CN102931392A - Lithium-ion power battery anode material lithium manganate and preparation method thereof - Google Patents
Lithium-ion power battery anode material lithium manganate and preparation method thereof Download PDFInfo
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- CN102931392A CN102931392A CN2012104365091A CN201210436509A CN102931392A CN 102931392 A CN102931392 A CN 102931392A CN 2012104365091 A CN2012104365091 A CN 2012104365091A CN 201210436509 A CN201210436509 A CN 201210436509A CN 102931392 A CN102931392 A CN 102931392A
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- lithium ion
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title abstract description 13
- 239000010405 anode material Substances 0.000 title abstract description 6
- 239000011572 manganese Substances 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 15
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 47
- 238000009413 insulation Methods 0.000 claims description 32
- 239000010406 cathode material Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NQGWALHZCVFGRE-UHFFFAOYSA-N [Ta].[N+](=O)(O)[O-] Chemical compound [Ta].[N+](=O)(O)[O-] NQGWALHZCVFGRE-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 3
- 235000019628 coolness Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 abstract 1
- 229940063655 aluminum stearate Drugs 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- TWFMKJHWXGLVDF-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O Chemical compound [Li].[Mn](=O)(=O)(O)O TWFMKJHWXGLVDF-UHFFFAOYSA-L 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses lithium-ion power battery anode material lithium manganate and a preparation method thereof. The molecular formula of the lithium manganate is Li<1+x>Mn<2-y>TayO4/zAl2O3, wherein 0<x<=0.2, 0<y<=0.2, and 0<z<=1.0. The preparation method includes the steps of proportionally mixing a lithium source compound, a manganese source compound and a tantalum element additive and subjecting the lithium source compound, the manganese source compound and the tantalum element additive to ball milling and high-temperature roasting to obtain the lithium manganate; and dispersing the lithium manganate in a dispersing agent, adding aluminum stearate for reaction to obtain precipitate, and finally subjecting the precipitate to two-section roasting, second annealing, cooling and sieving to obtain the lithium-ion power battery anode material lithium manganate. By means of a composite metal dual-doping mechanism, doping vario-property of two elements of tantalum and lithium is performed to the lithium manganate, a John-Teller effect is inhibited, and normal temperature and high temperature cycle performances of a lithium manganate material are greatly improved; and by means of sectional roasting and multi-time annealing processes, controllability of particle diameters and specific surface areas is achieved, tap density and processing performances of the material are improved, and simultaneously, oxygen defect levels during material sintering are effectively reduced.
Description
Technical field
The present invention relates to a kind of lithium ion power battery cathode material LiMn2O4, also relate to simultaneously its preparation method, belong to the cell positive material field.
Background technology
Along with the continuous expansion of field of lithium battery application and continually developing of new technology, the demand of world's lithium battery also will increase thereupon.Because particularly the development of dynamic lithium battery comes into one's own day by day, it is with the fastest developing speed wherein especially to be applied as the electrical source of power field of representative with electric motor car.And the alternative condition of the positive electrode of high-power lithium ion power battery is harsh, and the positive electrode of traditional small-scale lithium ion cell can not satisfy the demand of electrokinetic cell.Cobalt acid lithium is still in occupation of larger share in the present commercial lithium-ion batteries, especially proportion is larger in the communication apparatus such as portable computer, but because itself intrinsic character is limit, for the restriction that large current density requires, just determined that also cobalt acid lithium will certainly reduce even be substituted for the proportion in electrokinetic cell.And ternary material and lithium iron phosphate positive material also since inherently safe performance and energy density problem hindered being applied to the lithium-ion-power cell field.
The LiMn2O4 LiMn of spinel-type
2O
4Have stable three-dimensional lithium ion channel design, potential safety hazard is lower in charge and discharge process, and charges and discharge the voltage height, and energy density is large, is suitable for high-multiplying power discharge.And in recent years along with the updating of material and battery production technology, the cycle performance tool of LiMn2O4 is significantly improved, and normal temperature can reach more than 1000 times and charge and discharge circulation, and the security performances such as the super-charge super-discharge of battery are excellent.Comprehensive angle is considered, LiMn
2O
4Being the best novel anode material of high-performance power battery, also is as the anode material of lithium battery that is hopeful most to use at high-power power battery.But the problems such as the material tap density is less, the oxygen defect degree is higher that cause the defective such as the dissolving of the manganese of LiMn2O4 self, John-Teller effect and material processing cause the material electric property to reduce, and have seriously restricted LiMn
2O
4Application as positive electrode.
Summary of the invention
The purpose of this invention is to provide a kind of lithium ion power battery cathode material LiMn2O4.
In order to realize above purpose, the technical solution adopted in the present invention provides a kind of lithium ion power battery cathode material LiMn2O4, and described LiMn2O4 is the doping tantalum element, and the LiMn2O4 Li of surface-coated aluminum oxide
1+xMn
2-yTa
yO
4/ zAl
2O
3, 0＜x≤0.2,0＜y≤0.2,0＜z≤1.0 wherein.
The present invention also aims to provide a kind of preparation method of lithium ion power battery cathode material LiMn2O4.
The technical solution adopted in the present invention also is to provide a kind of preparation method of lithium ion power battery cathode material LiMn2O4, and step is as follows:
1) according to the mol ratio (1+x) of lithium, manganese, tantalum: (2-y): y takes by weighing respectively Li source compound, manganese source compound, tantalum element additive, mixes and ball milling 5～8h;
2) presoma with the step 1) ball milling carries out high-temperature roasting, and 400～600 ℃ of insulation 10～12h are warming up to 800～900 ℃ of insulation 20～30h again, cross 300 mesh sieves after the cooling;
3) with step 2) particle and dispersant after sieving add in the reactor according to mass ratio 1:5 ~ 8 ratios, ultrasonic dispersion and stirring, bath temperature remains on 50～55 ℃;
4) whipping process adds aluminium salt according to LiMn2O4 and aluminium salt mol ratio 1:2z, regulates pH to 9, continues to stir 2～4h;
5) sediment that step 4) is obtained carries out filtration washing, 100～120 ℃ of drying 12～24h;
6) product with drying carries out high-temperature roasting, 400～600 ℃ of insulation 5～10h, 800～950 ℃ of insulation 5～10h again heat up, 500～550 ℃ of annealing coolings, insulation 2～4h, be down to again 300～350 ℃ of insulation 2～4h, cross 300 mesh sieves after the cooling, obtain lithium ion power battery cathode material LiMn2O4 Li
1+xMn
2-yTa
yO
4/ zAl
2O
3, 0＜x≤0.2,0＜y≤0.2,0＜z≤1.0 wherein.
Described manganese source compound is manganese sulfate, manganese nitrate or manganese acetate.
Described Li source compound is lithium carbonate, lithium nitrate or lithium acetate.
Described tantalum element additive is tantalum pentoxide or nitric acid tantalum.
The rotating speed of ball milling is 300～400r/min in the described step 1).
Described step 2) and 6) in heating rate be 3～5 ℃/min.
Described dispersant is at least a in deionized water, the absolute ethyl alcohol.
Described aluminium salt is aluminum nitrate, aluminum sulfate or aluminium chloride.
The present invention adopts composition metal codope mechanism, and LiMn2O4 is carried out the doping vario-property of tantalum (Ta), lithium (Li) two elements: Ta5+ has larger ionic radius, can improve the lattice parameter of spinel structure, promotes the raising of lithium ion diffusion coefficient; The M-O key of Simultaneous Stabilization can improve the stability of LiMn2O4 frame structure.The Li+ of employing lower valency mixes and can improve the average valence of Mn, suppresses the J-T effect.Composite mixed ion has occupied the 16d position of Mn, greatly improves the cycle performance of lithium manganate material.
The present invention takes ultrasonic heterogeneous nucleation process to carry out LiMn2O4 and coats modification, by adopting lithium manganate particle as the nucleus matrix, control coating precipitation reaction concentration, ultrasonic wave disperses simultaneously, make the coating of precipitation be the nano particle Uniform Dispersion, uniform particles is adsorbed on the lithium manganate particle surface, by control sintering temperature and time, to obtain the LiMn2O4 function-graded material of core-shell structure, its effect can suppress dissolving and the decomposition of electrolyte on electrode of manganese, greatly improves LiMn2O4 chemical property at high temperature.
The present invention adopts the segmented baking modes, and temperature-rise period slowly carries out, and doped chemical is penetrated in the lattice.Carry out simultaneously the two-stage roasting double annealing, phase decomposition is carried out first in roasting, obtains the pure phase coating layer, improves temperature again, makes coating layer form fine and close core-shell structure; Annealing slows down first the generation of the internal stress defective of coating; It is intensive in order that intergranule is piled up, and forms the structure of certain particle size, high-tap density.The present invention reaches the controllability of grain diameter and specific area, improves tap density and the processing characteristics of material, effectively reduces simultaneously the oxygen defect degree in the material sintering.
Lithium manganate material electrical property and life-span that the present invention prepares are improved, and have good using value.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 manganic acid lithium electrode material;
Fig. 2 is for adopting lithium ion battery normal temperature and the high temperature circulation curve of the preparation of embodiment 1 manganic acid lithium electrode material;
Fig. 3 is for adopting lithium ion battery normal temperature and the high temperature circulation curve of the preparation of embodiment 2 manganic acid lithium electrode materials;
Fig. 4 is for adopting lithium ion battery normal temperature and the high temperature circulation curve of the preparation of embodiment 3 manganic acid lithium electrode materials;
Fig. 5 is for adopting lithium ion battery normal temperature and the high temperature circulation curve of the preparation of Comparative Examples manganic acid lithium electrode material.
Embodiment
The lithium ion power battery cathode material LiMn2O4 of present embodiment, molecular formula are Li
1.05Mn
1.9Ta
0.1O
4/ 0.5Al
2O
3
The preparation method of the lithium ion power battery cathode material LiMn2O4 of present embodiment, step is as follows:
1) according to lithium: manganese: tantalum mol ratio 1.05:1.9:0.1 takes by weighing lithium carbonate, manganese sulfate, tantalum pentoxide, mixes and with 300r/min ball milling 5h;
2) presoma with the step 1) ball milling carries out high-temperature roasting, and 600 ℃ of insulation 10h are warming up to 800 ℃ of insulation 20h again, and 3 ℃/min of heating rate crosses 300 mesh sieves after the cooling;
3) with step 2) particle after sieving and deionized water add in the reactor according to the ratio of mass ratio 1:5, ultrasonic dispersion and stirring, bath temperature remains on 50 ℃;
4) whipping process adds aluminum nitrate according to LiMn2O4 and aluminum nitrate mol ratio 1:1, and with the ammonia spirit that flow velocity 25rpm pumps into concentration 1mol/L, regulates pH to 9 and stop to add ammoniacal liquor, the lasting 2h that stirs;
5) sediment that step 4) is obtained carries out filtration washing, 100 ℃ of dry 12h;
6) product with drying carries out high-temperature roasting, and 600 ℃ of insulation 10h heat up 800 ℃ again and are incubated 10h, 3 ℃/min of heating rate, annealing is cooled to 500 ℃, insulation 2h, be down to again 300 ℃ of insulation 2h, cross 300 mesh sieves after the cooling, obtain lithium ion power battery cathode material LiMn2O4 Li
1.05Mn
1.9Ta
0.1O
4/ 0.5Al
2O
3
The scanning electron microscope (SEM) photograph of the manganic acid lithium electrode material of present embodiment, as shown in Figure 1.
Lithium ion battery normal temperature and the high temperature circulation curve of the manganic acid lithium electrode material preparation of present embodiment, as shown in Figure 2.
The lithium ion power battery cathode material LiMn2O4 of present embodiment, molecular formula are Li
1.1Mn
1.8Ta
0.2O
4/ 1.0Al
2O
3
The preparation method of the lithium ion power battery cathode material LiMn2O4 of present embodiment, step is as follows:
1) according to lithium: manganese: tantalum mol ratio 1.1:1.8:0.2 takes by weighing lithium nitrate, manganese nitrate and nitric acid tantalum, mixes and with 400r/min ball milling 6h;
2) presoma with the step 1) ball milling carries out high-temperature roasting, and 500 ℃ of insulation 11h are warming up to 850 ℃ of insulation 30h again, and 4 ℃/min of heating rate crosses 300 mesh sieves after the cooling;
3) with step 2) particle after sieving and absolute ethyl alcohol add in the reactor according to the ratio of mass ratio 1:6.5, ultrasonic dispersion and stirring, bath temperature remains on 55 ℃;
4) whipping process adds aluminium chloride according to LiMn2O4 and aluminium chloride mol ratio 1:2, and with the ammonia spirit that flow velocity 20rpm pumps into concentration 2mol/L, regulates pH to 9 and stop to add ammoniacal liquor, the lasting 3h that stirs;
5) sediment that step 4) is obtained carries out filtration washing, 110 ℃ of dry 24h;
6) product with drying carries out high-temperature roasting, and 400 ℃ of insulation 5h heat up 875 ℃ again and are incubated 7h, 4 ℃/min of heating rate, annealing is cooled to 525 ℃, insulation 3h, be down to again 330 ℃ of insulation 4h, cross 300 mesh sieves after the cooling, obtain lithium ion power battery cathode material LiMn2O4 Li
1.1Mn
1.8Ta
0.2O
4/ 1.0Al
2O
3
Lithium ion battery normal temperature and the high temperature circulation curve of the manganic acid lithium electrode material preparation of present embodiment, as shown in Figure 3.
Embodiment 3
The lithium ion power battery cathode material LiMn2O4 of present embodiment, molecular formula are Li
1.2Mn
1.95Ta
0.05O
4/ 0.1Al
2O
3
The preparation method of the lithium ion power battery cathode material LiMn2O4 of present embodiment, step is as follows:
1) according to lithium: manganese: tantalum mol ratio 1.2:1.95:0.05 takes by weighing lithium acetate, manganese acetate, nitric acid tantalum, mixes and with 350r/min ball milling 8h;
2) presoma with the step 1) ball milling carries out high-temperature roasting, and 400 ℃ of insulation 12h are warming up to 900 ℃ of insulation 25h again, and 5 ℃/min of heating rate crosses 300 mesh sieves after the cooling;
3) with step 2) particle after sieving and the mixed solution of deionized water and absolute ethyl alcohol add in the reactor according to the ratio of mass ratio 1:8, ultrasonic dispersion and stirring, bath temperature remains on 53 ℃;
4) whipping process adds aluminum sulfate according to LiMn2O4 and aluminum sulfate mol ratio 1:0.2, and with the ammonia spirit that flow velocity 23rpm pumps into concentration 3mol/L, regulates pH to 9 and stop to add ammoniacal liquor, the lasting 4h that stirs;
5) sediment that step 4) is obtained carries out filtration washing, 120 ℃ of dry 18h;
6) product with drying carries out high-temperature roasting, and 500 ℃ of insulation 8h heat up 950 ℃ again and are incubated 5h, 5 ℃/min of heating rate, annealing is cooled to 550 ℃, insulation 4h, be down to again 350 ℃ of insulation 3h, cross 300 mesh sieves after the cooling, obtain lithium ion power battery cathode material LiMn2O4 Li
1.2Mn
1.95Ta
0.05O
4/ 0.1Al
2O
3
Lithium ion battery normal temperature and the high temperature circulation curve of the manganic acid lithium electrode material preparation of present embodiment, as shown in Figure 4.
Comparative Examples
The lithium ion power battery cathode material LiMn2O4 of this Comparative Examples, its molecular formula are Li
1.1Mn
2O
4/ 0.5Al
2O
3
The preparation method of the lithium ion power battery cathode material LiMn2O4 of this Comparative Examples, step is as follows:
1) according to lithium: manganese mol ratio 1.1:2.0 takes by weighing lithium nitrate, manganese nitrate, mixes and with 400r/min ball milling 6h;
2) presoma with the step 1) ball milling carries out high-temperature roasting, and 500 ℃ of insulation 10h are warming up to 850 ℃ of insulation 30h again, and 4 ℃/min of heating rate crosses 300 mesh sieves after the cooling;
3) with step 2) particle after sieving and deionized water add in the reactor according to the ratio of mass ratio 1:5, ultrasonic dispersion and stirring, bath temperature remains on 55 ℃;
4) whipping process adds aluminum nitrate according to LiMn2O4 and aluminum nitrate mol ratio 1:1, and with the ammonia spirit that flow velocity 20rpm pumps into concentration 2mol/L, regulates pH to 9 and stop to add ammoniacal liquor, the lasting 2h that stirs;
5) sediment that step 4) is obtained carries out filtration washing, 100 ℃ of dry 12h;
6) product with drying carries out high-temperature roasting, and 400 ℃ of insulation 5h heat up 900 ℃ again and are incubated 7h, 4 ℃/min of heating rate, and annealing is cooled to 525 ℃, and insulation 2h is down to 330 ℃ of insulation 2h again, crosses 300 mesh sieves after the cooling, obtains lithium ion anode material LiMn2O4 Li
1.1Mn
2O
4/ 0.5Al
2O
3
Lithium ion battery normal temperature and the high temperature circulation curve of the manganic acid lithium electrode material preparation of this Comparative Examples, as shown in Figure 5.
Test to the lithium manganate material electric property of embodiment 1～3 and Comparative Examples preparation
The manganate cathode material for lithium of embodiment 1～3 and Comparative Examples is prepared into 1665132 model lithium-ion-power cells (the lamination soft-package battery of model H16*W65*L132mm), and compacted density is at 3.0g/cm
3More than, volume energy density is more than 370Wh/L; Battery core is under 3.0V-4.2V voltage, more than the 1C discharge gram volume performance 103mAh/g.
Utilize the lithium ion battery of the manganate cathode material for lithium preparation of embodiment 1～3 to have excellent cycle performance, 1C charges and discharge 1500 Capacitance reserves of circulation more than 80% under the normal temperature; Discharge is more than 95% of 1C capacity under the 6C multiplying power; 3C/10V overcharges that test battery is not on fire not to explode; High temperature circulation is excellent, and 55 ℃ of lower 1C charge and discharge 500 Capacitance reserves of circulation more than 80%; Have good security performance, acupuncture, push, overcharge, cross put etc. test do not explode, not on fire.Shown in the concrete measurement result table 1:
The manganate cathode material for lithium of table 1 embodiment 1～3 and Comparative Examples is prepared into the measurement result of battery
| Embodiment | 1C, 1500 times (%) | 6C multiplying power (%) | 3C/10V overcharges test | 55 ℃, 1C, 500 times (%) |
| 1 | 81.59 | 95.2 | Not on firely do not explode | 81.02 |
| 2 | 80.10 | 95.0 | Not on firely do not explode | 81.94 |
| 3 | 80.21 | 95.6 | Not on firely do not explode | 80.16 |
| Comparative Examples | 72.43(1000 inferior) | 94.7 | Not on firely do not explode | 77.37(200 inferior) |
Claims (9)
1. a lithium ion power battery cathode material LiMn2O4 is characterized in that, described LiMn2O4 is the doping tantalum element, and the LiMn2O4 Li of surface-coated aluminum oxide
1+xMn
2-yTa
yO
4/ zAl
2O
3, 0＜x≤0.2,0＜y≤0.2,0＜z≤1.0 wherein.
2. the preparation method of a lithium ion power battery cathode material LiMn2O4 as claimed in claim 1 is characterized in that, step is as follows:
1) according to the mol ratio (1+x) of lithium, manganese, tantalum: (2-y): y takes by weighing respectively Li source compound, manganese source compound, tantalum element additive, mixes and ball milling 5～8h;
2) presoma with the step 1) ball milling carries out high-temperature roasting, and 400～600 ℃ of insulation 10～12h are warming up to 800～900 ℃ of insulation 20～30h again, cross 300 mesh sieves after the cooling;
3) with step 2) particle and dispersant after sieving add in the reactor according to mass ratio 1:5 ~ 8 ratios, ultrasonic dispersion and stirring, bath temperature remains on 50～55 ℃;
4) whipping process adds aluminium salt according to LiMn2O4 and aluminium salt mol ratio 1:2z, regulates pH to 9, continues to stir 2～4h;
5) sediment that step 4) is obtained carries out filtration washing, 100～120 ℃ of drying 12～24h;
6) product with drying carries out high-temperature roasting, 400～600 ℃ of insulation 5～10h, 800～950 ℃ of insulation 5～10h again heat up, 500～550 ℃ of annealing coolings, insulation 2～4h, be down to again 300～350 ℃ of insulation 2～4h, cross 300 mesh sieves after the cooling, obtain lithium ion power battery cathode material LiMn2O4 Li
1+xMn
2-yTa
yO
4/ zAl
2O
3, 0＜x≤0.2,0＜y≤0.2,0＜z≤1.0 wherein.
3. the preparation method of a kind of lithium ion power battery cathode material LiMn2O4 according to claim 2 is characterized in that, described manganese source compound is manganese sulfate, manganese nitrate or manganese acetate.
4. the preparation method of a kind of lithium ion power battery cathode material LiMn2O4 according to claim 2 is characterized in that, described Li source compound is lithium carbonate, lithium nitrate or lithium acetate.
5. the preparation method of a kind of lithium ion power battery cathode material LiMn2O4 according to claim 2 is characterized in that, described tantalum element additive is tantalum pentoxide or nitric acid tantalum.
6. the preparation method of a kind of lithium ion power battery cathode material LiMn2O4 according to claim 2 is characterized in that, the rotating speed of ball milling is 300～400r/min in the described step 1).
7. the preparation method of a kind of lithium ion power battery cathode material LiMn2O4 according to claim 2 is characterized in that, described step 2) and 6) in heating rate be 3～5 ℃/min.
8. the preparation method of a kind of lithium ion power battery cathode material LiMn2O4 according to claim 2 is characterized in that, described dispersant is at least a in deionized water, the absolute ethyl alcohol.
9. the preparation method of a kind of lithium ion power battery cathode material LiMn2O4 according to claim 2 is characterized in that, described aluminium salt is aluminum nitrate, aluminum sulfate or aluminium chloride.
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| CN114433251A (en) * | 2022-01-27 | 2022-05-06 | 浙江大学 | Method for improving mechanical property of low-temperature dioxin degradation catalyst |
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| CN103972495A (en) * | 2014-05-16 | 2014-08-06 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of lithium ion battery positive pole material lithium nickelate manganate |
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| CN104466114A (en) * | 2014-10-17 | 2015-03-25 | 惠州龙为科技有限公司 | Preparation method of high-performance lithium manganite positive material |
| CN104485451A (en) * | 2014-11-10 | 2015-04-01 | 徐茂龙 | Preparation method of carbon nanotube-graphene modified lithium manganate cathode material |
| CN105016394A (en) * | 2015-07-08 | 2015-11-04 | 个旧圣比和实业有限公司 | Method for industrially preparing lithium manganate cathode material for lithium ion batteries |
| CN106898748A (en) * | 2017-03-17 | 2017-06-27 | 成都新柯力化工科技有限公司 | A kind of preparation method of the ternary lithium nickel cobalt manganese battery electrode material of core-shell structure |
| CN110993903B (en) * | 2019-11-13 | 2021-10-12 | 北京理工大学 | Tantalum modified high-nickel cathode material and preparation method and application thereof |
| CN114433251A (en) * | 2022-01-27 | 2022-05-06 | 浙江大学 | Method for improving mechanical property of low-temperature dioxin degradation catalyst |
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