CN102832389A - 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 PDFInfo
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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
Technical field
The present invention relates to a kind of cell positive material and preparation method thereof, relate in particular to a kind of anode active material of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery has been widely used in various mobile electronic products, electric tool and energy-storage system at present.In order to adapt to these Equipment of Development, people to high-energy-density, high power, long-life and cheaply the demand of lithium ion battery constantly increase.Lithium ion anode material is the critical material that influences battery performance and cost; But the lithium of the cobalt of commercial applications acid at present, LiMn2O4 and LiFePO 4 are difficult to have breakthrough again on specific capacity; And doping type lithium nickelate positive electrode has high power capacity and characteristics cheaply because of it; Receive publicity, be expected to become the leading lithium ion anode material in future market.Elements such as doping Co, Mn, Al, Mg can be stablized 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 (being the increase of nickel content) of x, the gram specific capacity is also high more, but in the building-up process, the alkaline matter of surface remnants is also many 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): Li is contained on the surface that has proved lithium nickelate and the nickelic positive electrode of doping type thereof 774-778.)
2CO
3, alkaline matter such as LiOH.Because strong alkaline substance is easy to suction, it has suppressed the flowability of positive electrode when the organic solvent mixing is sized mixing; This will bring great influence to slurrying and follow-up 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 need solve.
The positive electrode surface method for coating of being reported at present its objective is that obstruction electrolyte and the direct of positive electrode contact, and reduce the side reaction of electrode solid/liquid interfaces.The coating that is adopted is such as MgO (referring to CN1770514A Chinese patent document), AlF
3(referring to B.-C. Park, H.-B. Kim, H.J. Bang, J. Prakash, Y.-K. Sun, Industrial & Engineering Chemistry Research 47 (2008): 3876-3882), AlPO
4(referring to B. Kim; C. Kim; T.-G. Kim, D. Ahn, B. Park; Journal of The Electrochemical Society153 (2006): A1773-A1777 and CN1416189A Chinese patent document) and electro-conductive glass (referring to CN1797822A and CN1773763A Chinese patent document) etc.; Though can improve the electrochemical stability of material to a certain extent, these coatings can not with the alkali substance reaction of high nickel positive active material, can't reduce its alkalescence.In addition; Also there is report to adopt the compound of other aluminium, titanium and zirconium to add (referring to CN1773763A, CN1731605A, CN1416189A) in the positive electrode to; But the existing processes operation is not to design to " reducing the alkalescence of high nickel positive active material ", therefore fails 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 that the present invention will solve is the deficiency that overcomes prior art; Provide that a kind of alkaline matter content significantly reduces, drawing abillity improves, the also high nickel positive active material of lithium ion battery of the surface modification of corresponding raising of electrochemical stability, the preparation method of the high nickel positive active material of lithium ion battery of this surface modification that a kind of step is simple, operation is prone to row, cost is low also is provided.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of high nickel positive active material of lithium ion battery 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 is one or more among Mn, Al, Mg, the Ti; The coated with uniform lithium ion conductor compound of said base matter, said lithium ion conductor compound comprises LiAlO
2, Li
4Ti
5O
24, Li
2ZrO
3In one or more; The mass content of total lithium of impurity lithium salts (abbreviating the content of total impurities lithium as) is below 0.085% in the high nickel positive active material of the lithium ion battery of said surface modification.
The high nickel positive active material of the lithium ion battery of above-mentioned surface modification, said impurity lithium salts preferably is meant with 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 the high nickel positive active material of lithium ion battery of above-mentioned surface modification; May further comprise the steps: said base matter is mixed drying with the organic suspension liquid that contains aluminium organic solution, titaniferous organic solution or contain aluminium/titanium/zirconium; Dried mixture is calcined again, made the impurity lithium salts on base matter surface fully participate in reaction, generate the lithium ion conductor compound on the base matter surface at last, obtain the high nickel positive active material of lithium ion battery of surface modification.
Among the above-mentioned preparation method; Saidly contain the mixture that aluminium organic solution is preferably aluminium isopropoxide and organic solvent; Said titaniferous organic solution is preferably the mixture of butyl titanate and organic solvent, and the said organic suspension liquid that contains aluminium/titanium/zirconium is preferably the mixture of at least a (preferably comprising one or both metals) and organic solvent in the hydroxide of hydroxide, zirconium of hydroxide, the titanium of oxide, the aluminium of oxide, titanyl compound, the zirconium of aluminium.
Among the above-mentioned preparation method, the oxide of said aluminium is preferably nanometer Al
2O
3, said titanyl compound is preferably nano-TiO
2, the oxide of said zirconium is preferably nanometer ZrO
2, the hydroxide of said aluminium is preferably nanometer Al (OH)
3, said nanometer Al
2O
3, nano-TiO
2, nanometer ZrO
2, nanometer Al (OH)
3Average grain diameter all be preferably 1nm～250nm.
Among the above-mentioned preparation method, the mol ratio of the lithium in the impurity lithium salts on the addition of said aluminium isopropoxide, butyl titanate and said base matter surface is preferably (0.5～1.5): 1.Said nanometer Al
2O
3, nano-TiO
2, nanometer ZrO
2, nanometer Al (OH)
3The impurity lithium salts on addition and said base matter surface in the mol ratio of lithium be preferably (0.25～2): 1.
Among the above-mentioned preparation method, said organic solvent is preferably ethanol, propyl alcohol, acetone or isopropyl alcohol, the mass ratio (0.5～3) of the addition of said organic solvent and said base matter consumption: 1.
Among the above-mentioned preparation method, the content of the total impurities lithium on said base matter surface is preferably 0.09%～0.80%.
Among the above-mentioned preparation method; Said calcination process preferably includes heat temperature raising stage and holding stage; The heating rate in said heat temperature raising stage is preferably 1 ℃/min～10 ℃/min; The temperature of said holding stage preferably is controlled at 500 ℃～800 ℃, and temperature retention time preferably is controlled at 0.5h～15h; Keep oxygen atmosphere in the said calcination process or contain the oxygen air atmosphere.
Compared with prior art, the invention has the advantages that:
(1) the present invention utilizes remaining impurity lithium salts (alkali compounds that promptly contains lithium) of the nickelic surface of positive electrode active material of lithium ion battery self and the encapsulated additives among the preparation technology in calcination process, to react; So not only can eliminate the impurity lithium salts; Improve the processing characteristics of positive electrode active materials; And can form coating at nickelic surface of positive electrode active material, improve the electrochemical stability of positive electrode active materials;
(2) its surface generates coating layer in the product that obtains after the modification of the present invention, and this coating layer has lithium-ion electric leads, and helps the transmission of lithium ion at electrode interface;
(3) the nano material encapsulated additives that is adopted among the preparation technology of the present invention helps improving reactivity; In addition, because the organic solution or the suspension method for coating that adopt among the preparation technology of the present invention, it can realize evenly mixing and evenly coating, and coats dry more easily than use solution.
Generally speaking; The present invention has changed the Surface Physical Chemistry character of high nickel positive active material, solved the common problems such as alkaline matter suction that existing this type positive electrode in use faces, and method of modifying of the present invention is simple; The alkaline matter content of the high nickel positive active material of lithium ion battery after the modification significantly reduces; The range of decrease can reach more than 70%, and the moisture absorption problem of positive electrode active materials is resolved, and the stability of positive electrode active materials, fail safe and machinability all are improved significantly; " jelly " phenomenon in coating process, can not occur, the cycle performance of lithium ion battery and high temperature flatulence phenomenon are effectively improved.
Description of drawings
Fig. 1 is LiAlO in the embodiment of the invention 1
2X-ray diffractogram.
Fig. 2 is the sem photograph before the high nickel positive active material modification in the embodiment of the invention 1.
Fig. 3 is the sem photograph after the high nickel positive active material modification in the embodiment of the invention 1.
Fig. 4 is the forward and backward X-ray diffractogram of high nickel positive active material modification in the embodiment of the invention 1.
Fig. 5 is the first charge-discharge curve (button cell, 0.1C, 2.80V～4.30 V) before the high nickel positive active material modification in the embodiment of the invention 1.
Fig. 6 is the first charge-discharge curve after the high nickel positive active material modification in the embodiment of the invention 1 (button cell, 0.1C, 2.80 V～4.30 V).
Fig. 7 is the forward and backward cycle performance comparison diagram (1C, 2.80 V～4.30 V) of high nickel positive active material modification among the embodiment of the invention 1 and the embodiment 2.
Fig. 8 is LiAlO in the embodiment of the invention 2
2X-ray diffractogram.
Fig. 9 is the sem photograph after the high nickel positive active material modification in the embodiment of the invention 2.
Figure 10 is the forward and backward X-ray diffractogram of high nickel positive active material modification in the embodiment of the invention 2.
Figure 11 is the sem photograph after the high nickel positive active material modification in the embodiment of the invention 3.
Embodiment
Below in conjunction with Figure of description and specific embodiment the present invention is further described.
Embodiment 1:
The high nickel positive active material of a kind of lithium ion battery of surface modification of the present invention, its base matter are high nickel positive active material LiNi
0.8Co
0.15Al
0.05O
2, Al element wherein can be substituted by among Al, Mn, Mg, the Ti one or more; The coated with uniform of base matter has the lithium ion conductor compound, and this lithium ion conductor compound is LiAlO
2The content of the total impurities lithium in the high nickel positive active material of the lithium ion battery of surface modification is 0.083%, is 0.27 times before the modification.Impurity lithium salts in the present embodiment is meant with Li
2CO
3With LiOH be the alkaline impurities of main component, the content of total impurities lithium is meant alkaline impurities Li
2CO
3Mass content with lithium among the LiOH.Before the modification, base matter LiNi
0.8Co
0.15Al
0.05O
2The content of total impurities lithium be 0.308%.
The preparation method of the high nickel positive active material of lithium ion battery of the surface modification of present embodiment may further comprise the steps:
(1) aluminium isopropoxide is added in the organic solvent ethanol, under 60 ℃～70 ℃ (40 ℃～80 ℃ all can) temperature, fully stir, be made into and contain aluminium organic solution; Wherein, high nickel positive active material LiNi before the addition of aluminium isopropoxide and the modification
0.8Co
0.15Al
0.05O
2The mol ratio of the lithium in the surface impurity lithium salts is 1: 1;
(2) with the high nickel positive active material LiNi of base matter
0.8Co
0.15Al
0.05O
2The aluminium organic solution that contains that makes in (modification before raw material) and the step (1) is mixed; Wherein, The quality of control organic solvent ethanol is 1～2 times of base matter quality, stirs 0.2h～0.5h (0.1h～2h all can) it is mixed, and is then that mixture is dry;
(3) place heating furnace to calcine in the mixture after the step (2); Calcination process comprises heat temperature raising stage and holding stage; The heating rate in heat temperature raising stage is 3 ℃/min; Get into holding stage after being heated to 700 ℃, the temperature of holding stage is controlled at 700 ℃, and temperature retention time is 10h; Keep oxygen atmosphere in the calcination process, make the impurity lithium salts on base matter surface and coating fully participate in reaction, generate lithium ion conductor compound L iAlO on the base matter surface with additive
2,, obtain the high nickel positive active material of lithium ion battery of surface modification after natural cooling.For prove aluminium isopropoxide can with impurity lithium salts reaction, and generate LiAlO
2, with aluminium isopropoxide respectively with Li
2CO
3Mix with LiOH, adopt above-mentioned condition to carry out sintering.Detection shows (as shown in Figure 1) through X-ray diffraction (XRD), and the product of gained is single-phase LiAlO
2(corresponding XRD standard card is PDF#38-1464).
Through detecting the LiNi of the surface modification that present embodiment makes
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 high nickel positive active material of the lithium ion battery 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 (the Determination on content method of total impurities lithium adopts acid-base titration to get final product) before the modification.
Fig. 2 and Fig. 3 are respectively LiNi in the present embodiment
0.8Co
0.15Al
0.05O
2The electronic scanning Electronic Speculum figure (SEM) of positive electrode active materials before modification and after the modification; Visible from Fig. 2 and Fig. 3, still smooth, the no reunion fine powder of particle surface after the modification.Fig. 4 is the forward and backward X-ray diffractogram of high nickel positive active material modification in the present embodiment, and from XRD figure, positive electrode active materials has α-NaFeO
2Layer structure is with LiNiO
2Mutually identical, showing as in 2 θ values is the three strongest ones peak that (003), (101), (104) appear respectively in 18.75,36.69,44.48 places, and other dephasign peaks all do not occur before and after the modification.In addition, because the content of the coating on base matter surface is few after the content of the alkaline matter on the preceding base matter of modification surface and the modification, XRD can not detect.Therefore, after the positive electrode active materials modification of present embodiment, its granule-morphology and crystal structure do not change, and alkalescence is effectively reduced.
The LiNi of the surface modification that present embodiment obtains
0.8Co
0.15Al
0.05O
2Positive electrode active materials is at modification forward and backward first charge-discharge curve such as Fig. 5 and shown in Figure 6; The forward and backward cycle performance comparison diagram of high nickel positive active material modification is as shown in Figure 7 in the present embodiment; Visible by Fig. 5～Fig. 7; Though the gram specific capacity of positive electrode active materials descends to some extent, the stable circulation performance be improved significantly.
Embodiment 2:
The high nickel positive active material of a kind of lithium ion battery of surface modification of the present invention, its base matter are high nickel positive active material LiNi
0.8Co
0.15Al
0.05O
2, Al element wherein can be substituted by among Al, Mn, Mg, the Ti one or more; The coated with uniform of base matter has the lithium ion conductor compound, and this lithium ion conductor compound is LiAlO
2The content of the total impurities lithium in the high nickel positive active material of the lithium ion battery of surface modification is 0.0847%, is 0.28 times before the modification.Impurity lithium salts in the present embodiment is meant with Li
2CO
3With LiOH be the alkaline impurities of main component; The content of total impurities lithium is meant alkaline impurities Li
2CO
3Mass content with lithium among the LiOH.
The preparation method of the high nickel positive active material of lithium ion battery of the surface modification of present embodiment may further comprise the steps:
(1) aluminium hydroxide that average grain diameter is about 20nm adds in the organic solvent ethanol, fully stirs, and is made into to contain the aluminium organic suspension liquid; Wherein, high nickel positive active material LiNi before the addition of aluminium hydroxide and the modification
0.8Co
0.15Al
0.05O
2The mol ratio of the lithium in the surface impurity lithium salts is 1: 1; Before the modification, base matter LiNi
0.8Co
0.15Al
0.05O
2The content of total impurities lithium be 0.308%;
(2) with the high nickel positive active material LiNi of base matter
0.8Co
0.15Al
0.05O
2The aluminium organic suspension liquid that contains that makes in (modification before raw material) and the step (1) mixes; Wherein, The quality of control organic solvent ethanol is 1～2 times of base matter quality, stirs 0.2h～0.5h (0.1h～2h all can) it is mixed, and is then that mixture is dry;
(3) place heating furnace to calcine in the mixture after the step (2); Calcination process comprises heat temperature raising stage and holding stage; The heating rate in heat temperature raising stage is 3 ℃/min; Get into holding stage after being heated to 700 ℃, the temperature of holding stage is controlled at 700 ℃, and temperature retention time is 10h; Keep oxygen atmosphere in the calcination process, make the impurity lithium salts on base matter surface and coating fully participate in reaction, generate lithium ion conductor compound L iAlO on the base matter surface with additive
2,, obtain the high nickel positive active material of lithium ion battery of surface modification after natural cooling.For prove nano-aluminum hydroxide can with impurity lithium salts reaction, and generate LiAlO
2, with aluminium hydroxide respectively with Li
2CO
3Mix with LiOH, adopt above-mentioned condition to carry out sintering.Detection shows (referring to Fig. 8) through XRD, and the product of gained is LiAlO
2Material.Different is with Li
2CO
3Be the reactant in lithium source, the product of gained is single-phase LiAlO
2(corresponding XRD standard card is PDF#38-1464); With LiOH is the reactant in lithium source, and the product of gained is two LiAlO that mix mutually
2(corresponding XRD standard card is PDF#38-1464 and PDF#44-0224).
Through detecting the LiNi of the surface modification that present embodiment makes
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 high nickel positive active material of the lithium ion battery 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 (the Determination on content method of total impurities lithium is with embodiment 1) before the modification.Fig. 9 is LiNi in the present embodiment
0.8Co
0.15Al
0.05O
2Electronic scanning Electronic Speculum figure (SEM) after the positive electrode active materials modification; Visible from Fig. 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 is the forward and backward X-ray diffractogram of high nickel positive active material modification in the present embodiment, and 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 respectively in 18.75,36.69,44.48 places, and other dephasign peaks all do not occur before and after the modification.Therefore, after the positive electrode active materials modification of present embodiment, its granule-morphology and crystal structure do not change, and through surface modification, the alkaline matter content of positive electrode active materials is effectively reduced.Similar with embodiment 1, the LiNi of the surface modification that present embodiment obtains
0.8Co
0.15Al
0.05O
2The stable circulation performance of positive electrode active materials be improved significantly (referring to Fig. 7).
Embodiment 3:
Use additive to use instead embodiment 2 coatings in the present embodiment and be micron order aluminium hydroxide (1 μ m～2 μ m); Other preparation processes and technological parameter condition are identical with embodiment 2.
Through after the surface modification, the high nickel positive active material LiNi of the lithium ion that present embodiment makes
0.8Co
0.15Al
0.05O
2The pH value drop to 11.9 by 12.2, the content of the total impurities lithium of surface alkalinty material is 0.36 times before the modification.From reducing the effect of alkalescence, present embodiment is more a bit weaker than embodiment 1 and embodiment 2.
Figure 11 is LiNi in the present embodiment
0.8Co
0.15Al
0.05O
2SEM photo after the modification; Visible from Figure 11, the positive electrode remained on surface has some fine powders.
Embodiment 4:
Use additive to use instead embodiment 2 coatings in the present embodiment and be alumina in Nano level; Other preparation processes and technological parameter condition are identical with embodiment 2.
Through after the surface modification, the high nickel positive active material LiNi of the lithium ion that present embodiment makes
0.8Co
0.15Al
0.05O
2The pH value drop to 11.6 by 12.2, the content of the total impurities lithium of surface alkalinty material is 0.27 times before the modification.
Embodiment 5:
Use additive to use instead embodiment 2 coatings in the present embodiment and be nanoscale TiO
2, high nickel positive active material LiNi before its addition and the modification
0.8Co
0.15Al
0.05O
2The mol ratio of the lithium in the surface impurity lithium salts is 1.2: 1; Other preparation processes and technological parameter condition are identical with embodiment 2.
Through after the surface modification, the high nickel positive active material LiNi of the lithium ion that present embodiment makes
0.8Co
0.15Al
0.05O
2The pH value drop to 11.7 by 12.2, the content of the total impurities lithium of surface alkalinty material is 0.28 times before the modification.
Embodiment 6:
In the present embodiment base matter of embodiment 2 used instead and be LiNi
0.6Co
0.2Mn
0.2O
2Other preparation processes and technological parameter condition are identical with embodiment 2.
Through after the surface modification, the high nickel positive active material LiNi of the lithium ion that present embodiment makes
0.6Co
0.2Mn
0.2O
2The pH value drop to 11.4 by 11.8, the content of the total impurities lithium in the high nickel positive active material of the lithium ion battery of surface modification reduces to 0.04% by original 0.10%, the content of the total impurities lithium of surface alkalinty material is 0.4 times before the modification.
The high nickel positive active material LiNi of base matter 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 is one or more among Mn, Al, Mg, the Ti) can prepare through soft chemical method and solid sintering technology, specifically may further comprise the steps:
At first, with sulfuric acid (or nitric acid) solution and the NaOH/NH of the nickel of certain mol proportion, cobalt sulfuric acid solution, M
4The co-precipitation of OH alkali lye obtains presoma hydroxide after the washing and drying; Press then certain mol proportion with presoma hydroxide with LiOH or Li
2CO
3Mix, place electric furnace under 600 ℃～850 ℃ temperature in mixture, under oxygen atmosphere, roasting 15h～25h obtains and LiNiO
2Identical stratiform rock salt structure (a-Na
2FeO
2) single-phase LiNi
xCo
yM
zO
2Adopt that this method makes its surface alkalinty material of positive electrode active materials---the mass content of the total impurities lithium in the impurity lithium salts is in 0.09%～0.80% scope.More than the modification object LiNi that uses among each embodiment
0.8Co
0.15Al
0.05O
2And LiNi
0.6Co
0.2Mn
0.2O
2Promptly adopt said method to make.
Claims (9)
1. the high nickel positive active material of the lithium ion battery of a surface modification, 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 is one or more among Mn, Al, Mg, the Ti; It is characterized in that: the coated with uniform lithium ion conductor compound of said base matter, said lithium ion conductor compound comprises LiAlO
2, Li
4Ti
5O
24, Li
2ZrO
3In one or more; The mass content of total impurities lithium is below 0.085% in the high nickel positive active material of the lithium ion battery of said surface modification.
2. the high nickel positive active material of the lithium ion battery of surface modification according to claim 1, it is characterized in that: said impurity lithium salts is meant with Li
2CO
3And/or LiOH is the alkaline impurities of main component.
3. the preparation method of the high nickel positive active material of lithium ion battery of a surface modification according to claim 1 or claim 2; May further comprise the steps: said base matter is mixed drying with the organic suspension liquid that contains aluminium organic solution, titaniferous organic solution or contain aluminium/titanium/zirconium; Dried mixture is calcined again, made the impurity lithium salts on base matter surface fully participate in reaction, generate the lithium ion conductor compound on the base matter surface at last, obtain the high nickel positive active material of lithium ion battery of surface modification.
4. preparation method according to claim 3; It is characterized in that: saidly contain the mixture that aluminium organic solution is aluminium isopropoxide and organic solvent; Said titaniferous organic solution is the mixture of butyl titanate and organic solvent, the mixture of at least a and organic solvent in the hydroxide of the oxide of the oxide that the said organic suspension liquid that contains aluminium/titanium/zirconium is an aluminium, titanyl compound, zirconium, the hydroxide of aluminium, titanium, the hydroxide of zirconium.
5. preparation method according to claim 4 is characterized in that: the oxide of said aluminium is nanometer Al
2O
3, said titanyl compound is a nano-TiO
2, the oxide of said zirconium is nanometer ZrO
2, the hydroxide of said aluminium is nanometer Al (OH)
3, said nanometer Al
2O
3, nano-TiO
2, nanometer ZrO
2, nanometer Al (OH)
3Average grain diameter be 1nm～250nm.
6. preparation method according to claim 5 is characterized in that: the mol ratio of the lithium in the impurity lithium salts on the addition of said aluminium isopropoxide or butyl titanate and said base matter surface is (0.5～1.5): 1; Said nanometer Al
2O
3, nano-TiO
2, nanometer ZrO
2, nanometer Al (OH)
3The impurity lithium salts on addition and said base matter surface in the mol ratio of lithium be (0.25～2): 1.
7. according to claim 4 or 5 or 6 described preparation methods, it is characterized in that: said organic solvent is ethanol, propyl alcohol, acetone or isopropyl alcohol, the mass ratio (0.5～3) of the addition of said organic solvent and said base matter consumption: 1.
8. according to each described preparation method in the claim 3～6, it is characterized in that: the content of the total impurities lithium on said base matter surface is 0.09%～0.80%.
9. according to each described preparation method in the claim 3～6; It is characterized in that: said calcination process comprises heat temperature raising stage and holding stage; The heating rate in said heat temperature raising stage is 1 ℃/min～10 ℃/min; The temperature of said holding stage is controlled at 500 ℃～800 ℃, and temperature retention time is controlled at 0.5h～15h; Keep oxygen atmosphere in the said calcination process or contain the oxygen air atmosphere.
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