Lithium nickel cobalt manganese oxide positive active material having concentration gradient of nickel, cobalt, and manganese and precursor thereof and preparation methods

Abstract

A precursor of a modified ternary material for a lithium ion battery positive material belongs to the technical field of application of lithium ion battery positive materials. A molecular formula of the precursor is: (Ni.sub.1/3Co.sub.1/3Mn.sub.1/3)(OH).sub.2, and the precursor consists of three layers. An inner layer of the precursor is a ternary material with the Co content of more than ⅓ and equal Ni and Mn content, and the molecular formula of the inner layer of the precursor is: (Ni.sub.1/3−xCol/.sub.3+2xMn.sub.1/3−x(OH).sub.2, where 0<x<⅓. An outer layer of the precursor is a ternary material with the Co content of greater than 0 to ⅓ and equal Ni and Mn content, and the molecular formula of the outer layer of the precursor is: (Ni.sub.0.5−yCo.sub.2yMn.sub.0.5−y)(OH).sub.2, where 0<y<⅙. An intermediate layer of the precursor is a concentration gradient composite material of the two materials of the inner layer and the outer layer of the precursor. The modified ternary material containing the precursor has the chemical formula of Li(Ni.sub.1/3Co.sub.1/3Mn.sub.1/3)O.sub.2. The inside of each microscopic particle of the ternary material consists of three parts, namely, an inner layer, an intermediate layer and an outer layer. The present invention effectively improves the cyclic stability, thermal stability and compacted density, and has a high cost-performance advantage.

Claims

1. A precursor of a modified ternary material for a lithium ion battery positive electrode material, wherein the precursor has a composition of the following molecular formula: Ni.sub.1/3Co.sub.1/3Mn.sub.1/3(OH).sub.2; and consists of three layers, wherein: an inner layer of the precursor is a first ternary material with a first cobalt content of greater than ⅓ and identical first nickel and first manganese contents, and the molecular formula of said inner layer of the precursor is: (Ni.sub.1/3−xCo.sub.1/3+2xMn.sub.1/3−x)(OH).sub.2, where 0<x <⅓; an outer layer of the precursor is a second ternary material with a second cobalt content of greater than 0 to ⅓ and equal second nickel and second manganese contents, and the molecular formula of said outer layer of the precursor is: (Ni.sub.0.5−yCo.sub.2yMn.sub.0.5−y)(OH).sub.2, where 0<y<⅙; and an intermediate layer of the precursor is a concentration-gradient composite material of the first ternary material of the inner layer and the second ternary material of the outer layer of the precursor.

2. A modified ternary material for a lithium ion battery positive electrode material having the precursor of claim 1.

3. A process for preparing a precursor of a modified ternary material for a lithium ion battery positive electrode material, wherein the particular steps are as follows: (1) adding a ternary salt solution A of nickel, cobalt and manganese into a reaction kettle at a certain rate, wherein the molar ratio of Ni:Co:Mn =(⅓−x):(⅓+2x):(⅓−x), where 0<x<⅓, carrying out a coprecipitation reaction with an alkali solution to obtain a first solid-liquid mixture, the molecular formula of a first precipitated solid portion of the first solid-liquid mixture being (Ni.sub.1/3−xCo.sub.1/3+2xMn.sub.1/3−x)(OH).sub.2, where 0<x <⅓, so as to form an inner layer part of the precursor; (2) adjusting a flow rate of the alkali solution during the addition of the ternary salt solution A and during an addition of a ternary salt solution B of nickel, cobalt and manganese to keep a pH value of a solution in the reaction kettle between 10-12; first, continuing the addition of the ternary salt solution A of nickel, cobalt and manganese into the reaction kettle at a decreasing rate with a decrement of 100-1,000 ml per hour, and at the same time, adding the ternary salt solution B of nickel, cobalt and manganese into the reaction kettle at an increasing rate with a increment of 100-1,000 ml per hour from zero, wherein the molar ratio of the ternary salt solution B is Ni:Co:Mn =(0.5−y):2y:(0.5−y), where 0<y<⅙; so as to form an intermediate layer part of the above precursor which connects the inner layer and an outer layer and has a concentration gradient in the precursor; (3) when the injection speed of the ternary salt solution A of nickel, cobalt and manganese has decreased to zero, continuing the injection of the ternary salt solution B until a predetermined amount of the ternary salt solution B has been added into the reaction kettle with a constant speed at a certain rate, so as to form the outer layer of the precursor coated outside of the intermediate layer part of the precursor; and (4) separating a second precipitated solid from a second solid-liquid mixture after the reaction in step (3) is completed by means of centrifugal filtration, washing the same to be neutral, and oven-drying the same at 60° C.-200° C. for 4-10 h; the general molecular formula of the second precipitated solid obtained being (Ni.sub.1/3Co.sub.1/3Mn.sub.1/3)(OH).sub.2, and the second precipitated solid being the precursor of the modified ternary material.

4. A process for preparing a modified ternary material for a lithium ion battery positive electrode material, wherein the modified ternary material includes a precursor that has a composition of the following molecular formula: Ni.sub.1/3Co.sub.1/3Mn.sub.1/3(OH).sub.2; and consists of three layers, wherein: an inner layer of the precursor is a first ternary material with a first cobalt content of greater than ⅓ and identical first nickel and first manganese contents, and the molecular formula of said inner layer of the precursor is: (Ni.sub.1/3−xCo.sub.1/3+2xMn.sub.1/3−x)(OH).sub.2, where 0<x<⅓; an outer layer of the precursor is a second ternary material with a second cobalt content of 0 to ⅓ and equal second nickel and second manganese contents, and the molecular formula of said outer layer of the precursor is: (Ni.sub.0.5−yCo.sub.2yMn.sub.0.5−y)(OH).sub.2, where 0<y<⅙; and an intermediate layer of the precursor is a concentration-gradient composite material of the first ternary material and the second ternary material of the inner layer and the outer layer of the precursor, and wherein the modified ternary material is prepared by crushing the precursor obtained by the preparation process for a precursor of claim 3, then mixing the same with a lithium source and calcining, wherein mixing the powder of said precursor with the lithium source and calcining at 300° C.-1,200° C. for 8-30 h forms the modified ternary material.

5. The process for preparing a modified ternary material according to claim 4, wherein said lithium source is lithium carbonate or lithium hydroxide.

6. A process for preparing a modified ternary material wherein the particular steps are as follows: first, obtaining a precursor of a modified ternary material with a general molecular formula of (Ni.sub.1/3Co.sub.1/3Mn.sub.1/3)(OH).sub.2 and having three layers, wherein: an inner layer of the precursor is a first ternary material with a first cobalt content of greater than ⅓ and identical first nickel and first manganese contents, and the molecular formula of said inner layer of the precursor is: (Ni.sub.1/3−xCo.sub.1/3+2xMn.sub.1/3−x)(OH).sub.2, where 0<x<⅓; an outer layer of the precursor is a second ternary material with a second cobalt content of 0 to ⅓ and equal second nickel and second manganese contents, and the molecular formula of said outer layer of the precursor is: (Ni.sub.0.5 −yCo.sub.2yMn.sub.0.5−y)(OH).sub.2, where 0<y<⅙; and an intermediate layer of the precursor is a concentration-gradient composite material of the first ternary material and the second ternary material of the of the inner layer and the outer layer of the precursor and wherein the modified ternary material is prepared by crushing the precursor obtained by the preparation process for a precursor of claim 3, then mixing the same with a lithium source and calcining, wherein mixing the powder of said precursor with the lithium source and calcining at 300° C.-1,200° C. for 8-30 h forms the modified ternary material; and wherein the mixing the precursor with the lithium source is at a molar ratio of 1:1 to 1:1.2, wherein the calcining is a multi-stage calcination in a muffle furnace, with the calcination temperature of 300° C.-1,200° C. and the calcination time of 8-30 h, and after the multi-stage calcination, cooling, crushing and sieving to obtain the modified ternary material, wherein said lithium source is lithium carbonate or lithium hydroxide.

7. A process for preparing a modified ternary material for a lithium ion battery positive electrode material, wherein the modified ternary material includes a precursor that has a composition of the following molecular formula: Ni.sub.1/3Co.sub.1/3Mn.sub.1/3(OH).sub.2; and consists of three layers, wherein: an inner layer of the precursor is a first ternary material with a first cobalt content of greater than ⅓ and identical first nickel and first manganese contents, and the molecular formula of said inner layer of the precursor is: (Ni.sub.1/3−xCo.sub.1/3+2xMn.sub.1/3−x)(OH).sub.2, where 0<x<⅓; an outer layer of the precursor is a second ternary material with a second cobalt content of 0 to ⅓ and equal second nickel and second manganese contents, and the molecular formula of said outer layer of the precursor is: (Ni.sub.0.5−yCo.sub.2yMn.sub.0.5−y)(OH).sub.2, where 0<y<⅙; and an intermediate layer of the precursor is a concentration-gradient composite material of the first ternary material and the second ternary material of the inner layer and the outer layer of the precursor, and wherein the modified ternary material is prepared by crushing the precursor, then mixing the same with a lithium source and calcining, wherein mixing the powder of said precursor with the lithium source and calcining at 300° C.-1,200° C. for 8-30 h forms the modified ternary material.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an XRD spectrum of the modified ternary material of Example 1 of the present invention and Comparative example 1;

(2) FIG. 2 is an initial charge-discharge curve diagram of the modified ternary material of Example 1 of the present invention and Comparative example 1;

(3) FIG. 3 is a 3.0-4.3 V cycle curve diagram of the modified ternary material of Example 1 of the present invention and Comparative example 1;

(4) FIG. 4 is a 3.0-4.5 V cycle curve diagram of the modified ternary material of Example 1 of the present invention and Comparative example 1;

(5) FIG. 5-1 is an electron micrograph of the modified ternary material of Example 2 of the present invention;

(6) FIG. 5-2 is an electron micrograph of Comparative example 2; and

(7) FIG. 6 is a DSC diagram of the modified ternary material of Example 2 of the present invention and Comparative example 2.

PARTICULAR EMBODIMENTS

(8) The present invention is described in detail hereinafter by means of embodiments, and the embodiments are provided for easy understanding, and limit by no means the present invention.

COMPARATIVE EXAMPLE 1

(9) 27.5 L of a nickel, cobalt and manganese salt solution with a concentration of 2 M was prepared, wherein the molar ratio of nickel:cobalt:manganese is 1:1:1.

(10) The prepared salt solution mentioned above was injected at a speed of 1 L/h into a reaction kettle with a rotation speed of 200 rps, and simultaneously a 6 M NaOH solution was injected therein, and the flow rate of the alkali solution was adjusted to keep the pH value between 10 and 11. After 27.5 h, the salt solution was completely injected into the reaction kettle, and the reaction for preparing a precursor was completed. The solid-liquid mixture after the reaction was completed was separated by centrifugation, washed to be neutral and then oven-dried at 100° C. for 10 h. The oven-dried precursor was mixed well with lithium carbonate according to a molar ratio of 1:1.05, and then calcined in a muffle furnace at 900° C. for 10 h, and the material calcined was crushed and sieved to obtain a ternary material of homogeneous LiNi.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2.

EXAMPLE 1

(11) 25 L of a 2 M nickel, cobalt and manganese salt solution A was prepared, in which the molar ratio of nickel:cobalt:manganese was 0.315:0.37:0.315; and 2.5 L of a 2 M nickel and manganese salt solution B was prepared, in which the molar ratio of nickel:manganese was 0.5:0.5.

(12) The salt solution A was injected at a speed of 1 L/h into a reaction kettle with a rotation speed of 200 rps, and a 6 M NaOH solution was injected simultaneously, the flow rate of the alkali solution was adjusted, and the pH value was kept by means of an on-line pH value controller between 10 and 11. After the reaction had been carried out for 24 h, the injection speed of the salt solution A was decreased at a speed of 0.5 L/h, and at the same time, the flow rate of the salt solution B was increased gradually from zero at a speed increment of 0.5 L/h; after 2 h, the salt solution A was completely injected into the reaction kettle, and the salt solution B was injected continuously into the reaction kettle at a speed of 1 L/h; after 1.5 h, the salt solution B was completely injected into the reaction kettle, and the solid-liquid mixture, after the reaction was completed, was separated by centrifugation, washed to be neutral and then oven-dried at 100° C. for 10 h to obtain a precursor with the molecular formula of Ni.sub.1/3Co.sub.1/3Mn.sub.1/3(OH).sub.2. The oven-dried precursor was mixed well with lithium carbonate at a molar ratio of 1:1.05 and then calcined in a muffle furnace at 900° C. for 10 h, and the material calcined was crushed and sieved to obtain a modified ternary material.

(13) It can be seen from FIG. 1 that the XRD curves of the products obtained in Example 1 and Comparative example 1 had sharp shape, and there were no other impurity peaks by comparing the two curves, which indicated that a layered structure of the modified ternary material of Example 1 was achieved without impurity phases. The tap densities of the materials of Example 1 and Comparative example 1 were 2.48 g/cm.sup.3 and 2.40 g/cm.sup.3, respectively, the tap density of the modified ternary material was increased to a certain extent compared with the homogeneous ternary material; after the materials had been made into a 2032 button battery, the initial discharge specific capacities at 3.0-4.3 V 0.2 C were 159.1 mAh/g and 161.8 mAh/g, respectively, as shown in FIG. 2; the capacity retention rates after 200 cycles at 3.0-4.3 V 1 C were 89.43% and 84.08%, respectively, as shown in FIG. 4; and the capacity retention rates after 100 cycles at 3.0-4.5 V 1 C were 86.81% and 80.18%, respectively, as shown in FIG. 3.

(14) It can be seen from the test data mentioned above that the other properties of the modified ternary material in Example 1 were all superior to the homogeneous ternary material except that the initial cycle performance thereof was inferior to the homogeneous ternary material with a gap of 2.7 mAh/g.

COMPARATIVE EXAMPLE 2

(15) 25 L of a nickel, cobalt and manganese salt solution with a concentration of 2 M was prepared, wherein the molar ratio of nickel:cobalt:manganese is 1:1:1.

(16) The prepared salt solution mentioned above was injected at a speed of 1 L/h into a reaction kettle with a rotation speed of 200 rps, and a 6 M NaOH solution was injected simultaneously, the flow rate of the alkali solution was adjusted, and the pH value was kept by an on-line pH value controller between 10-11. After the reaction had been carried out for 25 h, the salt solution had been reacted completely, and so far, the reaction for preparing a precursor was completed. The solid-liquid mixture, after the reaction was completed, was separated by centrifugation, washed to be neutral and then oven-dried at 100° C. for 10 h. The oven-dried precursor was mixed well with lithium carbonate according to a molar ratio of 1:1.05, and then calcined in a muffle furnace at 900° C. for 10 h, and the material calcined was crushed and sieved to obtain a ternary material of homogeneous LiNi.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2.

EXAMPLE 2

(17) 20 L of a 2 M nickel, cobalt and manganese salt solution A was prepared, in which the molar ratio of nickel:cobalt:manganese was 0.29:0.42:0.29; and 5 L of a 2 M nickel and manganese salt solution B was prepared, in which the molar ratio of nickel:manganese was 0.5:0.5.

(18) The salt solution A was injected at a speed of 1 L/h into a reaction kettle with a rotation speed of 200 rps, and a 6 M NaOH solution was injected simultaneously, the flow rate of the alkali solution was adjusted, and the pH value was kept by means of an on-line pH value controller between 10-11. After the reaction had been carried out for 19 h, the injection speed of the salt solution A was decreased at a speed of 1 L/h, and at the same time, the flow rate of the salt solution B was increased gradually from zero at a speed increment of 0.5 L/h; after 2 h, the salt solution A was completely injected into the reaction kettle, and the salt solution B was injected continuously at a speed of 1 L/h into the reaction kettle; and after 4 h, the salt solution B was completely injected into the reaction kettle, and thus the reaction for preparing a precursor was completed. The solid-liquid mixture, after the reaction was completed, was separated by centrifugation, washed to be neutral and then oven-dried at 100° C. for 10 h. The oven-dried precursor was mixed well with lithium carbonate at a molar ratio of 1:1.05 and then calcined in a muffle furnace at 900° C. for 10 h, and the material calcined was crushed and sieved to obtain a modified ternary material.

(19) The tap densities of the materials of Example 2 and Comparative example 2 were 2.55 g/cm.sup.3 and 2.38 g/cm.sup.3, respectively, the tap density of the modified ternary material was increased to a certain extent compared with the homogeneous ternary material; and after the materials had been made into a 2032 button battery, the initial discharge specific capacities at 3.0-4.3 V 0.1 C were 154.7 mAh/g and 161 mAh/g, respectively. The capacity retention rates after 200 cycles at 3.0-4.3 V 1 C were 91.05% and 84.52%, respectively; the capacity retention rates after 100 cycles at 3.0-4.5 V 1 C were 88.93% and 80.54%, respectively; and the 4.3 V DSC decomposition temperatures were: 286° C. and 277° C. FIG. 5-1 and FIG. 5-2 are electron micrographs of Example 2 and Comparative example 2, respectively; and FIG. 6 is a DSC diagram of Example 2 and Comparative example 2.

EXAMPLE 3

(20) 20 L of a 2 M nickel, cobalt and manganese salt solution A was prepared, in which the molar ratio of nickel:cobalt:manganese was 0.3:0.4:0.3; and 5 L of a 2 M nickel, cobalt and manganese salt solution B was prepared, in which the molar ratio of nickel:cobalt:manganese was 0.45:0.1:0.45.

(21) The salt solution A was injected at a speed of 1 L/h into a reaction kettle with a rotation speed of 200 rps, and a 6 M NaOH solution was injected simultaneously, the flow rate of the alkali solution was adjusted, and the pH value was kept by means of an on-line pH value controller between 10-11. After the reaction had been carried out for 19.5 h, the injection speed of the salt solution A was decreased at a speed of 0.1 L/h, and at the same time, the flow rate of the salt solution B was increased gradually from zero at a speed increment of 0.1 L/h; after 5 h, the salt solution A was completely injected into the reaction kettle, and the salt solution B was injected continuously at a speed of 1 L/h into the reaction kettle; and after 4.5 h, the salt solution B was completely injected into the reaction kettle, and thus the reaction for preparing a precursor was completed. The solid-liquid mixture, after the reaction was completed, was separated by centrifugation, washed to be neutral and then oven-dried at 200° C. for 4 h. The oven-dried precursor was mixed well with lithium carbonate at a molar ratio of 1:1.05 and then calcined in a muffle furnace at 900° C. for 10 h, and the material calcined was crushed and sieved to obtain a modified ternary material.

(22) The tap densities of the materials of Example 3 and Comparative example 2 were 2.52 g/cm.sup.3 and 2.38 g/cm.sup.3, respectively, the tap density of the modified ternary material is increased to a certain extent compared with the homogeneous ternary material; and after the materials had been made into a 2032 button battery, the initial discharge specific capacities at 3.0-4.3 V 0.1 C were 158.9 mAh/g and 161 mAh/g, respectively. The capacity retention rates after 200 cycles at 3.0-4.3 V 1 C were 89.79% and 84.52%, respectively; the capacity retention rates after 100 cycles at 3.0-4.5 V 1 C were 87.04% and 80.54%, respectively; and the 4.3 V DSC decomposition temperatures were: 284° C. and 277° C.

EXAMPLE 4

(23) 17.5 L of a 2.7 M nickel, cobalt and manganese salt solution A was prepared, in which the molar ratio of nickel:cobalt:manganese was 0.262:0.476:0.262; and 7.5 L of a 2.7 M nickel and manganese salt solution B was prepared, in which the molar ratio of nickel:manganese was 0.5:0.5.

(24) The salt solution A was injected at a speed of 1 L/h into a reaction kettle with a rotation speed of 1,000 rps, and a 6 M NaOH solution was injected simultaneously, the flow rate of the alkali solution was adjusted, and the pH value was kept by means of an on-line pH value controller between 10-11. After the reaction had been carried out for 16.5 h, the injection speed of the salt solution A was decreased at a speed of 1 L/h, and at the same time, the flow rate of the salt solution B was increased gradually from zero at a speed increment of 1 L/h; after 2 h, the salt solution A was completely injected into the reaction kettle, and the salt solution B was injected continuously at a speed of 1 L/h into the reaction kettle; and after 6 h, the salt solution B was completely injected into the reaction kettle, and thus the reaction for preparing a precursor was completed. The solid-liquid mixture, after the reaction was completed, was separated by centrifugation, washed to be neutral and then oven-dried at 100° C. for 10 h. The oven-dried precursor was mixed well with lithium carbonate at a molar ratio of 1:1.05 and then calcined in a muffle furnace at 900° C. for 10 h, and the material calcined was crushed and sieved to obtain a modified ternary material.

(25) The tap densities of the materials of Example 4 and Comparative example 2 were 2.55 g/cm.sup.3 and 2.38 g/cm.sup.3, respectively, the tap density of the modified ternary material is increased to a certain extent compared with the homogeneous ternary material; and after the materials had been made into a 2032 button battery, the initial discharge specific capacities at 3.0-4.3 V 0.1 C were 151.3 mAh/g and 161 mAh/g respectively. The capacity retention rates after 200 cycles at 3.0-4.3 V 1 C were 92.18% and 84.52%, respectively; the capacity retention rates after 100 cycles at 3.0-4.5 V 1 C were 90.93% and 80.54% respectively; the capacity retention rates after 50 cycles at 3.0-4.3 V 1 C under 55° C. were 87.05% and 84.13%, respectively; and the 4.3 V DSC decomposition temperatures were: 288° C. and 277° C., and the heat release amounts were respectively: 539.5 J/g and 554.9 J/g.

EXAMPLE 5

(26) 17.5 L of a 2 M nickel, cobalt and manganese salt solution A was prepared, in which the molar ratio of nickel:cobalt:manganese was 0.27:0.46:0.27; and 7.5 L of a 2 M nickel, cobalt and manganese salt solution B was prepared, in which the molar ratio of nickel:cobalt:manganese was 0.45:0.1:0.45.

(27) The salt solution A was injected at a speed of 1 L/h into a reaction kettle with a rotation speed of 200 rps, and a 6 M NaOH solution was injected simultaneously, the flow rate of the alkali solution was adjusted, and the pH value was kept by means of an on-line pH value controller between 10-11. After the reaction had been carried out for 16.5 h, the injection speed of the salt solution A was decreased at a speed of 1 L/h, and at the same time, the flow rate of the salt solution B was increased gradually from zero at a speed increment of 0.5 L/h; after 2 h, the salt solution A was completely injected into the reaction kettle, and the salt solution B was injected continuously at a speed of 1 L/h into the reaction kettle; and after 6.5 h, the salt solution B was completely injected into the reaction kettle, and thus the reaction for preparing a precursor was completed. The solid-liquid mixture, after the reaction was completed, was separated by centrifugation, washed to be neutral and then oven-dried at 60° C. for 10 h. The oven-dried precursor was mixed well with lithium carbonate at a molar ratio of 1:1.05, and then calcined in a muffle furnace at 300° C. for 4 h, calcined at 800° C. for 4 h, and calcined at 1,000° C. for 20 h, and the material calcined was crushed and sieved to obtain a modified ternary material.

(28) The tap densities of the materials of Example 5 and Comparative example 2 were 2.55 g/cm.sup.3 and 2.38 g/cm.sup.3, respectively, the tap density of the modified ternary material is increased to a certain extent compared with the homogeneous ternary material; and after the materials had been made into a 2032 button battery, the initial discharge specific capacities at 3.0-4.3 V 0.1 C were 154.5 mAh/g and 161 mAh/g, respectively. The capacity retention rates after 200 cycles at 3.0-4.3 V 1 C were 90.11% and 84.52%, respectively; the capacity retention rates after 100 cycles at 3.0-4.5 V 1 C were 87.79% and 80.54%, respectively; the capacity retention rates after 50 cycles at 3.0-4.3 V 1 C under 55° C. were 88.15% and 84.13%, respectively; and the 4.3 V DSC decomposition temperatures were: 287° C. and 277° C.

EXAMPLE 6

(29) 16 L of a 2 M nickel, cobalt and manganese salt solution A was prepared, in which the molar ratio of nickel:cobalt:manganese was 0.29:0.42:0.29; and 9 L of a 2 M nickel, cobalt and manganese salt solution B was prepared, in which the molar ratio of nickel:cobalt:manganese was 0.4:0.2:0.4.

(30) The salt solution A was injected at a speed of 1 L/h into a reaction kettle with a rotation speed of 200 rps, and a 6 M NaOH solution was injected simultaneously, the flow rate of the alkali solution was adjusted, and the pH value was kept by means of an on-line pH value controller between 10-11. After the reaction had been carried out for 14 h, the injection speed of the salt solution A was decreased at a speed of 1 L/h, and at the same time, the flow rate of the salt solution B was increased gradually from zero at a speed increment of 0.25 L/h; after 4 h, the salt solution A was completely injected into the reaction kettle, and the salt solution B was injected continuously at a speed of 1 L/h into the reaction kettle; and after 7 h, the salt solution B was completely injected into the reaction kettle, and thus the reaction for preparing a precursor was completed. The solid-liquid mixture, after the reaction was completed, was separated by centrifugation, washed to be neutral and then oven-dried at 150° C. for 8 h. The oven-dried precursor was mixed well with lithium carbonate at a molar ratio of 1:1.05 and then calcined in a muffle furnace at 1,200° C. for 8 h, and the material calcined was crushed and sieved to obtain a modified ternary material.

(31) The tap densities of the materials of Example 6 and Comparative example 2 were 2.55 g/cm.sup.3 and 2.38 g/cm.sup.3, respectively, the tap density of the modified ternary material is increased to a certain extent compared with the homogeneous ternary material; and after the materials had been made into a 2032 button battery, the initial discharge specific capacities at 3.0-4.3 V 0.1 C were 158.9 mAh/g and 161 mAh/g, respectively. The rate performances of the materials at 1 C and 2 C were 150.5 mAh/g and 144.7 mAh/g, and 146 mAh/g and 136 mAh/g, respectively, from which it can be seen that the rate performance of the material of Example 6 was apparently better than that of Comparative example 2. The capacity retention rates after 200 cycles at 3.0-4.3 V 1 C were 90.2% and 84.52%, respectively; the capacity retention rates after 100 cycles at 3.0-4.5 V 1 C were 88.59% and 80.54%, respectively; and the 4.3 V DSC decomposition temperatures were: 287.5° C. and 277° C.

(32) In summary, the precursor of a modified ternary material for a lithium ion battery positive electrode material of the present invention has a molecular formula of: Ni.sub.1/3Co.sub.1/3Mn.sub.1/3(OH).sub.2; and the precursor consists of three layers, wherein an inner layer of the precursor is a ternary material with a cobalt content of greater than ⅓ and identical nickel and manganese contents, and the molecular formula of said inner layer of the precursor is: (Ni.sub.1/3−xCo.sub.1/3+2xMn.sub.1/3−x)(OH).sub.2, where 0<x≦⅓; an outer layer of the precursor is a ternary material with a cobalt content of 0 to ⅓ and equal nickel and manganese contents, and the molecular formula of said outer layer of the precursor is: (Ni.sub.0.5−yCo.sub.2yMn.sub.0.05−y)(OH).sub.2, where 0≦y<⅙; and an intermediate layer of the precursor is a concentration-gradient composite material of the two materials of the inner layer and the outer layer of the above precursor. The chemical formula of the modified ternary material having the above precursor is Li(Ni.sub.1/3Co.sub.1/3Mn.sub.1/3)O.sub.2, and therefore, the interior of the microscopic particles of this modified material is composed of three parts, namely, an inner layer being of a ternary material with a relatively high cobalt content and equal nickel and manganese contents; an outer layer being of a ternary material with a relatively low cobalt content or no cobalt and equal nickel and manganese contents; and an intermediate layer being of a concentration-gradient composite material of the two materials of the inner layer and the outer layer. The preparation of a modified ternary material having the above precursor is: dividing the preparation procedure into two stages for carrying out structure design and productive preparation when the precursor of a ternary material is prepared by a coprecipitation method, i.e., after the precursor material prepared is washed and oven-dried, mixing the same with a lithium source and calcining, and cooling to obtain a modified ternary positive electrode material. Compared with the LiNi.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 material with a homogeneous internal structure, in addition to having a similar discharge specific capacity, the modified LiNi.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 material having a precursor with different internal structures has a higher tap density, and better cycle stability and safety performance, and the rate performance of the material is also increased largely, having an apparent cost-performance advantage, and being more suitable for the application on a power battery.

(33) Although the present invention has been described hereinabove in conjunction with the drawings, the present invention is not limited to the particular embodiments described above, the particular embodiments described above are merely illustrative and are not limitative, many variations can be made by those skilled in the art under the teaching of the present invention without departing from the purpose of the present invention, and these all fall into the protection of the present invention.