried sample in air atmosphere into
Row sintering, sintering temperature are 450 DEG C, sintering time 8h.(3) sample comminution sintered, sieving are obtained into combined oxidation
Object surface coats lithium manganate cell positive electrode material.
Embodiment 6
A kind of preparation method of complex oxide surface cladding cell positive material, includes the following steps successively：(1) will
Six water lanthanum chlorides of 27.95g and 15.36g zirconium chlorides are dissolved in 2500ml absolute ethyl alcohols, and 3ml levulinics are added in absolute ethyl alcohol
Ketone rapidly joins LiMn2O4 fertile material 3000g well prepared in advance wherein, and the urine of 40g is added under stirring
Element, after stirring evenly, temperature rises to 80 DEG C, and 100 DEG C of vapor is passed through with 5g/min speed from feed liquid bottom, is passed through 25min
After stop, at this temperature until stirring is to dry, be put into 100 DEG C of dryings in baking oven.(2) by dried sample in air gas
It is sintered under atmosphere, sintering temperature is 500 DEG C, sintering time 8h.(3) sample comminution sintered, sieving are answered
It closes oxide surface and coats lithium manganate cell positive electrode material.
Embodiment 7
A kind of preparation method of complex oxide surface cladding cell positive material, includes the following steps successively：(1) will
19.40g columbium pentachlorides and 19.13g chromium chloride hexahydrates are dissolved in 2500ml absolute ethyl alcohols, and 3ml levulinics are added in absolute ethyl alcohol
Ketone rapidly joins LiMn2O4 fertile material 3000g well prepared in advance wherein, and the urine of 40g is added under stirring
Element, after stirring evenly, temperature rises to 70 DEG C, and 100 DEG C of vapor is passed through with 4g/min speed from feed liquid bottom, is passed through 25min
After stop, at this temperature until stirring is to dry, be put into 100 DEG C of dryings in baking oven.(2) by dried sample in air gas
It is sintered under atmosphere, sintering temperature is 500 DEG C, sintering time 8h.(3) sample comminution sintered, sieving are answered
It closes oxide surface and coats lithium manganate cell positive electrode material.
Embodiment 8
A kind of preparation method of complex oxide surface cladding cell positive material, includes the following steps successively：(1) will
Six water yttrium chlorides of 23.35g, 9.00g zirconium chlorides and 7.85g magnesium chloride hexahydrates are dissolved in 2500ml absolute ethyl alcohols, absolute ethyl alcohol
Middle addition 3ml acetylacetone,2,4-pentanediones rapidly join LiMn2O4 fertile material 3000g well prepared in advance wherein under stirring,
And the urea of 45g is added, after stirring evenly, temperature rises to 70 DEG C, from feed liquid bottom with 4g/min speed be passed through 90 DEG C water steam
Gas stops after being passed through 30min, at this temperature until stirring to doing, is put into 100 DEG C of dryings in baking oven.It (2) will be dried
Sample is sintered in air atmosphere, and sintering temperature is 500 DEG C, sintering time 8h.(3) by the sample comminution sintered,
Sieving obtains complex oxide surface and coats lithium manganate cell positive electrode material.
Complex oxide surface cladding battery manganese cathode material prepared by the present invention is verified by manganese dissolution experiment, manganese
Dissolution experiment specific steps：1. accurate weighing detected materials 1.00g or 2.00g are put into the sample bottle of 10ml；2. accurate measure
Electrolyte 5ml, is appended to sample bottle；3. after sample bottle is sealed with double lids, after mixing, being statically placed in 0-5 in 60 DEG C of thermostat
It；It is completed at 4.60 DEG C after standing, is gently mixed, is cooled to room temperature, open double lids, draw the liquid filtering on top, accurately
It acquires 1ml and carries out sour dissolving, manganese element content is measured with ICP.
Claims (7)
1. a kind of preparation method of complex oxide surface cladding cell positive material, it is characterised in that include following step successively
Suddenly：（1）Various metals source is dissolved in organic solvent, inhibitor is added in organic solvent, it, will be previously prepared under stirring
Good fertile material is added thereto, and urea is added, and after stirring evenly, temperature rises to 70 ~ 90 DEG C, and being passed through water from feed liquid bottom steams
Gas is put into 80 DEG C ~ 100 DEG C dryings in baking oven at this temperature until stirring to doing；The step（1）Middle source metal be aluminium,
Titanium, magnesium, lanthanum, niobium, chromium, yttrium, zirconium alkoxide or chlorate at least two；Step（1）Middle inhibitor is acetylacetone,2,4-pentanedione, levulinic
Ketone is 0.1 ~ 0.5 with the metal ion molar ratio in source metal；Fertile material is LiMn2O4；（2）Dried sample is existed
It is sintered under ventilation atmosphere, sintering temperature is 350 ~ 650 DEG C, and sintering time is 6 ~ 15h；（3）By the sample comminution sintered,
Sieving obtains complex oxide surface and coats cell positive material.
2. a kind of preparation method of complex oxide surface cladding cell positive material according to claim 1, feature
It is：The covering amount of the composite oxides of the material is mass ratio 0.1 ~ 2%.
3. a kind of preparation method of complex oxide surface cladding cell positive material according to claim 1, feature
It is：Organic solvent is absolute ethyl alcohol or isopropanol, and the mass ratio of organic solvent and source metal is 30:1~100:1.
4. a kind of preparation method of complex oxide surface cladding cell positive material according to claim 1, feature
It is：The step（1）Middle fertile material is the finished product sample after crushing, sieving.
5. a kind of preparation method of complex oxide surface cladding cell positive material according to claim 1, feature
It is：The step（1）The middle amount that urea is added is urea and the metal molar ratio in source metal is 3:1 ~6:1.
6. a kind of preparation method of complex oxide surface cladding cell positive material according to claim 1, feature
It is：The step（1）In be passed through that the amount of vapor is vapor and the metal ion molar ratio in source metal is 10:1 ~
100:1, steam temperature is 70 ~ 120 DEG C, and it is 1g/min ~ 20g/min to be passed through speed.
7. a kind of preparation method of complex oxide surface cladding cell positive material according to claim 1, feature
It is：The step（2）Middle ventilation atmosphere is air or oxygen.
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| CN1744354A (en) * | 2005-10-10 | 2006-03-08 | 西安交通大学 | Surface modification method of cathode active material for lithium ion battery |
| CN103606660A (en) * | 2013-11-06 | 2014-02-26 | 中国科学院化学研究所 | Alumina-coated granules, as well as preparation method and application thereof |
| CN103811765A (en) * | 2014-02-27 | 2014-05-21 | 广西师范大学 | Two-dimensional nanocrystalline metal oxide composite coating lithium manganate positive electrode material and preparation method thereof |
| CN103943837A (en) * | 2014-04-11 | 2014-07-23 | 浙江大学 | Preparation methods of antimony trioxide and antimony trioxide composite material and applications of antimony trioxide and antimony trioxide composite material in sodium-ion batteries |
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| CN1744354A (en) * | 2005-10-10 | 2006-03-08 | 西安交通大学 | Surface modification method of cathode active material for lithium ion battery |
| CN103606660A (en) * | 2013-11-06 | 2014-02-26 | 中国科学院化学研究所 | Alumina-coated granules, as well as preparation method and application thereof |
| CN103811765A (en) * | 2014-02-27 | 2014-05-21 | 广西师范大学 | Two-dimensional nanocrystalline metal oxide composite coating lithium manganate positive electrode material and preparation method thereof |
| CN103943837A (en) * | 2014-04-11 | 2014-07-23 | 浙江大学 | Preparation methods of antimony trioxide and antimony trioxide composite material and applications of antimony trioxide and antimony trioxide composite material in sodium-ion batteries |
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