Positive active material for secondary lithium battery, method for preparing the same and secondary lithium battery containing the positive active material
10164249 ยท 2018-12-25
Assignee
Inventors
Cpc classification
H01M4/505
ELECTRICITY
H01M4/131
ELECTRICITY
Y02E60/10
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
C01G51/66
CHEMISTRY; METALLURGY
C01G53/66
CHEMISTRY; METALLURGY
H01M4/525
ELECTRICITY
C01G53/50
CHEMISTRY; METALLURGY
International classification
H01M4/36
ELECTRICITY
H01M4/525
ELECTRICITY
H01M4/131
ELECTRICITY
Abstract
The present invention provides a positive active material for use in a secondary lithium battery, a method for preparing the positive active material and a secondary lithium battery containing the positive active material. The positive active material includes a core of lithium transition metal oxide represented by Formula Li.sub.xM.sub.yN.sub.1-yO.sub.2-A.sub. and a coating layer of lithium transition metal silicate represented by Formula xLi.sub.2O.yNO.sub.a.SiO.sub.2-B.sub.which in-situ formed on the core, wherein 0.8x1.3, 0.6y1.0, 0.01x2.1, 0.2y1.5, 0.1a3.0, 00.2, 00.4, 00.5, 00.5. The positive active material according to the present invention has high capacity, desirable cycling performance and safety performance, as well as desirable thermal stability.
Claims
1. A positive active material for a secondary lithium battery, comprising: a core of lithium transition metal oxide represented by Formula Li.sub.xM.sub.yN.sub.1-yO.sub.2-A.sub. and a coating layer of lithium transition metal silicate represented by Formula xLi.sub.2O.yNO.sub.a.SiO.sub.2-B.sub. which in-situ formed on the core, wherein element represented by M is at least one of Ni, Co and Mn; element represented by N and N each is at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ra, Al, Ga, In, Ge, Sn, Sc, Ti, B, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, W, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; element represented by A and B each is at least one of N, F, P, 5, Cl, Se; and 0.8x1.3, 0.6y1.0, 0.01x2.1, 0.2y1.5, 0.1a3.0, 00.2, 00.4, 00.5, 00.5.
2. The positive active material of claim 1, wherein in the lithium transition metal oxide represented by Formula Li.sub.xM.sub.yN.sub.1-yO.sub.2-A.sub., the element represented by M is combination of elements Ni, Co, Mn; and the element represented by N is at least one of Mg, Al, Ti, B, V, Mo, W, Ni, Co, Mn, Y, Ce; 0.7y1.0.
3. The positive active material of claim 2, wherein the element represented by M in the lithium transition metal oxide represented by Formula Li.sub.xM.sub.yN.sub.1-yO.sub.2-A.sub. is Co, Ni.sub.0.5Co.sub.0.5, Ni.sub.0.7Co.sub.0.3, Ni.sub.0.8Co.sub.0.2, Ni.sub.0.9Co.sub.0.1, Ni.sub.1/3Co.sub.1/3Mn.sub.1/3, Ni.sub.0.5Co.sub.0.2Mn.sub.0.3, Ni.sub.0.6Co.sub.0.2Mn.sub.0.2, Ni.sub.0.8Co.sub.0.01Mn.sub.0.1 or combinations thereof.
4. The positive active material of claim 1, wherein the element represented by N in Formula Li.sub.xM.sub.yN.sub.1-yO.sub.2-A.sub. is at least one of Mg, Al, Ti, B, Mo, Zr, V, Ce, W, and 0.95y1.0.
5. The positive active material of claim 1, wherein the element represented by A in the lithium transition metal oxide represented by Formula Li.sub.xM.sub.yN.sub.1-yO.sub.2-A.sub. is N and/or F, and 00.1.
6. The positive active material of claim 1, wherein the element represented by B in the lithium transition metal silicate represented by Formula xLi.sub.2O.yNO.sub.a.SiO.sub.2-B.sub. is N and/or F, and 00.2.
7. The positive active material of claim 1, wherein in the lithium transition metal silicate represented by Formula xLi.sub.2O.yNO.sub.a.SiO.sub.2-B.sub., 0.1x1, 0.2y1.0.
8. The positive active material of claim 1, wherein the coating layer of lithium transition metal silicate represented by Formula xLi.sub.2O.yNO.sub.a.SiO.sub.2-B.sub. is Li.sub.2O.NO.SiO.sub.2-B.sub., 0.5Li.sub.2O.NO.sub.1.5.Si.sub.2-B.sub.,Li.sub.2O.NO.sub.2.SiO.sub.2-B.sub. or combinations thereof.
9. The positive active material of claim 1, wherein the weight content of the coating layer of lithium transition metal silicate represented by Formula xLi.sub.2O.yNO.sub.a.SiO.sub.2-B.sub. in the positive active material is 0.01%-30%.
10. A secondary lithium battery, comprising a positive electrode, a negative electrode and a separator between the positive electrode and the negative electrode, wherein the positive electrode comprises the positive active material of claim 1.
11. The positive active material of claim 1, wherein in the lithium transition metal oxide represented by Formula Li.sup.xM.sub.yN.sub.1-yO.sub.2-A.sub.,the element represented by M is one or two of Ni, Co, and the element represented by N is one or more of the Mg, Al, Ti, B, V, Mo, W, Ni, Co, Mn, Y, Ce; 0.7y1.0.
12. The positive active material of claim 1, wherein the element represented by N in Formula Li.sub.xM.sub.yN.sub.1-yO.sub.2-A.sub. is at least one of Mg, Al, Ti, B, Mo, Zr, V, Ce, W, and 0.99y1.0.
13. The positive active material of claim 1, wherein the weight content of the coating layer of the lithium transition metal silicate represented by Formula xLi.sub.2O.yNO.sub.a.SiO.sub.2-B.sub. in the positive active material is 0.01%-5.0%.
Description
DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS
EXAMPLE 1
(1) The positive active material of Example 1 includes a core of Li.sub.1.07Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 obtained via coprecipitation method and 0.5 wt % of coating layer of 0.5Li.sub.2O.0.1NiO.0.5CoO.sub.3/2.0.3MnO.sub.3/2.0.1MnO.sub.2.SiO.sub.2 having a thickness of 100-200 nm.
(2) The method for preparing the positive active material of Example 1 includes the steps of:
(3) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.1:0.5:0.4 in deionized water and obtaining a mixed solution of 1 mol/L; adding 1 mol/L NaOH solution in the mixed solution, fully stirring the mixed solution and maintaining the temperature at 75 C., and obtaining loose coprecipitate after full reaction; repeatedly washing the coprecipitate with deionized water and ethanol; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of coprecipitate and LiOH.H.sub.2O in air at 900 C. for 10 hours, and obtaining the core of Li.sub.1.07Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2.
(4) Mixing nano SiO.sub.2 with the core of Li.sub.1.07Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 at a mass ratio of 0.0025:1; milling the mixture of nano SiO.sub.2 and the core of Li.sub.1.07Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 in a planetary ball mill having a rotation speed of 300 r/min for 5 hours; sintering the fully milled mixture of nano SiO.sub.2 and the core of Li.sub.1.07Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 in air at 750 C. for 10 hours and obtaining a positive active material including a core of Li.sub.1.07Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 and a coating layer of 0.5Li.sub.2O.0.1NiO.0.5CoO.sub.3/2.0.3MnO.sub.3/2.0.1MnO.sub.2.SiO.sub.2.
EXAMPLE 2
(5) The positive active material of Example 2 includes a core of Li.sub.1.10Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 obtained via coprecipitation method and 0.01 wt % of coating layer of 0.55Li.sub.2O.1/3NiO.1/3CoO.sub.3/2.1/3MnO.sub.2.SiO.sub.2 having a thickness of 100-500 nm coated on the core.
(6) The method for preparing the positive active material of Example 2 includes the steps of:
(7) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 1.0:1.0:1.0 in deionized water and obtaining a mixed solution of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution, fully stirring the mixed solution and maintaining the temperature at 75 C., and obtaining loose coprecipitate after full reaction; repeatedly washing the coprecipitate with deionized water and ethanol; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of coprecipitate and LiOH.H.sub.2O in air at 900 C. for 20 hours, and obtaining the core of Li.sub.1.10Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2.
(8) Mixing Li.sub.2SiO.sub.3 and the core of Li.sub.1.10Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 at a mass ratio of 0.0001:1; milling the mixture of Li.sub.2SiO.sub.3 and the core of Li.sub.1.10Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 in a planetary ball mill having a rotation speed of 300 r/min for 5 hours; sintering the fully milled mixture of Li.sub.2SiO.sub.3 and the core of Li.sub.1.10N.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 in air at 550 C. for 10 hours and obtaining a positive active material including the core of Li.sub.1.10Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 and the coating layer of 0.55Li.sub.2O.1/3NiO.1/3CoO.sub.3/2.1/3MnO.sub.2.SiO.sub.2.
EXAMPLE 3
(9) The positive active material of Example 3 includes a core of Li.sub.1.05Ni.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 obtained via combustion method and 30.0 wt % of coating layer of 0.54Li.sub.2O.0.3NiO.0.2NiO.sub.3/2.0.2CoO.sub.3/2.0.3MnO.sub.2.SiO.sub.2 having a thickness of 50-80 nm coated on the core.
(10) The method for preparing the positive active material of Example 3 includes the steps of:
(11) Dissolving lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate at an atom ratio of 1.07:0.50:0.20:0.30 in ethanol in a container and obtaining a mixed solution; adding glycerol into the mixed solution after lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate being fully dissolved, the ratio of glycerol to the total metal ions is 3:1; stirring the mixed solution in the contained in a water bath at 80 C. to evaporate the ethanol; moving the container to a resistance furnace and heating after the ethanol being fully evaporated, until the residue of the mixed solution fully combusting; collecting the combustion product and sintering the combustion products in air at 750 C. for 5 hours and obtaining the core of Li.sub.1.05Ni.sub.0.5CO.sub.0.2Mn.sub.0.3O.sub.2;
(12) Dissolving H.sub.4SiO.sub.4 and Li.sub.1.05Ni.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 at a mass ratio of 0.19:1 in 500 mL deionized water in a container and obtaining a mixed solution; after H.sub.4SiO.sub.4 and Li.sub.1.05Ni.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 being fully dissolved, moving the container having the mixed solution to a water bath at 80 C. and stirring to evaporate the water; moving the container into an oven at 160 C. for 5 hours and obtaining black powder; sintering the black powder in air at 650 C. for 10 hours, and obtaining a positive active material including the core of Li.sub.1.05Ni.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 and the coating layer of 0.54Li.sub.2O.0.3NiO.0.2NiO.sub.3/2.0.2CoO.sub.3/2.0.3MnO.sub.2.SiO.sub.2.
EXAMPLE 4
(13) The positive active material of Example 4 includes a core of Li.sub.1.20Ni.sub.0.5Co.sub.0.2Mn.sub.0.29Zr.sub.0.01O.sub.1.98F.sub.0.04 obtained via sol gel method and 3.0 wt % of coating layer of 0.53Li.sub.2O.0.3NiO.0.2NiO.sub.3/2.0.2CoO.sub.3/2.0.3MnO.sub.2.0.01ZrO.sub.2.SiO.sub.1.98F.sub.0.04 having a thickness of 100-200 nm coated on the core.
(14) The method for preparing the positive active material of Example 4 includes the steps of:
(15) Dissolving lithium acetate, nickel acetate, cobalt acetate, manganese acetate, nano titanium dioxide, ammonium fluoride at an atom ratio of 1.23:0.50:0.20:0.29:0.01:0.04 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, cobalt acetate, manganese acetate, nano-titanium dioxide, ammonium fluoride being fully dissolved, the ratio of citric acid to the total metal ions is 2:1; stirring the mixed solution in the container in a water bath at 85 C. to evaporate the water and obtaining gelatinous substance; moving the container to an oven at a 160 C. and heating for 5 hours, and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 750 C. for 25 hours and obtaining the core of Li.sub.1.20Ni.sub.0.5Co.sub.0.2Mn.sub.0.29Zr.sub.0.01O.sub.1.98F.sub.0.04;
(16) Dissolving orthosilicate ester and Li.sub.1.20Ni.sub.0.5Co.sub.0.2Mn.sub.0.29Zr.sub.0.01O.sub.1.98F.sub.0.04 at a mass ratio of 0.0268:1 in 500 mL alcohol in a container and obtaining a mixed solution; setting the container having the mixed solution in a water bath at 70 C. and stirring to evaporate the alcohol and the orthosilicate ester; placing the container in an oven at 160 C. for 5 hours and obtaining black powder; sintering the black powder in air at 850 C. for 10 hours, and obtaining a positive active material including the core of Li.sub.1.20Ni.sub.0.5Co.sub.0.2Mn.sub.0.29Zr.sub.0.01O.sub.1.98F.sub.0.04 and a coating layer of 0.53Li.sub.2O.0.3NiO.0.2NiO.sub.3/2.0.2CoO.sub.3/2.0.3MnO.sub.2.0.01ZrO.sub.2.SiO.sub.1.98F.sub.0.04.
EXAMPLE 5
(17) The positive active material of Example 5 includes a core of Li.sub.0.98Ni.sub.0.6Co.sub.0.18Mn.sub.0.2Ti.sub.0.02O.sub.2 obtained via coprecipitation method and 0.40 wt % of coating layer of 0.49Li.sub.2O.0.2NiO.0.4Ni.sub.3/2.0.18CoO.sub.3/2.0.2MnO.sub.0.2.0.02TiO.sub.2.SiO.sub.2 having a thickness of 10-15 nm.
(18) The method for preparing the positive active material of Example 5 includes the steps of:
(19) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4, nano TiO.sub.2 at an atom ratio of 0.60:0.18:0.20:0.02 in deionized water and obtaining a mixed solution of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution, fully stirring the mixed solution and maintaining the temperature at 75 C., and obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate with Li.sub.2CO.sub.3 and sintering the mixture of the sintered coprecipitate and Li.sub.2CO.sub.3 in air at 750 C. for 10 hours, and obtaining a core of Li.sub.0.98Ni.sub.0.6Co.sub.0.18Mn.sub.0.2Mn.sub.0.02O.sub.2.
(20) Mixing SiO.sub.2 with the core of Li.sub.0.98Ni.sub.0.6Co.sub.0.18Mn.sub.0.2Ti.sub.0.02O.sub.2 at a mass ratio of 0.002:1; milling the mixture of SiO.sub.2 and the core of Li.sub.0.98Ni.sub.0.6Co.sub.0.18Mn.sub.0.2Ti.sub.0.02O.sub.2 in a planetary ball mill having a rotation speed of 500 r/min for 5 hours; sintering the fully milled mixture in air at 900 C. for 2 hours and obtaining a positive active material including the core of Li.sub.0.98Ni.sub.0.6Co.sub.0.18Mn.sub.0.2Ti.sub.0.02O.sub.2 and the coating layer of 0.49Li.sub.2O.0.2NiO.0.4NiO.sub.3/2.0.18CoO.sub.3/2.0.2MnO.sub.2.0.02TiO.sub.2.SiO.sub.2.
EXAMPLE 6
(21) The positive active material of Example 6 includes a core of Li.sub.0.92Ni.sub.0.75Co.sub.0.15Mn.sub.0.1O.sub.2 obtained via Pechini method and 0.35 wt % of coating layer of 0.45Li.sub.2O.0.1NiO.0.65NiO.sub.3/2.0.15CoO.sub.3/2.0.1MnO.sub.2.SiO.sub.2 having a thickness of 15-20 nm.
(22) The method for preparing the positive active material of Example 6 includes the steps of:
(23) Dissolving LiNO.sub.3, NiNO.sub.3, CoNO.sub.3, MnNO.sub.3 at an atom ratio of 0.94:0.75:0.15:0.10 in deionized water in a container and obtaining a metal ion solution having a metal ion concentration of 1 mol/L; dissolving citric acid in polyethylene glycol and obtaining a citric acid solution of 1.5 mol/L; mixing the metal ion solution and the citric acid solution at a ratio of 2:1, and heating the container having the mixture of the metal ion solution and the citric acid solution in an oil bath at 130 C. until the mixture in the container turning into black sticky substance; moving the container into a Muffle furnace and prefiring at 300 C. for 5 hours; milling the prefired product into powder, sintering the powder in air at 800 C. for 10 hours, and obtaining the core of Li.sub.0.92Ni.sub.0.75Co.sub.0.15Mn.sub.0.1O.sub.2
(24) Mixing SiO.sub.2 with the core of Li.sub.0.92Ni.sub.0.75Co.sub.0.15Mn.sub.0.1O.sub.2 at a mass ratio of 0.0023:1; milling the mixture of SiO.sub.2 and the core of Li.sub.0.92Ni.sub.0.75Co.sub.0.15Mn.sub.0.1O.sub.2 in a planetary ball mill having a rotation speed of 500 r/min for 5 hours; sintering the fully milled mixture in air at 600 C. for 2 hours and obtaining a positive active material including the core of Li.sub.0.92Ni.sub.0.75Co.sub.0.15Mn.sub.0.1O.sub.2 and the coating layer of 0.45Li.sub.2O.0.1NiO0.65NiO.sub.3/2.0.15CoO.sub.3/2.0.1MnO.sub.2.SiO.sub.2.
EXAMPLE 7
(25) The positive active material of Example 7 includes a core of Li.sub.1.02Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 obtained via coprecipitation method and 0.50 wt % of coating layer of 0.51Li.sub.2O.0.09NiO.0.63NiO.sub.3/2.0.09CoO.sub.3/2.0.09MnO.sub.2.0.1V.sub.2O.sub.5.SiO.sub.2 having a thickness of 40-50 nm.
(26) The method for preparing the positive active material of Example 7 includes the steps of:
(27) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.80:0.10:0.10 in deionized water and obtaining a mixed solution of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution, stirring the mixed solution and maintaining the temperature at 75 C., and obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of the coprecipitate and LiOH.H.sub.2O in air at 900 C. for 20 hours, and obtaining the core of Li.sub.1.02Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2.
(28) Milling SiO.sub.2, NH.sub.4VO.sub.3 and the core of Li.sub.1.02Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 at a mass ratio of 0.0045:0.0004:1 in a planetary ball mill having a rotation speed of 300 r/min for 5 hours; sintering the fully milled mixture of SiO.sub.2, NH.sub.4VO.sub.3 and the core of Li.sub.1.02Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 in air at 750 C. for 10 hours and obtaining a positive active material including the core of Li.sub.1.02Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 and the coating layer of 0.51Li.sub.2O.0.09NiO.0.63NiO.sub.3/2.0.09CoO.sub.3/2.0.09MnO.sub.2.0.1V.sub.2O.sub.5.SiO.sub.2.
EXAMPLE 8
(29) The positive active material of Example 8 includes a core of Li.sub.1.06Ni.sub.0.82Co.sub.0.10Mn.sub.0.07Zr.sub.0.004Mg.sub.0.002Ti.sub.0.004O.sub.2 obtained via coprecipitation method and 0.25 wt % of coating layer of 0.531Li.sub.2O.0.07NiO.0.75NiO.sub.3/2.0.1CoO.sub.3/2.0.07MnO.sub.2.0.004ZrO.sub.2.0.002MgO.sub.2.0.1TiO.sub.2.SiO.sub.2 having a thickness of 12-15 nm.
(30) The method for preparing the positive active material of Example 8 includes the steps of:
(31) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.82:0.10:0.07 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; mixing the washed red coprecipitate with Li.sub.2CO.sub.3, nano ZrO.sub.2, nano MgO, nanoTiO.sub.2 in an inclined mixer having a rotation speed of 50 r/min for 5 hours; sintering the mixture of the washed coprecipitate, Li.sub.2CO.sub.3, nano ZrO.sub.2, nano MgO and nanoTiO.sub.2 in air at 800 C. for 5 hours, and obtaining the core of Li.sub.1.07Ni.sub.0.82Co.sub.0.10Mn.sub.0.07Zr.sub.0.004Mg.sub.0.002Ti.sub.0.004O.sub.2.
(32) Dissolving methyl silicate and Li.sub.1.07Ni.sub.0.82Co.sub.0.10Mn.sub.0.07Zr.sub.0.004Mg.sub.0.002Ti.sub.0.004O.sub.2 at a mass ratio of 0.0035:1 in 500 mL alcohol in a container and obtaining a mixed solution after fully dissolution; adding 1 mol citric acid into the mixed solution after full dissolution of the methyl silicate, setting the container having the mixed solution in a water bath at 70 C. and stirring to evaporate the alcohol; placing the container in an oven at 160 C. for 5 hours and obtaining black powder; sintering the black powder in air at 650 C. for 5 hours, and obtaining a positive active material including the core of Li.sub.1.07Ni.sub.0.82Co.sub.0.10Mn.sub.0.07Zr.sub.0.004Mg.sub.0.002Ti.sub.0.004O.sub.2 and the coating layer of 0.531Li.sub.2O.0.07NiO.0.75NiO.sub.3/2.0.1CoO.sub.3/2.0.07MnO.sub.2.0.004ZrO.sub.2.0.002MgO.sub.2.0.1TiO.sub.2.SiO.sub.2.
EXAMPLE 9
(33) The positive active material of Example 9 includes a core of Li.sub.0.97Ni.sub.0.9Co.sub.0.05Mn.sub.0.04Mg.sub.0.01O.sub.2 obtained via coprecipitation method and 0.15 wt % of coating layer of 0.5Li.sub.2O.0.04NiO.0.86NiO.sub.3/2.0.05CoO.sub.3/2.0.04MnO.sub.2.0.01MgO.SiO.sub.2 having a thickness of 8-10 nm.
(34) The method for preparing the positive active material of Example 9 includes the steps of:
(35) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.9:0.05:0.04 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, while maintaining the temperature at 70 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; mixing the coprecipitate with nano MgO in an inclined mixer having a rotation speed of 50 r/min for 5 hours; mixing the mixture of the coprecipitate and nano MgO with LiOH.H.sub.2O, sintering the mixture in air at 800 C. for 10 hours, and obtaining the core of Li.sub.0.97Ni.sub.0.9Co.sub.0.05Mn.sub.0.04Mg.sub.0.01O.sub.2.
(36) Mixing H.sub.4SiO.sub.4 with the core of Li.sub.0.97Ni.sub.0.9Co.sub.0.05Mn.sub.0.04Mg.sub.0.01O.sub.2 at a mass ratio of 0.0011:1; milling the mixture of the core of Li.sub.0.97Ni.sub.0.9Co.sub.0.05Mn.sub.0.04Mg.sub.0.01O.sub.2 and H.sub.4SiO.sub.4 in a planetary ball mill having a rotation speed of 500 r/min for 5 hours; sintering the milled mixture of H.sub.4SiO.sub.4 and the core of Li.sub.0.97Ni.sub.0.9Co.sub.0.05Mn.sub.0.04Mg.sub.0.01O.sub.2 in air at 600 C. for 2 hours and obtaining a positive active material including the core of Li.sub.0.97Ni.sub.0.9Co.sub.0.05Mn.sub.0.04Mg.sub.0.01O.sub.2 and the coating layer of 0.5Li.sub.2O.0.04NiO.0.86NiO.sub.3/2.0.05CoO.sub.3/2.0.04MnO.sub.2.0.01MgO.SiO.sub.2.
EXAMPLE 10
(37) The positive active material of Example 10 includes a core of Li.sub.1.08Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 obtained via solid milling method and 17.0 wt % of coating layer of 0.54Li.sub.2O.1/3NiO.1/3CoO.sub.3/2.1/3MnO.sub.2.SiO.sub.2 having a thickness of 20-50 nm.
(38) The method for preparing the positive active material of Example 10 includes the steps of:
(39) Mixing Li.sub.2CO.sub.3, nickel oxalate, cobalt oxalate, MnCO.sub.3 at a molar ratio of 0.56:1.0:1.0:1.0 in a zirconia sander having a rotation speed of 1000 r/min for 5 hours, the diameter of the zirconia milling media is 3 mm, and the ratio of zirconia milling media to the mixture of Li.sub.2CO.sub.3, nickel oxalate, cobalt oxalate and MnCO.sub.3 is 1:1; removing the zirconia milling media and sintering the remained mixture in air at 750 C. for 5 hours and obtaining the core of Li.sub.1.08Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2.
(40) Dissolving TEOS and the core of Li.sub.1.08Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 at a mass ratio of 0.1030:1 in 500 mL alcohol in a container and obtaining a mixed solution after TEOS and the core of Li.sub.1.08Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 being fully hydrolyzed; setting the container having the mixed solution in a water bath at 70 C. and stirring so as to evaporate the alcohol; placing the container in an oven at 180 C. for 5 hours and obtaining black powder; sintering the black powder in air at 850 C. for 6 hours, and obtaining a positive active material including the core of Li.sub.1.08Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 and the coating layer of 0.54Li.sub.2O.1/3NiO.1/3CoO.sub.3/2.1/3MnO.sub.2.SiO.sub.2.
EXAMPLE 11
(41) The positive active material of Example 11 includes a core of Li.sub.1.04Ni.sub.0.5CO.sub.0.2Mn.sub.0.28Zr.sub.0.02O.sub.1.98F.sub.0.04 obtained via coprecipitation and solid milling method and 2.0 wt % of a coating layer of 0.52Li.sub.2O.0.28NiO.0.22NiO.sub.3/2.0.2CoO.sub.3/2.0.28MnO.sub.2.0.02ZrO.sub.2.SiO.sub.1.98F.sub.0.04 having a thickness of 180-200 nm.
(42) The method for preparing the positive active material of Example 11 includes the steps of:
(43) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.50:0.20:0.28 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, while maintaining the temperature at 70 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; mixing the washed coprecipitate with LiOH.H.sub.2O, nano ZrO.sub.2 and NH.sub.4F in a zirconia sander having a rotation speed of 800 r/min and mixing for 5 hours, the diameter of the zirconia milling media is 3 mm, and the ratio of the zirconia milling media to the mixture of the washed coprecipitate and LiOH.H.sub.2O, nano ZrO.sub.2, NH.sub.4F is 1:1; removing the zirconia milling media and sintering the remained mixture in air at 950 C. for 24 hours and obtaining the core of Li.sub.1.04Ni.sub.0.5Co.sub.0.2Mn.sub.0.28Zr.sub.0.02O.sub.1.98F.sub.0.04.
(44) Mixing nano SiO.sub.2 with the core of Li.sub.1.04Ni.sub.0.5Co.sub.0.2Mn.sub.0.28Zr.sub.0.02O.sub.1.98F.sub.0.04 at a mass ratio of 0.0200:1; milling the mixture of SiO.sub.2 and the core of Li.sub.1.04Ni.sub.0.5Co.sub.0.2Mn.sub.0.28Zr.sub.0.02O.sub.1.98F.sub.0.04 in an inclined mixer having a rotation speed of 50r/min for 10 hours; sintering the fully milled mixture in air at 750 C. for 6 hours and obtaining a positive active material including the core of Li.sub.1.04Ni.sub.0.5Co.sub.0.2Mn.sub.0.28Zr.sub.0.02O.sub.1.98F.sub.0.04 and the coating layer of 0.52Li.sub.2O.0.28NiO.0.22NiO.sub.3/2.0.2CoO.sub.3/2.0.28MnO.sub.2.0.02ZrO.sub.2.SiO.sub.1.98F.sub.0.04.
EXAMPLE 12
(45) The positive active material of Example 12 includes a core of Li.sub.1.05Ni.sub.0.5Co.sub.0.2Mn.sub.0.28Zr.sub.0.02O.sub.1.98F.sub.0.04 obtained via sol-gel method and 2.0 wt % coating layer of 0.53Li.sub.2O.0.28NiO.0.22NiO.sub.3/2.0.2CoO.sub.3/2.0.28MnO.sub.2.0.02ZrO.sub.2.SiO.sub.1.98N.sub.0.01 having a thickness of 8-10 nm.
(46) The method for preparing the positive active material of Example 12 includes the steps of:
(47) Dissolving lithium acetate, nickel acetate, cobalt acetate, manganese acetate, nano titanium dioxide, ammonium fluoride at an atom ratio of 1.07:0.50:0.20:0.28:0.02:0.04 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, cobalt acetate, manganese acetate, nano titanium dioxide, ammonium fluoride being fully dissolved, the ratio of citric acid to the total metal ions is 2:1; stirring the mixed solution in the container in a water bath at 85 C., to evaporate the water and obtain gelatinous substance; placing the container in an oven at 160 C. for 5 hours, and obtaining brown-black substance; milling the brown-black substance in a zirconia sander having a rotation speed of 800 r/min for 5 hours, the diameter of the zirconia milling media is 2 mm, and the ratio of the zirconia milling media to the brown-black substance is 1:1; removing the zirconia milling media and sintering the remaining brown-black substance in air at 750 C. for 5 hours and obtaining the core of Li.sub.1.05Ni.sub.0.5Co.sub.0.2Mn.sub.0.28Zr.sub.0.02O.sub.1.98F.sub.0.04.
(48) Dissolving TEOS and the core of Li.sub.1.05Ni.sub.0.5Co.sub.0.2Mn.sub.0.28Zr.sub.0.02O.sub.1.98F.sub.0.04 at a mass ratio of 0.0480:1 in 500 mL glycol in a container and obtaining a mixed solution; setting the container having the mixed solution in a 800 L PTFE sealing container and placing and sealing the container in a stainless steel housing; placing the container in an oven at 175 C. for 5 hours and obtaining black powder; sintering the black powder in a mixed atmosphere of nitrogen and ammonia air at 550 C. for 10 hours, and obtaining a positive active material including the core of Li.sub.1.05Ni.sub.0.5Co.sub.0.2Mn.sub.0.28Zr.sub.0.02O.sub.1.98F.sub.0.04 and the coating layer of 0.53Li.sub.2O.0.28NiO.0.22NiO.sub.3/2.0.2CoO.sub.3/2.0.28MnO.sub.2.0.02ZrO.sub.2.SiO.sub.1.98N.sub.0.01.
EXAMPLE 13
(49) The positive active material of Example 13 includes a core of Li.sub.1.05Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.1.98N.sub.0.01 obtained via solid milling method and 7.0 wt % of coating layer of 0.52Li.sub.2O.0.1NiO.0.7NiO.sub.3/2.0.1CoO.sub.3/2.0.1MnO.sub.2.SiO.sub.2 having a thickness of 20-30 nm.
(50) The method for preparing the positive active material of Example 13 includes the steps of:
(51) Milling Li.sub.2CO.sub.3, nickel oxalate, cobalt oxalate, MnCO.sub.3, urea at a molar ratio of 0.53:0.8:0.1:0.1:0.15 in a zirconia sander having a rotation speed of 1000 r/min for 5 hours, the diameter of the zirconia milling media is 5 mm, and the ratio of the zirconia milling media to the mixture of Li.sub.2CO.sub.3, nickel oxalate, cobalt oxalate, MnCO.sub.3, urea is 1:2; removing the zirconia milling media and sintering the remaining mixture in air at 750 C. for 5 hours and obtaining the core of Li.sub.1.05Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.1.98N.sub.0.01.
(52) Placing the core of Li.sub.1.05Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.1.98N.sub.0.01 in a tube furnace at 500 C.; adopting nitrogen having a flow rate of 1 L/min as carrier gas; introducing a toluene solution having 0.2 mol/L TEOS into the tube furnace, to deposit TEOS on the surface of the core of Li.sub.1.05Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.1.98N.sub.0.01; sintering the core of Li.sub.1.05Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.1.98N.sub.0.01 having TEOS deposited thereon in air at 700 C. for 5 hours, and obtaining a positive active material including the core of Li.sub.1.05Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.1.98N.sub.0.01 and the coating layer of 0.52Li.sub.2O.0.1NiO.0.7NiO.sub.3/2.0.1CoO.sub.3/2.0.1MnO.sub.2.SiO.sub.2.
EXAMPLE 14
(53) The positive active material of Example 14 includes a core of Li.sub.1.08Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 obtained via coprecipitation method and 0.10 wt % of coating layer of 0.54Li.sub.2O.1/3NiO.1/3CoO.sub.3/2.1/3MnO.sub.2.SiO.sub.2 having a thickness of 200-300 nm.
(54) The method for preparing the positive active material of Example 14 includes the steps of:
(55) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 1.0:1.0:1.0 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, as well as maintaining the temperature at 75 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours and obtaining secondary particles of oxide or hydroxide A; milling nickel oxalate, cobalt oxalate, MnCO.sub.3 at a molar ratio of 1.0:1.0:1.0 in a zirconia sander having a rotation speed of 1000 r/min for 5 hours, the diameter of the zirconia milling media is 5 mm, and the ratio of zirconia milling media to the mixture of nickel oxalate, cobalt oxalate, MnCO.sub.3 is 1:1; removing the zirconia milling media and sintering the remaining mixture in air at 700 C. for 5 hours and obtaining oxide or hydroxide or carbonate B of the primary particles; mixing A and B, and mixing the mixture f A and B with LiOH.H.sub.2O, sintering the mixture of A , B and LiOH.H.sub.2O in air at 800 C. for 5 hours, and obtaining the core of Li.sub.1.08Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2.
(56) Sintering the mixture of SiO.sub.2 and the core of Li.sub.1.08Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 at a mass ratio of 0.0005:1 in air at 700 C. for 10 hours and obtaining a positive active material including the core of Li.sub.1.08Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 and a coating layer of 0.54Li.sub.2O.1/3NiO.1/3CoO.sub.3/2.1/3MnO.sub.2.SiO.sub.2.
EXAMPLE 15
(57) The positive active material of Example 15 includes a core of Li.sub.1.03Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 obtained via coprecipitation method and 0.5 wt % of coating layer of 0.52Li.sub.2O.0.1NiO.0.7NiO.sub.3/2.0.1CoO.sub.3/2.0.1MnO.sub.2.SiO.sub.2 having a thickness of 15-20 nm.
(58) The method for preparing the positive active material of Example 15 includes the steps of:
(59) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.80:0.10:0.10 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, as well as maintaining the temperature at 70 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; fully mixing the washed coprecipitate with LiOH.H.sub.2O and sintering the mixture of the coprecipitate and LiOH.H.sub.2O in air at 850 C. for 10 hours, and obtaining the core of Li.sub.1.03Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2.
(60) Mixing and milling H.sub.4SiO.sub.4 with the core of Li.sub.1.03Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 at a mass ratio of 0.0034:1 in an inclined mixer having a rotation speed of 30 r/min for 10 hours; sintering the fully milled mixture in air at 850 C. for 6 hours and obtaining a positive active material including the core of Li.sub.1.03Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 and the coating layer of 0.52Li.sub.2O.0.1NiO..0.7NiO.sub.3/2.0.1CoO.sub.3/2.0.1MnO.sub.2.SiO.sub.2.
EXAMPLE 16
(61) The positive active material of Example 16 includes a core of Li.sub.1.04Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2obtained via coprecipitation method and 0.7 wt % of coating layer of 0.52Li.sub.2O.0.1NiO.0.7NiO.sub.3/2.0.1CoO.sub.3/2.0.1MnO.sub.2.SiO.sub.2 having a thickness of 15-20 nm.
(62) The method for preparing the positive active material of Example 16 includes the steps of:
(63) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.8:0.1:0.1 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 70 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repatedly; sintering the washed coprecipitate in air at 850 C. for 10 hours; fully mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of the coprecipitate and LiOH.H.sub.2O in air at 850 C. for 10 hours, and obtaining the core of Li.sub.1.04Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2.
(64) Mixing and milling H.sub.4SiO.sub.4 with the core of Li.sub.1.04Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 at a mass ratio of 0.0060:1 in a planetary ball mill having a rotation speed of 500 r/min for 5 hours; sintering the fully milled mixture in air at 500 C. for 2 hours and obtaining a positive active material including the core of Li.sub.1.04Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 and the coating layer of 0.52Li.sub.2O.0.1NiO.0.7NiO.sub.3/2.0.1CoO.sub.3/2.0.1MnO.sub.2.SiO.sub.2.
EXAMPLE 17
(65) The positive active material of Example 17 includes a core of Li.sub.1.05CoO.sub.2 obtained via coprecipitation method and 0.01 wt % of a coating layer of 0.53Li.sub.2O.CoO.sub.3/2.SiO.sub.2 having a thickness of 50100 nm.
(66) The method for preparing the positive active material of Example 17 includes the steps of:
(67) Preparing 1 mol/L CoSO.sub.4 solution; slowly dripping 1 mol/L NH.sub.4HCO.sub.3 solution at a dripping rate of 1 L/h into the CoSO.sub.4 solution; after coprecipitation, filtering and washing the coprecipitate with deionized water, and obtaining CoCO.sub.3 after drying; mixing Li.sub.2CO.sub.3 and CoCO.sub.3 at a molar ratio of 1.07:1 in a planetary ball mill having a rotation speed of 200 r/min for 5 hours; sintering the fully mixed mixture of Li.sub.2CO.sub.3 and CoCO.sub.3 in air at 900 C. for 10 hours;
(68) Adding H.sub.4SiO.sub.4 and the sintered product in a container having 500 mL alcohol; heating the container in a water bath at 75 C. and stirring to evaporate the alcohol; placing the container in an oven at 180 C. for 5 hours, and obtaining black powder; sintering the black powder in air at 650 C. for 6 hours, and obtaining a positive active material including the core of Li.sub.1.05CoO.sub.2and the coating layer of 0.53Li.sub.2O.CoO.sub.3/2.SiO.sub.2.
EXAMPLE 18
(69) The positive active material of Example 18 includes a core of Li.sub.1.01CoO.sub.0.89Mg.sub.0.05Al.sub.0.04Ti.sub.0.02O.sub.2 obtained via sol-gel method and 0.4 wt % of coating layer of 0.51Li.sub.2O.0.89CoO.sub.3/2.0.05MgO.0.04AlO.sub.3/2.0.02TiO.sub.2.SiO.sub.2 having a thickness of 1520 nm. The core of Li.sub.1.01Co.sub.0.89Mg.sub.0.05Al.sub.0.04Ti.sub.0.02O.sub.2 is consisted of monocrystalline particles.
(70) The method for preparing the positive active material of Example 18 includes the steps of:
(71) Dissolving lithium acetate, cobalt acetate, nano magnesia, nano alumina and nano titanium dioxide at a metal atom ratio of 1.03:0.89:0.05:0.04:0.02 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, cobalt acetate, nano magnesia, nano alumina and nano titanium dioxide being fully dissolved, the ratio of citric acid to the total metal ions is 2:1; stirring the mixed solution in the container in a water bath at 85 C., to evaporate the water and obtain gelatinous substance; placing the container in an oven at 160 C. for 5 hours and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 900 C. for 24 hours and obtaining the core of Li.sub.1.01CoO.sub.0.89Mg.sub.0.05Al.sub.0.04Ti.sub.0.02O.sub.2;
(72) Dispersing the core of Li.sub.1.01Co.sub.0.89Mg.sub.0.05Al.sub.0.04Ti.sub.0.02O.sub.2 in 0.2% H.sub.4SiO.sub.4 solution having a concentration of 500 g/L and obtaining a mixed solution; placing the mixed solution in water bath of 85 C., to evaporate the water and obtain gelatinous substance; sintering the gelatinous substance in air at 750 C. for 5 hours, and obtaining a positive active material including the core of Li.sub.1.01Co.sub.0.89Mg.sub.0.05Al.sub.0.04Ti.sub.0.02O.sub.2 and the coating layer of 0.51Li.sub.2O.0.89CoO.sub.3/20.05MgO.0.04AlO.sub.3/2.0.02TiO.sub.2.SiO.sub.2.
EXAMPLE 19
(73) The positive active material of Example 19 includes a core of Li.sub.0.98Co.sub.0.6Al.sub.0.38Ti.sub.0.02O.sub.2 obtained via coprecipitation method and 2.00 wt % of coating layer of 0.49Li.sub.2O.0.6CoO.sub.3/2.0.38AlO.sub.3/2.0.02TiO.sub.2.SiO.sub.2 having a thickness of 100150 nm. The core of Li.sub.0.98Co.sub.0.6Al.sub.0.38Ti.sub.0.02O.sub.2 is consisted of monocrystalline particles.
(74) The method for preparing the positive active material of Example 19 includes the steps of:
(75) Preparing 1 mol/L CoSO.sub.4 solution; slowly dripping 1 mol/L NH.sub.4HCO.sub.3 solution at a dripping rate of 1 L/h into the CoSO.sub.4 solution; after coprecipitation, filtering and washing the coprecipitate with deionized water, obtaining CoCO.sub.3 after drying; mixing Li.sub.2CO.sub.3, CoCO.sub.3, nano Al.sub.2O.sub.3 and nano TiO.sub.2 at a molar ratio of 1.01:0.60:0.38:0.02 in a planetary ball mill having a rotation speed of 200 r/min for 5 hours; sintering the fully mixed mixture of Li.sub.2CO.sub.3, CoCO.sub.3, nano Al.sub.2O.sub.3 and nano TiO.sub.2 in air at 800 C. for 18 hours;
(76) Mixing and milling SiO.sub.2 with the sintered mixture above at a mass ratio of 0.01:1 in a planetary ball mill having a rotation speed of 300 r/min for 5 hours; sintering the fully milled mixture in air at 750 C. for 10 hours and obtaining a positive active material including the core of Li.sub.0.98Co.sub.0.6Al.sub.0.8Ti.sub.0.02O.sub.2 and the coating layer of 0.49Li.sub.2O.0.6CoO.sub.3/2.0.38AlO.sub.3/20.02TiO.sub.2.SiO.sub.2.
EXAMPLE 20
(77) The positive active material of Example 20 includes a core of Li.sub.1.02Ni.sub.0.85Co.sub.0.10Al.sub.0.05O.sub.2 obtained via coprecipitation method and 0.45 wt % of coating layer of 0.51Li.sub.2O.0.85NiO.sub.3/20.1CoO.sub.3/2.0.05AlO.sub.3/2.SiO.sub.2 having a thickness of 1520 nm.
(78) The method for preparing the positive active material of Example 20 includes the steps of:
(79) Dissolving NiSO.sub.4, CoSO.sub.4, Al(NO.sub.3).sub.3 at an atom ratio of 0.85:0.10:0.05 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C. and dripping ammonia into the mixed solution to maintain the pH value at 10.6; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of the coprecipitate and LiOH.H.sub.2O in air at 750 C. for 10 hours, and obtaining a core of Li.sub.1.02Ni.sub.0.85Co.sub.0.10Al.sub.0.05O.sub.2.
(80) Mixing and milling SiO.sub.2 with the core of Li.sub.1.02Ni.sub.0.85Co.sub.0.10Al.sub.0.05O.sub.2 at a mass ratio of 0.0025:1 in a planetary ball mill having a rotation speed of 300 r/min for 5 hours; sintering the fully milled mixture in air at 750 C. for 10 hours and obtaining a positive active material including the core of Li.sub.1.02Ni.sub.0.85Co.sub.0.10Al.sub.0.05O.sub.2 and the coating layer of 0.51Li.sub.2O.0.85NiO.sub.3/20.1CoO.sub.3/2.0.05AlO.sub.3/2.SiO.sub.2.
EXAMPLE 21
(81) The positive active material of Example 21 includes a core of Li.sub.1.05Ni.sub.0.90Co.sub.0.08Al.sub.0.02O.sub.2 obtained via sol-gel method and 2.5 wt % of coating layer of 0.53Li.sub.2O.0.9NiO.sub.3/20.08CoO.sub.3/2.0.02AlO.sub.3/2.SiO.sub.2 having a thickness of 100150 nm.
(82) The method for preparing the positive active material of Example 21 includes the steps of:
(83) Dissolving lithium acetate, nickel acetate, cobalt acetate, aluminum nitrate at an atom ratio of 1.09:0.90:0.08:0.02 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, cobalt acetate, aluminum nitrate being fully dissolved, the ratio of citric acid to the total metal ions is 2:1; stirring the mixed solution in the container in a water bath at 85 C. to evaporate the water and obtain gelatinous substance; placing the container in an oven at 160 C. for 5 hours, and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 750 C. for 5 hours and obtaining the core of Li.sub.1.05Ni.sub.0.90Co.sub.0.08Al.sub.0.02O.sub.2;
(84) Dispersing the sintered core of Li.sub.1.05Ni.sub.0.90Co.sub.0.08Al.sub.0.02O.sub.2 in 0.8% orthosilicate solution at a concentration of 500 g/L and obtaining a mixed solution; setting the mixed solution in water bath of 85 C. to evaporate the water and obtain gelatinous substance; sintering the gelatinous substance in air at 750 C. for 5 hours, and obtaining a positive active material including the core of Li.sub.1.05Ni.sub.0.90Co.sub.0.08Al.sub.0.02O.sub.2 and the coating layer of 0.53Li.sub.2O.0.9NiO.sub.3/20.08CoO.sub.3/2.0.02AlO.sub.3/2.SiO.sub.2.
EXAMPLE 22
(85) The positive active material of Example 22 includes a core of Li.sub.1.09Ni.sub.0.88Co.sub.0.10Al.sub.0.01Ti.sub.0.01O.sub.2 obtained via sol-gel method and 0.80 wt % of coating layer of 0.55Li.sub.2O.0.88NiO.sub.3/2.0.1CoO.sub.3/2.0.01AlO.sub.3/2.0.01TiO.sub.2.SiO.sub.2 having a thickness of 5080 nm.
(86) The method for preparing the positive active material of Example 22 includes the steps of:
(87) Dissolving lithium acetate, nickel acetate, cobalt acetate, aluminum nitrate, nano titanium dioxide at an atom ratio of 1.11:0.88:0.10:0.01:0.01 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, cobalt acetate, aluminum nitrate, nano titanium dioxide being fully dissolved, the ratio of citric acid to the total metal ions is 2:1; stirring the mixed solution in the container in a water bath at 85 C. to evaporate the water and obtain gelatinous substance; placing the container in an oven at 160 C. for 5 hours and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 750 C. for 5 hours and obtaining the core of Li.sub.1.09Ni.sub.0.88Co.sub.0.10Al.sub.0.01Ti.sub.0.01O.sub.2;
(88) Dispersing the sintered core of Li.sub.1.09Ni.sub.0.88Co.sub.0.10Al.sub.0.01Ti.sub.0.01O.sub.2 in 0.3% silicic acid solution having a concentration of 500 g/L and obtaining a mixed solution; placing the solution in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; sintering the gelatinous substance in air at 600 C. for 18 hours, and obtaining a positive active material including the core of Li.sub.1.09Ni.sub.0.88Co.sub.0.10Al.sub.0.01Ti.sub.0.01O.sub.2 and the coating layer of 0.55Li.sub.2O.0.88NiO.sub.3/2.0.1CoO.sub.3/2.0.01AlO.sub.3/2.0.01TiO.sub.2.SiO.sub.2.
EXAMPLE 23
(89) The positive active material of Example 23 includes a core of Li.sub.0.98Ni.sub.0.50Mn.sub.0.50O.sub.2 obtained via solvothermal method and 2.10 wt % of coating layer of 0.49Li.sub.2O.0.5NiO.0.5MnO.sub.2.SiO.sub.2 having a thickness of 80100 nm.
(90) The method for preparing the positive active material of Example 23 includes the steps of:
(91) Dissolving nickel acetate and manganese acetate at an atom ratio of 0.50:0.50 in deionized water in a container and obtaining a mixed solution; adding sodium persulfate in the mixed solution after nickel acetate and manganese acetate being fully dissolved in the deionized water, with the ratio of sodium persulfate to the metal ions being 2:1; placing the container containing mixed solution in a PTFE airtight container, placing the container in a stainless steel housing, and putting the container enclosed by the housing in an oven at 135 C. and reacting for 24 hours; after cooling down, washing the reaction product with deionized water repeatedly; sintering the mixture of the washed reaction product and LiOH.H.sub.2O in air at 750 C. for 10 hours, and obtaining the core of Li.sub.0.98Ni.sub.0.50Mn.sub.0.50O.sub.2.
(92) Dispersing the sintered core powder of Li.sub.0.98Ni.sub.0.50Mn.sub.0.50O.sub.2 in 0.8% orthosilicate solution having a concentration of 500 g/L and obtaining a mixed solution; setting the mixed solution in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; sintering the gelatinous substance in air at 800 C. for 20 hours, and obtaining a positive active material including the core of Li.sub.0.98Ni.sub.0.50Mn.sub.0.50O.sub.2 and the coating layer of 0.49Li.sub.2O.0.5NiO.0.5MnO.sub.2.SiO.sub.2.
EXAMPLE 24
(93) The positive active material of Example 24 includes a core of Li.sub.1.07Ni.sub.0.80Mn.sub.0.20O.sub.2 obtained via coprecipitation method and 0.05 wt % of coating layer of 0.54Li.sub.2O.0.2NiO.0.6NiO.sub.3/2.0.2MnO.sub.2.SiO.sub.2 having a thickness of 100150 nm.
(94) The method for preparing the positive active material of Example 24 includes the steps of:
(95) Dissolving NiSO.sub.4 and MnSO.sub.4 at an atom ratio of 0.80:0.20 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; dripping ammonia into the mixed solution to control the pH value of the mixed solution at 10.3; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours and obtaining second particles consisting of primary particles having an average size of 400-600 nm; fully mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of the coprecipitate and LiOH.H.sub.2O in air at 750 C. for 10 hours, and obtaining the core of Li.sub.1.07Ni.sub.0.80Mn.sub.0.20O.sub.2.
(96) Mixing and milling SiO.sub.2 with the core of Li.sub.1.07Ni.sub.0.80Mn.sub.0.20O.sub.2 at a mass ratio of 0.0003:1 in a planetary ball mill having a rotation speed of 300 r/min for 5 hours; sintering the fully milled mixture in air at 750 C. for 10 hours and obtaining a positive active material including the core of Li.sub.1.07Ni.sub.0.80Mn.sub.0.20O.sub.2 and the coating layer of 0.54Li.sub.2O.0.2NiO.0.6NiO.sub.3/20.2MnO.sub.2.SiO.sub.2.
EXAMPLE 25
(97) The positive active material of Example 25 includes a core of Li.sub.1.04Ni.sub.0.85Mn.sub.0.12Al.sub.0.03O.sub.2 obtained via sol-gel method and 2.50 wt % of coating layer of 0.52Li.sub.2O.0.12NiO.0.73NiO.sub.3/2.0.12MnO.sub.2.0.03AlO.sub.3/2.SiO.sub.2 having a thickness of 2040 nm.
(98) The method for preparing the positive active material of Example 25 includes the steps of:
(99) Dissolving lithium acetate, nickel acetate, manganese acetate, aluminum nitrate at an atom ratio of 1.07:0.85:0.12:0.03 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, manganese acetate, aluminum nitrate being fully dissolved, with the ratio of citric acid to the total metal ions being 2:1; setting the container having the mixed solution in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; placing the container in an oven at 160 C. for 5 hours, and obtaining brown-black substance; milling the brown-black substance into powder, and sintering the powder in air at 750 C. for 5 hours and obtaining the core of Li.sub.1.04Ni.sub.0.85Mn.sub.0.12Al.sub.0.03O.sub.2;
(100) Dispersing the sintered core powder of Li.sub.1.04Ni.sub.0.85Mn.sub.0.12Al.sub.0.03O.sub.2 in 0.8% silicic acid solution having a concentration of 500 g/L and obtaining a mixed solution; setting the mixed solution in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; sintering the gelatinous substance in air at 600 C. for 20 hours, and obtaining a positive active material including the core of Li.sub.1.04Ni.sub.0.85Mn.sub.0.12AlO.sub.0.03O.sub.2 and the coating layer of 0.52Li.sub.2O.0.12NiO.0.73NiO.sub.3/2.0.12MnO.sub.2.0.03AlO.sub.3/2.SiO.sub.2.
COMPARATIVE EXAMPLE 1
(101) The positive active material of Comparative Example 1 includes a core of Li.sub.1.09Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 obtained via coprecipitation method and 0.03 wt % of coating layer of Al.sub.2O.sub.3 having a thickness of 50-100 nm.
(102) The method for preparing the positive active material of Comparative Example 1 includes the steps of:
(103) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.1:0.5:0.4 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of the coprecipitate and LiOH.H.sub.2O in air at 900 C. for 20 hours, and obtaining the core of Li.sub.1.09Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 consisting of secondary particles formed by primary particles having a particle size of 4.0-6.0 m.
(104) Mixing nano Al.sub.2O.sub.3 powder with the core of Li.sub.1.09Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 at a mass ratio of 0.003:0.97; milling the mixture of nano Al.sub.2O.sub.3 powder and the core of Li.sub.1.09Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 in a planetary ball mill having a rotation speed of 300 r/min for 5 hours; sintering the fully milled mixture in air at 900 C. for 10 hours and obtaining a positive active material including the core of Li.sub.1.09Ni.sub.0.1Co.sub.0.5Mn.sub.0.4O.sub.2 the a coating layer of Al.sub.2O.sub.3.
COMPARATIVE EXAMPLE 2
(105) The positive active material of Comparative Example 2 is Li.sub.1.10Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 obtained via coprecipitation method.
(106) The method for preparing the positive active material of Comparative Example 2 includes the steps of:
(107) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 1.0:1.0:1.0 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of the coprecipitate and LiOH.H.sub.2O in air at 850 C. for 10 hours, and obtaining positive active material of Li.sub.1.10Ni.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 consisting of secondary particles formed by primary particles having a particle size of 0.8-1.0 m.
COMPARATIVE EXAMPLE 3
(108) The positive active material of Comparative Example 3 is Li.sub.1.08Ni.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 obtained via coprecipitation method.
(109) The method for preparing the positive active material of Comparative Example 3 includes the steps of:
(110) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 5.0:2.0:3.0 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of the coprecipitate and LiOH.H.sub.2O in air at 800 C. for 10 hours, and obtaining the positive active material of Li.sub.1.08Ni.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2.
COMPARATIVE EXAMPLE 4
(111) The positive active material of Comparative Example 4 is Li.sub.0.98Ni.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2 obtained via sol-gel method.
(112) The method for preparing the positive active material of Comparative Example 4 includes the steps of:
(113) Dissolving lithium acetate, nickel acetate, cobalt acetate, manganese acetate at an atom ratio of 0.99:0.60:0.20:0.20 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, cobalt acetate, manganese acetate being fully dissolved, with the ratio of citric acid to the total metal ions being 2:1; stirring the mixed solution in the container in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; placing the container in an oven at 160 C. for 5 hours, and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 750 C. for 10 hours and obtaining the positive active material of Li.sub.0.98Ni.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2.
COMPARATIVE EXAMPLE 5
(114) The positive active material of Comparative Example 5 includes a core of Li.sub.0.9Ni.sub.0.75Co.sub.0.15Mn.sub.0.1O.sub.2 obtained via coprecipitation method and 0.05 wt % of coating layer of MgO having a thickness of 10-15 nm.
(115) The method for preparing the positive active material of Comparative Example 5 includes the steps of:
(116) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.75:0.15:0.10 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; mixing the washed coprecipitate with LiOH.H.sub.2O and sintering the mixture of the washed coprecipitate an LiOH.H.sub.2O in air at 700 C. for 5 hours, and obtaining the core of Li.sub.0.9Ni.sub.0.75Co.sub.0.15Mn.sub.0.1O.sub.2 consisting of secondary particles formed by primary particles having a particle size of 4.0-6.0 m.
(117) Mixing and milling nano MgO powder with the core of Li.sub.0.9Ni.sub.0.75Co.sub.0.15Mn.sub.0.1O.sub.2 at a mass ratio of 0.0005:1 in a planetary ball mill having a rotation speed of 500 r/min for 5 hours; sintering the fully milled mixture in air at 900 C. for 10 hours and obtaining a positive active material including the core of Li.sub.0.9Ni.sub.0.75Co.sub.0.15Mn.sub.0.1O.sub.2 and the coating layer of MgO.
COMPARATIVE EXAMPLE 6
(118) The positive active material of Comparative Example 6 is Li.sub.1.03Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 obtained via coprecipitation method.
(119) The method for preparing the positive active material of Comparative Example 6 includes the steps of:
(120) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 8.0:1.0:1.0 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate with LiOH.H.sub.2O; sintering the mixture of sintered coprecipitate and LiOH.H.sub.2O in air at 900 C. for 8 hours, and obtaining the positive active material of Li.sub.1.03Ni.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 consisting of secondary particles formed by primary particles having a particle size of 0.7-0.8 m.
COMPARATIVE EXAMPLE 7
(121) The positive active material of Comparative Example 7 includes a core of Li.sub.1.07Ni.sub.0.82Co.sub.0.1Mn.sub.0.08O.sub.2 obtained via coprecipitation method and 0.12 wt % of coating layer of AlPO.sub.4 having a thickness of 12-15 nm.
(122) The method for preparing the positive active material of Comparative Example 7 includes the steps of:
(123) Dissolving NiSO.sub.4, CoSO.sub.4, MnSO.sub.4 at an atom ratio of 0.82:0.10:0.08 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; mixing the washed coprecipitate with LiOH.H.sub.2O and sintering the mixture of the washed coprecipitate and LiOH.H.sub.2O in air at 700 C. for 5 hours, and obtaining the core of Li.sub.1.07Ni.sub.0.82Co.sub.0.1Mn.sub.0.08O.sub.2.
(124) Mixing and milling nano AlPO.sub.4 powder with the core of Li.sub.1.07Ni.sub.0.82Co.sub.0.1Mn.sub.0.08O.sub.2 at a mass ratio of 0.0012:1 in a planetary ball mill having a rotation speed of 300 r/min for 5 hours; sintering the fully milled mixture in air at 800 C. for hours and obtaining a positive active material including the core of Li.sub.1.07Ni.sub.0.82Co.sub.0.1Mn.sub.0.08O.sub.2 and the coating layer of AlPO.sub.4.
COMPARATIVE EXAMPLE 8
(125) The positive active material of Comparative Example 8 is Li.sub.0.95Ni.sub.0.9Co.sub.0.05Mn.sub.0.05O.sub.2.
(126) The method for preparing the positive active material of Comparative Example 8 includes the steps of:
(127) Mixing Li.sub.2CO.sub.3, nickel oxalate, cobalt oxalate, MnCO.sub.3 at a molar ratio of 0.49:0.90:0.05:0.05 in a zirconia sander having a rotation speed of 1000 r/min for 5 hours, the diameter of the zirconia milling media is 5 mm, and the ratio of zirconia milling media to the mixture of Li.sub.2CO.sub.3, nickel oxalate, cobalt oxalate, MnCO.sub.3 is 1:2; removing the zirconia milling media and sintering the remaining mixture in air at 950 C. for 24 hours and obtaining the positive active material of Li.sub.0.95Ni.sub.0.9Co.sub.0.05Mn.sub.0.05O.sub.2.
COMPARATIVE EXAMPLE 9
(128) The positive active material of Comparative Example 9 is Li.sub.1.05CoO.sub.2 obtained via coprecipitation method.
(129) The method for preparing the positive active material of Comparative Example 9 includes the steps of:
(130) Preparing 1 mol/L CoSO.sub.4 solution; slowly dripping 1 mol/L NH.sub.4HCO.sub.3 solution at a dripping rate of 1 L/h into the CoSO.sub.4 solution; after coprecipitation, filtering and washing the coprecipite with deionized water and obtaining CoCO.sub.3 after drying; mixing Li.sub.2CO.sub.3 and CoCO.sub.3 at a molar ratio of 1.07:1 in a planetary ball mill having a rotation speed of 200 r/min for 5 hours; sintering the fully mixed mixture of Li.sub.2CO.sub.3 and CoCO.sub.3 in air at 900 C. for 10 hours, and obtaining the positive active material Li.sub.1.05CoO.sub.2.
COMPARATIVE EXAMPLE 10
(131) The positive active material of Comparative Example 10 is Li.sub.1.01Co.sub.0.89Mg.sub.0.05Al.sub.0.04Ti.sub.0.02O.sub.2 obtained via sol-gel method.
(132) The method for preparing the positive active material of Comparative Example 10 includes the steps of:
(133) Dissolving lithium acetate, cobalt acetate, nano magnesia, nano alumina, nano titanium dioxide at an atom ratio of 1.03:0.89:0.05:0.04:0.02 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, cobalt acetate, nano magnesia, nano alumina, nano titanium dioxide being fully dissolved, the ratio of citric acid to the total metal ions is 2:1; stirring the solution in the container in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; placing the container in an oven at 160 C. for 5 hours, and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 900 C. for 24 hours and obtaining the positive active material of Li.sub.1.01Co.sub.0.89Mg.sub.0.05Al.sub.0.04Ti.sub.0.02O.sub.2.
COMPARATIVE EXAMPLE 11
(134) The positive active material of Comparative Example 11 is Li.sub.0.98Co.sub.0.98Ti.sub.0.02O.sub.2 obtained via coprecipitation method consisting of monocrystalline particles.
(135) The method for preparing the positive active material of Comparative Example 11 includes the steps of:
(136) Preparing 1 mol/L CoSO.sub.4 solution; slowly dripping 1 mol/L NH.sub.4HCO.sub.3 solution at a dripping rate of 1 L/h into the CoSO.sub.4 solution; after coprecipitation, filtering and washing the coprecipitate with the deionized water, and obtaining CoCO.sub.3 after drying; mixing Li.sub.2CO.sub.3, CoCO.sub.3 and TiO.sub.2 at a molar ratio of 1.01:0.98:0.02 in a planetary ball mill having a rotation speed of 200 r/min for 5 hours; sintering the fully mixed mixture of Li.sub.2CO.sub.3, CoCO.sub.3 and TiO.sub.2 in air at 800 C. for 18 hours, and obtaining the positive active material of Li.sub.0.98Co.sub.0.98Ti.sub.0.02O.sub.2.
COMPARATIVE EXAMPLE 12
(137) The positive active material of Comparative Example 12 is Li.sub.1.02Ni.sub.0.85Co.sub.0.10Al.sub.0.05O.sub.2 obtained via coprecipitation method.
(138) The method for preparing the positive active material of Comparative Example 12 includes the steps of:
(139) Dissolving NiSO.sub.4, CoSO.sub.4, Al(NO.sub.3).sub.3 at an atom ratio of 0.85:0.10:0.05 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; dripping ammonia in the mixed solution to control the pH value of the mixed solution at 10.6; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours; mixing the sintered coprecipitate with LiOH.H.sub.2O and sintering the mixture of the sintered coprecipitate and LiOH.H.sub.2O in air at 750 C. for 10 hours, and obtaining the positive active material of Li.sub.1.02Ni.sub.0.85Co.sub.0.10Al.sub.0.05O.sub.2.
COMPARATIVE EXAMPLE 13
(140) The positive active material of Comparative Example 13 is Li.sub.1.05Ni.sub.0.90Co.sub.0.08Al.sub.0.02O.sub.2 obtained via sol-gel method.
(141) The method for preparing the positive active material of Comparative Example 13 includes the steps of:
(142) Dissolving lithium acetate, nickel acetate, cobalt acetate, aluminum nitrate at an atom ratio of 1.09:0.90:0.08:0.02 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, cobalt acetate, aluminum nitrate being fully dissolved, the ratio of the citric acid to the total metal ions is 2:1; stirring the mixed solution in the container in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; placing the container in an oven at 160 C. for 5 hours, and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 750 C. for 5 hours and obtaining the positive active material of Li.sub.1.05Ni.sub.0.90Co.sub.0.08Al.sub.0.02O.sub.2.
COMPARATIVE EXAMPLE 14
(143) The positive active material of Comparative Example 14 is Li.sub.1.09Ni.sub.0.88Co.sub.0.10Al.sub.0.01Ti.sub.0.01O.sub.2 obtained via sol-gel method.
(144) The method for preparing the positive active material of Comparative Example 14 includes the steps of:
(145) Dissolving lithium acetate, nickel acetate, cobalt acetate, aluminum nitrate, nano titanium dioxide at an atom ratio of 1.11:0.88:0.10:0.01:0.01 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, cobalt acetate, aluminum nitrate, nano titanium dioxide being fully dissolved, the ratio of the citric acid to the total metal ions is 2:1; stirring the mixed solution in the container in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; placing the container the gelatinous substance in an oven at 160 C. for 5 hours, and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 750 C. for 5 hours and obtaining the positive active material of Li.sub.1.09Ni.sub.0.88Co.sub.0.10Al.sub.0.01Ti.sub.0.01O.sub.2.
COMPARATIVE EXAMPLE 15
(146) The positive active material of Comparative Example 15 is Li.sub.0.98Ni.sub.0.50Mn.sub.0.50O.sub.2 obtained via sol-gel method.
(147) The method for preparing the positive active material of Comparative Example 15 includes the steps of:
(148) Dissolving lithium acetate, nickel acetate, manganese acetate at an atom ratio of 1.02:0.50:0.50 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, manganese acetate being fully dissolved, the ratio of the citric acid to the total metal ions is 2:1; stirring the mixed solution in the container in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; placing the container having the gelatinous substance in an oven at 160 C. for 5 hours, and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 750 C. for 5 hours and obtaining the positive active material of Li.sub.0.98Ni.sub.0.50Mn.sub.0.50O.sub.2.
COMPARATIVE EXAMPLE 16
(149) The positive active material of Comparative Example 16 is Li.sub.1.07Ni.sub.0.80Mn.sub.0.20O.sub.2 obtained via coprecipitation method.
(150) The method for preparing the positive active material of Comparative Example 16 includes the steps of:
(151) Dissolving NiSO.sub.4, MnSO.sub.4 at an atom ratio of 0.80:0.20 in deionized water and obtaining a mixed solution having a concentration of 1 mol/L; adding 1 mol/L NaOH solution into the mixed solution and stirring, and maintaining the temperature at 75 C.; dripping ammonia in the mixed solution to control the pH value of the mixed solution at 10.3; obtaining loose coprecipitate after full reaction; washing the coprecipitate with deionized water and ethanol repeatedly; sintering the washed coprecipitate in air at 500 C. for 5 hours; fully mixing the sintered coprecipitate and LiOH.H.sub.2O; sintering the mixture of the sintered coprecipitate and LiOH.H.sub.2O in air at 750 C. for 10 hours, and obtaining the positive active material of Li.sub.1.07Ni.sub.0.80Mn.sub.0.20O.sub.2.
COMPARATIVE EXAMPLE 17
(152) The positive active material of Comparative Example 17 is Li.sub.1.04Ni.sub.0.85Mn.sub.0.12Al.sub.0.03O.sub.2 obtained via sol-gel method.
(153) The method for preparing the positive active material of Comparative Example 17 includes the steps of:
(154) Dissolving lithium acetate, nickel acetate, manganese acetate, aluminum nitrate at an atom ratio of 1.07:0.85:0.12:0.03 in deionized water in a container and obtaining a mixed solution; adding citric acid into the mixed solution after lithium acetate, nickel acetate, manganese acetate, aluminum nitrate being fully dissolved, the ratio of the citric acid to the total metal ions is 2:1; stirring the mixed solution in the container in a water bath of 85 C. to evaporate the water and obtain gelatinous substance; placing the container having the gelatinous substance in an oven at 160 C. for 5 hours, and obtaining brown-black substance; milling the brown-black substance into powder, sintering the powder in air at 750 C. for 5 hours and obtaining the positive active material of Li.sub.1.04Ni.sub.0.85Mn.sub.0.12Al.sub.0.03O.sub.2.
PREPARATION OF LITHIUM ION BATTERIES
(155) The positive active materials according to Examples 1 to 25, Comparative Examples 1 to 17 are adopted as positive active materials to manufacture lithium ion batteries via same process, to analyze the electrochemical performance of lithium-containing transition metal oxides. The method for preparing lithium ion batteries includes the following steps.
(156) The positive active materials according to Examples 1 to 25, Comparative Examples 1 to 17 are adopted as the positive active materials of the positive plates, respectively. Artificial graphite is adopted as negative active material of the negative plate. The positive plate, the negative plate and the separator are winded to form a secondary lithium battery after soldering terminal, packaging the aluminum foil, filling electrolyte and pumping the air. The discharge cut-off voltage of each secondary lithium battery is 2.80 V. The charge cut-off voltage of each secondary lithium battery is 4.50 V (relative to the electric potential of lithium 4.55 V). The design capacity of each secondary lithium battery is 2500 mAh.
PERFORMANCE ANALYSIS
(157) The performances of lithium ion batteries according to Examples 1 to 25 and Comparative Examples 1 to 17 are assessed and shown in Table 1.
(158) 1. Cycling performance: Each secondary lithium battery is charged at a constant current of 0.5 C (1225 mA) at 25 C. until the voltage reaches 4.50 V. Each secondary lithium battery is then charged at a constant voltage of 4.50 V until the current reaches 0.05 C (123 mA). Each secondary lithium battery is further discharged at a current of 0.5 C (1225 mA) until the voltage reaches 2.80 V. The charging and discharging cycle is repeated for 1000 times. The discharge capacity of the first cycle and the discharge capacity of the 1000th cycle are determined. The capacity retention rate of each secondary lithium battery is calculated according to the following formula:
The capacity retention rate=(discharge capacity of the 1000th cycle/discharge capacity of the first cycle)100%
(159) 2. High temperature storage performance: Each secondary lithium battery is charged at a constant current of 0.5 C (1225 mA) at 25 C. until the voltage reaches 4.50V. Each secondary lithium battery is charged at a constant voltage of 4.50 V until the current reaches 0.05 C (123 mA). The thickness of each secondary lithium battery prior to storage and the first discharge capacity is determined. Each fully charged secondary lithium battery is stored in an oven at 60 C. for 100 days. The thickness of each secondary lithium battery after storage is determined. The expansion rate of each secondary lithium battery after storage is calculated. Each stored secondary lithium battery is charged at a constant current of 0.5 C (1225 mA) until the voltage reaches 4.50 V. Each secondary lithium battery is charged at a constant voltage of 4.50 V until the current reaches 0.05 C (123 mA). Each secondary lithium battery is discharged at a constant current of 0.5 C (1225 mA) until the voltage reaches 2.80 V. The charge and discharge cycle is repeated for five cycles. The final discharge capacity is recorded. The capacity retention rate relative to the first discharge capacity is calculated according to the following formula.
Expansion rate of a stored secondary lithium battery=(thickness of a stored secondary lithium battery thickness of a secondary lithium battery prior to storage)/ thickness of a secondary lithium battery prior to storage100%.
Capacity retention rate of a stored secondary lithium battery=(discharge capacity after 100 days storage)/(discharge capacity of the first cycle)100%.
(160) 3. Safety performance test: Each secondary lithium battery is charged at a constant current of 0.5 C (1225 mA) at 25 C. until the voltage reaches 4.50 V. Each secondary lithium battery is charged at a constant voltage of 4.50 V until the current reaches 0.05 C (123 mA). Each secondary lithium battery is disassembled in a glovebox full of Argon. The positive plate of each secondary lithium battery is taken out and washed in DMC solution. After the DMC has completely evaporated, the positive active material is scratched from the positive plate. 10 mg scratched positive active material of each secondary lithium battery is put in an aluminum crucible. The aluminum crucible is sealed after 0.1 L electrolyte has been added. The scanning temperature of the DSC test is 50500 C. and the heating rate is 10 C./min.
(161) TABLE-US-00001 TABLE 1 Performance Test Results of lithium ion batteries according to Examples and Comparative Examples Capacity retention Capacity rate of Expansion retention second rate of rate of a lithium stored stored Maximum battery second second DSC after lithium lithium DSC heat Exothermic cycling battery battery release (J/g) peak () Example 1 83.40% 4.60% 87.20% 651 299 Example 2 91.70% 5.10% 87.10% 641 321 Example 3 82.30% 7.30% 83.10% 793 311 Example 4 90.40% 2.70% 89.10% 802 308 Example 5 76.20% 11.50% 86.10% 810 260 Example 6 83.15% 4.60% 87.00% 821 271 Example 7 81.40% 9.20% 81.30% 891 247 Example 8 80.10% 11.95% 81.20% 893 257 Example 9 70.20% 4.20% 76.10% 951 226 Example 10 86.20% 3.25% 90.10% 630 336 Example 11 84.30% 4.25% 86.80% 810 309 Example 12 85.90% 2.60% 89.90% 768 312 Example 13 81.90% 6.20% 84.30% 782 277 Example 14 95.70% 1.20% 94.10% 620 327 Example 15 84.40% 3.90% 87.60% 930 249 Example 16 85.30% 4.05% 89.80% 910 254 Example 17 73.10% 10.10% 82.40% 1231 245 Example 18 79.30% 15.60% 79.40% 1160 239 Example 19 77.90% 11.10% 85.10% 1210 242 Example 20 64.70% 14.30% 89.20% 921 234 Example 21 74.80% 14.10% 76.30% 861 231 Example 22 75.40% 11.40% 84.50% 1127 234 Example 23 80.30% 8.10% 91.40% 731 282 Example 24 89.10% 15.30% 85.00% 810 247 Example 25 75.20% 15.30% 87.20% 870 259 Comparative Example 1 78.10% 5.10% 81.00% 693 295 Comparative Example 2 75.30% 7.30% 84.20% 657 315 Comparative Example 3 65.70% 12.20% 73.80% 851 290 Comparative Example 4 52.20% 23.60% 65.20% 860 270 Comparative Example 5 61.20% 12.2% 67.50% 852 266 Comparative Example 6 56.80% 30.70% 65.70% 971 232 Comparative Example 7 58.10% 25.10% 71.30% 954 238 Comparative Example 8 55.60% 20.50% 63.50% 1052 211 Comparative Example 9 60.40% 25.70% 52.30% 1391 214 Comparative Example 10 65.00% 32.70% 41.20% 1379 222 Comparative Example 11 42.00% 28.90% 35.00% 1381 221 Comparative Example 12 56.70% 29.00% 70.60% 1161 216 Comparative Example 13 68.00% 38.10% 72.90% 1263 221 Comparative Example 14 69.30% 24.40% 70.60% 1345 203 Comparative Example 15 72.20% 18.60% 70.00% 862 262 Comparative Example 16 70.10% 19.80% 70.80% 970 212 Comparative Example 17 68.40% 33.20% 50.30% 1051 221
(162) It is clearly shown in Table 1 that:
(163) 1) The positive active material having a core of lithium transition metal oxide and a coating layer according to the present invention has remarkably improved charge-discharge cycle performance at 2.80 V4.50 V. Comparing Examples 1 to 25 and Comparative Examples 1 to 17, after 1000 cycles, the positive active material having a core of lithium transition metal oxide and a coating layer according to the present invention has a higher capacity retention rate than that of ordinary lithium transition metal oxide positive active material. The positive active material having a core of lithium transition metal oxide and a coating layer has desirable cycling performance, especially the cycling performance at high voltage of 4.50 V, because the coating layer can stabilize the core and prevent phase change.
(164) 2) The positive active material having a core of lithium transition metal oxide and a coating layer according to the present invention has remarkably improved high temperature storage performance at 4.50 V. Comparing Examples 1 to 25 and Comparative Examples 1 to 17, the positive active material having a core of lithium transition metal oxide and a coating layer according to the present invention has a much lower thickness expansion rate after charged to 4.50 v and stored at 60 C. for 100 days than that of ordinary lithium transition metal oxide positive active material. The positive active material having a core of lithium transition metal oxide and a coating layer of the present invention has desirable cycling performance The high temperature storage performance at 4.50 v is improved remarkably, because the coating layer has higher chemical stability and higher electrochemical stability, which can remarkably reduce the catalytic activity of the positive active material.
(165) 3) The positive active material having a core of lithium transition lithium transition metal oxide and a coating layer according to the present invention has remarkably improved safety performance at 4.50 V. Comparing Examples 1 to 25 and Comparative Examples 1 to 17, when the secondary lithium battery using the positive active material having a core of lithium transition metal oxide and a coating layer according to the present invention is charged to 4.55 V, DSC exotherm of the secondary lithium battery is much less than that of a secondary lithium battery using ordinary lithium transition metal oxide positive active material. Silicate has stable crystal structure. The coating layer of silicate can improve the thermal stability of the positive active material and the safety performance of the secondary lithium battery. The coating layer in situ formed on the core can effectively eliminate the sites having high reactivity on the surface of the core, reduce the catalytic activity of the final product in the secondary lithium battery and, therefore, obtain stable positive active material.
(166) Summarizing the above, the positive active material and method for preparing the same according to the present invention have the following advantages.
(167) Firstly, the coating layer can conduct lithium ions. Compared with other coating layer of oxide, the coating layer according to the present invention has higher lithium-ion conductivity.
(168) Secondly, the coating layer has stable chemical stability and electrochemical stability. Even after being charged to 4.70 V, the skeleton of silica-oxygen structure still can protect the core, which will remarkably reduce the catalytic activity of the core and improve the chemical stability of the positive active material. In addition, the silicate has stable crystal structure. The coating layer of silicate can improve the thermal stability of the positive active material, thereby improving the safety performance of the secondary lithium battery.
(169) Thirdly, the coating layer is in-situ formed on the core. Part of the coating layer comes from the core. Therefore, the coating layer can be uniformly formed on the core.
(170) Fourthly, the coating layer is apt to be formed on the sites having high reactivity of the core. The method according to the present invention can effectively eliminate the sites having high reactivity on the surface of the core, thereby reducing the catalytic activity of the final product in the secondary lithium battery and obtaining stable positive active material.
(171) Fifthly, the method according to the present invention can reduce the oxidizing ability of the core in charging state. The M.sup.4+ having strong oxidizing ability on the surface of the core is coated by the coating layer and cannot contact the electrolyte. Therefore, the M.sup.4+ can hardly oxidize and decompose the electrolyte.
(172) Many modifications and other embodiments of the inventions set forth herein will come to mind to one skilled in the art to which these inventions pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the inventions are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Moreover, although the foregoing descriptions and the associated drawings describe example embodiments, it should be appreciated that alternative embodiments without departing from the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.