CN113060773A - Preparation method and application of full-concentration-gradient high-nickel ternary material - Google Patents
Preparation method and application of full-concentration-gradient high-nickel ternary material Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion battery electrode materials, and particularly discloses a preparation method and application of a full-concentration-gradient high-nickel ternary material. The preparation method of the full-concentration gradient high-nickel ternary material is characterized by comprising the following steps of: preparing a nickel-rich salt solution A and a nickel-poor salt solution B, slowly introducing the solution A into a reaction kettle during the coprecipitation reaction, and simultaneously introducing the solution B into a solution A storage tank at a certain flow rate. After the reaction is finished, filtering, separating, washing and drying to obtain a full-concentration gradient high-nickel ternary precursor material, mixing the precursor material with lithium salt, and calcining to obtain the full-concentration gradient high-nickel ternary material. The material has the relative content of nickel elements continuously reduced from the core to the surface layer, and the relative content of cobalt and manganese elements continuously increased, so that the full radial concentration gradient change of the content of the nickel elements from the core to the surface layer is constructed. The material has high capacity and stable surface interface, and can buffer the lattice volume change generated in circulation, thereby improving the cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrode materials, and particularly discloses a preparation method and application of a full-concentration-gradient high-nickel ternary material.
Background
In the face of increasingly severe resource pressure and environmental crisis, the development of renewable energy sources and the transformation and storage of energy sources are imperative. The lithium ion battery has the advantages of high working voltage, high energy density, long cycle life, light weight, small volume, low self-discharge rate, no memory effect, environmental protection and the like, and is gradually paid attention by broad scholars. As a power battery, the positive electrode material of the lithium ion battery must have a high specific capacity. The anode material used by the existing lithium ion battery mainly comprises lithium iron phosphate and a ternary material, wherein the lithium iron phosphate has the characteristics of high safety, long cycle life and the like, but has poor conductivity and low actual specific capacity of only 140mAh/g, and cannot completely meet the high requirement of the power battery on energy density.
A large number of researches prove that the actually-achieved specific capacity (200mAh/g) of the material can be effectively improved by improving the content of nickel serving as a main active ingredient in the ternary material, so that the energy density of the lithium ion battery taking the ternary material as a cathode material is greatly improved, and the ternary material with high nickel is gradually favored by a large number of lithium ion battery practitioners.
While an increase in nickel content increases the actual reversible capacity of the material, it will at the same time result in a high nickel ternary material that is less thermally stable and less cyclic than a low nickel ternary material. The reason for this is that, first, the thermal decomposition temperature decreases and the heat release increases due to the increase in the nickel content, which means that the thermal stability of the material deteriorates. Li deintercalated at the same potential in high nickel materials+More than the low nickel content material, Ni4+Has high content and strong reducibility, and is easy to be changed into Ni3+To maintain charge balance, the material may release oxygen, which deteriorates stability. Secondly, the high nickel material is easily mixed with H in the air2O、CO2Reaction to LiOH and Li2CO3The processing difficulty of the battery is increased, the polarization of the battery is increased, and the electrochemical performance is poor. Therefore, increasing the surface interface stability of a high nickel material is key to improving its cycle performance.
To solve the above problems, many industry researchers have conducted related research. For example, chinese patent CN108172799A discloses a core-shell structure cathode material and a preparation method thereof, in which an aluminum hydroxide coating layer is formed on the surface of an NCM precursor, and then the precursor is filtered, washed, dried, and then a lithium source is added to perform a heat treatment to obtain an NCM material with an aluminum oxide coated surface. The precursor with the core-shell structure prepared by the method has the advantages of uniform pore distribution, moderate spacing and large specific surface area. The precursor and lithium salt are further processed to obtain the lithium ion battery anode material which shows long-cycle stability and good rate performance. For another example, chinese patent CN103236537B discloses a method for preparing a ternary precursor with a multilayer core-shell structure, in which a ternary material is used as a core, and a binary material and a unitary material are used as shell materials to form a three-layer core-shell structure, thereby improving the cycle performance of the material and improving the safety of the electrode during the working process.
Although the core-shell structure (core: high nickel material, shell: low nickel material) can improve the cycling stability and thermal stability of the material, researches show that the cycling core-shell structure material is separated at the joint of the core and the shell, so that the continuous stability of the core-shell structure in the ultra-long-term cycling can not be ensured. For the core-shell structure material, the high nickel material existing in the core generates 9-10% volume deformation in charge-discharge cycle, while the low nickel shell material has only 2-3% volume deformation, and the volume shrinkage and expansion in different degrees cause the core-shell separation of the core-shell material in long-time charge-discharge cycle.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a full-concentration gradient high-nickel ternary material. The preparation method has the advantages of simple process, good repeatability, low cost and environmental friendliness, and the prepared full-concentration gradient high-nickel ternary material has excellent cycle performance and rate capability.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a full-concentration gradient high-nickel ternary material with a structural formula of Li (Ni)xCoyMnz)O2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.4, z is more than or equal to 0.05 and less than or equal to 0.4, and x + y + z is 1.
The material is spherical or quasi-spherical, and from the core to the surface layer, the relative content of nickel elements is continuously reduced, the relative content of cobalt and manganese elements is continuously increased, and a full radial concentration gradient change structure of the nickel ion content from the core to the surface layer is constructed.
The preparation method of the full-concentration gradient high-nickel lithium ion battery anode material comprises the following steps of:
(1) preparing a nickel-rich salt solution A and a nickel-poor salt solution B with the total concentration of transition metal ions of 1-2.5 mol/L by using three transition metal salts of nickel salt, cobalt salt and manganese salt.
The nickel-cobalt-manganese ion ratio in the nickel-rich salt solution A is as follows: co and Mn being 0.7-0.95: 0-0.2: 0-0.1.
The nickel-cobalt-manganese ion ratio in the nickel-rich salt solution B is as follows: co and Mn being 0.2-0.6: 0.1-0.4: 0.1-0.5.
(2) Preparing 4-10 mol/L alkali solution.
(3) Preparing 10-30 g/L of complexing agent 1 and 80-130 g/L of complexing agent 2.
(4) Firstly, adding a complexing agent 1 with the volume of 25-35% of the reactor into a reaction kettle, and using a metering pump to make the nickel-rich solution A at a speed u1And simultaneously introducing the complexing agent 2 and the alkali solution into the reaction kettle at a rate of 20-40 mL/h. And the nickel-poor solution B is fed at a velocity u2Adding into a storage tank of the nickel-rich solution A, arranging a stirring device in the storage tank and mixing. And introducing inert gas for gas protection in the feeding reaction process, controlling the temperature in the kettle to be 45-60 ℃, controlling the pH to be 10-12, and controlling the stirring speed in the kettle to be 400-1000 r/min. And stopping feeding the complexing agent 2 and the alkali solution after the solution in the storage tank of the nickel-rich solution A is fed completely.
(5) And adjusting the stirring speed in the kettle to 150-400 r/min, and aging at constant temperature for 8-12 h.
(6) Filtering to perform solid-liquid separation, washing for 3 times by using deionized water, and drying the solid part at constant temperature of 120 ℃ for 12 hours to obtain the precursor of the full-concentration gradient high-nickel ternary material.
(7) And (3) mixing the precursor obtained in the step (6) with lithium salt and then calcining, wherein the calcining procedure is as follows: heating to 480-500 ℃ at the speed of 2 ℃/min, keeping the temperature for 6h, heating to 720-770 ℃ at the speed of 2 ℃/min, keeping the temperature for 10-20 h, and finally cooling to room temperature at the speed of 3 ℃/min. Obtaining the full concentration gradient high nickel ternary material.
Preferably, in the step (1), the nickel salt is one of nickel sulfate, nickel nitrate and nickel chloride, the cobalt salt is one of cobalt sulfate, cobalt nitrate and cobalt chloride, and the manganese salt is one of manganese sulfate, manganese nitrate and manganese chloride.
Preferably, the alkali solution in (2) is one or more of lithium hydroxide solution, sodium hydroxide solution and potassium hydroxide solution.
Preferably, the complexing agent in (3) is one of ammonia water, ammonium sulfate, ethylenediamine and ammonium citrate.
Preferably, the feed rate in (4) follows u1＝3u2。
Preferably, the inert gas in (4) is nitrogen or argon.
Preferably, the molar ratio of the precursor to the lithium salt in (7) is 1: 1.01-1.05 (lithium excess), and the lithium salt is lithium hydroxide or lithium carbonate.
Compared with the prior art, the invention has the beneficial effects that: the relative content of nickel element is continuously reduced and the relative content of cobalt and manganese element is continuously increased from the core to the surface layer of the material, so that the full radial concentration gradient change of the nickel ion content from the core to the surface layer is constructed. Firstly, the total content of the material is higher, so that the material has higher reversible capacity; secondly, the nickel content of the surface layer of the material is low, and unstable Ni in circulation is reduced4+The relative content of the electrolyte reduces the release of oxygen and the residual alkali content on the surface, thereby reducing the corrosion speed of the electrolyte on the surface of the material. More importantly, the material has a full concentration gradient structure which can be generated in a buffer cycleThe lattice volume change of the lithium ion battery maintains the lithium ion transmission performance and the electronic conductivity in the working process, and improves the cycle and rate performance of the lithium ion battery.
Drawings
Fig. 1 is an SEM image of the full concentration gradient high nickel ternary material obtained in example 1.
Fig. 2 is a cross-sectional SEM image and elemental relative content line scan image of the full concentration gradient high nickel ternary material obtained in example 1.
FIG. 3 is an XRD pattern of the full concentration gradient high nickel ternary material obtained in example 1
FIG. 4 is a cyclic voltammogram of the full concentration gradient high nickel ternary material obtained in example 1 at a sweep rate of 0.5 mV/s.
Fig. 5 shows residual alkali contents of the positive electrode materials used for assembling the lithium-ion half cells in example 1, comparative example 1, and comparative example 2.
FIG. 6 is a graph comparing the cycle performance of the lithium ion half cells of example 1, comparative example 1, and comparative example 2 at a current of 0.5C at a cutoff voltage of 3.0-4.3V.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
Step 1: nickel sulfate, cobalt sulfate and manganese sulfate are used as transition metal salts, a nickel-rich salt solution A (Ni: Co: Mn: 0.9:0.1:0) and a nickel-poor salt solution B (Ni: Co: Mn: 0.45:0.25:0.3) with the total concentration of transition metal ions of 2mol/L are prepared, and a sodium hydroxide solution of 8mol/L, an ammonia solution 1 of 20g/L and an ammonia solution 2 of 102g/L are prepared.
Step 2: firstly, an ammonia solution 1 with the volume of 30 percent of the reactor is added into a reaction kettle with the volume of 5L, and the nickel-rich solution A is introduced into the reaction kettle at a speed of 60mL/h, the ammonia solution 2 at a speed of 30mL/h and the sodium hydroxide solution at a variable speed by a metering pump. Meanwhile, the nickel-poor solution B is introduced into a storage tank of the nickel-rich solution A at the speed of 20mL/h, and a stirring device is arranged in the storage tank and mixed at any time. And introducing nitrogen for inert gas protection in the reaction process, controlling the temperature in the kettle to be 50 ℃, the pH to be 11.20, and stirring the mixture in the kettle at the rotating speed of 800 r/min. After the feeding reaction is finished, the stirring speed in the kettle is adjusted to 300r/min, and the kettle is aged for 10 hours at constant temperature. Then filtering to carry out solid-liquid separation, washing for 3 times by using deionized water, and drying the solid part at constant temperature of 120 ℃ for 12 hours to obtain the precursor of the full-concentration gradient high-nickel ternary material.
And step 3: and (3) mixing the precursor obtained in the step (2) with lithium hydroxide according to the stoichiometric ratio of 1:1.03 (excess lithium), and then calcining, wherein the calcining procedure is as follows: heating to 500 deg.C at 3 deg.C/min, maintaining at constant temperature for 6h, heating to 750 deg.C at 2 deg.C/min, maintaining at constant temperature for 15h, and cooling to room temperature at 3 deg.C/min. Obtaining the full concentration gradient high nickel ternary material.
And 4, step 4: preparing a positive pole piece: and (3) weighing the full-concentration-gradient high-nickel ternary material obtained in the step (3), the binder PVDF and the conductive agent SP according to the mass ratio of 8:1:1, dissolving in NMP, and stirring to prepare slurry with a certain viscosity. Coating the slurry on a current collector copper foil, drying at 100 ℃, rolling, cutting a piece of the positive pole piece, weighing, calculating and recording the mass of the active substance for later use.
And 5: and (4) assembling the positive and negative pole pieces, the metal lithium pieces and the polyolefin diaphragm in the step (4), adding an electrolyte, sealing and standing to obtain the lithium ion half battery.
Step 6: and (5) carrying out various electrochemical performance tests on the lithium ion half-cell obtained in the step (5).
Example 2
Step 1: nickel nitrate, cobalt nitrate and manganese nitrate are used as transition metal salts, a nickel-rich salt solution A (Ni: Co: Mn: 0.7:0.2:0.1) and a nickel-poor salt solution B (Ni: Co: Mn: 0.6:0.3:0.2) with a total transition metal ion concentration of 2.5mol/L are prepared, and a 10mol/L sodium hydroxide solution, a 30g/L ammonia solution 1 and an 80g/L ammonia solution 2 are prepared.
Step 2: first, an ammonia solution 1 having a tank volume of 30% was charged into a 5L reactor, and the nickel-rich solution A was introduced into the reactor at a rate of 60mL/h, the ammonia solution 2 at a rate of 20mL/h, and the sodium hydroxide solution at a variable rate by using a metering pump. Meanwhile, the nickel-poor solution B is introduced into a storage tank of the nickel-rich solution A at the speed of 20mL/h, and a stirring device is arranged in the storage tank and mixed at any time. And introducing nitrogen for inert gas protection in the reaction process, controlling the temperature in the kettle at 45 ℃, controlling the pH to be 11, and controlling the stirring speed in the kettle at 400 r/min. After the feeding reaction is finished, the stirring speed in the kettle is adjusted to 300r/min, and the kettle is aged for 8 hours at constant temperature. Then filtering to carry out solid-liquid separation, washing for 3 times by using deionized water, and drying the solid part at constant temperature of 120 ℃ for 12 hours to obtain the precursor of the full-concentration gradient high-nickel ternary material.
And step 3: and (3) mixing the precursor obtained in the step (2) with lithium hydroxide according to the stoichiometric ratio of 1:1.01 (excess lithium), and then calcining, wherein the calcining procedure is as follows: heating to 480 deg.C at 3 deg.C/min, maintaining at constant temperature for 6h, heating to 750 deg.C at 2 deg.C/min, maintaining at constant temperature for 15h, and cooling to room temperature at 3 deg.C/min. Obtaining the full concentration gradient high nickel ternary material.
The other steps were in accordance with example 1.
Example 3
Step 1: nickel chloride, cobalt chloride and manganese chloride are used as transition metal salts, a nickel-rich salt solution A (Ni: Co: Mn: 0.95:0.0:0.05) and a nickel-poor salt solution B (Ni: Co: Mn: 0.2:0.4:0.4) with the total concentration of transition metal ions of 1mol/L are prepared, a lithium hydroxide solution of 4mol/L, an ammonia solution 1 of 30g/L and an ammonia solution 2 of 80g/L are prepared.
Step 2: first, an ammonia solution 1 having a tank volume of 25% was charged into a 5L reactor, and the nickel-rich solution A was introduced into the reactor at a rate of 45mL/h, the ammonia solution 2 at a rate of 20mL/h, and the lithium hydroxide solution at a variable rate by a metering pump. Meanwhile, the nickel-poor solution B is introduced into a storage tank of the nickel-rich solution A at the speed of 15mL/h, and a stirring device is arranged in the storage tank and mixed at any time. Argon is introduced in the reaction process for inert gas protection, the temperature in the kettle is controlled at 55 ℃, the PH is 12, and the stirring speed in the kettle is 600 r/min. After the feeding reaction is finished, the stirring speed in the kettle is adjusted to 150r/min, and the kettle is aged for 12 hours at constant temperature. Then filtering to carry out solid-liquid separation, washing for 3 times by using deionized water, and drying the solid part at constant temperature of 120 ℃ for 12 hours to obtain the precursor of the full-concentration gradient high-nickel ternary material.
And step 3: and (3) mixing the precursor obtained in the step (2) with lithium hydroxide according to the stoichiometric ratio of 1:1.04 (excess lithium), and then calcining, wherein the calcining procedure is as follows: heating to 500 deg.C at 3 deg.C/min, maintaining at constant temperature for 6h, heating to 720 deg.C at 2 deg.C/min, maintaining at constant temperature for 20h, and cooling to room temperature at 3 deg.C/min. Obtaining the full concentration gradient high nickel ternary material.
The other steps were in accordance with example 1.
Example 4
Step 1: nickel sulfate, cobalt sulfate and manganese sulfate are used as transition metal salts, a nickel-rich salt solution A (Ni: Co: Mn: 0.8:0.2:0) and a nickel-poor salt solution B (Ni: Co: Mn: 0.3:0.2:0.5) with a total transition metal ion concentration of 2mol/L are prepared, a potassium hydroxide solution of 6mol/L, an ammonium sulfate solution 1 of 20g/L and an ammonia solution 2 of 102g/L are prepared.
Step 2: first, a 5L reactor was charged with a 35% by volume ammonium sulfate solution 1, and the nickel-rich solution A was introduced into the reactor at 75mL/h, ammonium sulfate solution 2 at 30mL/h, and potassium hydroxide solution at varying rates by a metering pump. Meanwhile, the nickel-poor solution B is introduced into a storage tank of the nickel-rich solution A at the speed of 25mL/h, and a stirring device is arranged in the storage tank and mixed at any time. Argon is introduced in the reaction process for inert gas protection, the temperature in the kettle is controlled at 60 ℃, the PH is 10.5, and the stirring speed in the kettle is 800 r/min. After the feeding reaction is finished, the stirring speed in the kettle is adjusted to 200r/min, and the kettle is aged for 10 hours at constant temperature. Then filtering to carry out solid-liquid separation, washing for 3 times by using deionized water, and drying the solid part at constant temperature of 120 ℃ for 12 hours to obtain the precursor of the full-concentration gradient high-nickel ternary material.
And step 3: and (3) mixing the precursor obtained in the step (2) with lithium hydroxide according to the stoichiometric ratio of 1:1.05 (excess lithium), and then calcining, wherein the calcining procedure is as follows: heating to 500 deg.C at 3 deg.C/min, maintaining at constant temperature for 6h, heating to 770 deg.C at 2 deg.C/min, maintaining at constant temperature for 10h, and cooling to room temperature at 3 deg.C/min. Obtaining the full concentration gradient high nickel ternary material.
The other steps were in accordance with example 1.
Example 5
Step 1: nickel sulfate, cobalt sulfate and manganese sulfate are used as transition metal salts, a nickel-rich salt solution A (Ni: Co: Mn: 0.9:0.1:0) and a nickel-poor salt solution B (Ni: Co: Mn: 0.6:0.1:0.3) with the total concentration of transition metal ions of 2mol/L are prepared, a 10mol/L sodium hydroxide solution, a 30g/L ammonium citrate solution 1 and a 130g/L ammonium citrate solution 2 are prepared.
Step 2: firstly, adding 30% ammonium citrate solution 1 into a 5L reaction kettle, and introducing the nickel-rich solution A into the reaction kettle at a speed of 60mL/h, the ammonium citrate solution 2 at a speed of 30mL/h and the sodium hydroxide solution at a variable speed by using a metering pump. Meanwhile, the nickel-poor solution B is introduced into a storage tank of the nickel-rich solution A at the speed of 20mL/h, and a stirring device is arranged in the storage tank and mixed at any time. Argon is introduced in the reaction process for inert gas protection, the temperature in the kettle is controlled at 50 ℃, the PH is 11.50, and the stirring speed in the kettle is 1000 r/min. After the feeding reaction is finished, the stirring speed in the kettle is adjusted to 250r/min, and the kettle is aged for 10 hours at constant temperature. Then filtering to carry out solid-liquid separation, washing for 3 times by using deionized water, and drying the solid part at constant temperature of 120 ℃ for 12 hours to obtain the precursor of the full-concentration gradient high-nickel ternary material.
And step 3: and (3) mixing the precursor obtained in the step 2 with lithium carbonate in a stoichiometric ratio of 1:1.03 (lithium excess), and then calcining, wherein the calcining procedure is as follows: heating to 500 deg.C at 3 deg.C/min, maintaining at constant temperature for 6h, heating to 730 deg.C at 2 deg.C/min, maintaining at constant temperature for 15h, and cooling to room temperature at 3 deg.C/min. Obtaining the full concentration gradient high nickel ternary material.
The other steps were in accordance with example 1.
Example 6
Step 1: nickel sulfate, cobalt sulfate and manganese sulfate are used as transition metal salts, a nickel-rich salt solution A (Ni: Co: Mn: 0.6:0.2:0.2) and a nickel-poor salt solution B (Ni: Co: Mn: 0.5:0.4:0.1) with the total concentration of transition metal ions of 2mol/L are prepared, and a sodium hydroxide solution of 8mol/L, an ethylenediamine solution 1 of 10g/L and an ethylenediamine solution 2 of 80g/L are prepared.
Step 2: first, a 5L reactor was charged with an ethylenediamine solution 1 having a volume of 30% of the reactor, and the nickel-rich solution A was fed into the reactor at a rate of 60mL/h, the ethylenediamine solution 2 at a rate of 30mL/h, and the sodium hydroxide solution at a variable rate by a metering pump. Meanwhile, the nickel-poor solution B is introduced into a storage tank of the nickel-rich solution A at the speed of 20mL/h, and a stirring device is arranged in the storage tank and mixed at any time. And introducing nitrogen for inert gas protection in the reaction process, controlling the temperature in the kettle to be 50 ℃, controlling the pH to be 10, and controlling the stirring speed in the kettle to be 800 r/min. After the feeding reaction is finished, the stirring speed in the kettle is adjusted to 400r/min, and the kettle is aged for 10 hours at constant temperature. Then filtering to carry out solid-liquid separation, washing for 3 times by using deionized water, and drying the solid part at constant temperature of 120 ℃ for 12 hours to obtain the precursor of the full-concentration gradient high-nickel ternary material.
And step 3: and (3) mixing the precursor obtained in the step (2) with lithium carbonate according to the stoichiometric ratio of 1:1.03 (excess lithium), and then calcining, wherein the calcining procedure is as follows: heating to 500 deg.C at 3 deg.C/min, maintaining at constant temperature for 6h, heating to 760 deg.C at 2 deg.C/min, maintaining at constant temperature for 15h, and cooling to room temperature at 3 deg.C/min. Obtaining the full concentration gradient high nickel ternary material.
The other steps were in accordance with example 1.
Comparative example 1
Step 1: nickel sulfate, cobalt sulfate and manganese sulfate are used as transition metal salts, a nickel-rich salt solution (Ni: Co: Mn: 0.75:0.15:0.1) with the total concentration of transition metal ions of 2mol/L is prepared, a sodium hydroxide solution of 8mol/L, an ammonia solution of 20 g/L1 and an ammonia solution of 102 g/L2 are prepared.
Step 2: first, an ammonia solution 1 having a tank volume of 30% was charged into a 5L reactor, and the nickel-rich solution was introduced into the reactor at 60mL/h, the ammonia solution 2 at 30mL/h, and the sodium hydroxide solution at varying rates by a metering pump. And introducing nitrogen for inert gas protection in the reaction process, controlling the temperature in the kettle to be 50 ℃, the pH to be 11.20, and stirring the mixture in the kettle at the rotating speed of 800 r/min. After the feeding reaction is finished, the stirring speed in the kettle is adjusted to 300r/min, and the kettle is aged for 10 hours at constant temperature. Then filtering to carry out solid-liquid separation, washing for 3 times by using deionized water, and drying the solid part at the constant temperature of 120 ℃ for 12 hours to obtain the high-nickel ternary material precursor.
The other steps were in accordance with example 1.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Table 1 ICP element analysis table for high nickel ternary material in example 1 and comparative example 1
Table 2 performance test table for lithium ion half cell assembled in examples and comparative examples
| Sample (I) | First discharge capacity 0.1C (mAh/g) | Capacity retention after 200 cycles (%) |
| Example 1 | 202.6 | 87.1 |
| Example 2 | 185.6 | 84.6 |
| Example 3 | 197.2 | 85.3 |
| Example 4 | 194.6 | 86.4 |
| Example 5 | 200.8 | 79.4 |
| Example 6 | 184.1 | 86.8 |
| Comparative example 1 | 198.9 | 75.0 |
As can be seen from table 2 and fig. 6, the cycle performance of each example was excellent, and the capacity retention rate was high; the comparative example was poor in cycle performance and low in capacity retention.
Claims (9)
1. A full concentration gradient high nickel ternary material is characterized in that the relative content of nickel elements in the material from a core to a surface layer is continuously reduced, and the relative content of cobalt and manganese elements is continuously increased, so that a full radial concentration gradient change structure of the nickel element content from the core to the surface layer is constructed; the material has high capacity and stable surface interface, and can buffer the lattice volume change generated in circulation, thereby improving the cycle performance.
2. The method for preparing the full concentration gradient high nickel ternary material as claimed in claim 1, characterized by comprising the following key steps:
(1) adding a complexing agent 1 with the volume of 25-35% of the reaction kettle into the reaction kettle, and using a metering pump to enable the nickel-rich solution A to be at a speed u1The complexing agent 2 and the alkali solution are simultaneously introduced into the reaction kettle at a certain speed;
(2) the nickel-poor solution B is fed at a speed u2Adding the nickel-rich solution A into a storage tank, and arranging a stirring device in the storage tank for timely mixing;
(3) introducing inert gas for protection in the feeding reaction process, controlling the temperature in the kettle to be 45-60 ℃, controlling the pH to be 10-12, and controlling the stirring speed in the kettle to be 400-1000 r/min;
(4) stopping feeding the complexing agent 2 and the alkali solution after the solution feeding in the nickel-rich solution A storage tank is finished, aging for x hours, and filtering and separating to obtain a precursor;
(5) and (3) mixing the precursor obtained in the step (4) with lithium salt, and then calcining, wherein the calcining procedure is as follows: heating to 480-500 ℃ at the speed of 2 ℃/min, keeping the temperature for 6h, heating to 720-770 ℃ at the speed of 2 ℃/min, keeping the temperature for 10-20 h, and finally cooling to room temperature at the speed of 3 ℃/min to obtain the full-concentration gradient high-nickel ternary material.
3. The method for preparing the full-concentration-gradient high-nickel ternary material according to claim 2, wherein the ratio of nickel ions to cobalt ions to manganese ions in the nickel-rich salt solution A is as follows: co and Mn being 0.7-0.95: 0-0.2: 0-0.1; the nickel, cobalt and manganese ion ratio in the nickel-poor salt solution B is as follows: co and Mn being 0.2-0.6: 0.1-0.4: 0.1-0.5.
4. The method for preparing the full concentration gradient high nickel ternary material as claimed in claim 2, wherein the alkali solution is one or more of lithium hydroxide solution, sodium hydroxide solution and potassium hydroxide solution.
5. The method for preparing the full concentration gradient high nickel ternary material according to claim 2, wherein the complexing agent 1 and the complexing agent 2 are respectively one of ammonia water, ammonium sulfate, ethylenediamine and ammonium citrate.
6. The method for preparing the full concentration gradient high nickel ternary material according to claim 2, wherein u is1＝3u2。
7. The method for preparing the full concentration gradient high nickel ternary material as claimed in claim 2, wherein the inert gas is nitrogen or argon.
8. The method for preparing the full-concentration-gradient high-nickel ternary material according to claim 2, wherein the molar ratio of the precursor to the lithium salt is 1: 1.01-1.05, and the lithium salt is lithium hydroxide or lithium carbonate.
9. A lithium ion battery, characterized in that, the positive electrode material uses a full concentration gradient high nickel ternary material as claimed in claim 1.
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