CN102219262A - 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 PDF

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CN102219262A
CN102219262A CN2011101207072A CN201110120707A CN102219262A CN 102219262 A CN102219262 A CN 102219262A CN 2011101207072 A CN2011101207072 A CN 2011101207072A CN 201110120707 A CN201110120707 A CN 201110120707A CN 102219262 A CN102219262 A CN 102219262A
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manganese
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CN102219262B (en
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连芳
李栋
仇卫华
李福燊
周国治
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Hunan jinfuli new energy Limited by Share Ltd
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University of Science and Technology Beijing USTB
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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

A kind of improved low fever solid phase reaction prepares the method for the rich lithium nickel manganese oxide of stratiform
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 outstanding advantages such as lithium ion battery has the operating voltage height, energy density is big, 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 electronic installation miniaturization ands such as pick up camera, mobile telephone, notebook computer, portable tester.Simultaneously, lithium ion battery also will become ideal used for electric vehicle light-duty high-energy power 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 electric 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 energy storage and the lower Cheng Ben $/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, 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, 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 at present the rich lithium nickel manganese oxide of preparation generally adopted is coprecipitation method, have multicomponent mixture evenly, the advantage of controllable particle size distribution.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 preparation flow of material, 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.Low-temperature solid-phase method synthetic initial stage material is that the form with slurry exists, and must carry out drying treatment before roasting.Carry out the exsiccant process at slurry, material is exposed in the air for a long time, Mn occurs 2+Oxidation in various degree causes occurring the impurity phase in the final synthetic product, has influenced the chemical property of material.Especially drying material is prone to and hardens, and follow-uply need 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 bigger, 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 at 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 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 saggar 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 promptly at first the lithium source mixes the short period of time stirring with oxalic acid (citric acid or sugar), again with transition metal ion acetate adding the carrying out ball milling of premix.The present invention simplifies technological process on the basis of the experimental study of constantly improving the molten reaction mechanism of cold cut, the material of weighing is in proportion added together, at the reactant particle (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 (as nickelous acetate and manganous acetate) spreads in the cold cut crucible zone and in this little reaction zone chemical reaction takes place, compare the operating process of not only having simplified synthesis technique with two-step approach, and quickened 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 technology of slurry, and accurately the component of control material has overcome 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 at 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 technology with material, prolong the diffusion time of metallic cation, reduce textural defect, synthesized the ideal 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 the bonding strength and the density of second particle by re-baking, helps finishing smoothly of operations such as slurrying in the electrodes of lithium-ion batteries production process, coating.
Description of drawings
Obtain the microstructure figure of powder after the initial stage slurry spraying drying of Fig. 1 for embodiment 1 preparation.
Fig. 2 prepares the microstructure figure that obtains powder after the slurry vacuum-drying for comparative example.
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 of forming.
Fig. 5 is the Li of embodiment 2 preparations 1.3Mn 0.01Ni 0.69O 2(Li 1+xMn yNi 1-x-yO 2,X=0.3 wherein, microstructure figure y=0.01).
Fig. 6 is the Li of embodiment 3 preparations 1.11Mn 0.56Ni 0.33O 2(Li 1+xMn yNi 1-x-yO 2,X=0.11 wherein, X-ray diffractogram y=0.56) 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,X=0.13 wherein, y=0.57) half-cell of Zu Chenging 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 below in conjunction with example to the present invention, 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 saggar of packing into behind the ball milling is warming up to 600 ℃ of roastings 12 hours after pressing alms bowl, has 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,X=0.2 wherein, 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 saggar of packing into behind the ball milling is warming up to 750 ℃ of roastings 15 hours after pressing alms bowl, has 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,X=0.3 wherein, 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 saggar of packing into behind the ball milling is warming up to 850 ℃ of roastings 13 hours after pressing alms bowl, has 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,X=0.11 wherein, 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 saggar of packing into behind the ball milling is warming up to 800 ℃ of roastings 15 hours after pressing alms bowl, has 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,X=0.13 wherein, 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,X=0.2 wherein, y=0.6).

Claims (2)

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, 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 slurry, and be standby; 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 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 saggar 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%.
2. prepare the method for the rich lithium nickel manganese oxide of stratiform according to right 1 described improved low fever solid phase reaction, it is characterized in that described other crystalline phases comprise oblique system C2/m phase, spinel Fd-3m phase and cube Fm-3m phase.
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CN103545519A (en) * 2013-07-19 2014-01-29 北京科技大学 Carbon-coated lithium-rich positive electrode material as well as preparation method thereof
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
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CN109148856A (en) * 2018-08-24 2019-01-04 南开大学 A kind of preparation method of high circulation capacity reactance voltage decline lithium-rich positive electrode

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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
CN103545519A (en) * 2013-07-19 2014-01-29 北京科技大学 Carbon-coated lithium-rich positive electrode material as well as 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
CN104466167A (en) * 2014-12-17 2015-03-25 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
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
CN106910887A (en) * 2015-12-22 2017-06-30 国联汽车动力电池研究院有限责任公司 A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode
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
CN109148856A (en) * 2018-08-24 2019-01-04 南开大学 A kind of preparation method of high circulation capacity reactance voltage decline lithium-rich positive electrode
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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