CN102219262B - Improved method for preparing layered enriched lithium-manganese-nickel oxide by low-heat solid-phase reaction - Google Patents
Improved method for preparing layered enriched lithium-manganese-nickel oxide by low-heat solid-phase reaction Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 13
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims abstract description 13
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 14
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims description 13
- 206010037660 Pyrexia Diseases 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000011029 spinel Substances 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 36
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 229940071125 manganese acetate Drugs 0.000 abstract 1
- 238000003801 milling Methods 0.000 abstract 1
- 229940078494 nickel acetate Drugs 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000010406 cathode material Substances 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
- 238000009841 combustion method Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 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
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
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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 provides an improved method for preparing layered enriched lithium-manganese-nickel oxide by low-heat solid-phase reaction. The method comprises the following steps: weighing lithium hydroxide monohydrate, nickel acetate and manganese acetate, and oxalic acid dihydrate according to the stoichiometry as follows: Li1+xMnyNi1-x-yO2, x being more than 0 and less than or equal to 1/3, y being more than 0 and less than 1, and x+y being more than 0 and less than 1 (wherein the mole ratio of LiOH.H2O to C2H2O4.2H2O is 1:1-1.2), and adding into a ball milling tank together for balling milling for 0.5-2h; obtaining slurry, adding deionized water in the slurry to adjust concentration, spraying and drying the slurry, and roasting the dried powder to obtain the final product -Li1+xMnyNil-x-yO2. The improved method has the following advantages: the process flow is short, the component of the material can be accurately controlled, the problems of material loss and inaccurate stoichiometry caused by repeatedly washing the product in a liquid phase method are overcome, the generation of a large quantity of waste water is avoided; simultaneously, the shape and particle size of a synthesized material can be controlled, the engineering index requirement can be achieved, the impurity pollution caused by dependence of a synthetic material by a solid phase method on crushing process can be overcome, the enriched lithium-manganese-nickel oxide has typical layered structure property, the particle size is 3-12mum, the specific capacity is high, and the cyclic performance is stable.
Description
Technical field
The invention belongs to the anode material for lithium-ion batteries preparing technical field, be specifically related to the method that a kind of improved low fever solid phase reaction prepares the rich lithium nickel manganese oxide material of stratiform.
Background technology
But the outstanding advantages such as lithium ion battery has the operating voltage height, energy density is large, specific storage is high, operating temperature range is wide, self-discharge is little, have extended cycle life, memory-less effect fast charging and discharging and non-environmental-pollution are the ideal sources of the electronic installation miniaturization ands such as pick up camera, mobile telephone, notebook computer, portable tester.Simultaneously, lithium ion battery also will become desirable used for electric vehicle light high-energy propulsion source and accumulation power supply safely and efficiently.Applying of the especially large-scale lithium ion battery of lithium ion battery proposed harsher requirement to the consistence of battery core and security and price, wherein reduce critical material raw materials cost, simplify preparation technology, stably manufactured is particularly important in batches.
In the lithium-ion energy storage battery positive electrode material, the rich lithium nickel manganese oxide Li of stratiform
1+xMn
yNi
1-x-yO
2The theoretical specific capacity of (wherein 0≤x≤1/3,0≤y≤1,0≤x+y≤1) is spinel LiMn up to 380mAh/g
2O
4The LiFePO of theoretical capacity (148mAh/g) or olivine structural
4The twice of material (theoretical capacity 170mAh/g) is many; The rich lithium nickel manganese oxide actual specific capacity of stratiform also can reach 200～250mAh/g, is higher than the LiCoO of laminate structure far away
2Actual specific capacity (140mAh/g); And the main raw material reserves of rich lithium nickel manganese oxide are abundant, and material possesses price advantage, so Li
1+xMn
yNi
1-x-yO
2Design and use be expected to realize stored energy and the lower cost $/Wh of conversion.
It is existing open as the research of anode material for lithium-ion batteries to have the rich lithium nickel manganese oxide of laminate structure.Ilion has proposed the employing liquid phase method and has synthesized material Li in patent EP1189296A2
1+x(Mn
1-uNi
u)
1-yCo
yO
2(u ≈ 0.5, y＜1/3, x〉0).The patent ZL200610114206.2 of this group of applicant has proposed the synthetic material Li[Ni that prepared of liquid-phase coprecipitation
xLi
1/3-2x/3Mn
2/3-x/3] O
2(0＜x≤1/4).People (Yong Joon Park, Young-Sik Hong, xianglan Wu, et al, the structural investigation and electrochemical behavior of Li[Ni such as Yong Joon Park
xLi
1/3-2x/3Mn
2/3-x/3] O
2Compounds by a simple combustion method, Journal of Power Sources, 129 (2004): 288-295) adopt combustion synthesis method to prepare Li[Ni
xLi
1/3-2x/3Mn
2/3-x/3] O
2The Ni, Mn oxide electrode materials of the rich lithium of stratiform.J.-H. people (J.-H. Kim, Y. – K. Sun, the Electrochemical performance of Li[Ni such as Kim
xLi
1/3-2x/3Mn
2/3-x/3] O
2Cathode materials synthesized by a sol-gel method, Journal of Power Sources, 119-121 (2003): 166-170) adopt sol-gel method to synthesize the Ni, Mn oxide electrode materials of the rich lithium of stratiform.
What the rich lithium nickel manganese oxide of preparation generally adopted at present is coprecipitation method, has the advantage that multicomponent mixture is even, size distribution is controlled.But, in order to remove foreign ion such as the Na in the reaction system
+, SO
4 2-And Cl
-, need co-precipitation material repetitive scrubbing has been caused the loss of material, thereby cause the stoichiometry of material accurately to control.Simultaneously produced a large amount of waste water in the production process, limited the scale production of material and promote the use of.The low fever solid phase reaction method that immediate development is got up has effectively shortened the material preparation flow process, and synthesis temperature obviously reduces than traditional solid phase method, and patent ZL200510011676.1 discloses the method for utilizing low fever solid phase reaction to prepare laminar oxide material of lithium, cobalt, nickel and manganese; Patent ZL200510086505.5 discloses and has adopted low fever solid phase reaction to prepare the method for Li, Ni, Mn oxide material.The synthetic initial stage material of low-temperature solid-phase method is that the form with slurry exists, and must carry out drying treatment before roasting.Carry out dry process at slurry, material is exposed in the air for a long time, Mn occurs
2+Oxidation in various degree causes impurity phase occurring in the final synthetic product, has affected the chemical property of material.Especially drying material is prone to and hardens, and follow-uply need to carry out long-time ball milling reaching granularity requirements to material, and the microstructure of material and size-grade distribution can't effectively be controlled, and can bring metallic impurity into to material system at mechanical milling process simultaneously.Adopt vacuum-drying can solve the problem that traditional drying is brought the transition metal ion oxidation, but the high about 30% pair of vacuum apparatus damage of paste materials water content is larger, and the initial stage slurry that low-temperature solid-phase method makes carries out vacuum-drying, and not only efficient is low but also greatly reduce work-ing life of vacuum apparatus.
Summary of the invention
The object of the present invention is to provide a kind of method that low fever solid phase reaction prepares the rich lithium nickel manganese oxide material of stratiform of improving, preparation flow is simplified, and the characteristics of the initial stage slurry that makes for low fever solid phase reaction, improve technological process, solve the microstructure of material and the problem that size-grade distribution can't effectively be controlled, synthetic granularity reaches the material with typical layered structure feature of through engineering approaches index request.
Technical scheme of the present invention is: a kind of improved low fever solid phase reaction prepares the method for the rich lithium nickel manganese oxide of stratiform, may further comprise the steps:
(a) according to Li
1+xMn
yNi
1-x-yO
2, the stoichiometry of 0＜x≤1/3,0＜y＜1,0＜x+y＜1 takes by weighing Lithium Hydroxide Monohydrate, and nickelous acetate and manganous acetate take by weighing oxalic acid dihydrate again, add simultaneously in the ball grinder, carry out 0.5～2 h ball milling, obtain slurries; Wherein, LiOHH
2O:C
2H
2O
42H
2The O mol ratio is 1:1～1.2;
(b) slurry that obtains adds a small amount of deionized water, and concentration adjustment is 200～300g/l, carries out spraying drying, and the temperature of convection cell heating is controlled in 110～130 ℃ of scopes, obtains dry powder;
(c) with powder 400～550 ℃ of roastings 3～6 hours, the corundum sagger of packing into behind the ball milling is warming up to 600～850 ℃ of roastings 8～15 hours after pressing alms bowl, obtains having higher flowability, size composition is controlled at the Li of 3～12 μ m
1+xMn
yNi
1-x-yO
2Powder, and the Li of preparation
1+xMn
yNi
1-x-yO
2The principal crystalline phase of powder is stratiform petrofacies R-3m, accounts for more than 90%, and other crystalline phases are less than 10%.
Described other crystalline phases comprise oblique system C2/m phase, spinel Fd-3m phase and cube Fm-3m phase.
Advantage of the present invention:
1, simplifies the process of the synthetic multicomponent mixture slurry of low fever solid phase reaction, improved reaction efficiency.Patent ZL200510011676.1 adopt two-step approach namely at first the lithium source mixes the short period of time stirring with oxalic acid (citric acid or sugar), again ball milling is carried out in the transition metal ion acetate adding of premix.The present invention is on the basis of the experimental study of constantly improving the molten reaction mechanism of cold cut, and process simplification adds the material of in proportion weighing together, at the reactant particle (such as LiOHH
2O and C
2H
2O
42H
2O) under the effect by applied external force-ball milling crystal water is discharged, form the cold cut crucible zone on the surface, simultaneously, reactant molecule (such as nickelous acetate and manganous acetate) spreads in the cold cut crucible zone and in this little reaction zone chemical reaction occurs, compare the operating process of not only having simplified synthesis technique with two-step approach, and accelerated cold cut molten-diffusion-reaction-nucleation-process of growth, improved reaction efficiency.
2, the synthetic Li of the present invention
1+xMn
yNi
1-x-yO
2Material has typical laminate structure feature, and wherein stratiform petrofacies R-3m accounts for more than 90%, the oblique system C2/m phase that other are prone in synthetic rich lithium nickel manganese oxide materials process, and spinel Fd-3m phase and cube Fm-3m are less than 10% mutually.The present invention cooperates by low fever solid phase reaction and the spray-dired technique of slurry, can accurately control the component of material, has overcome the material unaccounted-for (MUF) that the resultant repetitive scrubbing causes in the liquid phase method and the serious problem of oxidation, has accurately controlled the stoichiometric ratio of material.Simultaneously for the oblique system C2/m phase that is prone in the rich lithium nickel manganese oxide material building-up process, the experiment conclusion of spinel Fd-3m phase and cube Fm-3m phase, the present invention combines the double roasting of above technique with material, prolong the diffusion time of metallic cation, reduce textural defect, synthesized desirable layer structure material, the ratio of other constitutional features microcells is very little.
3, the synthetic rich lithium nickel manganese oxide Li of the present invention
1+xMn
yNi
1-x-yO
2Powder has higher flowability, and size composition is controlled at 3～12 μ m, has overcome the contaminating impurity problem that changes powder size and bring of pulverizing that relies on.The present invention plays the effect of preliminary granulation with spraying drying to the powder of material, improves bonding strength and the density of second particle by re-baking, is conducive to finishing smoothly of the operations such as slurrying in the electrodes of lithium-ion batteries production process, coating.
Description of drawings
Fig. 1 is the microstructure figure that obtains powder after the initial stage slurry spraying drying of embodiment 1 preparation.
Fig. 2 is that comparative example prepares the microstructure figure that obtains powder after the slurry vacuum-drying.
Fig. 3 is the Li of embodiment 1 preparation
1.2Mn
0.6Ni
0.2O
2(Li
1+xMn
yNi
1-x-yO
2,Wherein x=0.2, y=0.6) the microstructure figure of powder.
Fig. 4 is the Li of embodiment 1 preparation
1.2Mn
0.6Ni
0.2O
2The cycle performance figure (charging and discharging currents 100mA/g, charging/discharging voltage scope 2.5-4.8V) of the half-cell that forms.
Fig. 5 is the Li of embodiment 2 preparations
1.3Mn
0.01Ni
0.69O
2(Li
1+xMn
yNi
1-x-yO
2,Wherein x=0.3, y=0.01) microstructure figure.
Fig. 6 is the Li of embodiment 3 preparations
1.11Mn
0.56Ni
0.33O
2(Li
1+xMn
yNi
1-x-yO
2,Wherein x=0.11, y=0.56) X-ray diffractogram and structure refinement result.
Fig. 7 is the Li of embodiment 4 preparations
1.13Mn
0.57Ni
0.3O
2(Li
1+xMn
yNi
1-x-yO
2,Wherein x=0.13, y=0.57) half-cell that forms first with charging and discharging capacity-voltage curve second time (charging and discharging currents 100mA/g, charging/discharging voltage scope 2.5-4.8V).
Embodiment
For a more detailed description to the present invention below in conjunction with example, but be not limited to the following example.
Embodiment 1:
1) with Lithium Hydroxide Monohydrate LiOHH
2O, oxalic acid dihydrate C
2H
2O
42H
2O and nickelous acetate and manganous acetate join in the ball grinder simultaneously, wherein LiOHH
2O:C
2H
2O
42H
2The mol ratio of O is 1:1, and the mol ratio of Lithium Hydroxide Monohydrate and manganous acetate and nickelous acetate is 1.2:0.6:0.2, ball milling mixing 1h;
2) slurry that obtains adds deionized water, and concentration adjustment is 280g/l, carries out spraying drying, and the temperature of convection cell heating is controlled at 120 ℃, obtains dry powder;
3) with powder 450 ℃ of roastings 3 hours, the corundum sagger of packing into behind the ball milling is warming up to 600 ℃ of roastings 12 hours after pressing alms bowl, obtains higher flowability, size composition is controlled at the rich lithium nickel manganese oxide Li of stratiform of 3～8.5 μ m
1.2Mn
0.6Ni
0.2O
2(Li
1+xMn
yNi
1-x-yO
2,Wherein x=0.2, y=0.6).
Embodiment 2:
1) with Lithium Hydroxide Monohydrate LiOHH
2O, oxalic acid dihydrate C
2H
2O
42H
2O and nickelous acetate and manganous acetate join in the ball grinder simultaneously, wherein LiOHH
2O:C
2H
2O
42H
2The mol ratio of O is 1:1.2, and the mol ratio of Lithium Hydroxide Monohydrate and manganous acetate and nickelous acetate is 1.3:0.01:0.69, ball milling mixing 0.8h;
2) slurry that obtains adds deionized water, and concentration adjustment is 250g/l, carries out spraying drying, and the temperature of convection cell heating is controlled at 115 ℃, obtains dry powder;
3) with powder 500 ℃ of roastings 6 hours, the corundum sagger of packing into behind the ball milling is warming up to 750 ℃ of roastings 15 hours after pressing alms bowl, obtains higher flowability, size composition is controlled at the rich lithium nickel manganese oxide Li of stratiform of 4～12 μ m
1.3Mn
0.01Ni
0.69O
2(Li
1+xMn
yNi
1-x-yO
2,Wherein x=0.3, y=0.01).
Embodiment 3:
1) with Lithium Hydroxide Monohydrate LiOHH
2O, oxalic acid dihydrate C
2H
2O
42H
2O and nickelous acetate and manganous acetate join in the ball grinder simultaneously, wherein LiOHH
2O:C
2H
2O
42H
2The mol ratio of O is 1:1.15, and the mol ratio of Lithium Hydroxide Monohydrate and manganous acetate and nickelous acetate is 1.11:0.56:0.33, ball milling mixing 2h;
2) slurry that obtains adds deionized water, and concentration adjustment is 220g/l, carries out spraying drying, and the temperature of convection cell heating is controlled in 110 ℃ of scopes, obtains dry powder;
3) with powder 480 ℃ of roastings 4 hours, the corundum sagger of packing into behind the ball milling is warming up to 850 ℃ of roastings 13 hours after pressing alms bowl, obtains higher flowability, size composition is controlled at the rich lithium nickel manganese oxide Li of stratiform of 3～10 μ m
1.11Mn
0.56Ni
0.33O
2(Li
1+xMn
yNi
1-x-yO
2,Wherein x=0.11, y=0.56).
Embodiment 4:
1) with Lithium Hydroxide Monohydrate LiOHH
2O, oxalic acid dihydrate C
2H
2O
42H
2O and nickelous acetate and manganous acetate join in the ball grinder simultaneously, wherein LiOHH
2O:C
2H
2O
42H
2The mol ratio of O is 1:1.1, and the mol ratio of Lithium Hydroxide Monohydrate and manganous acetate and nickelous acetate is 1.13:0.57:0.30, ball milling mixing 1.5h;
2) slurry that obtains adds deionized water, and concentration adjustment is 200g/l, carries out spraying drying, and the temperature of convection cell heating is controlled in 130 ℃ of scopes, obtains dry powder;
3) with powder 550 ℃ of roastings 5 hours, the corundum sagger of packing into behind the ball milling is warming up to 800 ℃ of roastings 15 hours after pressing alms bowl, obtains higher flowability, size composition is controlled at the Li of 3～12 μ m
1.13Mn
0.57Ni
0.3O
2(Li
1+xMn
yNi
1-x-yO
2,Wherein x=0.13, y=0.57).
Comparative example:
1) with LiOHH
2O:C
2H
2O
42H
2The mol ratio of O is that the ratio of 1:1 joins in the homogenizer and to mix 2 minutes, is that the ratio of 1.2:0.6:0.2 joins in the ball grinder ball milling mixing 1h with manganous acetate and nickelous acetate according to the mol ratio of Lithium Hydroxide Monohydrate and manganous acetate and nickelous acetate again.
2) the slurry vacuum-drying that obtains obtains dry powder behind the ball milling.
Powder was obtained final product Li in 12 hours 850 ℃ of roastings
1.2Mn
0.6Ni
0.2O
2(Li
1+xMn
yNi
1-x-yO
2,Wherein x=0.2, y=0.6).
Claims (1)
1. an improved low fever solid phase reaction prepares the method for the rich lithium nickel manganese oxide of stratiform, it is characterized in that, specifically may further comprise the steps:
Step 1: according to Li
1+xMn
yNi
1-x-yO
2, 0＜x≤1/3,0＜y＜1,0＜x+y＜1 wherein, stoichiometry take by weighing Lithium Hydroxide Monohydrate, nickelous acetate and manganous acetate take by weighing oxalic acid dihydrate again, add simultaneously in the ball grinder, carry out 0.5～2 h ball milling, obtain slurry, and be for subsequent use; Wherein, LiOHH
2O:C
2H
2O
42H
2The O mol ratio is 1:1～1.2;
Step 2: the slurry that step 1 is obtained adds a small amount of deionized water, and concentration adjustment is 200～300g/l, carries out spraying drying, and the temperature of convection cell heating is controlled in 110～130 ℃ of scopes, obtains dry powder;
Step 3: step 2 is obtained powder 400～550 ℃ of roastings 3～6 hours, and the corundum sagger of packing into behind the ball milling is warming up to 600～850 ℃ of roastings 8～15 hours, the Li that obtain having higher flowability, size composition is controlled at 3～12 μ m behind the pressure alms bowl
1+xMn
yNi
1-x-yO
2Powder, described Li
1+xMn
yNi
1-x-yO
2Principal crystalline phase be stratiform petrofacies R-3m, account for more than 90%, other crystalline phases are less than 10%, wherein, described other crystalline phases comprise oblique system C2/m phase, spinel Fd-3m phase and cube Fm-3m phase.
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| CN103094550B (en) * | 2011-10-31 | 2015-02-18 | 北京有色金属研究总院 | Preparation method of lithium-rich anode material |
| WO2014065839A1 (en) * | 2012-10-28 | 2014-05-01 | Karl Kharas | Sustainable production of oxalic acid, ethylene glycol, ethylene, propylene and oxygen by electrolytic reaction of carbon dioxide with water |
| CN103545519B (en) * | 2013-07-19 | 2015-09-09 | 北京科技大学 | Coated lithium-rich anode material of a kind of carbon and preparation method thereof |
| CN105280882A (en) * | 2014-06-30 | 2016-01-27 | 中兴通讯股份有限公司 | High-performance positive pole piece of lithium-rich lithium-ion battery |
| CN104157870A (en) * | 2014-08-13 | 2014-11-19 | 青岛乾运高科新材料股份有限公司 | Two-step high-energy ball milling method for preparation of lithium manganate solid solution anode material rich in lithium |
| CN104466167B (en) * | 2014-12-17 | 2017-01-25 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing positive material LiNi1/3Co1/3Mn1/3O2 of lithium ion battery |
| CN106910887B (en) * | 2015-12-22 | 2020-05-26 | 国联汽车动力电池研究院有限责任公司 | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material |
| CN107104231A (en) * | 2016-02-19 | 2017-08-29 | 松下知识产权经营株式会社 | Positive active material and battery |
| CN109148856B (en) * | 2018-08-24 | 2021-07-06 | 南开大学 | Preparation method of high-cycle-capacity voltage-fading-resistant lithium-rich layered cathode material |
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