CN104425810A - Modified lithium nickel manganese oxygen material, preparation method of modified lithium nickel manganese oxygen material, and lithium ion battery - Google Patents

Modified lithium nickel manganese oxygen material, preparation method of modified lithium nickel manganese oxygen material, and lithium ion battery Download PDF

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Publication number
CN104425810A
CN104425810A CN201310382284.0A CN201310382284A CN104425810A CN 104425810 A CN104425810 A CN 104425810A CN 201310382284 A CN201310382284 A CN 201310382284A CN 104425810 A CN104425810 A CN 104425810A
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lithium
presoma
nickel manganese
lithium nickel
modification
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刘三兵
翟丽娟
朱广燕
海滨
刘云建
卢磊
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Chery Automobile Co Ltd
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SAIC Chery Automobile Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

Abstract

The invention discloses a modified lithium nickel manganese oxygen material, a preparation method of the modified lithium nickel manganese oxygen material, and a lithium ion battery. The molecular formula of the modified lithium nickel manganese oxygen material is LiNi(0.5-x/2)MxMn(1.5-x/2)O(4-y)Fy, wherein x is greater than or equal to 0.004 and is less than or equal to 0.2, y is greater than or equal to 0.002 and is less than or equal to 0.1, and M is one of Co, Al, Cr, Zr, Fe and Ti. The existence of the Mn<3+> ions is eliminated effectively by co-doping of anions and cations, the generation of a Jahn-Teller effect can be inhibited, and the average valence of Mn can be increased; the electronegativity of fluorine is greater than that of oxygen, and the capability of attracting electrons is high; the fluorine is doped, so that the structure of the LiNi0.43Ti0.14Mn1.43O3.95F0.05 material is relatively stable, and the reversibility is enhanced when the LiNi0.43Ti0.14Mn1.43O3.95F0.05 material is used as an electrode material; the interfacial characterization between the electrode material and electrolyte is improved; the dissolving and the erosion of the electrolyte to the material is relieved in the charge and discharge processes.

Description

Lithium nickel manganese oxide material of a kind of modification and preparation method thereof, lithium ion battery
Technical field
The invention belongs to technical field of lithium ion, be specifically related to lithium nickel manganese oxide material of a kind of modification and preparation method thereof, lithium ion battery.
Background technology
Along with the exhaustion day by day of fossil fuel, new energy technology is acknowledged as current new and high technology, and battery industry, as the important component part of new energy field, has become the focus of global economic development.Wherein, the plurality of advantages such as energy density is high, voltage platform is high owing to having for lithium ion battery, long service life, self discharge is little, memory-less effect, operating temperature range are wide, environmentally safe, are used widely.With regard to the composition of lithium ion battery, form primarily of positive pole, negative pole, barrier film, electrolyte, shell and other parts, wherein, positive and negative electrode material is active material, usual negative material is graphite, specific capacity is 320mAh/g ~ 370mAh/g, and much larger than the specific capacity of positive electrode, therefore can positive electrode performance promote is the decisive factor that performance of lithium ion battery improves.LiNi 0.5mn 1.5o 4the platform of 4.7V is mainly there is, corresponding Ni in charge and discharge process 2+/ Ni 4+oxidation-reduction process, theoretical specific capacity is 146.7mAh/g, compares LiCoO 2, LiMn 2o 4, LiFePO 4there is higher energy density, be hopeful to be applied as electrokinetic cell, therefore become the focus of current Study on Li-ion batteries.
But, current LiNi 0.5mn 1.5o 4the cycle performance, high rate performance etc. of material can not be satisfactory, often produce Mn in preparation process 3+, Li xni 1-xo 2deng impurity, the more difficult product preparing stoichiometric proportion, in circulating battery process, these impurity can cause cycle performance poor.And LiNi 0.5mn 1.5o 4in charge and discharge process, voltage is high, and make the oxidized decomposition of the anolyte portion of electrode surface, these all limit its commercial applications.In order to address this problem a lot of scholar, doping vario-property is carried out to it, but LiNi 0.5mn 1.5o 4the performance change of material is less, and there is doping and control the problems such as inaccurate, and the material property of preparation is not good.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, provides lithium nickel manganese oxide material of a kind of modification and preparation method thereof, lithium ion battery, effectively eliminates Mn by anion, cationic codope 3+the existence of ion, can suppress the generation of jahn teller effect, and the average valence of manganese is improved.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of lithium nickel manganese oxide material of modification, and the molecular formula of the lithium nickel manganese oxide material of this modification is LiNi 0.5-x/2m xmn 1.5-x/2o 4-yf y, wherein, 0.004≤x≤0.2,0.002≤y≤0.1, M is the one in Co, Al, Cr, Zr, Fe, Ti.
Preferably, when the cumulative particle sizes percentile of the lithium nickel manganese oxide material of described modification reaches 50%, corresponding particle diameter is 7 ~ 20 μm, and specific area is 0.12 ~ 0.8m 2/ g.
Preferably, described LiNi 0.5-x/2m xmn 1.5-x/2o 4-yf ymaterial is complete spinelle octahedral structure.
The present invention also provides a kind of preparation method of lithium nickel manganese oxide material of modification, comprises the following steps:
According to amount of substance ratio Li:Ni:M:Mn:F=(1.02 ~ 1.06) × (1-y): (0.5-x/2): x:(1.5-x/2): y takes presoma, the presoma of nickel, the presoma of M, the presoma of manganese, the lithium fluoride of lithium respectively, and the mixing precursor obtained after mixing is carried out the lithium nickel manganese oxide material LiNi that calcination obtains described modification 0.5-x/2m xmn 1.5-x/2o 4-yf y, wherein, 0.004≤x≤0.2,0.002≤y≤0.1, M is the one in Co, Al, Cr, Zr, Fe, Ti.
Preferably, the presoma of described lithium is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithia;
The presoma of described nickel is one or more in nickel nitrate, nickel acetate, nickel hydroxide, nickelous carbonate, nickel chloride, nickel oxide, nickel protoxide;
The presoma of described M is the one in aluminium chloride, aluminum nitrate, aluminium oxide, aluminium hydroxide, cobalt nitrate, cobalt chloride, cobalt oxide, chromium oxide, chromium chloride, chromic nitrate, chromium hydroxide, iron oxide, ferrous carbonate, iron chloride, ferric nitrate, iron hydroxide, titanium oxide, titanium chloride, butyl titanate, tetraisopropyl titanate, titanium hydroxide, zirconia, zirconium hydroxide, zirconium nitrate, zirconium chloride;
The presoma of described manganese is one or more in manganese nitrate, manganese acetate, manganese carbonate, manganous hydroxide, manganese dioxide, mangano-manganic oxide, manganese chloride.
Preferably, the concrete steps of described mixing comprise: the presoma of the presoma of the presoma of the presoma of described lithium, described nickel, described M, described manganese, described lithium fluoride are mixed by the method for ball milling.
Preferably, the concrete steps of described mixing also comprise: the mixture by obtaining after the method mixing of ball milling is added solvent again, and wherein, the ratio of the amount of described solvent and described mixture is 0.5 ~ 2ml/g, be modulated into the abnormal starchiness of stream, after drying, obtain described mixing persursor material.
Preferably, the concrete steps of described calcination are:
(1) described mixing precursor is heated to 400 ~ 600 DEG C with 0.5 ~ 10 DEG C/min programming rate, insulation 2 ~ 20h;
(2) take out the material that described step (1) obtains, make described material carry out fragmentation, the particle diameter obtaining the material after fragmentation is 0.4 ~ 20 μm;
(3) material that step (2) obtains is heated to 750 ~ 950 DEG C with 0.5 ~ 10 DEG C/min programming rate, calcination 2 ~ 24h;
(4) material that step (3) obtains is down to 600 ~ 700 DEG C with 0.5 ~ 10 DEG C/min cooling rate, annealing 2 ~ 24h; Be cooled to room temperature, obtain the lithium nickel manganese oxide material LiNi of described modification 0.5-x/2m xmn 1.5-x/2o 4-yf ymaterial.
The present invention also provides a kind of lithium ion battery, and its positive pole includes the lithium nickel manganese oxide material of above-mentioned modification.
By LiNi 0.5-x/2m xmn 1.5-x/2o 4-yf ymaterial, as cell positive material, in charge and discharge process, suppresses the generation of Jahn-Teller effect effectively by anion, cationic codope.The electronegativity of fluorine is larger than oxygen, and attract electronic capability strong, doped with fluorine makes LiNi 0.5-x/2m xmn 1.5-x/2o 4-yf ymaterial structure is more stable, LiNi 0.5-x/2m xmn 1.5-x/2o 4-yf ymaterial strengthens as invertibity during electrode material, and improves the interfacial characteristics between electrode material and electrolyte, to alleviate in charge and discharge process electrolyte to LiNi 0.5-x/2m xmn 1.5-x/2o 4-yf ythe dissolving of material, erosion.The preparation technology of this material is simple, and cost is low, is easy to suitability for industrialized production.
Accompanying drawing explanation
LiNi prepared by Fig. 1 embodiment of the present invention 1 0.43ti 0.14mn 1.43o 3.95f 0.05the stereoscan photograph of material;
Fig. 2 is LiNi of the prior art 0.5mn 1.5o 4stereoscan photograph;
The LiNi of Fig. 3 prepared by the embodiment of the present invention 1 0.43ti 0.14mn 1.43o 3.95f 0.05the first charge-discharge cycle performance curve of material;
The LiNi of Fig. 4 prepared by the embodiment of the present invention 1 0.43ti 0.14mn 1.43o 3.95f 0.05the discharge cycles performance curve of material.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of lithium nickel manganese oxide material of Ti, F doping vario-property, and the molecular formula of the lithium nickel manganese oxide material of this modification is LiNi 0.43ti 0.14mn 1.43o 3.95f 0.05, the preparation method of the lithium nickel manganese oxide material of this modification comprises the following steps:
(1) lithium carbonate and lithium nitrate, nickel acetate, butyl titanate, manganese acetate, lithium fluoride is taken respectively according to amount of substance ratio Li:Ni:Ti:Mn:F=0.9975:0.43:0.14:1.43:0.05, add planetary ball mill, with the rotating speed ball milling 6h of 350r/min, ball milling mixes.Add a certain amount of ethanol, the amount ratio of ethanol and said mixture is 1(mL/g), be modulated into the abnormal starchiness of stream, dry, obtain mixing presoma.This Rheological Phase Method is adopted to prepare presoma, than the doping level being easier to accurate control anion fluorine ion and cationic titanium ion.
(2) above-mentioned presoma is heated to 500 DEG C with 3 DEG C/min programming rate, insulation 6h, carries out preliminary treatment; Take out material and carry out fragmentation, ball milling mixes, and obtains powder body material, and the particle size range of this powder body material is 10 ~ 18 μm; Then temperature programmed control, sinters in air atmosphere, is heated to 800 DEG C, calcination 2h with 5 DEG C/min programming rate; The cooling rate of 0.5 DEG C/min is down to 600 DEG C again, annealing 15h; Last Temperature fall, to room temperature, namely obtains LiNi 0.43ti 0.14mn 1.43o 3.95f 0.05material, specific area is 0.2m 2/ g.
As shown in Figure 1, this LiNi 0.43ti 0.14mn 1.43o 3.95f 0.05the photo of the ESEM of material shows: this material is complete spinelle octahedral structure, even particle size, and particle size is 1 ~ 5 μm.LiNi 0.43ti 0.14mn 1.43o 3.95f 0.05the spinelle octahedral structure of material belongs to thermodynamically metastable fixed structure, and have three-dimensional deintercalate lithium ions tunnel fast in charge and discharge process, Stability Analysis of Structures during removal lithium embedded, there will not be and subside or phase transformation, has good cyclical stability, high rate performance.As shown in Figure 2, LiNi of the prior art 0.5mn 1.5o 4structure imperfect, or not close to perfect condition, granular size is uneven, and the irregular or polyhedron state of pattern, therefore its chemical property is far from the LiNi in the present embodiment 0.43ti 0.14mn 1.43o 3.95f 0.05the electrochemical performance of material.
The preparation method of battery pole piece:
By LiNi 0.43ti 0.14mn 1.43o 3.95f 0.05material, conductive agent acetylene black, binding agent PVDF(Kynoar) mix according to mass ratio 8:1:1, use NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on aluminium foil, put into baking oven, at 110 DEG C, dry 3h, take out and be washed into pole piece, vacuumize 12 hours at 85 DEG C again, carry out compressing tablet, and then vacuumize 12 hours at 85 DEG C, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is the LiPF of 1.2mol/L 6eC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
As shown in Figure 3, charge and discharge cycles test is carried out to this button cell: charging/discharging voltage scope is 3.5 ~ 4.9V, 1st ~ 5 charging and discharging currents are 0.1C, and 6th ~ 10 times charging and discharging currents is 0.2C, and 11st ~ 110 charging and discharging currents are 1C(1C=130mA/g).When charging and discharging currents is 0.1C, first charge-discharge specific capacity is respectively 150.595mAh/g, 128.182mAh/g, and coulombic efficiency is 85.12%, in addition in charge and discharge process, does not occur platform at about 4V, and 4V platform corresponds to Mn 3+/ Mn 4+oxidation-reduction process, illustrate does not have Mn in charge and discharge process 3+/ Mn 4+oxidation-reduction process, namely effectively eliminate Mn by the codope of anion fluorine ion, cationic titanium ion 3+the existence of ion, can suppress the generation of Jahn-Teller effect, and the average valence of manganese is improved.The electronegativity of fluorine is larger than oxygen, and attract electronic capability strong, doped with fluorine makes LiNi 0.43ti 0.14mn 1.43o 3.95f 0.05material structure is more stable, LiNi 0.43ti 0.14mn 1.43o 3.95f 0.05material strengthens as invertibity during electrode material, and improves the interfacial characteristics between electrode material and electrolyte, to alleviate in charge and discharge process electrolyte to LiNi 0.43ti 0.14mn 1.43o 3.95f 0.05the dissolving of material, erosion.The preparation technology of this material is simple, and cost is low, is easy to suitability for industrialized production.
As shown in Figure 4, be the condition of 1C at charging and discharging currents under, first discharge specific capacity is 121.159mAh/g, and 100 specific capacities that circulate are 118.015mAh/g, and capability retention is 97.4%, and the cyclical stability of this battery is better.
Embodiment 2
The present embodiment provides a kind of lithium nickel manganese oxide material of Cr, F doping vario-property, and the molecular formula of the lithium nickel manganese oxide material of this modification is LiNi 0.45cr 0.1mn 1.45o 3.98f 0.02, the preparation method of the lithium nickel manganese oxide material of this modification comprises the following steps:
(1) lithium acetate, nickel oxide and nickel chloride, chromic nitrate, manganous hydroxide, lithium fluoride is taken respectively according to amount of substance ratio Li:Ni:Cr:Mn:F=0.9996:0.45:0.1:1.45:0.02, add planetary ball mill, with the rotating speed ball milling 4h of 400r/min, ball milling mixes.Add a certain amount of ethanol and distilled water, the amount ratio of ethanol and distilled water and said mixture is 0.8(mL/g), be modulated into the abnormal starchiness of stream, dry, obtain mixing presoma.
(2) above-mentioned presoma is heated to 400 DEG C with 4 DEG C/min programming rate, insulation 20h, carries out preliminary treatment; Take out material and carry out fragmentation, ball milling mixes, and obtains powder body material, and the particle size range of this powder body material is 15 ~ 20 μm; Then temperature programmed control, sinters in air atmosphere, is heated to 900 DEG C, calcination 6h with 3 DEG C/min programming rate; The cooling rate of 5 DEG C/min is down to 700 DEG C again, annealing 2h; Last Temperature fall, to room temperature, namely obtains LiNi 0.45cr 0.1mn 1.45o 3.98f 0.02material, when the cumulative particle sizes percentile of this material reaches 50%, corresponding particle diameter is 7 μm, and specific area is 0.12m 2/ g.
Use above-mentioned LiNi 0.45cr 0.1mn 1.45o 3.98f 0.02material carries out lithium ion battery assembling as positive electrode, the Integration Assembly And Checkout method of battery is as embodiment 1, be the condition of 1C at charging and discharging currents under, first discharge specific capacity is 126.007mAh/g, the specific capacity after 100 times that circulates is 120.463mAh/g, capability retention is 95.6%, and the cyclical stability of this battery is better.
Embodiment 3
The present embodiment provides a kind of lithium nickel manganese oxide material of Co, F doping vario-property, and the molecular formula of the lithium nickel manganese oxide material of this modification is LiNi 0.498co 0.004mn 1.498o 3.9f 0.1, the preparation method of the lithium nickel manganese oxide material of this modification comprises the following steps:
(1) lithium hydroxide, nickel nitrate, cobalt nitrate, manganese chloride, lithium fluoride is taken respectively according to amount of substance ratio Li:Ni:Co:Mn:F=0.954:0.498:0.004:1.498:0.1, add planetary ball mill, with the rotating speed ball milling 8h of 300r/min, ball milling mixes.Add a certain amount of water, the amount ratio of water and said mixture is 2(mL/g), be modulated into the abnormal starchiness of stream, dry, obtain mixing presoma.
(2) above-mentioned presoma is heated to 600 DEG C with 5 DEG C/min programming rate, insulation 5h, carries out preliminary treatment; Take out material and carry out fragmentation, ball milling mixes, and obtains powder body material, and the particle size range of this powder body material is 0.4 ~ 1.0 μm; Then temperature programmed control, sinters in air atmosphere, is heated to 950 DEG C, calcination 24h with 0.5 DEG C/min programming rate; The cooling rate of 10 DEG C/min is down to 650 DEG C again, annealing 10h; Last Temperature fall, to room temperature, namely obtains LiNi 0.498co 0.004mn 1.498o 3.9f 0.1material, when the cumulative particle sizes percentile of this material reaches 50%, corresponding particle diameter is 20 μm, and specific area is 0.8m 2/ g.
Use above-mentioned LiNi 0.498co 0.004mn 1.498o 3.9f 0.1material carries out lithium ion battery assembling as positive electrode, the Integration Assembly And Checkout method of battery is as embodiment 1, be the condition of 1C at charging and discharging currents under, first discharge specific capacity is 121.25mAh/g, the specific capacity after 100 times that circulates is 114.218mAh/g, capability retention is 94.2%, and the cyclical stability of this battery is better.
Embodiment 4
The present embodiment provides a kind of lithium nickel manganese oxide material of Al, F doping vario-property, and the molecular formula of the lithium nickel manganese oxide material of this modification is LiNi 0.47al 0.06mn 1.47o 3.96f 0.04, the preparation method of the lithium nickel manganese oxide material of this modification comprises the following steps:
(1) lithium nitrate, nickel acetate, aluminium hydroxide, manganese acetate and manganese dioxide, lithium fluoride is taken respectively according to amount of substance ratio Li:Ni:Al:Mn:F=0.9984:0.47:0.06:1.47:0.04, add planetary ball mill, with the rotating speed ball milling 6h of 350r/min, ball milling mixes.Add a certain amount of ethanol, the amount ratio of ethanol and said mixture is 0.5(mL/g), be modulated into the abnormal starchiness of stream, dry, obtain mixing presoma.
(2) above-mentioned presoma is heated to 400 DEG C with 10 DEG C/min programming rate, insulation 9h, carries out preliminary treatment; Take out material and carry out fragmentation, ball milling mixes, and obtains powder body material, and the particle size range of this powder body material is 5 ~ 10 μm; Then temperature programmed control, sinters in air atmosphere, is heated to 750 DEG C, calcination 12h with 10 DEG C/min programming rate; The cooling rate of 8 DEG C/min is down to 600 DEG C again, annealing 24h; Last Temperature fall, to room temperature, namely obtains LiNi 0.47al 0.06mn 1.47o 3.96f 0.04material, when the cumulative particle sizes percentile of this material reaches 50%, corresponding particle diameter is 10 μm, and specific area is 0.4m 2/ g.
Use above-mentioned LiNi 0.47al 0.06mn 1.47o 3.96f 0.04material carries out lithium ion battery assembling as positive electrode, the Integration Assembly And Checkout method of battery is as embodiment 1, be the condition of 1C at charging and discharging currents under, first discharge specific capacity is 114.162mAh/g, the specific capacity after 100 times that circulates is 110.876mAh/g, capability retention is 97.1%, and the cyclical stability of this battery is better.
Embodiment 5
The present embodiment provides a kind of lithium nickel manganese oxide material of Zr, F doping vario-property, and the molecular formula of the lithium nickel manganese oxide material of this modification is LiNi 0.44zr 0.12mn 1.44o 3.97f 0.03, the preparation method of the lithium nickel manganese oxide material of this modification comprises the following steps:
(1) lithium carbonate, nickel acetate, zirconium nitrate, manganese acetate, lithium fluoride is taken respectively according to amount of substance ratio Li:Ni:Zr:Mn:F=0.9991:0.44:0.12:1.44:0.03, add planetary ball mill, with the rotating speed ball milling 3h of 600r/min, ball milling mixes.Add a certain amount of ethanol, the amount ratio of ethanol and said mixture is 0.8(mL/g), be modulated into the abnormal starchiness of stream, dry, obtain mixing presoma.
(2) above-mentioned presoma is heated to 550 DEG C with 0.5 DEG C/min programming rate, insulation 2h, carries out preliminary treatment; Take out material and carry out fragmentation, ball milling mixes, and obtains powder body material, and the particle size range of this powder body material is 4 ~ 8 μm; Then temperature programmed control, sinters in air atmosphere, is heated to 800 DEG C, calcination 15h with 6 DEG C/min programming rate; The cooling rate of 4 DEG C/min is down to 620 DEG C again, annealing 18h; Last Temperature fall, to room temperature, namely obtains LiNi 0.44zr 0.12mn 1.44o 3.97f 0.03material, when the cumulative particle sizes percentile of this material reaches 50%, corresponding particle diameter is 15 μm, and specific area is 0.5m 2/ g.
Use above-mentioned LiNi 0.44zr 0.12mn 1.44o 3.97f 0.03material carries out lithium ion battery assembling as positive electrode, the Integration Assembly And Checkout method of battery is as embodiment 1, be the condition of 1C at charging and discharging currents under, first discharge specific capacity is 118.762mAh/g, the specific capacity after 100 times that circulates is 109.974mAh/g, capability retention is 92.6%, and the cyclical stability of this battery is better.
Embodiment 6
The present embodiment provides a kind of lithium nickel manganese oxide material of Fe, F doping vario-property, and the molecular formula of the lithium nickel manganese oxide material of this modification is LiNi 0.4fe 0.2mn 1.4o 3.998f 0.002, the preparation method of the lithium nickel manganese oxide material of this modification comprises the following steps:
(1) lithium carbonate, nickel acetate, ferric nitrate, manganese acetate, lithium fluoride is taken respectively according to amount of substance ratio Li:Ni:Fe:Mn:F=1.029:0.4:0.2:1.4:0.002, add planetary ball mill, with the rotating speed ball milling 8h of 300r/min, ball milling mixes.Add a certain amount of ethanol, the amount ratio of ethanol and said mixture is 1.2(mL/g), be modulated into the abnormal starchiness of stream, dry, obtain mixing presoma.
(2) above-mentioned presoma is heated to 450 DEG C with 8 DEG C/min programming rate, insulation 10h, carries out preliminary treatment; Take out material and carry out fragmentation, ball milling mixes, and obtains powder body material, and the particle size range of this powder body material is 7 ~ 12 μm; Then temperature programmed control, sinters in air atmosphere, is heated to 900 DEG C, calcination 10h with 8 DEG C/min programming rate; The cooling rate of 2 DEG C/min is down to 680 DEG C again, annealing 20h; Last Temperature fall, to room temperature, namely obtains LiNi 0.4fe 0.2mn 1.4o 3.998f 0.002material, when the cumulative particle sizes percentile of this material reaches 50%, corresponding particle diameter is 12 μm, and specific area is 0.6m 2/ g.
Use above-mentioned LiNi 0.4fe 0.2mn 1.4o 3.998f 0.002material carries out lithium ion battery assembling as positive electrode, the Integration Assembly And Checkout method of battery is as embodiment 1, be the condition of 1C at charging and discharging currents under, first discharge specific capacity is 125.819mAh/g, the specific capacity after 100 times that circulates is 115.502mAh/g, capability retention is 91.8%, and the cyclical stability of this battery is better.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.

Claims (9)

1. a lithium nickel manganese oxide material for modification, is characterized in that, the molecular formula of the lithium nickel manganese oxide material of this modification is LiNi 0.5-x/2m xmn 1.5-x/2o 4-yf y, wherein, 0.004≤x≤0.2,0.002≤y≤0.1, M is the one in Co, Al, Cr, Zr, Fe, Ti.
2. the lithium nickel manganese oxide material of modification according to claim 1, is characterized in that, when the cumulative particle sizes percentile of the lithium nickel manganese oxide material of described modification reaches 50%, corresponding particle diameter is 7 ~ 20 μm, and specific area is 0.12 ~ 0.8m 2/ g.
3. the lithium nickel manganese oxide material of modification according to claim 1 and 2, is characterized in that, described LiNi 0.5-x/2m xmn 1.5-x/2o 4-yf ymaterial is complete spinelle octahedral structure.
4. a preparation method for the lithium nickel manganese oxide material of modification, its spy is, comprises the following steps:
According to amount of substance ratio Li:Ni:M:Mn:F=(1.02 ~ 1.06) × (1-y): (0.5-x/2): x:(1.5-x/2): y takes presoma, the presoma of nickel, the presoma of M, the presoma of manganese, the lithium fluoride of lithium respectively, and the mixing precursor obtained after mixing is carried out the lithium nickel manganese oxide material LiNi that calcination obtains described modification 0.5-x/2m xmn 1.5-x/2o 4-yf y, wherein, 0.004≤x≤0.2,0.002≤y≤0.1, M is the one in Co, Al, Cr, Zr, Fe, Ti.
5. the preparation method of the lithium nickel manganese oxide material of modification according to claim 4, is characterized in that,
The presoma of described lithium is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithia;
The presoma of described nickel is one or more in nickel nitrate, nickel acetate, nickel hydroxide, nickelous carbonate, nickel chloride, nickel oxide, nickel protoxide;
The presoma of described M is the one in aluminium chloride, aluminum nitrate, aluminium oxide, aluminium hydroxide, cobalt nitrate, cobalt chloride, cobalt oxide, chromium oxide, chromium chloride, chromic nitrate, chromium hydroxide, iron oxide, ferrous carbonate, iron chloride, ferric nitrate, iron hydroxide, titanium oxide, titanium chloride, butyl titanate, tetraisopropyl titanate, titanium hydroxide, zirconia, zirconium hydroxide, zirconium nitrate, zirconium chloride;
The presoma of described manganese is one or more in manganese nitrate, manganese acetate, manganese carbonate, manganous hydroxide, manganese dioxide, mangano-manganic oxide, manganese chloride.
6. the preparation method of the lithium nickel manganese oxide material of modification according to claim 4, it is characterized in that, the concrete steps of described mixing comprise: the presoma of the presoma of the presoma of the presoma of described lithium, described nickel, described M, described manganese, described lithium fluoride are mixed by the method for ball milling.
7. the preparation method of the lithium nickel manganese oxide material of modification according to claim 6, it is characterized in that, the concrete steps of described mixing also comprise: the mixture by obtaining after the method mixing of ball milling is added solvent again, wherein, the ratio of the amount of described solvent and described mixture is 0.5 ~ 2ml/g, be modulated into the abnormal starchiness of stream, after drying, obtain described mixing presoma.
8. the preparation method of the lithium nickel manganese oxide material of modification according to claim 4, is characterized in that, the concrete steps of described calcination are:
(1) described mixing precursor is heated to 400 ~ 600 DEG C with 0.5 ~ 10 DEG C/min programming rate, insulation 2 ~ 20h;
(2) take out the material that described step (1) obtains, make described material carry out fragmentation, the particle diameter obtaining the material after fragmentation is 0.4 ~ 20 μm;
(3) material that step (2) obtains is heated to 750 ~ 950 DEG C with 0.5 ~ 10 DEG C/min programming rate, calcination 2 ~ 24h;
(4) material that step (3) obtains is down to 600 ~ 700 DEG C with 0.5 ~ 10 DEG C/min cooling rate, annealing 2 ~ 24h; Be cooled to room temperature, obtain the lithium nickel manganese oxide material LiNi of described modification 0.5-x/2m xmn 1.5-x/2o 4-yf ymaterial.
9. a lithium ion battery, is characterized in that, its positive pole includes the lithium nickel manganese oxide material of the modification described in claims 1 to 3 any one.
CN201310382284.0A 2013-08-28 2013-08-28 Modified lithium nickel manganese oxygen material, preparation method of modified lithium nickel manganese oxygen material, and lithium ion battery Pending CN104425810A (en)

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