CN112340783A - Modification method for reducing residual alkali on surface of high-nickel ternary cathode material, high-nickel ternary cathode material prepared by modification method and lithium ion battery - Google Patents
Modification method for reducing residual alkali on surface of high-nickel ternary cathode material, high-nickel ternary cathode material prepared by modification method and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a modification method for reducing residual alkali on the surface of a high-nickel ternary cathode material, which comprises the following steps: (1) uniformly mixing the high-nickel ternary positive electrode material with a solvent to form slurry; (2) the slurry is quickly leached by adopting a solvent, then is subjected to filter pressing and drying, and then a product obtained by drying is sintered to obtain a high-nickel ternary cathode material with low residual alkali; the solvent is selected from one of deionized water, ammonia water and alcoholOne kind or mixture of several kinds. According to the invention, the high-nickel ternary cathode material is firstly pulped, and then the residual alkali on the surface of the material is reduced by a quick leaching method, so that the residual alkali on the surface of the material is further reduced; the LiOH and Li on the surface of the material are reduced without obviously increasing the specific surface area2CO3(ii) a Meanwhile, the falling-out of lattice lithium is reduced, the first discharge specific capacity of the high-nickel ternary positive electrode material is kept not to be reduced due to water washing, the high-temperature cycle performance and the high-temperature storage performance of the high-nickel ternary positive electrode material are further improved, and the increase of high-temperature cycle DCR is reduced.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a modification method for reducing residual alkali on the surface of a high-nickel ternary cathode material.
Background
LiNi of nickel cobalt lithium manganate materialxMnyCozO2In the (x + y + z ═ 1), the value of x is higher than 0.6, the material is generally called as a high-nickel ternary cathode material, Ni serves as an active component in the ternary cathode material, the higher the Ni content is, the more electrons can participate in electrochemical reaction, the higher the material specific discharge capacity is, along with the improvement of the national requirements on energy density of power batteries, and the release of a subsidy and energy density hook policy, the application and development of the high-nickel ternary cathode material are greatly promoted. In the ternary material system, the average valence state of nickel is gradually increased from +2 to +3 with the increase of the nickel content. However, Ni3+The ions are not stable in air and are easy to spontaneously reduce into Ni2+Simultaneously with the precipitation of lithium, LiOH and Li are formed on the surface layer of the particles2CO3And the like. Excessive residual lithium on the particle surface can bring many hazards, for example, the excessive residual lithium on the material surface can cause higher pH value, and the excessive residual alkali can cause gelation of slurry in the electrode plate preparation process, so that the slurry is unevenly coated to form jelly, and the coating is influenced; the battery has poor high-temperature storage performance and severe swelling; the problems of poor high-temperature circulation performance, circulating water-jumping and the like of the power battery are caused.
The common method for reducing the residual alkali on the surface of the high-nickel material is mainly water washing, and the water washing method comprises the following steps: 1) over 80% of companies or research institutions will use high nickel positive electrodesAdding the material and deionized water or mixed solvent into a washing kettle, stirring and washing, and then discharging water, wherein the method can effectively reduce residual alkali on the surface of the high-nickel material, but the method has obvious defects that LiOH and Li on the surface are in the washing process2CO3Li in crystal lattice constantly dissolved in water+The Li is continuously migrated out and finally leads to the surface of the material2CO3Higher, in the lattice Li+The reduction finally results in low specific capacity of the material and poor high-temperature cycle; 2) through water phase coating and secondary sintering, the method can uniformly coat the surface of the material so as to improve the cycle performance of the material, but the initial charge-discharge efficiency of the anode material is greatly reduced, and the anode material is not suitable for coating of a high nickel material. Therefore, a modification method for reducing residual alkali on the surface of the high-nickel ternary cathode material is urgently needed to be found, and the high-temperature cycle performance, the high-temperature storage performance and the like are improved on the premise of ensuring the specific capacity and other performances of the high-nickel ternary cathode material.
Disclosure of Invention
The invention aims to solve the technical problem of providing a modification method for reducing residual alkali on the surface of a high-nickel ternary cathode material, which can effectively reduce the residual alkali on the surface of the material, does not influence the first discharge specific capacity of the high-nickel cathode material, and further improves the high-temperature cycle performance and the high-temperature storage performance of the high-nickel ternary cathode material.
The technical scheme adopted by the invention for solving the technical problems is as follows: the modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material comprises the following steps:
(1) uniformly mixing the high-nickel ternary positive electrode material with a solvent to form slurry;
(2) the slurry is quickly leached by adopting a solvent, then is subjected to filter pressing and drying, and then a product obtained by drying is sintered to obtain a high-nickel ternary cathode material with low residual alkali;
the solvent is one or a mixture of several selected from deionized water, ammonia water and alcohol, and the preferred solvent is deionized water.
Further, the weight ratio of the high-nickel ternary positive electrode material to the solvent in the step (1) is 1-5: 1, the mixing and stirring speed is 300-1000 rpm, and the stirring time is 1-10 min. Preferably, the weight ratio of the high-nickel ternary cathode material to the solvent is 3:1, the stirring speed is 500rpm, and the stirring time is 3 min.
Further, in the step (2), the quick leaching time is 5-15 min, and the weight ratio of the high-nickel ternary positive electrode material to the solvent in the leaching process is 1: 1-10. Preferably, the weight ratio of the high-nickel ternary cathode material to the solvent is 1:2, and the leaching time is 10 min.
Further, in the step (2), the rapid leaching process is to spread the slurry at the bottom of the positive pressure filter, and to perform leaching by using a solvent.
And (3) further, carrying out filter pressing after the leaching in the step (2) is finished, wherein the filter pressing pressure is 0.1-0.3 MPa, and the filter pressing time is 10-60 min. Preferably, the pressure filtration pressure is 0.3MPa, and the pressure filtration time is 15 min.
Further, drying by adopting a vacuum double cone in the step (2), wherein the drying temperature is 100-300 ℃, and the drying time is 1-5 hours; and carrying out secondary sintering on the dried product in air or oxygen atmosphere, wherein the sintering temperature is 200-700 ℃, and the time is 1-10 h. Preferably, the drying temperature is 150 ℃, and the drying time is 2 h; the sintering temperature is 250 ℃, and the sintering time is 6 h. And uniformly mixing the dried material with a metal oxide coating agent MO (M is Ti, Mg, Al, Zr, B, W, Mo and Zn), and then transferring the mixture into an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 0.1-2% of that of the dried material.
Further, the high nickel anode material is Li1+xNiaCobMncN(1-a-b-c)O2+yWherein x is more than or equal to minus 0.1 and less than or equal to 0.1, a is more than or equal to 0.8, B is more than or equal to 0 and less than or equal to 0.15, c is more than or equal to 0 and less than or equal to 0.15, y is more than or equal to minus 0.1 and less than or equal to 0.1, wherein N is one or more of Al, Ti, Mg, Zr, B and Ca, and the preferred high-nickel anode material is LiNi0.83Co0.11Mn0.06O2。
The high-nickel ternary cathode material is prepared by the modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material.
Further, the high nickelThe specific surface area of the ternary positive electrode material is 0.3-0.6 m2G, surface residual alkali LiOH less than or equal to 1000ppm, Li2CO3≤1500ppm，Li(wt％)≥7.1％。
A lithium ion battery comprises a positive electrode, a negative electrode, an isolating membrane arranged between the positive electrode and the negative electrode at intervals, and electrolyte, wherein the positive electrode is made of the high-nickel ternary positive electrode material.
The invention has the beneficial effects that: according to the invention, the high-nickel ternary cathode material is firstly pulped and then quickly leached, so that residual alkali on the surface of the material is reduced, and continuous LiOH and CO in the air in the washing process are avoided2Reaction to form Li2CO3Further reducing residual alkali on the surface of the material; the LiOH and Li on the surface of the material are reduced without obviously increasing the specific surface area2CO3(ii) a Meanwhile, the falling-out of lattice lithium is reduced, the first discharge specific capacity of the high-nickel ternary positive electrode material is kept not to be reduced due to water washing, the high-temperature cycle performance and the high-temperature storage performance of the high-nickel ternary positive electrode material are further improved, and the increase of high-temperature cycle DCR is reduced.
Drawings
FIG. 1 is a graph comparing the first charge and discharge curves of example 1 of the present invention and comparative examples 1 and 2;
FIG. 2 is a graph comparing the high temperature cycle performance curves of example 1 of the present invention and comparative examples 1 and 2;
FIG. 3 is a graph comparing the high temperature cycle DCR curves of example 1 of the present invention and comparative examples 1 and 2.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 2.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 15kg of deionized water for 10min, and then performing pressure filtration with 0.3MPa for 15min (after leaching for 10min, continuing to perform pressure filtration for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent MgO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of the mass of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Example 2:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 7.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 15kg of deionized water for 10min, and then performing pressure filtration with 0.3MPa for 15min (after leaching for 10min, continuing to perform pressure filtration for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; mixing the dried material with a metal oxide coating agent TiO2And after uniformly mixing, transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of that of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so as to obtain the modified low-residual-alkali high-nickel ternary cathode material.
Example 3:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Measuring 1.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at the stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, and quickly adding the high-nickel ternary cathode material into the stirrerIn deionized water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 15kg of deionized water for 10min, and then performing pressure filtration with 0.3MPa for 15min (after leaching for 10min, continuing to perform pressure filtration for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; mixing the dried material with a metal oxide coating agent Al2O3And after uniformly mixing, transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of that of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so as to obtain the modified low-residual-alkali high-nickel ternary cathode material.
Example 4:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 2.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 7.5kg of deionized water for 10min, and then performing filter pressing with 0.3MPa for 15min (after leaching for 10min, continuing to perform filter pressing for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent ZnO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of that of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Example 5:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2As materials to be modifiedWeighing 2.5kg of deionized water, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry into a positive pressure filter, leaching with 75kg of deionized water for 10min, and then performing pressure filtration with 0.3MPa for 15min (after leaching for 10min, continuing to perform pressure filtration for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent ZnO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of that of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Example 6:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 2.5kg of ethanol as a material to be modified, adding the ethanol into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred ethanol, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 15kg of ethanol for 10min, and then performing filter pressing with 0.3MPa for 15min (after leaching for 10min, continuing to perform filter pressing for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; mixing the dried material with a metal oxide coating agent Al2O3And after uniformly mixing, transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of that of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so as to obtain the modified low-residual-alkali high-nickel ternary cathode material.
Example 7:
after one-time sinteringThe high nickel ternary cathode material: LiNi0.83Co0.11Mn0.06O2Taking 2.5kg of deionized water and ethanol as a material to be modified, wherein the mass ratio of the deionized water to the ethanol is 1:1, adding the mixed solution into a stirrer, wherein the stirring speed is 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred mixed solution water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
the viscous slurry was transferred to a positive pressure filter using a mass ratio of 15kg deionized water to ethanol of 1:1, leaching the mixed solution for 10min, and then performing filter pressing under the pressure of 0.3MPa for 15min (after leaching for 10min, continuing the filter pressing for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; mixing the dried material with a metal oxide coating agent Al2O3And after uniformly mixing, transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of that of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so as to obtain the modified low-residual-alkali high-nickel ternary cathode material.
Example 8:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 2.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 1min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 15kg of deionized water for 10min, and then performing pressure filtration with 0.3MPa for 15min (after leaching for 10min, continuing to perform pressure filtration for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent MgO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of the mass of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Example 9:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 2.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 10min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 15kg of deionized water for 10min, and then performing pressure filtration with 0.3MPa for 15min (after leaching for 10min, continuing to perform pressure filtration for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent MgO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of the mass of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Example 10:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 2.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 15kg of deionized water for 5min, and then performing filter pressing with 0.3MPa for 10min (after leaching for 5min, continuing to perform filter pressing for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent MgO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of the mass of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Example 11:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 2.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 15kg of deionized water for 15min, and then performing filter pressing with 0.3MPa for 20min (after leaching for 15min, continuing to perform filter pressing for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent MgO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of the mass of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Comparative example 1:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 15kg of deionized water as a material to be modified, slowly stirring at a speed of 100rpm in a stirring kettle, weighing 7.5kg of high-nickel anode material, quickly adding the high-nickel anode material into the stirred deionized water, increasing the stirring speed to 500rpm, stirring for 30min, transferring the stirred material into a positive pressure filter, performing pressure filtration at a pressure of 0.3MPa for 15min, transferring the pressure-filtered material into a vacuum drying box, performing vacuum drying at a drying temperature of 150 ℃ for 2h, uniformly mixing the dried material with a metal oxide coating agent MgO, and transferring the mixture into an atmosphere box furnaceAnd (3) carrying out secondary sintering, wherein the mass of the coating agent is 1% of that of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 h. Obtaining the ternary cathode material with low residual alkali and high nickel.
Comparative example 2:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 7.5kg of high-nickel ternary positive electrode material as a material to be modified, adding the material into a positive pressure filter, leaching with 15kg of deionized water for 10min, and then performing filter pressing with 0.3MPa for 15min (after leaching for 10min, continuing to perform filter pressing for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent MgO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of the mass of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Comparative example 3:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 2.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 15kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 15kg of deionized water for 10min, and then performing pressure filtration with 0.3MPa for 15min (after leaching for 10min, continuing to perform pressure filtration for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent MgO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of the mass of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Comparative example 4:
selecting a high-nickel ternary cathode material after primary sintering: LiNi0.83Co0.11Mn0.06O2Weighing 2.5kg of deionized water as a material to be modified, adding the deionized water into a stirrer at a stirring speed of 100rpm, weighing 7.5kg of high-nickel ternary cathode material, quickly adding the high-nickel ternary cathode material into the stirred deionized water, increasing the stirring speed to 500rpm, and stirring for 3min to form viscous slurry;
transferring the viscous slurry to a positive pressure filter, leaching with 90kg of deionized water for 10min, and then performing pressure filtration with 0.3MPa for 15min (after leaching for 10min, continuing to perform pressure filtration for 5 min); transferring the filter-pressed material to a vacuum drying oven, and carrying out vacuum drying at the drying temperature of 150 ℃ for 2 h; and uniformly mixing the dried material with a metal oxide coating agent MgO, and transferring the mixture to an atmosphere box furnace for secondary sintering, wherein the mass of the coating agent is 1% of the mass of the dried material, the secondary sintering temperature is 250 ℃, and the sintering time is 6 hours, so that the modified low-residual-alkali high-nickel ternary cathode material is obtained.
Surface residual alkali and specific surface area test:
and (3) carrying out surface residual alkali and specific surface area tests on the modified low-residual-alkali high-nickel ternary cathode material, wherein the surface residual alkali (LiOH and Li)2CO3) The content adopts an acid-base titration method: titrating lithium carbonate and lithium hydroxide in the high nickel material with standard hydrochloric acid solution, determining the end point with pH electrode as the indicating electrode and potential change jump, and calculating LiOH and Li on the surface of the material2CO3Content (c); specific surface area test method: after measuring the adsorption amount of gas on the surface of the solid under different relative pressures in a liquid nitrogen environment, the monolayer adsorption amount of the sample is obtained based on the Bronual-Eltt-Taylor (BET) multilayer adsorption theory and the formula thereof, and the specific surface area of the solid is calculated.
Manufacturing the button cell:
mixing the low-residual-alkali high-nickel ternary positive electrode material with Super P and PVDF binder according to the mass ratio of 90: 5: 5 in NMP solvent, uniformly mixing to prepare slurry with the cobalt content of 45%, uniformly coating the slurry on an aluminum foil, drying for 3 hours by blowing at 60 ℃, transferring the pole piece to a vacuum oven at 120 ℃ for drying for 12 hours, punching the dried pole piece to form a circular pole piece with the diameter of 12 mm, taking the pole piece as a positive pole, taking Celgard 2400 as a diaphragm, taking a metal lithium piece as a negative pole, taking an electrolyte of 1M LiPF6 as an electrolyte, and dissolving the electrolyte in an EMC (electro magnetic compatibility) mode, wherein the ratio of DMC is 1: 1:1 to prepare the button type half cell.
The examples 1 to 11 and comparative examples 1 to 4 were subjected to the surface residual alkali, specific surface area and Li/Me tests in the above-mentioned manner, and the results are shown in Table 1:
TABLE 1
| Item | Lithium hydroxide (%) | Lithium carbonate (%) | Specific surface area (m)2/g) |
| Example 1 | 0.2647 | 0.0736 | 0.29 |
| Example 2 | 0.2403 | 0.0458 | 0.34 |
| Example 3 | 0.3158 | 0.1062 | 0.25 |
| Example 4 | 0.2955 | 0.1471 | 0.31 |
| Example 5 | 0.2327 | 0.0332 | 0.42 |
| Example 6 | 0.3406 | 0.1158 | 0.25 |
| Example 7 | 0.2774 | 0.1004 | 0.29 |
| Example 8 | 0.2703 | 0.1005 | 0.23 |
| Example 9 | 0.2106 | 0.0874 | 0.32 |
| Example 10 | 0.3054 | 0.1408 | 0.23 |
| Example 11 | 0.2005 | 0.0738 | 0.35 |
| Comparative example 1 | 0.2285 | 0.2044 | 0.58 |
| Comparative example 2 | 0.2754 | 0.1846 | 0.54 |
| Comparative example 3 | 0.3704 | 0.1558 | 0.22 |
| Comparative example 4 | 0.1885 | 0.0442 | 0.35 |
In comparative examples 1 and 2, Li is compared with example 12CO3The content of (2) is remarkably increased and the specific surface area is remarkably increased because, in comparative examples 1 and 2, in order to reduce LiOH on the surface of the material, the high-nickel ternary material is continuously stirred in a water washing kettle, and Li+Is removed from the crystal lattice of the ternary anode material and is mixed with CO in the air2Reaction to form Li2CO3Meanwhile, due to the continuous extraction of the crystal lattice lithium, Li is in the material+Obviously reduced, increased Li vacancy and resulting in specific surface area of materialThe product increases. Although the method can reduce LiOH on the surface of the material, the method also reduces lattice lithium, so that the structural stability of the high-nickel ternary material is damaged, and the material has poor cycle performance.
First charge and discharge test:
the button cell prepared from the high-nickel ternary positive electrode materials of the embodiments 1 to 11 and the comparative examples 1 to 4 is subjected to a first charge and discharge experiment, and the test method comprises the following steps: the first charge and discharge capacity was obtained by performing the charge at a rate of 2.8 to 4.3V and 0.1C (theoretical capacity design is 200mAh/g) and then performing the discharge at 0.1C to obtain a charge and discharge curve, and the results are shown in Table 2 below.
And (3) testing high-temperature cycle performance:
the button cell prepared by the high-nickel ternary positive electrode materials of the embodiments 1-11 and the comparative examples 1-4 is subjected to a high-temperature (45 ℃) cycle performance experiment, and the test method comprises the following steps: after the first charge and discharge at 2.8-4.3V 0.1C (the nominal capacity is 200mAh/g), the charge and discharge test is carried out at the multiplying power of 1C for 50 cycles, so as to obtain the capacity retention rate after 50 high-temperature cycles, and the results are shown in the following table 2.
High temperature cycle DCR performance test:
button cells of the high-nickel ternary positive electrode materials of examples 1-11 and comparative examples 1-4 were subjected to a high-temperature (45 ℃) cycling performance test, test method: after the first charge and discharge at 2.8-4.3V 0.1C (nominal capacity of 200mAh/g), the charge and discharge test is carried out by using the multiplying power of 1C, the cycle is continued for 50 times, the DCR performance is calculated according to the voltage change of the cycle, the DCR growth rate after 50 high-temperature cycles is obtained, and the result is shown in the following table 2.
TABLE 2
As can be seen from tables 1 and 2, although comparative examples 1 and 2 can also reduce the residual alkali on the surface of the high nickel material to the required level, they result in a reduction in the first charge and discharge capacity as compared to example 1. The cycle capacity retention rate of example 1 was 95.5% after 50 cycles of charge and discharge at a temperature of 45 ℃, but the cycle capacity retention rates of comparative examples 1 and 2 were 91.2% and90.7 percent. The cycle capacity retention ratio of example 1 was improved by about 5% compared to the cycle capacity retention ratios of comparative examples 1 and 2. The test further indicates that the method for reducing the residual alkali on the surface of the high nickel material only reduces the residual alkali on the surface of the residual alkali of the high nickel material and does not reduce Li in crystal lattices of the high nickel material+Washed away, whereas the conventional water washing method (comparative example 1) and liquid phase coating (comparative example 2) result in Li in the crystal lattice+Loss, Li in layered structure of high-nickel ternary material+Absence of Li during charging and discharging+Gradually decreases, further resulting in a decrease in high temperature cycle performance.
The button cell prepared in the embodiment 1 of the invention and the comparative examples 1 and 2 are subjected to a high-temperature (45 ℃) charge-discharge cycle experiment under the same conditions, and the test method comprises the following steps: after the first charge and discharge of 2.8-4.3V 0.1C (the nominal capacity is 200mAh/g), carrying out charge and discharge test by using the multiplying power of 1C, continuing for 50 cycles, and calculating the DCR performance according to the voltage change of the cycles; FIG. 3 is a DCR performance graph of example 1 and comparative examples 1 and 2 of the present invention, and it can be seen from FIG. 3 that the DCR growth rate of example 1 after 50 high temperature cycles is 120%, the DCR growth rates of comparative examples 1 and 2 after 50 high temperature cycles are 200% and 240%, the DCR growth rate of example 1 is about 100% lower than that of comparative examples 1 and 2, the DCR growth is slow, which indicates that the increase of internal resistance is small during the cycling process, and this test further indicates that the method for reducing residual alkali on the surface of high nickel material only reduces residual alkali on the surface of high nickel material, and does not reduce residual alkali on the surface of Li in the crystal lattice of high nickel ternary cathode material+Washed away, whereas the conventional water washing method (comparative example 1) and liquid phase coating (comparative example 2) result in Li in the crystal lattice+Loss, Li in layered structure of high-nickel ternary material+Absence of Li during charging and discharging+Gradually decreases, further resulting in a decrease in high temperature cycle performance. The mass ratio of the high-nickel ternary material to the deionized water in the slurry process in the comparative example 3 is 6:1, and the mass ratio of the ternary cathode material to the deionized water in the leaching process in the comparative example 4 is 1:12, so that the residual alkali on the surface of the high-nickel material can be reduced to the required standard, but the internal resistance of the ternary cathode material is increased, and the high-temperature cycle performance is reduced.
Claims (10)
1. The modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material is characterized by comprising the following steps of:
(1) uniformly mixing the high-nickel ternary positive electrode material with a solvent to form slurry;
(2) the slurry is quickly leached by adopting a solvent, then is subjected to filter pressing and drying, and then a product obtained by drying is sintered to obtain a high-nickel ternary cathode material with low residual alkali;
the solvent is one or a mixture of several selected from deionized water, ammonia water and alcohol.
2. The modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material according to claim 1, characterized in that: the weight ratio of the high-nickel ternary positive electrode material to the solvent in the step (1) is 1-5: 1, the mixing and stirring speed is 300-1000 rpm, and the stirring time is 1-10 min.
3. The modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material according to claim 1, characterized in that: the quick leaching time in the step (2) is 5-15 min, and the weight ratio of the high-nickel ternary positive electrode material to the solvent in the leaching process is 1: 1-10.
4. The modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material according to claim 3, characterized in that: and (3) in the quick leaching process in the step (2), the slurry is paved at the bottom of the positive pressure filter, and a solvent is adopted for leaching.
5. The modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material according to claim 4, characterized in that: and (3) performing filter pressing after the leaching in the step (2) is finished, wherein the filter pressing pressure is 0.1-0.3 MPa, and the filter pressing time is 10-60 min.
6. The modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material according to claim 1, characterized in that: drying by adopting a vacuum bipyramid in the step (2), wherein the drying temperature is 100-300 ℃, and the drying time is 1-5 h; and carrying out secondary sintering on the dried product in air or oxygen atmosphere, wherein the sintering temperature is 200-700 ℃, and the time is 1-10 h.
7. The modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material according to claim 1, characterized in that: the high nickel anode material is Li1+xNiaCobMncN(1-a-b-c)O2+yWherein x is more than or equal to minus 0.1 and less than or equal to 0.1, a is more than or equal to 0.8, B is more than or equal to 0 and less than or equal to 0.15, c is more than or equal to 0 and less than or equal to 0.15, y is more than or equal to minus 0.1 and less than or equal to 0.1, and N is one or more of Al, Ti, Mg, Zr, B and Ca.
8. The high-nickel ternary cathode material prepared by the modification method for reducing the residual alkali on the surface of the high-nickel ternary cathode material according to claims 1 to 7.
9. The high-nickel ternary positive electrode material according to claim 8, characterized in that: the specific surface area of the high-nickel ternary positive electrode material is 0.3-0.6 m2G, surface residual alkali LiOH less than or equal to 1000ppm, Li2CO3≤1500ppm，Li(wt％)≥7.1％。
10. Lithium ion battery, including positive pole, negative pole, interval barrier film between positive pole and negative pole to and electrolyte, its characterized in that: the positive electrode is made of the high-nickel ternary positive electrode material according to claim 8 or 9.
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Application publication date: 20210209 |