METHOD FOR PREPARING THE MATERIAL WITH COMPOSITION GRADIENT CHARACTERISTICS AND ITS APPLICATION IN BATTERY THEREOF

Abstract

The invention relates to a method for preparing materials with composition gradient characteristics. After mixing a lithium source with the prepared precursor, raise the temperature from room temperature to 300° C.˜600° C. at 2° C./min˜10° C./min and maintain it, and then sinter for 5 hours˜18 hours, cool with the furnace, then raise the temperature from room temperature to 600° C.˜1200° C. at 2° C./min˜10° C./min and maintain it, and sinter for 5 hours˜18 hours, and the material is thus obtained. The material prepared with the method provided by the invention has composition gradient characteristic, and its application to the positive electrode of battery enables the battery to have higher energy density and better thermal stability, and prolonged service life.

Claims

1. A method for preparing a material for the positive electrode of battery, comprising the following steps: after mixing the lithium source with the prepared precursor, firstly raise from room temperature to 300° C.˜600° C. at 2° C./min˜10° C./min and maintain it, then sinter for 5˜18 hours, cool with the furnace, then raise from room temperature to 600° C.˜1200 at 2° C./min˜10° C./min and maintain it, and then sintered for 5˜18 hours, and the material is thus obtained, the said lithium source is selected from one or more of lithium carbonate, lithium nitrate and lithium hydroxide; the said precursor has composition gradient characteristics.

2. The preparation method of the material for the positive electrode of battery according to claim 1, wherein the lithium source is blended with the precursor as per a molar ratio of 1.01˜1.1.

3. The preparation method of the material for the positive electrode of battery according to claim 1, wherein the said material has composition gradient characteristics.

4. The preparation method of the material for the positive electrode of battery according to claim 3, wherein the said material presents a nickel rich to nickel poor gradient from the inside to the outside.

5. The preparation method of the material for the positive electrode of battery according to claim 1, wherein the said precursor with the nominal composition shown in Ni.sub.xCo.sub.yMn.sub.zM.sub.1-x-y-z(OH).sub.2 is prepared first, where M is trace element; x, y and z are independently selected from any number from 0 to 1, and the sum of x, y and z is 0.8˜1.0.

6. The preparation method of the material for the positive electrode of battery according to claim 5, wherein the said trace elements Cr, Mg, Al, Ti, Zr, Zn, CA, Nb and W.

7. The method for preparing the material for the positive electrode of battery according to claim 5, wherein the said precursor has primary particles radiating from the inside to the outside.

8. The preparation method of the material for the positive electrode of battery according to claim 7, wherein the primary particles present a gradient from poor nickel to rich nickel from the outside to the inside.

9. The method for preparing the material for the positive electrode of battery according to claim 5, wherein the particle size distribution D50 of the said precursor is 5 microns to 15 microns.

10. The method for preparing the material for the positive electrode of battery according to claim 5, wherein the method for preparing the precursor comprises: put the first metal salt solution in the container, then add the second metal salt solution to the said first metal salt solution, synchronously, add the solution and ammonia in the said container to the reactor for coprecipitation, and maintain pH 9˜13 during the reaction, and the precursor is thus prepared; the total reaction time T.sub.total of the said coprecipitation can be calculated from the following formula II:
∫.sub.0.sup.T.sup.totalU.sub.M1(t)dt=V.sub.M1+V.sub.M2  II wherein, V.sub.M1 represents the initial volume of the first metal salt solution; V.sub.M2 represents the initial volume of the second metal salt solution; U.sub.M1(t) represents the feed rate of metal salt solution in the container to the reactor; t represents the reaction time.

11. The preparation method of the material for the positive electrode of battery according to claim 10, wherein the instant solution composition of each element when the solution in the said container is added to the reactor can be calculated by the following formula I: ${\mathrm{dC}}_{\mathrm{element}}\left(t\right)=\frac{\begin{array}{c}{U}_{M2}\left(t\right).Math.C_{\mathrm{element}-M2}.Math.\mathrm{dt}+V_{m1}.Math.C_{\mathrm{element}-M1}-\\ {\int }_0^t{U}_{M1}\left(t\right).Math.C_{\mathrm{element}}\left(t\right)\mathrm{dt}-U_{M1}\left(t\right).Math.{\mathrm{dC}}_{\mathrm{element}}\left(t\right).Math.\mathrm{dt}\end{array}}{V_{M1}-{\int }_0^t{U}_{M1}\left(t\right)\mathrm{dt}}$ wherein, element represents one of the metal elements Ni, Co, Mn, Cr, Mg, Al, Ti, Zr, Zn, Ca, Nb and W; C.sub.element-M1 represents the initial concentration of such metal element contained in the first metal salt solution; C.sub.element-M2 represents the initial concentration of such metal element contained in the second metal salt solution; U.sub.M2(t) represents the feed rate of the second metal salt solution; C.sub.element(t) represents the concentration of this metal element in the instant solution.

12. The method for preparing the material for the positive electrode of battery according to claim 10, wherein the stirring rate of the said reactor is 800 rpm˜1,300 rpm.

13. The method for preparing the material for the positive electrode of battery according to claim 10, wherein the temperature of the reaction liquid in the said reactor is 35° C.˜75° C.

14. The method for preparing the material for the positive electrode of battery according to claim 10, wherein the said reactor is protected by nitrogen or argon.

15. The preparation method of the material for the positive electrode of battery according to claim 1, wherein the application in battery manufacturing.

16. A material, wherein it is obtained by the preparation method of claim 1 and is used for the positive electrode of battery.

17. A battery, wherein it comprises a positive material, which is obtained by the preparation method in claim 1.

18. The battery according to claim 17, wherein the said battery is a lithium-ion battery.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0052] FIG. 1 is a schematic diagram of a coprecipitation reaction device;

[0053] FIG. 2 is an XRD atlas of the precursor material for the positive electrode of battery prepared with the coprecipitation method in example 1, example 2 and example 3;

[0054] FIG. 3 is a SEM graph of the precursor material for the positive electrode of battery prepared with the coprecipitation method in example 1, example 2 and example 3, and an EDS metal element distribution line scanning graph of the cross section of the material particles;

[0055] FIG. 4 is an XRD atlas of the material for the positive electrode of battery prepared in example 4, example 5 and example 10;

[0056] FIG. 5 is a SEM graph of the material for the positive electrode of battery prepared in example 4 and example 5 and an EDS metal element distribution point scanning graph of cross section of the material particles;

[0057] FIG. 6A is a comparison of the charge/discharge curves of the materials for the positive electrode of battery prepared in example 4, example 5 and example 10;

[0058] FIG. 6B is a cyclic performance test graph of the material for the positive electrode of battery prepared in example 4, example 5 and example 10;

[0059] FIG. 7 is a DSC curve graph of the material for the positive electrode of battery prepared in example 6 and example 10;

[0060] FIG. 8 is an XRD atlas of the material for the positive electrode of battery prepared in example 6 and example 7;

[0061] FIG. 9 is a SEM graph of the material for the positive electrode of battery prepared in example 6 and example 7 and an EDS metal element distribution point scanning graph of the cross section of the material particles;

[0062] FIG. 10A is a charge/discharge curve graph of the material for the positive electrode of battery prepared in example 6 and example 7;

[0063] FIG. 10B is a cyclic performance test graph of the material for the positive electrode of battery prepared in example 6 and example 7;

[0064] FIG. 11 is an XRD atlas of the material for the positive electrode of battery prepared in example 8 and example 11;

[0065] FIG. 12A is a charge/discharge curve graph of the material for the positive electrode of battery prepared in example 8 and example 11;

[0066] FIG. 12B is a cyclic performance test graph of the material for the positive electrode of battery prepared in example 8 and example 11.

DETAILED DESCRIPTION

[0067] The technical scheme of the invention is described in detail below in combination with the accompanying figures. The examples of the invention are only used to elaborate the technical scheme of the invention rather than limiting it. Although the invention is described in detail with reference to the better examples, general technicians in this field should understand that the technical scheme of the invention can be modified or equivalently replaced without deviating from the spirit and scope of the technical scheme of the invention, and all of them shall be covered by the claims of the invention.

[0068] FIG. 1 is a schematic diagram of a coprecipitation reaction device for implementing the method of the present invention. As shown in FIG. 1, the first metal salt solution M1 is contained in the container 300, and the second metal salt solution M2 is added to the container 300 through the connected pipeline 100 and mix with the first metal salt solution M1. The solution in the container 300 is also synchronously added to the reactor 400 through the pipeline 200 and the complexing agent (2 mol/L˜10 mol/L ammonia) for coprecipitation. The temperature of the reaction solution is 35° C.˜75° C., and nitrogen (N.sub.2) is introduced into the reactor 400 as a protective atmosphere. pH is used to detect the reaction solution in the reactor 400, and the pH in the reaction process is kept at 9˜13 by adding alkali solution (such as 2 mol/L˜10 mol/L NaOH solution or KOH solution).

[0069] The total reaction time of coprecipitation T.sub.total will depend on the volumes V.sub.M1 and V.sub.M2 of the two solutions and U.sub.M1(t), where T.sub.total can be calculated from the following formula II:

∫.sub.0.sup.T.sup.totalU.sub.M1(t)dt=V.sub.M1+V.sub.M2  II

[0070] In this example, the volume of the reactor 400 is 5 L, so the corresponding V.sub.M1, V.sub.M2 and U.sub.M1(t) are 0 l˜1.5 L, 0 l˜1.5 L and 0.011/h-0.21/h respectively, and the total reaction time T.sub.total is 5 hours˜300 hours:

[0071] The test methods used in the following examples of the invention are specifically described as follows:

[0072] 1) Structural characterization by X-ray diffraction (XRD)

[0073] The test equipment for X-ray diffraction is D2-XE-T. The target used for the instrument is copper target, and the X-ray wavelength is 1.5406 Å. Firstly, weight 1 g˜2 g sample, lay the samples in the center of the sample table as far as possible, and then use glass slides to smooth them to ensure that the samples are flush with the sample groove and that no sample is outside the groove. Finally, put the prepared sample table into Brooke D2-XE-T for test. The scanning range of X-ray 2θ is set to 10˜80°, the scanning step to 0.01°, and the X-ray exposure time of each step to 0.1 s.

[0074] 2) Morphological Characterization by Scanning Electron Microscopy (SEM)

[0075] First, bond a small amount of powder samples to the conductive tape of the sample table to ensure that the samples are evenly dispersed without agglomeration. Then, place the samples in the Joel JCM-7000 NeoScope desktop scanning electron microscope for observation. The element analysis of particle's cross section is carried out by Joel JED-2300 energy spectrometer (EDS) for data acquisition.

[0076] 3) Electrochemical Performance Test

[0077] Mix the prepared cathode material of lithium-ion battery with conductive agent (such as carbon black), binder (such as polyvinylidene fluoride) and solvent (such as N-methylpyrrolidone) to prepare electrode slurry, then coat it on aluminum based current collector, dry it to prepare electrode, and assemble into coin cells. After that, cycle the coin cells first for 4 turns at 2.75-4.4V with a current of 0.1 C, and then do cycle tests with a current of 0.5 C in the same voltage range.

[0078] 4) Thermal Stability Test

[0079] Firstly, cycle the prepared coin cells at 2.75-4.4V with a current of 0.1 C for 2 cycles, then charge it to 4.4V and remove it for disassembly after constant voltage. Add the recovered positive electrode sheet and quantitative lithium-ion battery electrolyte into a sealed crucible and test by differential scanning calorimetry (DSC), with the heating rate of 5° C./min.

Example 1

[0080] Prepare the first metal sulfate solution 0.72 L: prepare nickel sulfate, cobalt sulfate and manganese sulfate as per a molar ratio of 90:10:0 into 2 mol/L sulfate solution and put it in a container. Prepare 0.18 L second metal sulfate solution: prepare nickel sulfate, cobalt sulfate and manganese sulfate as per a molar ratio of 40:10:50) into 2 mol/L sulfate solution.

[0081] Add 1.0 L˜1.5 L mixture of deionized water and ammonia into the reactor, fill the reactor with nitrogen, adjust the rotating speed in the reactor to 800 rpm-1300 rpm, and set the temperature range of the reaction solution measured by the thermometer to 40° C.˜70° C.

[0082] Pump the second metal sulfate solution into the container at the rate of U.sub.M2(t) shown in formula III below and mix it with the first metal sulfate solution in the container, such as stirring at 250 rpm.

[00002]$\begin{array}{cc}{U}_{M2}\left(t\right)=\{\begin{array}{c}0L/h\left(0<t<24h\right)\\ 0.03L/h\left(24h<t<30h\right)\end{array}& \mathrm{III}\end{array}$

[0083] Synchronously, pump the solution in the container into the reactor at the rate of U.sub.M1(t)=0.03 L/h, pump 5 mol/L ammonia into the reactor at the rate of UC(t)=0.01˜0.04 L/h, and keep the pH value of the solution at 9˜13 with 4 mol/L NaOH solution.

[0084] After the reaction is over, spherical particles with particle size distribution D50 ranging from 5 microns to 15 microns can be obtained. The nominal component of the prepared precursor is Ni.sub.0.8Co.sub.0.1Mn.sub.0.1(OH).sub.2, and the composition gradient of the precursor from inside to outside is shown in FIG. 3. In FIG. 3, by observing the element analysis of the cross section of example 1, it can be seen that the material is an obvious core-shell structure. The inner composition of example 1 is rich in nickel and poor in manganese, while the outer shell composition of example 1 is rich in manganese and poor in nickel, and the component content of cobalt from the inner to the shell remains the same.

[0085] After washing the precursor with deionized water, put it into the oven for vacuum heating and drying. The oven temperature is set at 60° C.˜100° C., and the drying step can be completed after drying for 8˜12 hours.

Example 2

[0086] Prepare the first metal sulfate solution 0.80 L: prepare nickel sulfate, cobalt sulfate and manganese sulfate as per a molar ratio of 100:0:0 into 2 mol/L sulfate solution and put it in a container. Prepare the second metal sulfate solution 0.343 L: prepare nickel sulfate, cobalt sulfate and manganese sulfate as per a molar ratio of 1:1:1 into 2 mol/L sulfate solution.

[0087] Add 1.0 L˜1.5 L mixture of deionized water and ammonia into the reactor, fill the reactor with nitrogen, adjust the rotating speed in the reactor to 800 rpm-1300 rpm, and set the temperature range of the reaction solution measured by the thermometer to 40° C.˜70° C.

[0088] Pump the second metal sulfate solution into the container at the rate of U.sub.M2(t) shown in the following formula IV-1 and mix it with the first metal sulfate solution in the container, such as stirring at 250 rpm.

[00003]$\begin{array}{cc}{U}_{M2}\left(t\right)=\{\begin{array}{c}0.006L/h\left(0<t<6h\right)\\ 0.015L/h\left(6h<t<24h\right)\\ 0.006L/h\left(24h<t<30h\right)\end{array}& \mathrm{IV}‐1\end{array}$

[0089] Synchronously, pump the solution in the container into the reactor at the rate of U.sub.M1(t) shown in IV-2 below, pump 5 mol/L ammonia into the reactor at the rate of UC(t)=0.01˜0.04 L/h, and keep the pH value of the solution at 9˜13 with 4 mol/L NaOH solution.

[00004]$\begin{array}{cc}{U}_{M1}\left(t\right)=\{\begin{array}{c}0.08L/h\left(0<t<6h\right)\\ 0.03L/h\left(6h<t<24h\right)\\ 0.02L/h\left(24h<t<30h\right)\end{array}& \mathrm{IV}‐2\end{array}$

[0090] After the reaction is over, spherical particles with particle size distribution D50 ranging from 5 microns to 15 microns can be obtained. The nominal component of the prepared precursor is Ni.sub.0.8Co.sub.0.1Mn.sub.0.1(OH).sub.2, and the composition gradient of the precursor from inside to outside is shown in FIG. 3. In FIG. 3, by observing the element analysis of the cross section of example 2, it can be seen that from the core to the shell, the component content of nickel changes from high to low, and the component content of cobalt and manganese changes from low to high.

[0091] After the precursor is washed with deionized water, heat and dry it in an oven protected by nitrogen. Set the oven temperature at 60° C.˜100° C., and the drying step can be completed after drying for 8—12 hours.

Example 3

[0092] Prepare the first metal sulfate solution 0.6 L: prepare nickel sulfate, cobalt sulfate and manganese sulfate as per a molar ratio of 100:0:0 into 2 mol/L sulfate solution and put it in a container. Prepare the second metal sulfate solution 0.6 L: prepare nickel sulfate, cobalt sulfate and manganese sulfate as per a molar ratio of 60:20:20 into 2 mol/L sulfate solution.

[0093] Add 1.0 L˜1.5 L mixture of deionized water and ammonia into the reactor, fill the reactor with nitrogen, adjust the rotating speed in the reactor to 800 rpm˜1300 rpm, and set the temperature range of the reaction solution measured by the thermometer to 40° C.˜70° C.

[0094] Pump the second metal sulfate solution into the container at the rate of U.sub.M2(t)=0.01˜0.03 L/h and mix it with the first metal sulfate solution in the container, such as stirring at the speed of 200 rpm˜3000 rpm.

[0095] Synchronously, pump the solution in the container into the reactor at the rate of U.sub.M1(t)=0.04˜0.06 L/h, pump 5 mol/L ammonia into the reactor at the rate of U.sub.C(t)=0.01˜0.04 L/h, and keep the pH value of the solution at 9˜13 with 4 mol/L NaOH solution.

[0096] After the reaction is over, spherical particles with a particle size distribution D50 of about 5 to 15 microns can be obtained. The nominal component of the prepared precursor is Ni.sub.0.8Co.sub.0.1Mn.sub.0.1(OH).sub.2, and the composition gradient of the precursor from inside to outside is shown in FIG. 3. In FIG. 3, by observing the element analysis of the cross section of example 3, it can be seen that from the core to the shell, the component content of nickel changes from high to low, and the component content of cobalt and manganese changes from low to high.

[0097] After the precursor is washed with deionized water, heat and dry it in an oven filled with nitrogen. The oven temperature is set at 60° C.˜100° C., and the drying step can be completed after drying for 8˜12 hours.

Example 4

[0098] Mix a lithium source Li.sub.2CO.sub.3 or LiOH with the precursor prepared in example 1 as per a molar ratio of 1.01 to 1.1. Put the mixture into an oxygen protected furnace and sinter for 12˜18 hours, in which the temperature in the furnace is set to 700° C.˜1,000° C.

[0099] Characterize the sintered samples by SEM and XRD, and test the electrochemical properties of the sintered and prepared cathode materials.

Example 5

[0100] Mix a lithium source Li2CO.sub.3 or LiOH with the precursor prepared in example 2 as per a molar ratio of 1.01˜1.1. Put the mixture into an oxygen protected furnace and sinter for 12˜18 hours, in which the temperature in the furnace is set to 700° C.˜1,000° C.

[0101] Characterize the sintered samples by SEM and XRD, and test the electrochemical properties of the sintered and prepared cathode materials.

Example 6

[0102] Mix the lithium source Li2CO.sub.3 or LiOH with the precursor prepared in example 3 as per a molar ratio of 1.01˜1.1. Put the mixture into an oxygen protected furnace and sinter for 12˜18 hours, in which the temperature in the furnace is set to 700° C.˜1,000° C.

[0103] Characterize the sintered samples by SEM and XRD, and test the electrochemical properties of the sintered and prepared cathode materials.

Example 7

[0104] Mix a lithium source Li2CO.sub.3 or LiOH with the precursor prepared in example 3 as per a molar ratio of 1.01˜1.1.

[0105] Put the mixture into an oxygen protected furnace, raise the temperature 300° C.˜600 at 2° C./min˜10° C./min and maintain it. After sintering for 12˜18 hours, cool it with the furnace, put the cooled sample into a shaking machine and mix for 1˜5 hours. Then, put it into an oxygen protected furnace, raise it to 700° C.˜1,000° C. from room temperature at 2° C./min˜10° C./min and maintain it, sinter it for 12˜18 hours, and obtain the sintered cathode material sample cooling with the furnace.

[0106] Characterize the sintered samples by SEM and XRD, and test the electrochemical properties of the sintered and prepared cathode materials.

Example 8

[0107] Mix a lithium source Li.sub.2CO.sub.3 or LiOH with the precursor prepared in example 1 as per a molar ratio of 1.01 to 1.1.

[0108] Put the mixture into an air protected furnace, raise the temperature to 300° C.˜600° C. from room temperature at 2° C./min˜40° C./min and maintain it. After sintering for 12˜48 hours, cool it with the furnace, put the cooled sample into a shaking machine for mixing for 1˜5 hours. Then, put it into an air protected furnace, raise the temperature to 700° C.˜1000° C. from room temperature at 2° C./min˜10° C./min and maintain it, sinter for 12˜18 hours, and obtain sintered cathode material samples cooling with the furnace.

[0109] Characterize the sintered samples by SEM and XRD, and test the electrochemical properties of the sintered and prepared cathode materials.

Example 9

[0110] (1) First prepare 1 L of 2 mol/L M1 metal salt solution, and then 1 L of 2 mol/L M2 metal salt solution. See Table 1 for the specific components of M1 and M2 solutions.

[0111] (2) Then prepare 2 mol/L˜4 mol/L NaOH solution and 2 mol/L˜5 mol/L ammonia solution.

[0112] (3) Add 1 L˜1.5 L mixture of deionized water and ammonia into a 5 L reactor, and fill the reactor with nitrogen to maintain an oxygen free environment. Adjust the rotating speed in the reactor to 900 rpm 1300 rpm, set the solution temperature in the reactor to 40° C.˜70° C., and keep the pH value of the solution to 9˜13.

[0113] (4) Pump M2 solution into M1 solution at the rate of U.sub.M2(t), add a rotor to M1 solution, and set its speed to 200 rpm 600 rpm to keep the composition of M1 solution uniform all the time. At the same time, pump M1 solution into the reactor at the rate of U.sub.M1(t). See Table 1 for the specific rate settings of U.sub.M1(t) and U.sub.M2(t).

[0114] (5) At the same time, pump the ammonia water into the reactor at the speed of U.sub.C (t) and pump the corresponding NaOH to ensure that the pH value in the reactor is 9˜13. See Table 1 for the specific rate setting of U.sub.C(t).

[0115] (6) After the reaction is over, spherical particles with a particle size distribution D50 of about 5 microns to 15 microns can be obtained.

[0116] (7) Wash the precursor prepared by the above method with deionized water to recover the precursor.

[0117] (8) Put the washed precursor into a nitrogen protected oven for heating and drying. Set the oven temperature to 60° C.˜100° C., and the drying step can be completed after drying for 8˜12 hours.

[0118] (9) Mix the lithium source Li2CO.sub.3 or LiOH with the precursor as per a molar ratio of 1.01˜1.1. Put the mixture into an oxygen protected furnace, raise it to 300° C.˜600° C. from room temperature at 2˜10° C./min and maintain it. After sintering for 12˜48 hours, cool it with the furnace, and then put the cooled sample into a shaking machine for mixing for 1˜5 hours. After that, put it into an oxygen protected furnace, raise it to 700° C.˜1,000 from room temperature at 2° C./min˜10° C./min and maintain it, sinter it for 12˜18 hours, and obtain the sintered cathode material sample cooling with the furnace.

TABLE-US-00001 TABLE 1 Preparation condition for precursor Flow rate design of various solutions Flow Flow Flow rate of rate of rate of Sintering M1 M2 ammonia Li/TM condition No. of solution, solution, solution, molar for cathode sample Component of M1 solution Component of M2 solution L/h L/h L/h ratio material 1 Ni.sub.0.80Co.sub.0.20SO.sub.4 Ni.sub.0.40Co.sub.0.2Mn.sub.0.40SO.sub.4 0.03 0.015 0.03 1.05 1)600° C. 10 h 2)800° C. 12 h 2 Ni.sub.0.95Co.sub.0.05Cl.sub.2 Ni.sub.0.75Co.sub.0.15Al.sub.0.10Cl.sub.2 0.03 0.015 0.03 1.05 1)500° C. 10 h 2)850° C. 12 h 3 Ni.sub.0.95Co.sub.0.05SO.sub.4 Ni.sub.0.75Co.sub.0.15Ti.sub.0.10SO.sub.4 0.03 0.015 0.03 1.05 1)500° C. 10 h 2)750° C. 15 h 4 Ni.sub.0.90Co.sub.0.10SO.sub.4 Ni.sub.0.70Co.sub.0.20Mg.sub.0.1SO.sub.4 0.03 0.015 0.03 1.05 1)500° C. 10 h 2)800° C. 15 h 5 Ni.sub.0.90Co.sub.0.10(NO.sub.3).sub.2 Ni.sub.0.75Co.sub.0.15Fe.sub.0.10(NO.sub.3).sub.2 0.03 0.015 0.03 1.05 1)500° C. 10 h 2)800° C. 15 h 6 Ni.sub.0.90Mn.sub.0.10(NO.sub.3).sub.2 Ni.sub.0.75Mn.sub.0.15Fe.sub.0.10(NO.sub.3).sub.2 0.03 0.015 0.03 1.05 1)500° C. 10 h 2)800° C. 15 h 7 Ni.sub.0.90Mn.sub.0.10SO.sub.4 Ni.sub.0.7Mn.sub.0.20Mg.sub.0.10SO.sub.4 0.03 0.015 0.03 1.05 1)500° C. 10 h 2)800° C. 15 h Note: “1)” indicates the temperature and time of the first sintering; “2)” indicates the temperature and time of the second sintering.

Example 10

[0119] (1) Firstly, prepare 2 L metal salt solution. Prepare nickel sulfate, cobalt sulfate and manganese sulfate as per a molar ratio of 80:10:10 into 2 mol/L sulfate solution, and 2 mol/L˜4 mol/L NaOH solution and 2 mol/L˜5 mol/L ammonia solution.

[0120] (2) Add 1 L 1.5 L mixture of deionized water and ammonia into a 5 L reactor, and fill the reactor with nitrogen to maintain an oxygen free environment. Adjust the rotating speed in the reactor to 900-1300 rpm, and set the solution temperature in the reactor from 40° C.˜70° C.

[0121] (3) Pump the metal salt solution into the reactor at the rate of 0.04 L/h˜0.06 L/h, pump the ammonia solution into the reactor at the rate of 0.01-0.04 L/h, and use NaOH solution to ensure that the pH value in the reactor is maintained from 9˜13, and maintain the coprecipitation reaction until the metal salt solution is used up. After the reaction is over, spherical particles with a particle size distribution DSO of about 5 microns to 15 microns can be obtained, and the precursor is Ni.sub.0.8Co.sub.0.1Mn.sub.0.1(OH).sub.2 with uniform composition from inside to outside.

[0122] (4) Wash the precursor prepared with deionized water with the above method to recover the precursor.

[0123] (5) Put the washed precursor into a nitrogen protected oven for heating and drying. Set the oven temperature to 60° C.˜100° C., and the drying step can be completed after drying for 8˜12 hours.

[0124] (6) Mix a lithium source Li.sub.2CO.sub.3 or LiOH with the precursor as per a molar ratio of 1.01˜1.1. Put the mixture into an oxygen protected furnace for sintering for 12˜18 hours, with the temperature in the furnace set to 700° C.˜1,000° C. After sintering, ternary cathode material of LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with uniform internal and external components can be obtained.

[0125] (7) Test the electrochemical cycle life of the cathode material.

Example 11

[0126] Repeat steps (1) to (5) in example 10.

[0127] (6) Mix a lithium source Li2CO.sub.3 or LiOH with the precursor as per a molar ratio of 1.01˜1.1. Put the mixture into a furnace with air atmosphere and sinter for 12˜18 hours, with the temperature in the furnace set to 700° C.˜1,000° C. After sintering, ternary cathode material of LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with uniform internal and external components can be obtained.

[0128] (7) Test the electrochemical cycle life of the cathode material.

[0129] It can be seen from the above examples that the three precursor samples prepared by coprecipitation reaction in examples 1, 2 and 3 are characterized by XRD. It can be seen that the three precursors are pure M (OH).sub.2 (M is a metal element) and there is no impurity phase (see FIG. 2 for details). The particle size of the prepared precursors is about 10 μm. According to the analysis of metal elements in the cross section of the precursor by EDS, the three precursor particles have different composition gradients from the inside to the outside (see FIG. 3 for details).

[0130] In example 4 and example 5, each precursor prepared in example 1 and example 2 is mixed with a lithium source and sintered at high temperature to obtain a cathode material of battery with different composition gradient, with a nominal component of LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2. Example 10 with a unified composition from the inside out is also prepared as a comparison, and its component is LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2. It can be seen from XRD characterization that example 4, example 5 and example 10 are characterized as pure R-3m layered structure without any impurity phase (see FIG. 4 for details). Therefore, it can be seen that even various materials used for the positive electrode of battery with composition gradient also have a pure R-3m layered structure.

[0131] The element analysis of the cross section of the two materials for the positive electrode of battery prepared in examples 4 and 5 shows that the two materials maintain the composition gradient of the corresponding precursors, which is manifested in that the inner part of the particle is nickel rich phase and the outer layer of the particle is manganese rich phase (see FIG. 5 for details). Meanwhile, the primary particles of examples 4 and 5 are shown to grow radially from the center to the outer layer, which is characterized by the morphological characteristics of the composition gradient material.

[0132] The materials for the positive electrode of battery prepared in example 4, example 5 and example 10 are tested for charge/discharge curve comparison and cycle performance comparison. Example 4 and example 5 had similar unit discharge/capacity compared with example 10 (see FIG. 6A for details). With the same nominal component of LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2, the cycle life of the three materials for the positive electrode of battery with composition gradient characteristics is better than that of example 10 (see FIG. 6B for details). As can be seen from FIG. 6B, the cycle life of example 4 is the best. After 50 cycles, the discharge energy retention rate can reach 90%. In contrast, the discharge capacity retention rate of example 10 is 85.5% after 50 cycles. It can be seen that the cycle life of cathode materials with composition gradient can be greatly improved compared with cathode materials with uniform composition.

[0133] Furnishing a composition gradient to the cathode material of battery is more conducive to improve the thermal stability of the cathode material. Therefore, the thermal stability of example 6 (LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with composition gradient prepared by mixing the precursor prepared in example 3 with lithium source for one-step sintering) and example 10 (LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with unified composition from the inside to the outside) were studied. As shown in FIG. 7, compared with example 10, example 6 has a higher thermal decomposition temperature and less heat released in the whole heat release process, so example 6 has better thermal stability. Under the condition of maintaining the same nominal composition, the safety performance of cathode materials can be greatly improved by changing the composition gradient from inside to outside.

[0134] To maintain the composition gradient designed in the synthesis process of precursor will play a vital role in optimizing the cycle and safety performance of cathode materials. The process from precursor preparation to obtain the final cathode material for battery must undergo high-temperature sintering, but high-temperature sintering will lead to the diffusion of metal elements, so the solubility gradient of the precursor will disappear due to improper sintering process. Therefore, how to optimize the sintering process is very important for the preparation of ternary materials with composition gradient. In example 7, the precursor prepared in example 3 is also used to mix with lithium source for two-step sintering. As shown in FIG. 8, both the material prepared in example 6 and the material prepared in example 7 show a pure R-3m layered structure without any impurity phase. However, the internal appearance and element distribution of the two are very different. As shown in FIG. 9, the material prepared in example 6 shows a partial hollow phenomenon in the center, and the content of nickel element changes from the center to the outer layer, specifically from 80.33%±1.24% to 74.2%±1.31%, showing no significant gradient change. In example 7, there was no hollow phenomenon, and the content of nickel changed from 80.19%±1.22% to 69.53%±1.22%, showing a significant gradient change. Therefore, the material for the positive electrode of battery prepared by two-step sintering (i.e. example 7) is a more dense material and maintains the characteristics of the component gradient in the precursor. The electrochemical properties of example 6 and example 7 are shown in FIG. 10A and FIG. 10B. Both have similar unit discharge capacity, but the material prepared in example 7 shows a better cycle life. Therefore, the materials prepared by two-step sintering better retain the characteristics of component gradient, and can obtain a better cycle life as the positive electrode of battery. If the composition gradient characteristics of the precursor are retained during material preparation, the focus of the sintering process is to introduce low-temperature and high-temperature sintering means, so that it is easier to prepare materials with large composition gradient, compactness and long cycle life, which are applied to the positive electrode of battery, especially the positive electrode of lithium-ion battery.

[0135] The sintering of nickel rich cathode materials usually needs to be carried out in a pure oxygen atmosphere to ensure that nickel elements will not be reduced to Ni.sup.2+ ions in the sintering process, and enter the lithium-ion layer and cause mixed discharge of lithium and nickel, resulting in reduced discharge capacity of the materials. The application of pure oxygen sintering also greatly increases the production cost of high nickel materials. High nickel solubility gradient materials with the same nominal composition can form nickel rich core and nickel poor shell due to the particularity of design, which greatly reduces the dependence on pure oxygen sintering atmosphere in the sintering process. In example 8, the precursor with nominal component of Ni.sub.0.8Co.sub.0.1Mn.sub.0.1(OH).sub.2 prepared in example 1 is used, which is prepared by using two-step sintering in an air atmosphere. In example 11, the precursor with nominal component of Ni.sub.0.8Co.sub.0.1Mn.sub.0.1(OH).sub.2 with uniform composition from the inside to the outside is used, which is prepared by using one-step sintering in an air atmosphere. As shown in FIG. 11, the two materials prepared in example 8 and example 11 show a pure R-3m layered structure without any impurity phase. As shown in FIGS. 12A and 12B, example 8 has a similar unit discharge capacity as example 11, but example 8 with composition gradient characteristics has a longer cycle life than example 11. Therefore, compared with the material with uniform composition, the material with composition gradient can reduce the dependence on pure oxygen atmosphere in the sintering process and greatly reduce the production cost of the material.