CN102832389B - High-nickel positive active material of surface-modified lithium ion battery and preparation method of positive active material - Google Patents

High-nickel positive active material of surface-modified lithium ion battery and preparation method of positive active material Download PDF

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CN102832389B
CN102832389B CN201210359842.7A CN201210359842A CN102832389B CN 102832389 B CN102832389 B CN 102832389B CN 201210359842 A CN201210359842 A CN 201210359842A CN 102832389 B CN102832389 B CN 102832389B
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positive active
lithium
lithium ion
aluminium
nickel positive
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CN102832389A (en
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黄承焕
周友元
周新东
周耀
李厦
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湖南长远锂科有限公司
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a high-nickel positive active material of a surface-modified lithium ion battery. A matrix substance is the high-nickel positive active material LiNixCoyMzO2, the surface of the matrix substance is uniformly coated by a lithium-ion conductor compound which comprises at least one of LiAlO2, Li4Ti5O2 and Li2ZrO3; the content of the total impurity lithium in the positive active material is below 0.085%. The invention also discloses a preparation method of the positive active material. The preparation method comprises the following steps of: firstly mixing the matrix substance with an organic solution containing aluminum, an organic solution containing titanium or an organic suspension liquid containing aluminum/titanium/zirconium, drying, calcining the dried mixture, finally generating the lithium-ion conductor compound on the surface of the matrix substance, namely the high-nickel positive active material of the surface-modified lithium ion battery. The high-nickel positive active material disclosed by the invention has the advantages that the content of alkali substances is obviously reduced, the processing performance of the material is improved, and the electrochemical stability is improved.

Description

Lithium ion battery height nickel positive active material of surface modification and preparation method thereof
Technical field
The present invention relates to a kind of cell positive material and preparation method thereof, particularly relate to a kind of anode active material of lithium ion battery and preparation method thereof.
Background technology
Current lithium ion battery has been widely used in various mobile electronic product, electric tool and energy-storage system.In order to adapt to the development of these equipment, the demand of people to the lithium ion battery of high-energy-density, high power, long-life and low cost constantly increases.Lithium ion anode material is the critical material affecting battery performance and cost, but cobalt acid lithium, LiMn2O4 and the LiFePO 4 of commercial applications are difficult to there is breakthrough again in specific capacity at present, and doping type lithium nickelate positive electrode has the feature of high power capacity and low cost because of it, receive publicity, be expected to become the leading lithium ion anode material in future market.The elements such as doping Co, Mn, Al, Mg, can stablize the layer structure of lithium nickelate material, the cyclical stability of reinforcing material.For the nickelic positive electrode of doping type, LiNi xco ym zo 2(0.6≤x≤1, x+y+z=1,0≤y≤0.4,0≤z≤0.4, M is other doped chemicals), along with the increase (i.e. the increase of nickel content) of x, gram specific capacity is also higher, but in building-up process, the alkaline matter of surface residual is also more.At non-patent literature ([1] H.S. Liu, Z.R. Zhang, Z.L. Gong, Y.Yang, Electrochemical and Solid-State Letters 7 (2004): A190-A193. [2] J. Eom, M.G. Kim, J. Cho, Journal of the Electrochemical Society 155 (2008): A239-A245. [3] H. Kobayashi, S. Emura, Y. Arachi, K. Tatsumi, Journal of Power Sources 174 (2007): 774-778.) in demonstrate lithium nickelate and the nickelic positive electrode of doping type thereof surface contain Li 2cO 3, the alkaline matter such as LiOH.Because strong alkaline substance is easy to water suction, which inhibits the mobility of positive electrode when organic solvent mixing is sized mixing; This will bring great impact to slurrying and further battery performance.And these impurity lithium salts poorly conductives, be unfavorable for the transmission of ion.Therefore, how reducing the alkalescence of this type of nickelic positive electrode, eliminate its surface impurity lithium salts, is the key technical problem that this area needs to solve.
The positive electrode surface coating method reported at present, its objective is and hinder electrolyte to contact with the direct of positive electrode, reduce the side reaction of electrode solid/liquid interfaces.The coating adopted, such as MgO(is see CN1770514A Chinese patent literature), AlF 3(see B.-C. Park, H.-B. Kim, H.J. Bang, J. Prakash, Y.-K. Sun, Industrial & Engineering Chemistry Research 47 (2008): 3876-3882), AlPO 4(see B. Kim, C. Kim, T.-G. Kim, D. Ahn, B. Park, Journal of The Electrochemical Society153 (2006): A1773-A1777 and CN1416189A Chinese patent literature) and electro-conductive glass (see CN1797822A and CN1773763A Chinese patent literature) etc., although the electrochemical stability of material can be improved to a certain extent, but these coatings can not with the alkali substance reaction of high nickel positive active material, cannot reduce its alkalescence.In addition, also report is had to adopt the compound of other aluminium, titanium and zirconium to add (see CN1773763A, CN1731605A, CN1416189A) in positive electrode to, but existing technological operation not designs for " reducing the alkalescence of high nickel positive active material ", therefore fail to solve the problems referred to above that the nickelic positive electrode of lithium ion battery exists equally.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, there is provided that a kind of alkaline matter content significantly reduces, drawing abillity improves, the lithium ion battery height nickel positive active material of the electrochemical stability also surface modification of corresponding raising, the preparation method that a kind of step is simple, operate the lithium ion battery height nickel positive active material of this surface modification easy, that cost is low is also provided.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of lithium ion battery height nickel positive active material of surface modification, and its base matter is high nickel positive active material LiNi xco ym zo 2, wherein 0.6≤x≤1,0≤y≤0.4,0≤z≤0.4, and x+y+z=1, M are one or more in Mn, Al, Mg, Ti; The coated with uniform lithium ion conductor compound of described base matter, described lithium ion conductor compound comprises LiAlO 2, Li 4ti 5o 24, Li 2zrO 3in one or more; In the lithium ion battery height nickel positive active material of described surface modification, the mass content (content referred to as total impurities lithium) of total lithium of impurity lithium salts is below 0.085%.
The lithium ion battery height nickel positive active material of above-mentioned surface modification, described impurity lithium salts preferably refers to Li 2cO 3and/or LiOH is the alkaline impurities of main component.
As a total technical conceive, the present invention also provides a kind of preparation method of lithium ion battery height nickel positive active material of above-mentioned surface modification, comprise the following steps: described base matter is mixed with containing aluminium organic solution, titaniferous organic solution or the organic suspension liquid containing aluminium/titanium/zirconium, dry; Dried mixture is calcined again, makes the impurity lithium salts on base matter surface fully participate in reaction, finally at base matter Surface Creation lithium ion conductor compound, obtain the lithium ion battery height nickel positive active material of surface modification.
In above-mentioned preparation method, the described mixture being preferably aluminium isopropoxide and organic solvent containing aluminium organic solution, described titaniferous organic solution is preferably the mixture of butyl titanate and organic solvent, and the described organic suspension liquid containing aluminium/titanium/zirconium is preferably the mixture of at least one (preferably comprising one or both metals) in the hydroxide of the oxide of aluminium, titanyl compound, the oxide of zirconium, the hydroxide of aluminium, the hydroxide of titanium, zirconium and organic solvent.
In above-mentioned preparation method, the oxide of described aluminium is preferably nanometer Al 2o 3, described titanyl compound is preferably nano-TiO 2, the oxide of described zirconium is preferably nanometer ZrO 2, the hydroxide of described aluminium is preferably nanometer Al (OH) 3, described nanometer Al 2o 3, nano-TiO 2, nanometer ZrO 2, nanometer Al (OH) 3average grain diameter be all preferably 1nm ~ 250nm.
In above-mentioned preparation method, the mol ratio of the lithium in the addition of described aluminium isopropoxide, butyl titanate and the impurity lithium salts on described base matter surface is preferably (0.5 ~ 1.5): 1.Described nanometer Al 2o 3, nano-TiO 2, nanometer ZrO 2, nanometer Al (OH) 3addition and described base matter surface impurity lithium salts in lithium mol ratio be preferably (0.25 ~ 2): 1.
In above-mentioned preparation method, described organic solvent is preferably ethanol, propyl alcohol, acetone or isopropyl alcohol, the addition of described organic solvent and the mass ratio (0.5 ~ 3) of described base matter consumption: 1.
In above-mentioned preparation method, the content of the total impurities lithium on described base matter surface is preferably 0.09% ~ 0.80%.
In above-mentioned preparation method, described calcination process preferably includes heat temperature raising stage and holding stage, the heating rate in described heat temperature raising stage is preferably 1 DEG C/min ~ 10 DEG C/min, the temperature of described holding stage preferably controls at 500 DEG C ~ 800 DEG C, and temperature retention time preferably controls at 0.5h ~ 15h; Keep oxygen atmosphere in described calcination process or contain oxygen air atmosphere.
Compared with prior art, the invention has the advantages that:
(1) the present invention utilizes the impurity lithium salts of self remnants of the nickelic surface of positive electrode active material of lithium ion battery (namely containing the alkali compounds of lithium) to react in calcination process with the encapsulated additives in preparation technology, so not only can eliminate impurity lithium salts, improve the processing characteristics of positive electrode active materials, and can be formed coated at nickelic surface of positive electrode active material, improve the electrochemical stability of positive electrode active materials;
(2) its Surface Creation coating layer in the modified product obtained of the present invention, this coating layer has lithium ion conductance, is conducive to the transmission of lithium ion at electrode interface;
(3) the nano material encapsulated additives adopted in preparation technology of the present invention, is conducive to improving reactivity; In addition, due to the organic solution that adopts in preparation technology of the present invention or suspension method for coating, it can realize Homogeneous phase mixing and evenly coated, more coated than use solution easier to be dry.
Generally speaking, the present invention changes the Surface Physical Chemistry character of high nickel positive active material, solve the common problems such as the alkaline matter water suction that existing this kind of positive electrode in use faces, and method of modifying of the present invention is simple, the alkaline matter content of modified lithium ion battery height nickel positive active material significantly reduces, the range of decrease can reach more than 70%, the moisture absorption problem of positive electrode active materials is resolved, the stability of positive electrode active materials, fail safe and machinability are all improved significantly, " jelly " phenomenon is there will not be in coating process, cycle performance and the high temperature flatulence phenomenon of lithium ion battery are effectively improved.
Accompanying drawing explanation
Fig. 1 is LiAlO in the embodiment of the present invention 1 2x-ray diffractogram.
Fig. 2 is high nickel positive active material scanning electron microscope (SEM) photograph before modified in the embodiment of the present invention 1.
Fig. 3 is the scanning electron microscope (SEM) photograph that in the embodiment of the present invention 1, high nickel positive active material is modified.
Fig. 4 be in the embodiment of the present invention 1 high nickel positive active material before modified, after X-ray diffractogram.
Fig. 5 is high nickel positive active material first charge-discharge curve before modified in the embodiment of the present invention 1 (button cell, 0.1C, 2.80V ~ 4.30 V).
Fig. 6 is the first charge-discharge curve (button cell, 0.1C, 2.80 V ~ 4.30 V) that in the embodiment of the present invention 1, high nickel positive active material is modified.
Fig. 7 be in the embodiment of the present invention 1 and embodiment 2 high nickel positive active material before modified, after cycle performance comparison diagram (1C, 2.80 V ~ 4.30 V).
Fig. 8 is LiAlO in the embodiment of the present invention 2 2x-ray diffractogram.
Fig. 9 is the scanning electron microscope (SEM) photograph that in the embodiment of the present invention 2, high nickel positive active material is modified.
Figure 10 be in the embodiment of the present invention 2 high nickel positive active material before modified, after X-ray diffractogram.
Figure 11 is the modified scanning electron microscope (SEM) photograph of the high nickel positive active material in the embodiment of the present invention 3.
Embodiment
Below in conjunction with Figure of description and specific embodiment, the invention will be further described.
embodiment 1:
A lithium ion battery height nickel positive active material for surface modification of the present invention, its base matter is high nickel positive active material LiNi 0.8co 0.15al 0.05o 2, Al element wherein can be substituted by one or more in Al, Mn, Mg, Ti; The coated with uniform of base matter has lithium ion conductor compound, and this lithium ion conductor compound is LiAlO 2; The content of the total impurities lithium in the lithium ion battery height nickel positive active material of surface modification is 0.083%, is 0.27 times before modified.Impurity lithium salts in the present embodiment refers to Li 2cO 3be the alkaline impurities of main component with LiOH, the content of total impurities lithium refers to alkaline impurities Li 2cO 3with the mass content of the lithium in LiOH.Before modified, base matter LiNi 0.8co 0.15al 0.05o 2the content of total impurities lithium be 0.308%.
The preparation method of the lithium ion battery height nickel positive active material of the surface modification of the present embodiment, comprises the following steps:
(1) aluminium isopropoxide is added in organic solvent ethanol, fully stir at 60 DEG C ~ 70 DEG C (40 DEG C ~ 80 DEG C) temperature, be made into containing aluminium organic solution; Wherein, the addition of aluminium isopropoxide and high nickel positive active material LiNi before modified 0.8co 0.15al 0.05o 2the mol ratio of the lithium in surface impurity lithium salts is 1: 1;
(2) by base matter height nickel positive active material LiNi 0.8co 0.15al 0.05o 2(raw material before modified) and obtained mixing containing aluminium organic solution in step (1), wherein, the quality controlling organic solvent ethanol is 1 ~ 2 times of base matter quality, stirs 0.2h ~ 0.5h(0.1h ~ 2h) make it mix, then that mixture is dry;
(3) mixture after step (2) is placed in heating furnace to calcine, calcination process comprises heat temperature raising stage and holding stage, the heating rate in heat temperature raising stage is 3 DEG C/min, holding stage is entered after being heated to 700 DEG C, the temperature of holding stage controls at 700 DEG C, and temperature retention time is 10h; Keep oxygen atmosphere in calcination process, make the impurity lithium salts on base matter surface and coated additive fully participate in reacting, at base matter Surface Creation lithium ion conductor compound L iAlO 2, finally by natural cooling, obtain the lithium ion battery height nickel positive active material of surface modification.In order to prove that aluminium isopropoxide can react with impurity lithium salts, and generate LiAlO 2, by aluminium isopropoxide respectively with Li 2cO 3with LiOH mixing, above-mentioned condition is adopted to sinter.Detect through X-ray diffraction (XRD) and show (as shown in Figure 1), the product of gained is single-phase LiAlO 2(corresponding XRD standard card is PDF#38-1464).
After testing, the LiNi of surface modification that obtains of the present embodiment 0.8co 0.15al 0.05o 2the pH value of positive electrode active materials drops to 11.6 by 12.2, the content of the total impurities lithium in the lithium ion battery height nickel positive active material of surface modification reduces to 0.083% by original 0.308%, and the content of the total impurities lithium of surface alkalinty material is 0.27 times (assay method of the content of total impurities lithium adopts acid-base titration) before modified.
Fig. 2 and Fig. 3 is respectively LiNi in the present embodiment 0.8co 0.15al 0.05o 2positive electrode active materials before modification with modified electronic scanning Electronic Speculum figure (SEM); From Fig. 2 and Fig. 3, modified particle surface is smooth, soilless sticking fine powder still.Fig. 4 be in the present embodiment high nickel positive active material before modified, after X-ray diffractogram, from XRD figure, positive electrode active materials has α-NaFeO 2layer structure, with LiNiO 2mutually identical, showing as in 2 θ values is the three strongest ones peak that (003), (101), (104) appear in 18.75,36.69,44.48 places respectively, and before modified after all there is not other dephasign peaks.In addition, because the content of the content of the alkaline matter on base matter surface and the coating on modified base matter surface is before modified few, XRD inspection does not measure.Therefore, the positive electrode active materials of the present embodiment is modified, and its granule-morphology and crystal structure do not change, and alkalescence is effectively reduced.
The LiNi of the surface modification that the present embodiment obtains 0.8co 0.15al 0.05o 2positive electrode active materials before modification, after first charge-discharge curve as shown in Figure 5 and Figure 6, in the present embodiment high nickel positive active material before modified, after cycle performance comparison diagram as shown in Figure 7, from Fig. 5 ~ Fig. 7, although a gram specific capacity for positive electrode active materials declines to some extent, stable circulation performance be improved significantly.
embodiment 2:
A lithium ion battery height nickel positive active material for surface modification of the present invention, its base matter is high nickel positive active material LiNi 0.8co 0.15al 0.05o 2, Al element wherein can be substituted by one or more in Al, Mn, Mg, Ti; The coated with uniform of base matter has lithium ion conductor compound, and this lithium ion conductor compound is LiAlO 2; The content of the total impurities lithium in the lithium ion battery height nickel positive active material of surface modification is 0.0847%, is 0.28 times before modified.Impurity lithium salts in the present embodiment refers to Li 2cO 3be the alkaline impurities of main component with LiOH; The content of total impurities lithium refers to alkaline impurities Li 2cO 3with the mass content of the lithium in LiOH.
The preparation method of the lithium ion battery height nickel positive active material of the surface modification of the present embodiment, comprises the following steps:
(1) aluminium hydroxide average grain diameter being about 20nm adds in organic solvent ethanol, fully stirs, and is made into containing aluminium organic suspension liquid; Wherein, the addition of aluminium hydroxide and high nickel positive active material LiNi before modified 0.8co 0.15al 0.05o 2the mol ratio of the lithium in surface impurity lithium salts is 1: 1; Before modified, base matter LiNi 0.8co 0.15al 0.05o 2the content of total impurities lithium be 0.308%;
(2) by base matter height nickel positive active material LiNi 0.8co 0.15al 0.05o 2(raw material before modified) and obtained mixing containing aluminium organic suspension liquid in step (1), wherein, the quality controlling organic solvent ethanol is 1 ~ 2 times of base matter quality, stirs 0.2h ~ 0.5h(0.1h ~ 2h) make it mix, then that mixture is dry;
(3) mixture after step (2) is placed in heating furnace to calcine, calcination process comprises heat temperature raising stage and holding stage, the heating rate in heat temperature raising stage is 3 DEG C/min, holding stage is entered after being heated to 700 DEG C, the temperature of holding stage controls at 700 DEG C, and temperature retention time is 10h; Keep oxygen atmosphere in calcination process, make the impurity lithium salts on base matter surface and coated additive fully participate in reacting, at base matter Surface Creation lithium ion conductor compound L iAlO 2, finally by natural cooling, obtain the lithium ion battery height nickel positive active material of surface modification.In order to prove that nano-aluminum hydroxide can react with impurity lithium salts, and generate LiAlO 2, by aluminium hydroxide respectively with Li 2cO 3with LiOH mixing, above-mentioned condition is adopted to sinter.Detect through XRD and show (see Fig. 8), the product of gained is LiAlO 2material.Difference is with Li 2cO 3for the reactant in lithium source, the product of gained is single-phase LiAlO 2(corresponding XRD standard card is PDF#38-1464); Take LiOH as the reactant in lithium source, the product of gained is the LiAlO of two-phase mixtures 2(corresponding XRD standard card is PDF#38-1464 and PDF#44-0224).
After testing, the LiNi of surface modification that obtains of the present embodiment 0.8co 0.15al 0.05o 2the pH value of positive electrode active materials drops to 11.6 by 12.2, the content of the total impurities lithium in the lithium ion battery height nickel positive active material of surface modification reduces to 0.0847% by original 0.308%, and the content of the total impurities lithium of surface alkalinty material is 0.28 times (assay method of the content of total impurities lithium is with embodiment 1) before modified.Fig. 9 is LiNi in the present embodiment 0.8co 0.15al 0.05o 2the electronic scanning Electronic Speculum figure (SEM) that positive electrode active materials is modified; As seen from Figure 9, particle diameter in the distribution of particles of 50 nm ~ 200 nm at positive electrode active materials LiNi 0.8co 0.15al 0.05o 2the surface of particle.Figure 10 be in the present embodiment high nickel positive active material before modified, after X-ray diffractogram, from X-ray diffractogram, positive electrode active materials has α-NaFeO 2the LiNiO of layer structure 2phase, showing as in 2 θ values is the three strongest ones peak that (003), (101), (104) appear in 18.75,36.69,44.48 places respectively, and before modified after all there is not other dephasign peaks.Therefore, the positive electrode active materials of the present embodiment is modified, and its granule-morphology and crystal structure do not change, and by surface modification, the alkaline matter content of positive electrode active materials is effectively reduced.Similar to Example 1, the LiNi of the surface modification that the present embodiment obtains 0.8co 0.15al 0.05o 2the stable circulation performance of positive electrode active materials be improved significantly (see Fig. 7).
embodiment 3:
In the present embodiment, coated for embodiment 2 additive is used instead as micron order aluminium hydroxide (1 μm ~ 2 μm); Other preparation process and technological parameter condition identical with embodiment 2.
After surface modification, the lithium ion height nickel positive active material LiNi that the present embodiment is obtained 0.8co 0.15al 0.05o 2pH value drop to 11.9 by 12.2, the content of the total impurities lithium of surface alkalinty material is before modified 0.36 times.From reduce alkalescence effect, the present embodiment than embodiment 1 and embodiment 2 a bit weaker.
Figure 11 is LiNi in the present embodiment 0.8co 0.15al 0.05o 2modified SEM photo; From Figure 11, positive electrode remained on surface has some fine powders.
embodiment 4:
In the present embodiment, coated for embodiment 2 additive is used instead as alumina in Nano level; Other preparation process and technological parameter condition identical with embodiment 2.
After surface modification, the lithium ion height nickel positive active material LiNi that the present embodiment is obtained 0.8co 0.15al 0.05o 2pH value drop to 11.6 by 12.2, the content of the total impurities lithium of surface alkalinty material is before modified 0.27 times.
embodiment 5:
In the present embodiment, coated for embodiment 2 additive is used instead as nanoscale TiO 2, its addition and before modified high nickel positive active material LiNi 0.8co 0.15al 0.05o 2the mol ratio of the lithium in surface impurity lithium salts is 1.2: 1; Other preparation process and technological parameter condition identical with embodiment 2.
After surface modification, the lithium ion height nickel positive active material LiNi that the present embodiment is obtained 0.8co 0.15al 0.05o 2pH value drop to 11.7 by 12.2, the content of the total impurities lithium of surface alkalinty material is before modified 0.28 times.
embodiment 6:
In the present embodiment, the base matter of embodiment 2 is used instead as LiNi 0.6co 0.2mn 0.2o 2; Other preparation process and technological parameter condition identical with embodiment 2.
After surface modification, the lithium ion height nickel positive active material LiNi that the present embodiment is obtained 0.6co 0.2mn 0.2o 2pH value drop to 11.4 by 11.8, the content of the total impurities lithium in the lithium ion battery height nickel positive active material of surface modification reduces to 0.04% by original 0.10%, and the content of the total impurities lithium of surface alkalinty material is before modified 0.4 times.
Base matter height nickel positive active material LiNi of the present invention xco ym zo 2(wherein 0.6≤x≤1,0≤y≤0.4,0≤z≤0.4, and x+y+z=1, M are one or more in Mn, Al, Mg, Ti) can be prepared by soft chemical method and solid sintering technology, specifically comprise the following steps:
First, by sulfuric acid (or nitric acid) solution of the nickel of certain mol proportion, cobalt sulfuric acid solution, M and NaOH/NH 4the co-precipitation of OH alkali lye, obtains presoma hydroxide after washing and drying; Then certain mol proportion is pressed by presoma hydroxide with LiOH or Li 2cO 3mixing, mixture is placed in electric furnace at 600 DEG C ~ 850 DEG C temperature, under oxygen atmosphere, roasting 15h ~ 25h, obtains and LiNiO 2identical layered rock salt structure (a-Na 2feO 2) single-phase LiNi xco ym zo 2.Adopt the method obtained its surface alkalinty material of positive electrode active materials---the mass content of the total impurities lithium in impurity lithium salts is in 0.09% ~ 0.80% scope.The modification object LiNi used in each embodiment above 0.8co 0.15al 0.05o 2and LiNi 0.6co 0.2mn 0.2o 2namely be adopt said method to obtain.

Claims (3)

1. the preparation method of the lithium ion battery height nickel positive active material of a surface modification, comprise the following steps: base matter is mixed with containing aluminium organic solution, titaniferous organic solution or the organic suspension liquid containing aluminium/titanium/zirconium, dry, the mass content of the total impurities lithium on described base matter surface is 0.09% ~ 0.80%, and described impurity lithium salts refers to Li 2cO 3and/or LiOH is the alkaline impurities of main component; Described is the mixture of aluminium isopropoxide and organic solvent containing aluminium organic solution, described titaniferous organic solution is the mixture of butyl titanate and organic solvent, and the described organic suspension liquid containing aluminium/titanium/zirconium is the mixture of at least one in the hydroxide of the oxide of aluminium, titanyl compound, the oxide of zirconium, the hydroxide of aluminium, the hydroxide of titanium, zirconium and organic solvent; The oxide of described aluminium is nanometer Al 2o 3, described titanyl compound is nano-TiO 2, the oxide of described zirconium is nanometer ZrO 2, the hydroxide of described aluminium is nanometer Al (OH) 3, described nanometer Al 2o 3, nano-TiO 2, nanometer ZrO 2, nanometer Al (OH) 3average grain diameter be 1nm ~ 250nm; The mol ratio of the lithium in the addition of described aluminium isopropoxide or butyl titanate and the impurity lithium salts on described base matter surface is (0.5 ~ 1.5): 1; Described nanometer Al 2o 3, nano-TiO 2, nanometer ZrO 2, nanometer Al (OH) 3addition and described base matter surface impurity lithium salts in the mol ratio of lithium be (0.25 ~ 2): 1;
Dried mixture is calcined again, makes the impurity lithium salts on base matter surface fully participate in reaction, finally at base matter Surface Creation lithium ion conductor compound, obtain the lithium ion battery height nickel positive active material of surface modification;
The base matter of described lithium ion battery height nickel positive active material is high nickel positive active material LiNi xco ym zo 2, wherein 0.6≤x≤1,0≤y≤0.4,0≤z≤0.4 and x+y+z=1, M are one or more in Mn, Al, Mg, Ti; The coated with uniform lithium ion conductor compound of described base matter, described lithium ion conductor compound comprises LiAlO 2, Li 4ti 5o 24, Li 2zrO 3in one or more; In the lithium ion battery height nickel positive active material of described surface modification, the mass content of total impurities lithium is below 0.085%.
2. preparation method according to claim 1, is characterized in that: described organic solvent is ethanol, propyl alcohol, acetone or isopropyl alcohol, and the addition of described organic solvent and the mass ratio of described base matter consumption are (0.5 ~ 3): 1.
3. preparation method according to claim 1 and 2, it is characterized in that: described calcination process comprises heat temperature raising stage and holding stage, the heating rate in described heat temperature raising stage is 1 DEG C/min ~ 10 DEG C/min, the temperature of described holding stage controls at 500 DEG C ~ 800 DEG C, and temperature retention time controls at 0.5h ~ 15h; Keep oxygen atmosphere in described calcination process or contain oxygen air atmosphere.
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