CN104766970A - Synthetic method for lithium nickel manganese oxygen covered with lithium titanate - Google Patents

Synthetic method for lithium nickel manganese oxygen covered with lithium titanate Download PDF

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Publication number
CN104766970A
CN104766970A CN201510207998.7A CN201510207998A CN104766970A CN 104766970 A CN104766970 A CN 104766970A CN 201510207998 A CN201510207998 A CN 201510207998A CN 104766970 A CN104766970 A CN 104766970A
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source compound
lithium titanate
coated
solution
sintering
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公伟伟
王世银
宋文锋
池田一崇
宋振伟
陈敏
黄海翔
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HUNAN RESHINE NEW MATERIAL CO Ltd
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HUNAN RESHINE NEW MATERIAL 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • 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 preparing method for lithium nickel manganese oxygen covered with lithium titanate. The method comprises the following steps that firstly, Ni, Mn and M are added into pure water, and a mixed solution with the total molar concentration ranging from 1.0 mol/L to 3.0 mol/L is obtained; secondly, a complexing agent solution is added into the mixed solution, the pH value is mixed to be ranging from 9 to 12, and a supernatant solution is obtained; thirdly, the supernatant solution is oxidized, the solid centrifugal separation is carried out, drying is carried out, and precursor powder is obtained; fourthly, Li source compound is mixed with the precursor powder, a first time sintering is carried out, LiNi (0.5-x) Mn (1.5-y) M (x+y) O4 is obtained, pure water adding and the drying are carried out on the LiNi (0.5-x) Mn (1.5-y) M (x+y) O4, second Li source compound and TiO2 powder, and a mixed solid material is obtained; sixthly, secondary sintering is carried out on the mixed solid material, and an electrode material covered with the lithium titanate is obtained. According to the prepared electrode material covered with the lithium titanate, the cycle performance and the rate performance of the electrode material can be effectively improved.

Description

The synthetic method of the Li-Ni-Mn-O that lithium titanate is coated
Technical field
The present invention relates to field of lithium ion battery material, especially, relate to the synthetic method of the coated Li-Ni-Mn-O of a kind of lithium titanate.
Background technology
The anode material for lithium-ion batteries voltage that current commercialization uses is generally at 3.7V, and Novel Dual positive electrode LiNi 0.5mn 1.5o 4voltage can reach 4.8V, and it is applied in lithium ion battery, can improve the energy density of positive electrode, compare LiMn 2o 4, both theoretical capacities are close, are about 148mAh/g, LiNi 0.5mn 1.5o 4voltage is but than LiMn 2o 4exceed nearly 1V, energy density promotes about 25%, but it also exists high temperature cyclic performance difference, problem that high rate performance is general as anode material for lithium-ion batteries.Reason is, high voltage LiNi 0.5mn 1.5o 4spinel structure in charge and discharge cycles, structural stability is poor, Mn be easy to occur disproportionated reaction, cause the dissolving of Mn.And in existing electrolyte system, under the high voltage of 4.8V, electrolyte is easy in material surface oxidation Decomposition, and the barrier film in battery is the easy material surface at 4.8V also, is easy to aging, causes micro-short circuit in cyclic process, form potential safety hazard.
Summary of the invention
The object of the invention is the synthetic method of the Li-Ni-Mn-O providing a kind of lithium titanate coated, with the technical problem that the product electrical property solving Li-Ni-Mn-O prepared by conventional method is poor.
For achieving the above object, the technical solution used in the present invention is as follows:
A synthetic method for the Li-Ni-Mn-O that lithium titanate is coated, comprises the following steps:
1) by Ni source compound, Mn source compound and M source compound Ni:Mn:M=(0.5-x) in molar ratio: (1.5-y): (x+y) adds in pure water, be configured to the mixed solution that total mol concentration is 1.0 ~ 3.0mol/L, wherein, 0 < x < 0.5,0 < y < 1.5, M source compound is one or more in the soluble-salt of Al, B, Ti, Mg, V, Cr, Zr, Co, Cu, Nb, Mo, Fe, Hf, Zn, Ta, W.
2) under the atmosphere of protective gas, stir and heating condition under, in mixed solution, add enveloping agent solution, and add alkaline solution to pH value 9 ~ 12, carry out precipitation reaction, obtain aaerosol solution.
3) be oxidized aaerosol solution, solid centrifugation, dry, obtaining molecular formula is Ni (0.5-x)mn (1.5-y)m (x+y)the precursor powder of OOH.
4) by a Li source compound and precursor powder mixing, carry out first sintering, obtain LiN i (0.5-x)mn (1.5-y)m (x+y)o 4.
5) by LiN i (0.5-x)mn (1.5-y)m (x+y)o 4, the 2nd Li source compound, TiO 2powder, adds pure water, mixes, dispersion, dry, obtains hybrid solid material.
6) hybrid solid material is carried out double sintering, obtaining molecular formula is LiN i (0.5-x)mn (1.5-y)m (x+y)o 4li 4ti 5o 12li-Ni-Mn-O jacketed electrode material.
Further, step 2) in mixing speed be 400rpm ~ 700rpm, heating-up temperature is 30 ~ 90 DEG C.
Further, enveloping agent solution and mixed solution press complexing agent: the mixed in molar ratio of (Mn+Ni+M)=0.1 ~ 1.0.
Further, a Li source compound and precursor powder press Li:(Ni+Mn+M)=the mixed in molar ratio of 0.4 ~ 0.7, the sintering temperature of first sintering is 700 ~ 950 DEG C, and sintering time is 15 ~ 35 hours.
Further, TiO 2the quality sum of powder and the 2nd Li source compound is LiN i (0.5-x)mn (1.5-y)m (x+y)o 4the 3 ~ 7%, two Li source compound and TiO of quality 2the mol ratio of powder is 0.8 ~ 0.85:1.
Further, the sintering temperature of double sintering is 600 ~ 800 DEG C, and sintering time is 5 ~ 20 hours.
Further, Ni source compound is NiSO 4, NiCl 2, C 4h 6o 4ni, Ni (NO 3) 2, NiF 2in one or more, Mn source compound is MnSO 4, MnCl 2, Mn (CH 3cOO) 2, Mn (NO 3) 2, Mn (ClO 4) 2in one or more, a Li source compound and the 2nd Li source compound are respectively Li 2sO 4, LiCl, Li 2cO 3, LiOH, LiNO 3, CH 3one or more in COOLi, LiF.
Further, alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and enveloping agent solution is one or more in ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, second diamino, ammonium sulfate or ammoniacal liquor.
Further, after obtaining Li-Ni-Mn-O jacketed electrode material, also comprise the deironing of Li-Ni-Mn-O jacketed electrode material through screens.
Further, carry out 200-1000 order to Li-Ni-Mn-O jacketed electrode material to sieve deironing.
The present invention has following beneficial effect: Li-Ni-Mn-O jacketed electrode material prepared by the present invention, adopts Li 4ti 5o 12coated and element doping is to LiNi 0.5mn 1.5o 4carry out modification.Li 4ti 5o 12be called as zero strain material, in charge and discharge cycles process, hardly crystal transfer occur, Stability Analysis of Structures.Li 4ti 5o 12and LiNi 0.5mn 1.5o 4be all spinel structure, therefore Li 4ti 5o 12be easy to be coated on LiN i (0.5-x)mn (1.5-y)m (x+y)o 4surface, forms even, solid, effective protective layer.Stablize in charge and discharge cycles process, the crystalline structure of high voltage two-component particle changes, and effectively improves cycle performance and the high rate performance of electrode material, and, Li 4ti 5o 12voltage platform be 1.55V, platform is steady, effectively can reduce high voltage binary material surface voltage, reduces the decomposition of electrolyte, reduces interface resistance and polarization resistance, effectively improves cycle performance and the high rate performance of electrode material.Further, adopt wet type to stir the method for co-precipitation chemical synthesis, can prepare primary particle size is Nano grade, aggregates into the ball-type presoma of aggregate particle size micron level, on the basis of this presoma, can carry out more effective coated.The clad structure formed, more evenly, fine and close, effectively.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.Below with reference to figure, the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the flow chart of the coated Li-Ni-Mn-O of the lithium titanate of the preferred embodiment of the present invention;
Fig. 2 is the SEM figure of the Li-Ni-Mn-O of comparative example 1;
Fig. 3 is the SEM figure of the coated Li-Ni-Mn-O of the lithium titanate of embodiment 1;
Fig. 4 is the first charge-discharge specific capacity/voltage pattern of the coated Li-Ni-Mn-O of the lithium titanate of embodiment 2;
Fig. 5 is the first charge-discharge specific capacity/voltage pattern of the Li-Ni-Mn-O of comparative example 1;
Fig. 6 is the high rate performance specific capacity/voltage pattern of the coated Li-Ni-Mn-O of the lithium titanate of embodiment 3;
Fig. 7 is the high rate performance specific capacity/voltage pattern of the Li-Ni-Mn-O of comparative example 1;
Fig. 8 is the cycle performance resolution chart of the Li-Ni-Mn-O of the coated Li-Ni-Mn-O of the lithium titanate of embodiment 4 and comparative example 1;
Fig. 9 is the XRD figure of the Li-Ni-Mn-O of comparative example 1;
Figure 10 is the XRD figure of the coated Li-Ni-Mn-O of the lithium titanate of embodiment 1.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described in detail, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
With reference to Fig. 1, the preferred embodiments of the present invention provide the coated Li-Ni-Mn-O of a kind of lithium titanate, comprise the following steps:
S01: by Ni source compound, Mn source compound and M source compound Ni:Mn:M=(0.5-x) in molar ratio: (1.5-y): (x+y) adds in pure water, be configured to the mixed solution that total mol concentration is 1.0 ~ 3.0mol/L, wherein, 0 < x < 0.5,0 < y < 1.5, M source compound is one or more in the soluble-salt of Al, B, Ti, Mg, V, Cr, Zr, Co, Cu, Nb, Mo, Fe, Hf, Zn, Ta, W.
S02: under the atmosphere of protective gas, stir and heating condition under, in mixed solution, add enveloping agent solution, and add alkaline solution to pH value 9 ~ 12, carry out precipitation reaction, obtain aaerosol solution.
S03: oxidation aaerosol solution, solid centrifugation, dry, obtaining molecular formula is Ni (0.5-x)mn (1.5-y)m (x+y)the precursor powder of OOH.
S04: by a Li source compound and precursor powder mixing, carry out first sintering, obtain LiN i (0.5-x)mn (1.5-y)m (x+y)o 4.
S05: by LiN i (0.5-x)mn (1.5-y)m (x+y)o 4, the 2nd Li source compound, TiO 2powder, adds pure water, mixes, dispersion, dry, obtains hybrid solid material.
S06: hybrid solid material is carried out double sintering, obtaining molecular formula is LiN i (0.5-x)mn (1.5-y)m (x+y)o 4li 4ti 5o 12li-Ni-Mn-O jacketed electrode material.
Ni source compound, Mn source compound and M source compound are stoichiometrically configured to the mixed solution of 1.0 ~ 3.0mol/L, when the solubility of mixed solution is too low, production efficiency is low, production capacity is lower, and during excessive concentration, making the precursor powder particle size range obtained be not easy to control, its particle diameter is larger, finally cause the particle diameter of Li-Ni-Mn-O jacketed electrode material excessive, required particle size range cannot be reached.Above-mentioned reaction needed adds alkaline solution, the pH value of the whole reaction system of strict control is 9 ~ 12, and when pH value is too low, sedimentary particle diameter growth rate is too fast, make the particle diameter of precursor powder excessive, affect product property, when pH value is too high, the particle that in the precursor powder of preparation, particle diameter is less is more, produce more micro mist, be applied in lithium battery process, easily safety issue occur, and obtained Li-Ni-Mn-O jacketed electrode density of material is too small.
Precursor powder adopts coprecipitation preparation, M source compound is Doped ions, in coprecipitation, Ni source compound, Mn source compound and M source compound are through stirring, after precipitation reaction, oxidation is separated dry obtained precursor powder, and Ni source compound, Mn source compound and M source compound are ionic level mixing, Ni ion, Mn ion and M Ar ion mixing are even, and obtained precursor powder homogeneity is good.And in some synthetic method, first by Ni source compound, to obtain precursor through series reaction last for the mixing of Mn source compound, then with M source compound mixed sintering, Ni ion, Mn ion and M Ar ion mixing are uneven.M is doped chemical, can to LiNi 0.5mn 1.5o 4carry out modification, effectively improve cycle performance and the high rate performance of electrode material.M source compound is one or more in the soluble-salt of Al, B, Ti, Mg, V, Cr, Zr, Co, Cu, Nb, Mo, Fe, Hf, Zn, Ta, W.Protective gas can be N 2.
LiN i (0.5-x)mn (1.5-y)m (x+y)o 4, Li source compound, TiO 2powder, adds pure water and mixes, dispersion, dry, obtains hybrid solid material, Li source compound, TiO 2powder mixing is coated on LiN i (0.5-x)mn (1.5-y)m (x+y)o 4on, Li source compound, TiO 2powder forms Li in sintering process afterwards 4ti 5o 12.
Li-Ni-Mn-O jacketed electrode material prepared by the present invention, by adopting Li 4ti 5o 12coated and element doping is to LiNi 0.5mn 1.5o 4carry out modification.Li 4ti 5o 12be called as zero strain material, in charge and discharge cycles process, hardly crystal transfer occur.Li 4ti 5o 12and LiNi 0.5mn 1.5o 4be all spinel structure, therefore Li 4ti 5o 12be easy to be coated on LiN i (0.5-x)mn (1.5-y)m (x+y)o 4surface, forms even, solid, effective protective layer.Stablize in charge and discharge cycles process, the crystalline structure of high voltage two-component particle changes, and effectively improves cycle performance and the high rate performance of electrode material, and Li 4ti 5o 12voltage platform be 1.55V, platform is steady, effectively can reduce high voltage binary material surface voltage, reduces the decomposition of electrolyte, reduces interface resistance and polarization resistance, effectively improves cycle performance and the high rate performance of electrode material.Further, adopt wet type to stir the method for co-precipitation chemical synthesis, can prepare primary particle size is Nano grade, aggregates into the ball-type presoma of aggregate particle size micron level, on the basis of this presoma, can carry out more effective coated.The clad structure formed, more evenly, fine and close, effectively.
Alternatively, reaction low whipping speed is preferably 400rpm ~ 700rpm, and heating-up temperature is carry out under the condition of 30 ~ 90 DEG C.When mixing speed and heating-up temperature improper time, the size controlling difficulty of precursor powder, finally affects the quality of Li-Ni-Mn-O jacketed electrode material.
Alternatively, enveloping agent solution and mixed solution press complexing agent: the mixed in molar ratio of (Mn+Ni+M)=0.1 ~ 1.0.The reaction of mixed solution and enveloping agent solution can be carried out in a kettle., can add a certain amount of pure water and enveloping agent solution in advance in a kettle..
Alternatively, a Li source compound and precursor powder press Li:(Ni+Mn+M)=the mixed in molar ratio of 0.4 ~ 0.7, the sintering temperature of first sintering is 700 ~ 950 DEG C, and sintering time is 15 ~ 35 hours.Li source compound and precursor powder preferably press Li:(Ni+Mn+M)=the mixed in molar ratio of 0.4 ~ 0.7, when the two ratio is not in above-mentioned scope, generates dephasign more, cause productive rate lower.Carry out first sintering after one Li source compound and precursor powder mixing, sintering temperature is preferably 700 ~ 950 DEG C, when sintering temperature is too low, can not generate LiN i (0.5-x)mn (1.5-y)m (x+y)o 4, when sintering temperature is too high, other material can be generated, cause dephasign more; Sintering time is preferably 15 ~ 35 hours, coordinates suitable sintering temperature, can ensure LiN i (0.5-x)mn (1.5-y)m (x+y)o 4have higher purity, dephasign is few.
Alternatively, TiO 2the gross mass of powder and the 2nd Li source compound is LiN i (0.5-x)mn (1.5-y)m (x+y)o 4quality 3 ~ 7%, when mass ratio is too low, enough Li can not be generated 4ti 5o 12carry out coated to Li-Ni-Mn-O surface, thus do not reach covered effect, mass ratio is too high, and the lithium titanate of generation is too much, reduces lithium nickel manganese oxide material voltage.2nd Li source compound and TiO 2the mol ratio of powder is 0.8 ~ 0.85:1.Mol ratio is too low, can not form Li 4ti 5o 12, containing TiO 2dephasign, mol ratio is too high, forms rich lithium titanium oxygen compound dephasign.
Alternatively, the sintering temperature of double sintering is 600 ~ 800 DEG C, and sintering time is 5 ~ 20 hours.After obtaining hybrid solid material, carry out double sintering, the sintering temperature of double sintering is preferably 600 ~ 800 DEG C, and sintering time is preferably 5 ~ 20 hours.Sintering temperature is too low, when sintering time is too short, and Li source compound, TiO 2powder mixing can not generate Li 4ti 5o 12, sintering temperature is too high, when sintering time is long, can generate dephasign, cause productive rate lower, and cause energy waste.Sintering generates Li 4ti 5o 12coating layer, effectively can improve cycle performance and the high rate performance of electrode material.
Alternatively, Ni source compound is NiSO 4, NiCl 2, C 4h 6o 4ni, Ni (NO 3) 2, NiF 2in one or more, Mn source compound is MnSO 4, MnCl 2, Mn (CH 3cOO) 2, Mn (NO 3) 2, Mn (ClO 4) 2in one or more, a Li source compound and the 2nd Li source compound are respectively Li 2sO 4, LiCl, Li 2cO 3, LiOH, LiNO 3, CH 3one or more in COOLi, LiF.
Alternatively, alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and enveloping agent solution is one or more in ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, second diamino, ammonium sulfate or ammoniacal liquor.After the precipitation reaction, obtain aaerosol solution, aaerosol solution comprises sediment and solution, can carry out oxidation reaction, obtain precursor powder subsequently through centrifugation, washing, drying by suspension overflow to maturation tank.
Alternatively, after obtaining Li-Ni-Mn-O jacketed electrode material, also comprise the deironing of Li-Ni-Mn-O jacketed electrode material through screens.
Alternatively, carry out 200-1000 order to Li-Ni-Mn-O jacketed electrode material to sieve deironing.Preferably, carry out 400 orders to Li-Ni-Mn-O jacketed electrode material to sieve deironing.Finally obtain even-grained high-voltage anode material product LiN i (0.5-x)mn (1.5-y)m (x+y)o 4li 4ti 5o 12.
Embodiment 1
1) by NiSO 4, MnSO 4and Cr (NO 3) 3ni:Mn:Cr=1:3:1 adds in distilled water in molar ratio, is configured to the mixed solution that total mol concentration is 2.5mol/L.
2) under the atmosphere of protective gas, under the condition of 400rpm mixing speed and 30 DEG C; the ratio of ethylenediamine tetra-acetic acid and mixed solution presses ethylenediamine tetra-acetic acid: the mixed in molar ratio of (Mn+Ni+Cr)=0.1; and add NaOH solution adjust ph to 9; carry out precipitation reaction, obtain aaerosol solution.
3) be oxidized aaerosol solution, solid centrifugation, dry, obtaining molecular formula is Ni 0.4mn 1.2cr 0.4the precursor powder of OOH.
4) by Li 2cO 3and precursor powder presses Li 2cO 3: (Ni+Mn+Cr)=0.2 mixes, and at 700 DEG C, sintering carries out first sintering in 15 hours, obtains LiNi 0.4mn 1.2cr 0.4o 4.
5) by LiNi 0.4mn 1.2cr 0.4o 4, Li 2cO 3, TiO 2powder, adds pure water, mixes, dispersion, dry, obtains hybrid solid material, TiO 2powder and Li 2cO 3gross mass be LiNi 0.4mn 1.2cr 0.4o 4quality 7%, Li 2cO 3and TiO 2the mol ratio of powder is 0.8:1.
6) hybrid solid material is sintered 5 hours at 600 DEG C and carry out double sintering, be cooled to room temperature, cross 200 mesh sieve deironing, obtaining molecular formula is LiNi 0.4mn 1.2cr 0.4o 4li 4ti 5o 12li-Ni-Mn-O jacketed electrode material.
Embodiment 2
1) by NiCl 2, MnSO 4and AlCl 3ni:Mn:Al=6:18:1 adds in distilled water in molar ratio, is configured to the mixed solution that total mol concentration is 2.5mol/L.
2) under the atmosphere of protective gas, under the condition of 450rpm mixing speed and 40 DEG C; the ratio of disodium ethylene diamine tetraacetate and mixed solution presses disodium ethylene diamine tetraacetate: the mixed in molar ratio of (Mn+Ni+Al)=0.3; and add KOH solution adjust ph to 9.5; carry out precipitation reaction, obtain aaerosol solution.
3) be oxidized aaerosol solution, solid centrifugation, dry, obtaining molecular formula is Ni 0.48mn 1.44al 0.08the precursor powder of OOH.
4) LiCl and precursor powder are pressed LiCl:(Ni+Mn+Al)=0.6 mixing, at 750 DEG C, sintering carries out first sintering in 20 hours, obtains LiNi 0.48mn 1.44al 0.08o 4.
5) by LiNi 0.48mn 1.44al 0.08o 4, LiF, TiO 2powder, adds pure water, mixes, dispersion, dry, obtains hybrid solid material, TiO 2the quality sum of powder and LiF is LiNi 0.48mn 1.44al 0.08o 45%, LiF and TiO of quality 2the mol ratio of powder is 0.81:1.
6) hybrid solid material is sintered 10 hours at 700 DEG C and carry out double sintering, be cooled to room temperature, cross 300 mesh sieve deironing, obtaining molecular formula is LiNi 0.48mn 1.44al 0.08o 4li 4ti 5o 12li-Ni-Mn-O jacketed electrode material.
Embodiment 3
1) by Ni (NO 3) 2, C 4h 6o 4ni, Mn (NO 3) 2and B 2o 3ni:Mn:B=6:18:1 adds in pure water in molar ratio, is configured to the mixed solution that total mol concentration is 1.5mol/L.Wherein Ni (NO 3) 2and C 4h 6o 4the mol ratio of Ni is 1:1.
2) under the atmosphere of protective gas, under the condition of 500rpm mixing speed and 50 DEG C; the mixing enveloping agent solution of second diamino and ammonium sulfate and the ratio of mixed solution are by mixing enveloping agent solution: the mixed in molar ratio of (Mn+Ni+B)=0.7; and add KOH solution adjust ph to 10; carry out precipitation reaction, obtain aaerosol solution.Wherein the mol ratio of second diamino and ammonium sulfate is 2:1.
3) be oxidized aaerosol solution, solid centrifugation, dry, obtaining molecular formula is Ni 0.48mn 1.44b 0.08the precursor powder of OOH.
4) by Li 2sO 4and precursor powder presses Li 2sO 4: (Ni+Mn+B)=0.35 mixes, and at 950 DEG C, sintering carries out first sintering in 25 hours, obtains LiNi 0.48mn 1.44b 0.08o 4.
5) by LiNi 0.48mn 1.44b 0.08o 4, CH 3cOOLi, TiO 2powder, adds pure water, mixes, dispersion, dry, obtains hybrid solid material, TiO 2powder and CH 3the quality sum of COOLi is LiNi 0.48mn 1.44b 0.086%, LiF and TiO of the quality of O4 2the mol ratio of powder is 0.83:1.
6) hybrid solid material is sintered 15 hours at 740 DEG C and carry out double sintering, be cooled to room temperature, cross 500 mesh sieve deironing, obtaining molecular formula is LiNi 0.48mn 1.44b 0.08o 4li 4ti 5o 12li-Ni-Mn-O jacketed electrode material.
Embodiment 4
1) by NiF 2, MnCl 2and MgSO 4ni:Mn:Mg=9:27:4 adds in pure water in molar ratio, is configured to the mixed solution that total mol concentration is 1.5mol/L.
2) under the atmosphere of protective gas, under the condition of 600rpm mixing speed and 80 DEG C; the ratio of ammoniacal liquor and mixed solution presses ammoniacal liquor: the mixed in molar ratio of (Mn+Ni+Mg)=0.9; and add KOH solution adjust ph to 11, carry out precipitation reaction, obtain aaerosol solution.
3) be oxidized aaerosol solution, solid centrifugation, dry, obtaining molecular formula is Ni 0.45mn 1.35mg 0.2the precursor powder of OOH.
4) LiOH and precursor powder are pressed LiOH:(Ni+Mn+Mg)=0.5 mixing, at 800 DEG C, sintering carries out first sintering in 30 hours, obtains LiNi 0.45mn 1.35mg 0.2o4.
5) by LiNi 0.45mn 1.35mg 0.2o 4, LiNO 3, TiO 2powder, adds pure water, mixes, dispersion, dry, obtains hybrid solid material, TiO 2powder and LiNO 3quality sum be LiNi 0.45mn 1.35mg 0.2o 4quality 3%, LiNO 3and TiO 2the mol ratio of powder is 0.84:1.
6) hybrid solid material is sintered 18 hours at 780 DEG C and carry out double sintering, be cooled to room temperature, cross 800 mesh sieve deironing, obtaining molecular formula is LiNi 0.45mn 1.35mg 0.2o 4li 4ti 5o 12li-Ni-Mn-O jacketed electrode material.
Embodiment 5
1) by Ni (NO 3) 2, Mn (CH 3cOO) 2and Zr (NO 3) 4ni:Mn:Zr=1:1:18 adds in pure water in molar ratio, is configured to the mixed solution that total mol concentration is 2mol/L.
2) under the atmosphere of protective gas, under the condition of 700rpm mixing speed and 90 DEG C; the ratio of ammoniacal liquor and mixed solution presses ammoniacal liquor: the mixed in molar ratio of (Mn+Ni+Zr)=1; and add KOH solution adjust ph to 12, carry out precipitation reaction, obtain aaerosol solution.
3) be oxidized aaerosol solution, solid centrifugation, dry, obtaining molecular formula is Ni 0.1mn 0.1zr 1.8the precursor powder of OOH.
4) by CH 3cOOLi and precursor powder press CH 3cOOLi:(Ni+Mn+Zr)=0.7 mixing, at 900 DEG C, sintering carries out first sintering in 35 hours, obtains Li Ni 0.1mn 0.1zr 1.8o 4.
5) by Li Ni 0.1mn 0.1zr 1.8o4, LiCl, TiO 2powder, adds pure water, mixes, dispersion, dry, obtains hybrid solid material, TiO 2the quality sum of powder and LiCl is Li Ni 0.1mn 0.1zr 1.8o 43%, LiCl and TiO of quality 2the mol ratio of powder is 0.85:1.
6) hybrid solid material is sintered 20 hours at 800 DEG C and carry out double sintering, be cooled to room temperature, cross 1000 mesh sieve deironing, obtaining molecular formula is Li Ni 0.1mn 0.1zr 1.8o 4li 4ti 5o 12li-Ni-Mn-O jacketed electrode material.
Comparative example 1
1) by NiSO 4, MnSO 4ni:Mn=1:3 adds in pure water in molar ratio, is configured to the mixed solution that total mol concentration is 2mol/L.
2) under the atmosphere of protective gas, under the condition of 450rpm mixing speed and 40 DEG C; the ratio of disodium ethylene diamine tetraacetate and mixed solution presses disodium ethylene diamine tetraacetate: the mixed in molar ratio of (Mn+Ni)=0.3; and add KOH solution adjust ph to 9.5; carry out precipitation reaction, obtain aaerosol solution.
3) be oxidized aaerosol solution, solid centrifugation, dry, obtaining molecular formula is Ni 0.5mn 1.5the precursor powder of OOH.
4) LiCl and precursor powder are pressed LiCl:(Ni+Mn)=0.5 mixing, at 750 DEG C, sintering carries out first sintering in 20 hours, obtains LiNi 0.5mn 1.5o 4.
5) by LiNi 0.5mn 1.5o 4, LiF, TiO 2powder, adds pure water, mixes, dispersion, dry, obtains hybrid solid material, TiO 2the quality sum of powder and LiF is LiN i0.5mn 1.5o 45%, LiF and TiO of quality 2the mol ratio of powder is 0.81:1.
6) hybrid solid material is sintered 10 hours at 700 DEG C and carry out double sintering, be cooled to room temperature, cross 300 mesh sieve deironing, obtaining molecular formula is LiNi 0.5mn 1.5o 4li 4ti 5o 12li-Ni-Mn-O jacketed electrode material.
Data characterization
The product of the Li-Ni-Mn-O that the lithium titanate of Example 1 is coated and comparative example 1 carries out SEM sign, and test result is with reference to Fig. 2 and Fig. 3.For preventing accumulation of static electricity and improving imaging contrast's property, before carrying out SEM, sample carries out metal spraying process.The scanning electron microscopy used is JSM-6390LV.
Can find out from Fig. 2 and Fig. 3, the Li-Ni-Mn-O finished product not having lithium titanate coated, for the ball-type material of shaggy about the particle size 6um that large grain size is piled up, embodiment 1 is after lithium titanate is coated, ESEM shows, at the lithium titanate surface layer that the Surface Creation primary particle degree of ball-type Li-Ni-Mn-O is less.Illustrate that lithium titanate is relatively more even, fine and close, be effectively coated on binary material particle surface.
The product of the Li-Ni-Mn-O that the lithium titanate of Example 1 is coated and comparative example 1 carries out XRD test, and test result as shown in Figure 9 and Figure 10.The material phase analysis of sample carries out on the D-MAX2500VB type X-ray diffractometer of Japanese Rigaku Neo-Confucianism, main operating parameters: rated power 3kW, Cu target K α 1 ray (wavelength is 0.15406nm), tube voltage 40kV, tube current 300mA, sweep speed 5 °/min, step-length 0.02 °, sweep limits 10 ~ 80 °.The cell parameter of sample, unit cell volume and density applications Jade5.0 analyze.
The XRD display of comparative example 1 is the diffraction spectroscopy of spinel-type binary NiMn material, and the XRD display of embodiment 1 is the diffraction spectroscopy and the lithium titanate material diffraction spectroscopy that have spinel-type binary NiMn material.Relatively the XRD result of comparative example 1 and embodiment 15 illustrates, successfully synthesizes at the complete lithium titanate material of spinel-type binary material Surface coating crystal formation, the Li-Ni-Mn-O that namely lithium titanate is coated in the preparation method of embodiment 1.
The product of the Li-Ni-Mn-O that the lithium titanate of Example 2 is coated and comparative example 1 carries out initial charge and discharge capacity test first, and test result is as shown in table 2, Fig. 4 and Fig. 5.The battery made is that model 2025 buckles electricity.92g active material (electrode material prepared), 5g conductive agent acetylene black, 3g binding agent polyvinylidene fluoride (PVDF) and 140g Solvents N-methyl-2-Pyrrolidone (NMP) are stirred in de-airing mixer and forms uniform slurry.This slurry is coated on uniformly on the aluminium foil of 2um thickness, then oven dry, roll-in at 110 DEG C, gets pole piece.By pole piece, celgard2400 barrier film, aluminium flake, foam nickel sheet, buckle electric shell and be assembled into 2025 button cells.The detection (comprising first charge-discharge, high rate performance, cycle performance test) of charge-discharge performance is carried out at CT2001A LAND battery test system.Normal capacity is set as 1C=100mAh/g.Table 1 is for testing the discharge and recharge system of carrying out.
Table 1 discharge and recharge system
Table 2 initial charge and first discharge capacity test chart
In table 2, data come from Fig. 4 and Fig. 5, and from table 2, Fig. 4, Fig. 5, embodiment 2 slightly improves than the charge/discharge capacity of comparative example 1, because the theoretical capacity of lithium titanate is higher than the capacity of binary, so the capacity being coated with the binary material of lithium titanate slightly improves.
The product of the Li-Ni-Mn-O that the lithium titanate of Example 3 is coated and comparative example 1 carries out high rate performance test, and test result is as shown in table 3, Fig. 6 and Fig. 7.
Table 3 high rate performance test result
Table 3 data come from Fig. 6 and Fig. 7, and data and Fig. 6, Fig. 7 as can be seen from table 3, embodiment 3 improves high rate performance than comparative example 1.Nickel manganese binary material Surface coating lithium titanate, improves the stability of material crystal formation under high current charge-discharge condition, thus improves the high rate performance of binary material.Illustrate that nickel manganese binary material Surface coating lithium titanate improves the high rate performance of binary.
The product of the Li-Ni-Mn-O that the lithium titanate of Example 4 is coated and comparative example 1 carries out cycle performance test, and test result is as shown in table 4, Fig. 8.
Table 4 cycle performance test result
The data corresponding diagram 8 of table 4.Data and Fig. 8 as can be seen from table 4, the cyclical stability of embodiment 4 is than the good stability of comparative example 1.Be coated on the lithium titanate material on binary material surface, stabilize crystalline structure in charge and discharge process on the one hand, on the other hand, prevent the decomposition of electrolyte on binary material surface and the disproportionated reaction of Mn, therefore improve the cyclical stability of binary material.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a synthetic method for the Li-Ni-Mn-O that lithium titanate is coated, is characterized in that, comprises the following steps:
1) by Ni source compound, Mn source compound and M source compound Ni:Mn:M=(0.5-x) in molar ratio: (1.5-y): (x+y) adds in pure water, be configured to the mixed solution that total mol concentration is 1.0 ~ 3.0mol/L, wherein, 0 < x < 0.5,0 < y < 1.5, described M source compound is one or more in the soluble-salt of Al, B, Ti, Mg, V, Cr, Zr, Co, Cu, Nb, Mo, Fe, Hf, Zn, Ta, W;
2) under the atmosphere of protective gas, stir and heating condition under, in described mixed solution, add enveloping agent solution, and add alkaline solution to pH value 9 ~ 12, carry out precipitation reaction, obtain aaerosol solution;
3) be oxidized described aaerosol solution, solid centrifugation, dry, obtaining molecular formula is Ni (0.5-x)mn (1.5-y)m (x+y)the precursor powder of OOH;
4) by a Li source compound and the mixing of described precursor powder, carry out first sintering, obtain LiN i (0.5-x)mn (1.5-y)m (x+y)o 4;
5) by described LiN i (0.5-x)mn (1.5-y)m (x+y)o 4, the 2nd Li source compound, TiO 2powder, adds pure water, mixes, dispersion, dry, obtains hybrid solid material;
6) described hybrid solid material is carried out double sintering, obtaining molecular formula is LiN i (0.5-x)mn (1.5-y)m (x+y)o 4li 4ti 5o 12the coated Li-Ni-Mn-O of lithium titanate.
2. the Li-Ni-Mn-O that lithium titanate according to claim 1 is coated, is characterized in that, step 2) in mixing speed be 400rpm ~ 700rpm, heating-up temperature is 30 ~ 90 DEG C.
3. the Li-Ni-Mn-O that lithium titanate according to claim 1 is coated, is characterized in that, described enveloping agent solution and described mixed solution press complexing agent: the mixed in molar ratio of (Mn+Ni+M)=0.1 ~ 1.0.
4. the Li-Ni-Mn-O that lithium titanate according to claim 1 is coated, it is characterized in that, a described Li source compound and precursor powder press Li:(Ni+Mn+M)=the mixed in molar ratio of 0.4 ~ 0.7, the sintering temperature of described first sintering is 700 ~ 950 DEG C, and sintering time is 15 ~ 35 hours.
5. the Li-Ni-Mn-O that lithium titanate according to claim 1 is coated, is characterized in that, described TiO 2the quality sum of powder and described 2nd Li source compound is described LiN i (0.5-x)mn (1.5-y)m (x+y)o 4quality 3 ~ 7%, described 2nd Li source compound and described TiO 2the mol ratio of powder is 0.8 ~ 0.85:1.
6. the Li-Ni-Mn-O that lithium titanate according to claim 1 is coated, is characterized in that, the sintering temperature of described double sintering is 600 ~ 800 DEG C, and sintering time is 5 ~ 20 hours.
7. the Li-Ni-Mn-O that lithium titanate according to claim 1 is coated, is characterized in that, described Ni source compound is NiSO 4, NiCl 2, C 4h 6o 4ni, Ni (NO 3) 2, NiF 2in one or more, described Mn source compound is MnSO 4, MnCl 2, Mn (CH 3cOO) 2, Mn (NO 3) 2, Mn (ClO 4) 2in one or more, a described Li source compound and described 2nd Li source compound are respectively Li 2sO 4, LiCl, Li 2cO 3, LiOH, LiNO 3, CH 3one or more in COOLi, LiF.
8. the Li-Ni-Mn-O that lithium titanate according to claim 1 is coated, it is characterized in that, described alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and described enveloping agent solution is one or more in ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, second diamino, ammonium sulfate or ammoniacal liquor.
9. the Li-Ni-Mn-O that lithium titanate according to claim 1 is coated, is characterized in that, after obtaining described Li-Ni-Mn-O jacketed electrode material, also comprises the deironing of described Li-Ni-Mn-O jacketed electrode material through screens.
10. the Li-Ni-Mn-O that lithium titanate according to claim 9 is coated, is characterized in that, carries out 200-1000 order to sieve deironing to described Li-Ni-Mn-O jacketed electrode material.
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