CN102683645A - Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery - Google Patents

Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery Download PDF

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CN102683645A
CN102683645A CN2011100672908A CN201110067290A CN102683645A CN 102683645 A CN102683645 A CN 102683645A CN 2011100672908 A CN2011100672908 A CN 2011100672908A CN 201110067290 A CN201110067290 A CN 201110067290A CN 102683645 A CN102683645 A CN 102683645A
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lithium
preparation
nickel
mixed
rich manganese
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刘兆平
刘娟娟
王军
唐长林
赛喜雅勒图
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses a preparation method of a layered lithium-rich manganese base oxide of a positive material of a lithium ion battery. The preparation method comprises the following steps of: slowly adding transition metal brine solution, alkali liquor and ammonia water which conform to a stoichiometric ratio into a stirring reactor respectively; stirring and heating; aging, filtering, washing and drying the obtained precipitate to obtain a nickel cobalt and manganese composite precursor; proportioning and mixing with a lithium source according to the stoichiometric ratio; adding a fluxing agent of a certain proportion and uniformly mixing in a mechanical mode; placing mixed powder in a furnace for sintering; cooling to room temperature; fully washing with water; and removing remaining fluxing agent to obtain the layered lithium-rich manganese base oxide Li1+xNialphaCobetaMngammaO2 (wherein x is greater than 0 and is less than or equal to 0.33, alpha is greater than or equal to 0 and is less than 1, beta is greater than or equal to 1 and is less than 1, gamma is greater than 0 and is less than 1, and alpha and beta are not zero simultaneously.). According to the preparation method, the heating efficiency is greatly increased, the energy consumption is reduced, and meanwhile, the electrochemical performance of the material is improved; the prepared spherical layered lithium-rich manganese base oxide has no doped phase; and a product has a uniform average particle diameter and superior circulation performance.

Description

The preparation method of the lithium-rich manganese-based oxide of a kind of anode material for lithium-ion batteries stratiform
Technical field
The invention belongs to the secondary battery material preparation field, be specifically related to the preparation method of the lithium-rich manganese-based oxide of a kind of high-capacity lithium ion cell positive electrode stratiform.
Background technology
Lithium ion battery is widely used in people's daily life because of high energy density, like common mobile phone, digital camera, notebook computer and electric tool etc.Recently, in order further to improve its energy density, anode material for lithium-ion batteries turns to other novel anode material from business-like cobalt acid lithium, LiMn2O4 and nickel manganese cobalt acid lithium.Wherein, the lithium-rich manganese-based oxide Li of stratiform 1+xNi αCo βMn γO 2(0＜x≤0.33,0≤α＜1,0≤β＜1,0＜γ＜1 wherein, α. β is not zero simultaneously) because of its capacity superelevation, cost is low, cycle performance is excellent and the high extensive concern that causes people of thermal stability.Like Li 1.2Ni 0.2Mn 0.6O 2And Li 1.2Ni 0.4/3Co 0.4/3Mn 1.6/3O 2Under the current density of C/20, charge to 4.8V, discharge capacity can reach 260mAh/g, almost is the twice of commercialization cobalt acid lithium.The lithium-rich manganese-based oxide of stratiform is Li 2MnO 3And LiMO 2The solid solution form of (M is Mn, Ni, one or more elements of Co).
At present, be used for the synthetic lithium-rich manganese-based oxide anode material method of stratiform and mainly contain solid phase synthesis, liquid phase coprecipitation, sol-gel and spray drying etc.Wherein, the lithium-rich manganese-based oxide of spherical stratiform prepared of liquid phase coprecipitation method is because of its cycle performance is excellent, good processability and tap density height have obtained extensive use.Yet, in this process, there are shortcomings such as power consumption is high, purity is not enough in follow-up lithium salts and the presoma mixing high-temperature calcination process, still need seek new technology in later stage high-temperature calcination process.
The fused salt synthetic method usually adopt a kind of or several low-melting salts as reaction medium, reactant has certain solubility in fused salt, make that being reflected at atom level carries out.Reaction adopts suitable solvent that salt is dissolved after finishing, and behind filtration washing, can obtain synthetic product.Because low melting point salt is as reaction medium; Liquid phase appearance is arranged in the building-up process, and reactant has certain solubility therein, has accelerated the diffusion rate of ion greatly; Make reactant realize that in liquid phase atomic scale mixes, reaction is a solid-liquid reaction by consolidating reaction conversion just.This method has that technology is simple, synthesis temperature is low, temperature retention time is short, synthetic powder chemical composition is even, crystal morphology good, thing phase purity advantages of higher for the slotting lithium process of routine, in addition, salt is easily separated, and is also reusable.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of the lithium-rich manganese-based oxide of a kind of anode material for lithium-ion batteries stratiform; Adopting co-precipitation to combine with molten salt growth method prepares; Solve conventional liquid-phase coprecipitation and prepare in the process problems such as heating is inhomogeneous, time length, temperature height; Thereby improve the efficiency of heating surface, lower energy consumption, and improve the chemical property of material.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the preparation method of the lithium-rich manganese-based oxide of a kind of anode material for lithium-ion batteries stratiform, and it is characterized in that adopting co-precipitation-molten salt growth method to prepare, may further comprise the steps:
Transition metal saline solution, 0.1～8mol/L alkali lye and the concentration that 1) will meet stoichiometric proportion is that the ammoniacal liquor of 0.1～5mol/L slowly adds in the stirred reactor respectively; Stir and heating; The control pH value of reaction system is 6.5～13; At 0～100 ℃ of heated at constant temperature 1～24h; The gained deposition obtains nickel manganese cobalt composite precursor after ageing, filtration, washing, drying, wherein the total concentration of nickel, manganese, cobalt ions is 0.1～4mol/L in the transition metal saline solution, and said alkali lye is one or several in NaOH, sodium carbonate or the sodium oxalate;
2) nickel manganese cobalt precursor is mixed by the stoichiometric proportion proportioning with the lithium source, to wherein adding a certain proportion of flux, mix through mechanical system and obtain mixed-powder again;
3) mixed-powder with above-mentioned gained places the air atmosphere stove; Speed with 1～30 ℃/min heats up; At 400～700 ℃ of calcining at constant temperature 0.5～12h, then at 800～1050 ℃ of calcining at constant temperature 1～30h, last cool to room temperature; Fully wash with deionized water, final drying promptly obtains the lithium-rich manganese-based oxide anode material Li of stratiform 1+xNi αCo βMn γO 2, 0＜x≤0.33,0≤α＜1,0≤β＜1,0＜γ＜1 wherein, α. and β is not zero simultaneously.
As preferably, said nickel manganese cobalt composite precursor is one or several in nickel magnesium cobalt hydroxide, nickel manganese cobalt carbonate, nickel manganese cobalt oxalates or the Ni-Mn-Co-O thing.
As preferably, said lithium source is one or several in lithium nitrate, lithium carbonate, lithium acetate or the lithium hydroxide.
Preferred again, said flux is one or several in lithium chloride, potassium chloride or the sodium chloride, and the ratio of the total amount in the amount of said flux and nickel manganese cobalt precursor and lithium source is 1～20.
At last, said mechanical system be mixed into ball milling, grinding, spraying, stirring or ultrasonic in one or several.
Compared with prior art, the invention has the advantages that: adopt coprecipitation to combine and prepare, solve conventional liquid-phase coprecipitation and prepare problems such as inhomogeneous in the process, that the time long and the high power consumption that causes of temperature is high, material purity is not enough owing to heating with molten salt growth method; Improved the efficiency of heating surface greatly, lowered energy consumption, improved the chemical property of material simultaneously, the lithium-rich manganese-based oxide of stratiform of the present invention's preparation does not have dephasign; And the product average grain diameter is even; Cycle performance is excellent, and preparation method's technology of the present invention is simple, and production cost is low; Efficient energy-saving is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is gained Li in the embodiment of the invention 1 1.2Ni 0.2Mn 0.6O 2XRD figure;
Fig. 2 is the embodiment of the invention 1 gained Li 1.2Ni 0.2Mn 0.6O 2SEM figure;
Fig. 3 is the embodiment of the invention 1 gained Li 1.2Ni 0.2Mn 0.6O 2The charge-discharge test curve chart;
Fig. 4 is the embodiment of the invention 1 gained Li 1.2Ni 0.2Mn 0.6O 2The loop test curve chart.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
With nickelous sulfate and manganese sulfate mol ratio is that 1: 3 proportioning is mixed; The adding deionized water is mixed with the mixed solution of 2mol/L; Adopt the 2mol/L sodium carbonate liquor as precipitation reagent, the ammoniacal liquor of 0.2mol/L is added drop-wise in the reactor of continuous stirring as complexing agent simultaneously; And control reaction system the pH value be 8, at 60 ℃ of heated at constant temperature 10h.The gained deposition obtains nickel manganese carbonate precursor (Ni after ageing, filtration, washing, drying 0.25Mn 0.75) CO 3With (Ni 0.25Mn 0.75) CO 3Place 500 ℃ of following calcining at constant temperature 5h of air atmosphere stove, obtain Ni, Mn oxide presoma (Ni 0.25Mn 0.75) 3O 4
Gained Ni, Mn oxide presoma, lithium carbonate and potassium chloride are mixed by a certain percentage; Wherein the quality of potassium chloride is Ni, Mn oxide presoma and lithium carbonate gross mass 5 times, heats up with the speed of 5 ℃/min, then the gained powder is placed 500 ℃ of following constant temperature sintering 3h of air atmosphere stove; 800 ℃ of following constant temperature sintering 8h then; Naturally cool to room temperature, the deionized water cyclic washing obtains the lithium-rich manganese-based oxide Li of stratiform after the drying 1.2Ni 0.2Mn 0.6O 2Products therefrom is pure phase (accompanying drawing 1); It is the secondary micron spheric granules (accompanying drawing 2) that is assembled into by nano particle; 12.5mA/g charging and discharging currents density under discharge capacity can reach 250mAh/g (accompanying drawing 3), 50 circulation back capability retentions are greater than 80% (accompanying drawing 4).
Embodiment 2:
With nickelous sulfate, cobaltous sulfate and manganese sulfate mol ratio is that 1: 1: 4 proportioning is mixed; The adding deionized water is mixed with the mixed solution of 2mol/L; Adopt the 2mol/L sodium carbonate liquor as precipitation reagent, the ammoniacal liquor of 0.2mol/L is added drop-wise in the reactor of continuous stirring as complexing agent simultaneously; And control reaction system the pH value be 8, at 60 ℃ of heated at constant temperature 12h.The gained deposition obtains nickel cobalt manganese carbonate precursor (Ni after ageing, filtration, washing, drying 1/6Co 1/6Mn 4/6) CO 3
Gained nickel cobalt manganese carbonate precursor, lithium carbonate and sodium chloride are mixed by a certain percentage; Wherein the quality of sodium chloride is nickel cobalt manganese carbonate precursor and lithium carbonate gross mass 10 times, heats up with the speed of 5 ℃/min, then the gained powder is placed 500 ℃ of following constant temperature sintering 10h of air atmosphere stove; 900 ℃ of following constant temperature sintering 10h then; Naturally cool to room temperature, the deionized water cyclic washing obtains the lithium-rich manganese-based oxide Li of stratiform after the drying 1.2Ni 0.4/3Co 0.4/3Mn 1.6/3O 2Products therefrom is the secondary micron spheric granules that is assembled into by nano particle, and discharge capacity can reach 260mAh/g under the charging and discharging currents density of 12.5mA/g, and cycle performance is excellent.
Embodiment 3:
With nickelous sulfate, cobaltous sulfate and manganese sulfate mol ratio is that 2: 1: 7 proportioning is mixed; The adding deionized water is mixed with the mixed solution of 2mol/L; Adopt the 2mol/L sodium carbonate liquor as precipitation reagent, the ammoniacal liquor of 2mol/L is added drop-wise in the reactor of continuous stirring as complexing agent simultaneously; And control reaction system the pH value be 8, at 60 ℃ of heated at constant temperature 8h.The gained deposition obtains nickel cobalt manganese carbonate precursor (Ni after ageing, filtration, washing, drying 0.2Co 0.1Mn 0.7) CO 3
Gained nickel cobalt manganese carbonate precursor, lithium carbonate and potassium chloride are mixed by a certain percentage; Wherein the quality of potassium chloride is nickel cobalt manganese carbonate precursor and lithium carbonate gross mass 5 times, heats up with the speed of 8 ℃/min, then the gained powder is placed 500 ℃ of following constant temperature sintering 10h of air atmosphere stove; 900 ℃ of following constant temperature sintering 10h then; Naturally cool to room temperature, the deionized water cyclic washing obtains the lithium-rich manganese-based oxide Li of stratiform after the drying 1.2Ni 0.16Co 0.08Mn 0.56O 2Products therefrom is the secondary micron spheric granules that is assembled into by nano particle, and discharge capacity can reach 265mAh/g under the charging and discharging currents density of 12.5mA/g, and discharge capacity can reach 180mAh/g under the charging and discharging currents density of 250mA/g, and cycle performance is excellent.
Embodiment 4:
With nickelous sulfate, cobaltous sulfate and manganese sulfate mol ratio is that 1: 1: 4 proportioning is mixed; The adding deionized water is mixed with the mixed solution of 2mol/L; Adopt the 4mol/L sodium hydroxide solution as precipitation reagent, the ammoniacal liquor of 2mol/L is as complexing agent, is added drop-wise to simultaneously in the reactor of continuous stirring (nitrogen protection atmosphere); And control reaction system the pH value be 11.5, at 60 ℃ of heated at constant temperature 5h.The gained deposition obtains nickel cobalt manganese hydroxide presoma (Ni after ageing, filtration, washing, drying 1/6Co 1/6Mn 4/6) (OH) 2
Gained nickel cobalt manganese hydroxide presoma, lithium hydroxide and potassium chloride are mixed by a certain percentage; Wherein the quality of potassium chloride is nickel magnesium cobalt hydroxide presoma and lithium hydroxide gross mass 15 times, heats up with the speed of 8 ℃/min, then the gained powder is placed 500 ℃ of following constant temperature sintering 10h of air atmosphere stove; 800 ℃ of following constant temperature sintering 10h then; Naturally cool to room temperature, the deionized water cyclic washing obtains the lithium-rich manganese-based oxide Li of stratiform after the drying 1.2Ni 0.4/3Co 0.4/3Mn 1.6/3O 2Discharge capacity can reach 256mAh/g under the charging and discharging currents density of products therefrom 12.5mA/g, and cycle performance is excellent.
Embodiment 5:
With nickelous sulfate, cobaltous sulfate and manganese sulfate mol ratio is that 1: 1: 4 proportioning is mixed; The adding deionized water is mixed with the mixed solution of 2mol/L; Adopt the 2mol/L sodium carbonate liquor as precipitation reagent, the ammoniacal liquor of 0.2mol/L is added drop-wise in the reactor of continuous stirring as complexing agent simultaneously; And control reaction system the pH value be 8, at 60 ℃ of heated at constant temperature 10h.The gained deposition obtains nickel cobalt manganese carbonate precursor (Ni after ageing, filtration, washing, drying 1/6Co 1/6Mn 4/6) CO 3With (Ni 1/6Co 1/6Mn 4/6) CO 3Place 500 ℃ of following calcining at constant temperature 5h of air atmosphere stove, obtain Ni, Mn oxide presoma (Ni 1/6Co 1/6Mn 4/6) 3O 4
Gained nickel, cobalt and manganese oxide presoma, lithium carbonate and sodium chloride are mixed by a certain percentage; Wherein the quality of sodium chloride is nickel, cobalt and manganese oxide presoma and lithium carbonate gross mass 15 times, heats up with the speed of 5 ℃/min, then the gained powder is placed 500 ℃ of following constant temperature sintering 3h of air atmosphere stove; 900 ℃ of following constant temperature sintering 3h then; Naturally cool to room temperature, the deionized water cyclic washing obtains the lithium-rich manganese-based oxide Li of stratiform after the drying 1.2Ni 0.4/3Co 0.4/3Mn 1.6/3O 2Products therefrom is the secondary micron spheric granules that is assembled into by nano particle, and discharge capacity can reach 266mAh/g under the charging and discharging currents density of 12.5mA/g, and cycle performance is excellent.
Embodiment 6:
With nickelous sulfate and manganese sulfate mol ratio is that 1: 3 proportioning is mixed; The adding deionized water is mixed with the mixed solution of 0.2mol/L; Adopt the 0.2mol/L sodium oxalate solution as precipitation reagent, the ammoniacal liquor of 0.36mol/L is added drop-wise in the reactor of continuous stirring as complexing agent simultaneously; And control reaction system the pH value be 7, at 60 ℃ of heated at constant temperature 10h.The gained deposition obtains nickel manganese oxalates presoma after ageing, filtration, washing, drying.Nickel manganese oxalates is placed 500 ℃ of following calcining at constant temperature 5h of air atmosphere stove, obtain Ni, Mn oxide presoma (Ni 0.25Mn 0.75) 3O 4
Gained Ni, Mn oxide presoma, lithium carbonate and sodium chloride are mixed by a certain percentage; Wherein the quality of sodium chloride is Ni, Mn oxide presoma and lithium carbonate gross mass 10 times, heats up with the speed of 5 ℃/min, then the gained powder is placed 450 ℃ of following constant temperature sintering 3h of air atmosphere stove; 800 ℃ of following constant temperature sintering 12h then; Naturally cool to room temperature, the deionized water cyclic washing obtains the lithium-rich manganese-based oxide Li of stratiform after the drying 1.2Ni 0.2Mn 0.6O 2

Claims (5)

1. the preparation method of the lithium-rich manganese-based oxide of anode material for lithium-ion batteries stratiform is characterized in that adopting co-precipitation-molten salt growth method to prepare, and step is:
Transition metal saline solution, 0.1～8mol/L alkali lye and the concentration that 1) will meet stoichiometric proportion is that the ammoniacal liquor of 0.1～5mol/L slowly adds in the stirred reactor respectively; Stir and heating; The control pH value of reaction system is 6.5～13; At 0～100 ℃ of heated at constant temperature 1～24h; The gained deposition obtains nickel manganese cobalt composite precursor after ageing, filtration, washing, drying, wherein the total concentration of nickel, manganese, cobalt ions is 0.1～4mol/L in the transition metal saline solution, and said alkali lye is one or several in NaOH, sodium carbonate or the sodium oxalate;
2) nickel manganese cobalt precursor is mixed by the stoichiometric proportion proportioning with the lithium source, to wherein adding a certain proportion of flux, mix through mechanical system and obtain mixed-powder again;
3) mixed-powder with above-mentioned gained places the air atmosphere stove; Speed with 1～30 ℃/min heats up; At 400～700 ℃ of calcining at constant temperature 0.5～12h, then at 800～1050 ℃ of calcining at constant temperature 1～30h, last cool to room temperature; Fully wash with deionized water, final drying promptly obtains the lithium-rich manganese-based oxide anode material Li of stratiform 1+xNi αCo βMn γO 2, 0＜x≤0.33,0≤α＜1,0≤β＜1,0＜γ＜1 wherein, α. and β is not zero simultaneously.
2. preparation method according to claim 1 is characterized in that said nickel manganese cobalt composite precursor is one or several in nickel magnesium cobalt hydroxide, nickel manganese cobalt carbonate, nickel manganese cobalt oxalates or the Ni-Mn-Co-O thing.
3. preparation method according to claim 1 is characterized in that said lithium source is one or several in lithium nitrate, lithium carbonate, lithium acetate or the lithium hydroxide.
4. preparation method according to claim 1 is characterized in that said flux is one or several in lithium chloride, potassium chloride or the sodium chloride, and the ratio of the total amount in the amount of said flux and nickel manganese cobalt precursor and lithium source is 1～20.
5. preparation method according to claim 1, it is characterized in that said mechanical system be mixed into ball milling, grinding, spraying, stirring or ultrasonic in one or several.
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