CN102931392B - 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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- CN102931392B CN102931392B CN201210436509.1A CN201210436509A CN102931392B CN 102931392 B CN102931392 B CN 102931392B CN 201210436509 A CN201210436509 A CN 201210436509A CN 102931392 B CN102931392 B CN 102931392B
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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 19
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000010405 anode material Substances 0.000 title abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 18
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 47
- 238000009413 insulation Methods 0.000 claims description 38
- 239000010406 cathode material Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 159000000013 aluminium salts Chemical class 0.000 claims description 8
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 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
- NQGWALHZCVFGRE-UHFFFAOYSA-N [Ta].[N+](=O)(O)[O-] Chemical compound [Ta].[N+](=O)(O)[O-] NQGWALHZCVFGRE-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 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
- 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 4
- 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 4
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 230000007547 defect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000007873 sieving 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
- 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
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 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
- 238000001467 acupuncture Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 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
- 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
Classifications
-
- 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
Landscapes
- 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 its preparation method simultaneously, belong to 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 the development of particularly dynamic lithium battery comes into one's own day by day, be wherein especially applied as the electrical source of power field of representative with electric motor car with the fastest developing speed.And the alternative condition of the positive electrode of high-power lithium ion power battery is harsh, the positive electrode of traditional small-scale lithium ion cell can not meet the demand of electrokinetic cell.In current commercial lithium-ion batteries, cobalt acid lithium is still in occupation of larger share, especially in the communication apparatus such as portable computer, proportion is larger, but the character intrinsic due to itself limit, for the restriction that large current density requires, also just determine cobalt acid lithium and will certainly reduce even to be substituted for the proportion in electrokinetic cell.And ternary material and lithium iron phosphate positive material are also because inherently safe performance and energy density problem are hindered being applied to lithium-ion-power cell field.
The LiMn2O4 LiMn of spinel-type
2o
4have stable three-dimensional lithium ion tunnel structure, in charge and discharge process, potential safety hazard is lower, and charge and discharge voltage is high, and energy density is large, is suitable for high-multiplying power discharge.And updating in recent years along with material and battery production technology, the cycle performance tool of LiMn2O4 is significantly improved, and normal temperature can reach more than 1000 times charge and discharges 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, is also the anode material of lithium battery as being hopeful most to apply on high-power power battery.But the defects such as the dissolving of the manganese of LiMn2O4 self, John-Teller effect and material processing cause the problems such as material tap density is less, oxygen defect degree is higher to cause material electric property to reduce, and seriously constrain LiMn
2o
4as the application of positive electrode.
Summary of the invention
The object of this invention is to provide a kind of lithium ion power battery cathode material LiMn2O4.
In order to realize above object, the technical solution adopted in the present invention is to provide a kind of lithium ion power battery cathode material LiMn2O4, and described LiMn2O4 is doping tantalum element, and the LiMn2O4 Li of surface-coated aluminum oxide
1+xmn
2-yta
yo
4/ zAl
2o
3, wherein 0 < x≤0.2,0 < y≤0.2,0 < z≤1.0.
The present invention also aims to the preparation method that a kind of lithium ion power battery cathode material LiMn2O4 is provided.
The technical solution adopted in the present invention is also the preparation method providing a kind 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 Li source compound, manganese source compound, tantalum element additive respectively, mix and ball milling 5 ~ 8h;
2) presoma of step 1) ball milling is carried out high-temperature roasting, 400 ~ 600 DEG C of insulation 10 ~ 12h, then be warming up to 800 ~ 900 DEG C of insulation 20 ~ 30h, after cooling, cross 300 mesh sieves;
3) by step 2) sieve after particle and dispersant add in reactor according to mass ratio 1:5 ~ 8 ratio, ultrasonic disperse also stirs, and bath temperature remains on 50 ~ 55 DEG C;
4) whipping process adds aluminium salt according to LiMn2O4 and aluminium salt mol ratio 1:2z, regulates pH to 9, Keep agitation 2 ~ 4h;
5) sediment step 4) obtained carries out filtration washing, 100 ~ 120 DEG C of drying 12 ~ 24h;
6) product of drying is carried out high-temperature roasting, 400 ~ 600 DEG C of insulation 5 ~ 10h, heat up 800 ~ 950 DEG C of insulation 5 ~ 10h again, annealing cooling 500 ~ 550 DEG C, insulation 2 ~ 4h, be down to 300 ~ 350 DEG C of insulation 2 ~ 4h again, cross 300 mesh sieves after cooling, obtain lithium ion power battery cathode material LiMn2O4 Li
1+xmn
2-yta
yo
4/ zAl
2o
3, wherein 0 < x≤0.2,0 < y≤0.2,0 < z≤1.0.
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.
In described step 1), the rotating speed of ball milling is 300 ~ 400r/min.
Described step 2) and 6) in heating rate be 3 ~ 5 DEG C/min.
Described dispersant is at least one in deionized water, absolute ethyl alcohol.
Described aluminium salt is aluminum nitrate, aluminum sulfate or aluminium chloride.
The present invention adopts composition metal codope mechanism, LiMn2O4 is carried out to the doping vario-property of tantalum (Ta), lithium (Li) two element: Ta5+ has larger ionic radius, the lattice parameter of spinel structure can be improved, promote the raising of lithium ion diffusion coefficient; The M-O key of Simultaneous Stabilization can improve the stability of LiMn2O4 frame structure.Adopt the Li+ of lower valency doping can improve the average valence of Mn, suppress J-T effect.Composite mixed ion occupies the 16d position of Mn, greatly improves the cycle performance of lithium manganate material.
The present invention takes ultrasonic nonhomogen-ous nucleation method to carry out LiMn2O4 coating modification, by adopting lithium manganate particle as nucleus matrix, control coating precipitation reaction concentration, ultrasonic wave dispersion simultaneously, the coating of precipitation is made to be that nano particle is dispersed, uniform particles is adsorbed on lithium manganate particle surface, by controlling sintering temperature and time, to obtain the lithium manganate gradient functional 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 segmented baking modes, and temperature-rise period slowly carries out, and doped chemical penetrates in lattice.Carry out two-stage roasting double annealing, roasting first carries out phase decomposition simultaneously, obtains pure phase coating layer, then improves temperature, makes coating layer form fine and close core-shell structure; Annealing first slows down the generation of coated internal stress defect; Finally make to pile up between crystal grain intensive in order, form 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 the oxygen defect degree in material sintering simultaneously.
The lithium manganate material electrical property that the present invention prepares and life-span are improved, and have good using value.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 manganic acid lithium electrode material;
Fig. 2 is the lithium ion battery normal temperature and high temperature circulation curve that adopt embodiment 1 manganic acid lithium electrode material to prepare;
Fig. 3 is the lithium ion battery normal temperature and high temperature circulation curve that adopt embodiment 2 manganic acid lithium electrode material to prepare;
Fig. 4 is the lithium ion battery normal temperature and high temperature circulation curve that adopt embodiment 3 manganic acid lithium electrode material to prepare;
Fig. 5 is the lithium ion battery normal temperature and high temperature circulation curve that adopt comparative example manganic acid lithium electrode material to prepare.
Embodiment
Embodiment 1
The lithium ion power battery cathode material LiMn2O4 of the present embodiment, molecular formula is 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 the present embodiment, step is as follows:
1) according to lithium: manganese: tantalum mol ratio 1.05:1.9:0.1 takes lithium carbonate, manganese sulfate, tantalum pentoxide, to mix and with 300r/min ball milling 5h;
2) presoma of step 1) ball milling is carried out high-temperature roasting, 600 DEG C of insulation 10h, then be warming up to 800 DEG C of insulations 20h, heating rate 3 DEG C/min, after cooling, cross 300 mesh sieves;
3) by step 2) sieve after particle and deionized water add in reactor according to the ratio of mass ratio 1:5, ultrasonic disperse also stirs, and bath temperature remains on 50 DEG C;
4) whipping process adds aluminum nitrate according to LiMn2O4 and aluminum nitrate mol ratio 1:1, and pumps into the ammonia spirit of concentration 1mol/L with flow velocity 25rpm, regulates pH to 9 to stop adding ammoniacal liquor, Keep agitation 2h;
5) sediment step 4) obtained carries out filtration washing, 100 DEG C of dry 12h;
6) product of drying is carried out high-temperature roasting, 600 DEG C of insulation 10h, then heat up 800 DEG C and be incubated 10h, heating rate 3 DEG C/min, annealing is cooled to 500 DEG C, insulation 2h, be down to 300 DEG C of insulation 2h again, cross 300 mesh sieves after 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 the present embodiment, as shown in Figure 1.
Lithium ion battery normal temperature prepared by the manganic acid lithium electrode material of the present embodiment and high temperature circulation curve, as shown in Figure 2.
Embodiment 2
The lithium ion power battery cathode material LiMn2O4 of the present embodiment, molecular formula is 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 the present embodiment, step is as follows:
1) according to lithium: manganese: tantalum mol ratio 1.1:1.8:0.2 takes lithium nitrate, manganese nitrate and nitric acid tantalum, to mix and with 400r/min ball milling 6h;
2) presoma of step 1) ball milling is carried out high-temperature roasting, 500 DEG C of insulation 11h, then be warming up to 850 DEG C of insulations 30h, heating rate 4 DEG C/min, after cooling, cross 300 mesh sieves;
3) by step 2) sieve after particle and absolute ethyl alcohol add in reactor according to the ratio of mass ratio 1:6.5, ultrasonic disperse also stirs, and bath temperature remains on 55 DEG C;
4) whipping process adds aluminium chloride according to LiMn2O4 and aluminium chloride mol ratio 1:2, and pumps into the ammonia spirit of concentration 2mol/L with flow velocity 20rpm, regulates pH to 9 to stop adding ammoniacal liquor, Keep agitation 3h;
5) sediment step 4) obtained carries out filtration washing, 110 DEG C of dry 24h;
6) product of drying is carried out high-temperature roasting, 400 DEG C of insulation 5h, then heat up 875 DEG C and be incubated 7h, heating rate 4 DEG C/min, annealing is cooled to 525 DEG C, insulation 3h, be down to 330 DEG C of insulation 4h again, cross 300 mesh sieves after 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 prepared by the manganic acid lithium electrode material of the present embodiment and high temperature circulation curve, as shown in Figure 3.
Embodiment 3
The lithium ion power battery cathode material LiMn2O4 of the present embodiment, molecular formula is 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 the present embodiment, step is as follows:
1) according to lithium: manganese: tantalum mol ratio 1.2:1.95:0.05 takes lithium acetate, manganese acetate, nitric acid tantalum, to mix and with 350r/min ball milling 8h;
2) presoma of step 1) ball milling is carried out high-temperature roasting, 400 DEG C of insulation 12h, then be warming up to 900 DEG C of insulations 25h, heating rate 5 DEG C/min, after cooling, cross 300 mesh sieves;
3) by step 2) sieve after particle and the mixed solution of deionized water and absolute ethyl alcohol add in reactor according to the ratio of mass ratio 1:8, ultrasonic disperse also stirs, and bath temperature remains on 53 DEG C;
4) whipping process adds aluminum sulfate according to LiMn2O4 and aluminum sulfate mol ratio 1:0.2, and pumps into the ammonia spirit of concentration 3mol/L with flow velocity 23rpm, regulates pH to 9 to stop adding ammoniacal liquor, Keep agitation 4h;
5) sediment step 4) obtained carries out filtration washing, 120 DEG C of dry 18h;
6) product of drying is carried out high-temperature roasting, 500 DEG C of insulation 8h, then heat up 950 DEG C and be incubated 5h, heating rate 5 DEG C/min, annealing is cooled to 550 DEG C, insulation 4h, be down to 350 DEG C of insulation 3h again, cross 300 mesh sieves after 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 prepared by the manganic acid lithium electrode material of the present embodiment and high temperature circulation curve, as shown in Figure 4.
Comparative example
The lithium ion power battery cathode material LiMn2O4 of this comparative example, its molecular formula is Li
1.1mn
2o
4/ 0.5Al
2o
3.
The preparation method of the lithium ion power battery cathode material LiMn2O4 of this comparative example, step is as follows:
1) according to lithium: manganese mol ratio 1.1:2.0 takes lithium nitrate, manganese nitrate, to mix and with 400r/min ball milling 6h;
2) presoma of step 1) ball milling is carried out high-temperature roasting, 500 DEG C of insulation 10h, then be warming up to 850 DEG C of insulations 30h, heating rate 4 DEG C/min, after cooling, cross 300 mesh sieves;
3) by step 2) sieve after particle and deionized water add in reactor according to the ratio of mass ratio 1:5, ultrasonic disperse also stirs, and bath temperature remains on 55 DEG C;
4) whipping process adds aluminum nitrate according to LiMn2O4 and aluminum nitrate mol ratio 1:1, and pumps into the ammonia spirit of concentration 2mol/L with flow velocity 20rpm, regulates pH to 9 to stop adding ammoniacal liquor, Keep agitation 2h;
5) sediment step 4) obtained carries out filtration washing, 100 DEG C of dry 12h;
6) product of drying is carried out high-temperature roasting, 400 DEG C of insulation 5h, then heat up 900 DEG C and be incubated 7h, heating rate 4 DEG C/min, annealing is cooled to 525 DEG C, insulation 2h, then is down to 330 DEG C of insulation 2h, crosses 300 mesh sieves, obtain lithium ion anode material LiMn2O4 Li after cooling
1.1mn
2o
4/ 0.5Al
2o
3.
Lithium ion battery normal temperature prepared by the manganic acid lithium electrode material of this comparative example and high temperature circulation curve, as shown in Figure 5.
To the test of lithium manganate material electric property prepared by embodiment 1 ~ 3 and comparative example
The manganate cathode material for lithium of embodiment 1 ~ 3 and comparative example 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
3above, volume energy density is at more than 370Wh/L; Battery core is under 3.0V-4.2V voltage, and 1C electric discharge gram volume plays more than 103mAh/g.
The lithium ion battery utilizing the manganate cathode material for lithium of embodiment 1 ~ 3 to prepare has excellent cycle performance, and under normal temperature, 1C charge and discharge 1500 capacity that circulate remain on more than 80%; Under 6C multiplying power, electric discharge is more than 95% of 1C capacity; 3C/10V overcharges that test battery is not on fire not to explode; High temperature circulation is excellent, and at 55 DEG C, 1C charge and discharge 500 capacity that circulate remain on more than 80%; There is good security performance, acupuncture, extrude, overcharge, cross to put etc. test do not explode, not on fire.Shown in concrete measurement result table 1:
The manganate cathode material for lithium of table 1 embodiment 1 ~ 3 and comparative example is prepared into the measurement result of battery
| Embodiment | 1C, 1500 times (%) | 6C multiplying power (%) | 3C/10V overcharges test | 55 DEG C, 1C, 500 times (%) |
| 1 | 81.59 | 95.2 | Not on firely not explode | 81.02 |
| 2 | 80.10 | 95.0 | Not on firely not explode | 81.94 |
| 3 | 80.21 | 95.6 | Not on firely not explode | 80.16 |
| Comparative example | 72.43(1000 secondary) | 94.7 | Not on firely not explode | 77.37(200 secondary) |
Claims (8)
1. a lithium ion power battery cathode material LiMn2O4, is characterized in that, described LiMn2O4 is doping tantalum element, and the LiMn2O4 Li of surface-coated aluminum oxide
1+xmn
2-yta
yo
4/ zAl
2o
3, wherein 0 < x≤0.2,0 < y≤0.2,0 < z≤1.0;
The operating procedure of its preparation method is: 1) according to the mol ratio (1+x) of lithium, manganese, tantalum: (2-y): y takes Li source compound, manganese source compound, tantalum element additive respectively, mixes and ball milling 5 ~ 8h;
2) presoma of step 1) ball milling is carried out high-temperature roasting, wherein high-temperature roasting refers to 400 ~ 600 DEG C of insulation 10 ~ 12h, then is warming up to 800 ~ 900 DEG C of insulation 20 ~ 30h, crosses 300 mesh sieves after cooling;
3) by step 2) sieve after particle and dispersant add in reactor according to mass ratio 1:5 ~ 8 ratio, ultrasonic disperse also stirs, and bath temperature remains on 50 ~ 55 DEG C;
4) whipping process adds aluminium salt according to LiMn2O4 and aluminium salt mol ratio 1:2z, regulates pH to 9, Keep agitation 2 ~ 4h;
5) sediment step 4) obtained carries out filtration washing, 100 ~ 120 DEG C of drying 12 ~ 24h;
6) product of drying is carried out high-temperature roasting, wherein high-temperature roasting refers to 400 ~ 600 DEG C of insulation 5 ~ 10h, heat up 800 ~ 950 DEG C of insulation 5 ~ 10h again, annealing cooling 500 ~ 550 DEG C, insulation 2 ~ 4h, be down to 300 ~ 350 DEG C of insulation 2 ~ 4h again, cross 300 mesh sieves after cooling, obtain lithium ion power battery cathode material LiMn2O4 Li
1+xmn
2-yta
yo
4/ zAl
2o
3, wherein 0 < x≤0.2,0 < y≤0.2,0 < z≤1.0;
Described tantalum element additive is tantalum pentoxide or nitric acid tantalum.
2. a preparation method for lithium ion power battery cathode material LiMn2O4 as claimed in claim 1, it is characterized in that, step is as follows:
1) according to the mol ratio (1+x) of lithium, manganese, tantalum: (2-y): y takes Li source compound, manganese source compound, tantalum element additive respectively, mix and ball milling 5 ~ 8h;
2) presoma of step 1) ball milling is carried out high-temperature roasting, 400 ~ 600 DEG C of insulation 10 ~ 12h, then be warming up to 800 ~ 900 DEG C of insulation 20 ~ 30h, after cooling, cross 300 mesh sieves;
3) by step 2) sieve after particle and dispersant add in reactor according to mass ratio 1:5 ~ 8 ratio, ultrasonic disperse also stirs, and bath temperature remains on 50 ~ 55 DEG C;
4) whipping process adds aluminium salt according to LiMn2O4 and aluminium salt mol ratio 1:2z, regulates pH to 9, Keep agitation 2 ~ 4h;
5) sediment step 4) obtained carries out filtration washing, 100 ~ 120 DEG C of drying 12 ~ 24h;
6) product of drying is carried out high-temperature roasting, 400 ~ 600 DEG C of insulation 5 ~ 10h, heat up 800 ~ 950 DEG C of insulation 5 ~ 10h again, annealing cooling 500 ~ 550 DEG C, insulation 2 ~ 4h, be down to 300 ~ 350 DEG C of insulation 2 ~ 4h again, cross 300 mesh sieves after cooling, obtain lithium ion power battery cathode material LiMn2O4 Li
1+xmn
2-yta
yo
4/ zAl
2o
3, wherein 0 < x≤0.2,0 < y≤0.2,0 < z≤1.0;
Described tantalum element additive is tantalum pentoxide or nitric acid tantalum.
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, in described step 1), the rotating speed of ball milling is 300 ~ 400r/min.
6. 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 DEG C/min.
7. 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 one in deionized water, absolute ethyl alcohol.
8. 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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