CN113314700A - Dual-action modified high-nickel positive electrode material of lithium ion battery and preparation method of dual-action modified high-nickel positive electrode material - Google Patents
Dual-action modified high-nickel positive electrode material of lithium ion battery and preparation method of dual-action modified high-nickel positive electrode material Download PDFInfo
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Abstract
The invention belongs to the technical field of high-nickel anode materials of lithium ion batteries and preparation thereof, and particularly provides a dual-action modified high-nickel anode material of a lithium ion battery and a preparation method thereof, which are used for solving the defects of poor electrochemical performance and poor cycle stability (especially in a high-temperature environment) of the conventional high-nickel anode material of the lithium ion battery. The lithium ion battery high-nickel anode material is synthesized by a main phase and a dopant, wherein the main phase is a high-nickel-cobalt binary anode material, a high-nickel NCA ternary anode material or a high-nickel NCM ternary anode material, and the dopant is zirconium metaphosphate; the introduction of a very small amount of zirconium metaphosphate realizes double synergistic modification of bulk phase doping and surface coating of the high-nickel anode material through a high-temperature solid phase method, effectively reduces cation mixed discharge of the high-nickel anode material, and simultaneously effectively inhibits interface side reaction, so that the modified high-nickel anode material of the lithium ion battery has excellent cycle stability and rate capability, and can meet the requirement of charging and discharging with larger rate.
Description
Technical Field
The invention belongs to the technical field of high-nickel anode materials of lithium ion batteries and preparation thereof, and particularly relates to a dual-action modified high-nickel anode material of a lithium ion battery and a preparation method thereof.
Background
In recent years, the development of new energy automobiles becomes the main direction of transformation development of the global automobile industry and is also a strategic measure for coping with the crisis of climate change and promoting the development of green energy; with the high-speed development of new energy automobiles, the requirements on batteries for electric automobiles are increasingly improved; the lithium ion battery has the advantages of high energy density, light weight, environmental protection and the like, and becomes an indispensable important component in the field of new energy automobile power batteries. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm and electrolyte; the positive electrode material is one of the key materials of the lithium ion battery, and the performance of the positive electrode material directly determines the performance of the lithium ion battery.
In order to pursue higher energy density and lower cost, high nickel cathode materials (molar ratio Ni is more than or equal to 50%) are receiving wide attention; in particular, the high nickel NCM ternary positive electrode material LiNi0.8Co0.1Mn0.1O2High nickel NCA ternary positive electrode material LiNi0.8Co0.15Al0.05O2And high nickel-cobalt binary positive electrode material LiNi0.9Co0.1O2. However, the research of the high nickel cathode material mainly has two problems: one is Li in the material+And Ni2+With a similar radius, Ni increasing with the nickel content2+Readily occupiable Li+The position of (a) exacerbates cation shuffling; secondly, the surface of the material has side reaction with electrolyte, which seriously affects the electrochemical performance and hinders the commercial practical application of the material.
Aiming at the problems, in order to improve the performance of the high-nickel cathode material, modification methods such as an optimized synthesis process, bulk phase doping, surface coating and the like are generally adopted; however, the existing modification methods cannot simultaneously solve two problems of cation mixed-discharging and interface side reaction, so that the electrochemical performance of the high-nickel cathode material is still poor and needs to be further improved.
Disclosure of Invention
The invention aims to provide a dual-action modified high-nickel positive electrode material of a lithium ion battery and a preparation method thereof aiming at the defects of poor electrochemical performance and poor cycle stability (especially at high temperature) of the high-nickel positive electrode material of the lithium ion battery; according to the invention, zirconium metaphosphate is used as a dopant, and double synergistic modification of bulk phase doping and surface coating of the high-nickel anode material is realized by a high-temperature solid phase method, so that cation mixed-row of the high-nickel anode material is effectively reduced, and interface side reaction is effectively inhibited, so that the modified high-nickel anode material of the lithium ion battery has excellent cycle stability and rate capability, and can meet the requirement of charging and discharging with larger rate; and the synthesis process is simple, the manufacturing cost is low, and the large-scale industrial production is easy to realize.
In order to achieve the purpose, the invention adopts the technical scheme that:
the high-nickel anode material for the lithium ion battery is characterized by being synthesized by a main phase and a dopant, wherein the main phase is a high-nickel (the molar ratio Ni is more than or equal to 80%) nickel-cobalt binary anode material, a high-nickel (the molar ratio Ni is more than or equal to 80%) NCA ternary anode material or a high-nickel (the molar ratio Ni is more than or equal to 80%) NCM ternary anode material, the dopant is zirconium metaphosphate, and the molar ratio of the main phase to the dopant is (1-x) x, and x is 0.001-0.05.
Further, the main phase is LiNi0.9Co0.1O2、LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2。
Further, the main phase is LiNi0.9Co0.1O2The preparation method of the dual-action modified high-nickel cathode material for the lithium ion battery comprises the following steps of:
step 1, dissolving a lithium source raw material in deionized water, adding zirconium metaphosphate, and uniformly mixing to obtain mixed slurry;
step 2, adding Ni into the mixed slurry obtained in the step 10.9Co0.1(OH)2The precursor is ground uniformly by using absolute ethyl alcohol as a dispersing agent and then dried to obtain mixture powder;
step 3, putting the mixture powder obtained in the step 2 into an oven for drying to obtain a dried sample;
and 4, putting the dried sample obtained in the step 3 into a tubular furnace, heating to 400-650 ℃ at the speed of 1-10 ℃/min for pre-sintering for 6-15 h in an oxygen atmosphere, heating to 700-950 ℃ at the speed of 1-10 ℃/min for roasting for 15-25 h, and naturally cooling to room temperature to obtain the dual-action modified high-nickel cathode material for the lithium ion battery.
Further, the main phase is LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2The preparation method of the dual-action modified high-nickel cathode material for the lithium ion battery comprises the following steps of:
step 1, dissolving a lithium source raw material in deionized water, adding zirconium metaphosphate, and uniformly mixing to obtain mixed slurry;
step 2, adding Ni into the mixed slurry obtained in the step 10.8Co0.15Al0.05(OH)2Precursor or Ni0.8Co0.1Mn0.1(OH)2The precursor is ground uniformly by using absolute ethyl alcohol as a dispersing agent and then dried to obtain mixture powder;
step 3, putting the mixture powder obtained in the step 1 into an oven for drying to obtain a dried sample;
and 4, putting the dried sample obtained in the step 3 into a tube furnace, heating to 400-650 ℃ at the speed of 1-10 ℃/min for pre-sintering for 6-15 h under the oxygen atmosphere (the oxygen flow rate is 100-1000 mL/min), heating to 700-950 ℃ at the speed of 1-10 ℃/min for roasting for 15-25 h, and finally naturally cooling to room temperature to obtain the dual-action modified high-nickel anode material LiNi of the lithium ion battery0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2。
Further, the lithium source raw material, zirconium metaphosphate and precursor (Ni)0.9Co0.1(OH)2Precursor, Ni0.8Co0.15Al0.05(OH)2Precursor or Ni0.8Co0.1Mn0.1(OH)2Precursor) is 1.10: x (1-x), wherein x is 0.001-0.05. The lithium source raw material is at least one of lithium carbonate, lithium nitrate, lithium acetate, lithium chloride and lithium hydroxide. The temperature of the oven is as follows: and (3) drying at the temperature of 80-125 ℃ for the following time: 10 to 20 hours. (ii) a The flow rate of oxygen in the oxygen atmosphere is 100-1000 ml/min.
In terms of working principle:
the invention adopts the double synergistic modification of bulk phase doping and surface coating, and extremely small amount of zirconium metaphosphate is doped to introduce Zr4+And PO4 3-The cell volume and the interlayer spacing of the lithium layer then expand slightly; this is mainly due to Zr4+Ionic radius (0.072nm) relative to Li+With a larger radius of the ions of phosphate radical (PO)4 3-) Polyanionic moieties substituted with oxyanions (O)2-) Such that Li+The diffusion channel is further widened, which is beneficial to Li+Pull-out and pull-in of; and, a phosphate polyanion group (PO) having a strong covalent P-O bond4 3-) The material has excellent structural stability, can achieve the effect of stabilizing the oxygen layer of the anode material, and improves the crystal structural stability of the material; at the same time, the zirconium metaphosphate is in contact with the main phaseThe surface residual alkali in-situ reaction generates a coating layer, so that the alkalinity of the surface of the material is reduced, the corrosion effect of HF on the anode material is effectively inhibited, the dissolution of transition metal ions from crystal lattices is inhibited, the interface side reaction is reduced, the generation of microcracks is inhibited, the surface stability is improved, and the excellent cycle stability is realized. Meanwhile, the alkalinity is reduced, the hygroscopicity of the material is reduced, and the processability is obviously improved. Therefore, the zirconium metaphosphate is doped and coated with the modified lithium ion battery high-nickel anode material with double functions, not only the processing performance and the normal-temperature electrochemical performance are improved, but also the electrochemical performance and the thermal stability at high temperature are obviously improved, and the discharging safety of the material at high temperature is greatly improved. The working principle of the invention is shown in fig. 1.
In conclusion, the beneficial effects of the invention are as follows:
1. the invention adopts the traditional high-temperature solid phase method to achieve the dual synergistic modification of bulk phase doping and surface coating; the precursor is used as the blending sintering of the base material, the target product particles are in a sphere-like shape, and the particle size distribution is uniform; compared with a coprecipitation method and a sol-gel method, the high-temperature solid phase method has simpler process and low manufacturing cost, is easy to realize large-scale industrial production, does not generate toxic and harmful substances in the preparation process, and accords with the concept of green environmental protection;
2. the invention reduces the cation mixed discharge of the material by doping the zirconium metaphosphate in a very small amount, and enlarges Li+The diffusion channel improves the stability of the crystal structure of the material; meanwhile, the coating layer is generated by in-situ reaction with surface residual alkali, so that the alkalinity of the material surface is reduced, the interface side reaction is effectively inhibited, the surface stability is improved, and the rate capability and the cycle stability of the material are obviously improved;
3. according to the dual-action modified high-nickel cathode material for the lithium ion battery, the lithium loss of the material at high temperature is made up by increasing the lithium by 10-20%, and the specific discharge capacity of the material is increased; the zirconium metaphosphate is doped and coated with the dual-action modified high-nickel cathode material of the lithium ion battery, so that the processing performance and the normal-temperature electrochemical performance are improved, more importantly, the electrochemical performance and the thermal stability at high temperature are obviously improved, and the discharging safety of the material at high temperature is greatly improved;
4. the dual-action modified high-nickel cathode material for the lithium ion battery provided by the invention has higher specific discharge capacity and excellent cycle performance; with LiNi0.9Co0.1O2For example, when the constant current charge-discharge rate is 0.5C and the charge-discharge cutoff voltage is 2.8-4.3V at the room temperature of 25 +/-1 ℃, the initial discharge specific capacity of the cathode material reaches 187.3mAh/g, the initial discharge specific capacity reaches 180.9mAh/g after 100 cycles, and the capacity retention rate is 93.7%. At the high temperature of 50 +/-1 ℃, the constant current charge-discharge multiplying power is 0.5C, and when the charge-discharge cutoff voltage is 2.8-4.3V, the initial discharge specific capacity of the anode material reaches 190.7mAh/g, reaches 183.9mAh/g after 100 cycles, and the capacity retention rate is 96.4%.
5. The raw materials involved in the process of the invention have wide sources and low price, are non-toxic and pollution-free, and are environment-friendly and harmless.
Drawings
FIG. 1 is a schematic diagram of the principle of zirconium metaphosphate doping and coating dual-action modified lithium ion battery high-nickel anode material.
Fig. 2 is a flow chart of a preparation process of the dual-action modified high-nickel positive electrode material of the lithium ion battery in example 1 of the present invention.
Fig. 3 is an XRD chart of the dual-purpose modified high-nickel positive electrode material of the lithium ion battery in example 1 of the present invention.
Fig. 4 is an SEM image of the high nickel positive electrode material of the dual-purpose modified li-ion battery in example 1 of the present invention.
Fig. 5 is a cycle performance curve diagram of the dual-action modified high-nickel positive electrode material of the lithium ion battery in example 1 of the present invention at a magnification of 0.5C.
Fig. 6 is a charge-discharge curve diagram of the high-nickel cathode material of the dual-action modified lithium ion battery in example 1 of the present invention at a magnification of 0.5C.
Fig. 7 is a graph of rate performance of the dual-action modified high-nickel cathode material of the lithium ion battery in example 1 of the present invention.
Fig. 8 is an Element Distribution Spectrum (EDS) of the dual-action modified high-nickel cathode material of the lithium ion battery in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, comparative examples and the accompanying drawings.
Example 1
This example provides a dual-function modified high-nickel positive electrode material for lithium ion batteries, which is synthesized from a main phase and a dopant, wherein the main phase is LiNi0.9Co0.1O2The doping agent is zirconium metaphosphate, the molar ratio of the main phase to the doping agent is (1-x), x and x are 0.005; the preparation process of the high-nickel cathode material of the lithium ion battery is shown in figure 2, and specifically comprises the following steps:
0.9231g of LiOH H are weighed according to the measurement2Dissolving O in 10ml of deionized water, adding 0.0407g of zirconium metaphosphate, and uniformly mixing to obtain mixed slurry;
1.8446g of Ni were added to the mixed slurry0.9Co0.1(OH)2The precursor is continuously and fully ground uniformly in an agate mortar by using absolute ethyl alcohol as a dispersing agent, and mixture powder is obtained after drying;
then placing the mixture powder into an oven, and drying for 10-20 hours at 80-125 ℃ to obtain a dried sample;
finally, the dried sample is put into a tube furnace, the temperature is raised to 480 ℃ at the speed of 2 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 300ml/min), the temperature is raised to 720 ℃ at the speed of 2 ℃/min for roasting for 20h, the temperature is naturally lowered to the room temperature, the material is taken out and ground and sieved, and the dual-action modified high-nickel anode material LiNi of the lithium ion battery is obtained0.9Co0.1O2。
The modified lithium ion battery high nickel anode material LiNi with double functions0.9Co0.1O2The XRD pattern is shown in figure 3, and the XRD result shows that the material has alpha-NaFeO2A layered structure of the type in which no observable zirconium metaphosphate heterophase is found in the material, indicating that zirconium metaphosphate has entered the crystal lattice of the parent material; the SEM picture is shown in FIG. 4, which illustrates that the material not only has alpha-NaFeO2The particle size distribution is uniform; meanwhile, many tiny particles are not easily found on the surface of the material particles, which shows that the zirconium metaphosphate still has a very small amount to coat the surface of the parent particles. The material is subjected to constant current charge and discharge tests, and the test results are shown in fig. 5-7, so that the positive electrode material has high specific discharge capacity and excellent cycling stability, the constant current charge and discharge multiplying power is 0.5C at the room temperature of 25 +/-1 ℃, the first specific discharge capacity of the positive electrode material reaches 187.3mAh/g when the charge and discharge cutoff voltage is 2.8-4.3V, the first specific discharge capacity of the positive electrode material reaches 180.9mAh/g after 100 cycles, and the capacity retention rate is 93.7%. At the high temperature of 50 +/-1 ℃, the constant current charge-discharge multiplying power is 0.5C, and when the charge-discharge cutoff voltage is 2.8-4.3V, the initial discharge specific capacity of the anode material reaches 190.7mAh/g, reaches 183.9mAh/g after 100 cycles, and the capacity retention rate is 96.4%. The Element Distribution Spectrogram (EDS) test is carried out on the cathode material, the EDS spectrogram is shown in figure 8, it is easy to see that Li, Ni, Co and O elements are uniformly distributed, Zr and P elements are uniformly distributed in a bulk phase, a coating layer with obvious distribution is also obviously formed, the concentration distribution of Zr and P is obviously low and sparse, and the reason is that the doping amount and the coating amount of zirconium metaphosphate are very small.
Comparative example
0.9231g of LiOH. H were weighed out in a molar ratio of 10% excess of the lithium source2Dissolving O in 10ml of deionized water, adding 1.8539g of precursor, fully and uniformly grinding to obtain mixed slurry, adding absolute ethyl alcohol serving as a dispersing agent, continuously and fully and uniformly grinding in an agate mortar, drying to obtain mixture powder, and drying in an oven to obtain a dried sample; finally, the dried sample is put into a tube furnace, the temperature is raised to 480 ℃ at the speed of 2 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 300ml/min), the temperature is raised to 720 ℃ at the speed of 2 ℃/min for roasting for 20h, the temperature is naturally lowered to the room temperature, the material is taken out and ground and sieved, and the parent cathode material LiNi which is not doubly modified is obtained0.9Co0.1O2. The matrix anode material is subjected to electrochemical test, and the charge-discharge cut-off voltage is 2.8-4 at the room temperature of 25 +/-1 ℃.At 3V, the initial discharge specific capacity of the parent anode material which is not doubly modified under the charge-discharge rate of 0.5C is 190.4mAh/g, the coulombic efficiency of the first circle is 77.5%, and the capacity retention rate is 89.0% after 100 circles of circulation. Under 50 +/-1 ℃, when the charge-discharge cutoff voltage is 2.8-4.3V, the material has the first discharge specific capacity of 221.4mAh/g under the charge-discharge multiplying power of 0.5C, the first-turn coulombic efficiency of 89.1 percent, and the capacity retention rate of only 84.8 percent after 100 cycles;
therefore, in the embodiment, the lithium ion battery high-nickel cathode material LiNi modified by zirconium metaphosphate doping and coating dual functions0.9Co0.1O2The electrochemical performance of the catalyst is comprehensively superior to that of a comparative example, and the catalyst is more obvious particularly at high temperature.
Example 2
This example provides a dual-function modified high-nickel positive electrode material for lithium ion batteries, which is synthesized from a main phase and a dopant, wherein the main phase is LiNi0.9Co0.1O2The doping agent is zirconium metaphosphate, the molar ratio of the main phase to the doping agent is (1-x), x and x are 0.0025; the lithium ion battery high-nickel cathode material is prepared by the same preparation process (zirconium metaphosphate: 0.0204g) as that of the embodiment 1, and the effect and the performance of the lithium ion battery high-nickel cathode material are basically the same as those of the embodiment 1 through tests.
Example 3
This example provides a dual-function modified high-nickel positive electrode material for lithium ion batteries, which is synthesized from a main phase and a dopant, wherein the main phase is LiNi0.9Co0.1O2The doping agent is zirconium metaphosphate, the molar ratio of the main phase to the doping agent is (1-x), x and x are 0.01; the lithium ion battery high-nickel cathode material is prepared by the same preparation process (zirconium metaphosphate: 0.0814g) as that of the example 1, and the effect and the performance of the lithium ion battery high-nickel cathode material are basically the same as those of the example 1.
Example 4
This example provides a dual-function modified high-nickel positive electrode material for lithium ion batteries, which is synthesized from a main phase and a dopant, wherein the main phase is LiNi0.9Co0.1O2The doping agent is zirconium metaphosphate, the molar ratio of the main phase to the doping agent is (1-x), x and x are 0.02; by adopting the embodiments1 (zirconium metaphosphate: 0.1628g) to obtain the high nickel cathode material of the lithium ion battery, and the effect and the performance of the high nickel cathode material are basically the same as those of the high nickel cathode material of the lithium ion battery in the embodiment 1.
Example 5
This example provides a dual-function modified high-nickel positive electrode material for lithium ion batteries, which is synthesized from a main phase and a dopant, wherein the main phase is LiNi0.8Co0.15Al0.05O2The doping agent is zirconium metaphosphate, the molar ratio of the main phase to the doping agent is (1-x), x and x are 0.005; the high-nickel cathode material of the lithium ion battery specifically comprises the following steps:
0.9231g of LiOH H are weighed according to the measurement2Dissolving O in 10ml of deionized water, adding 0.0407g of zirconium metaphosphate, and uniformly mixing to obtain mixed slurry;
1.8432g of Ni was added to the mixed slurry0.8Co0.15Al0.05(OH)2The precursor is continuously and fully ground uniformly in an agate mortar by using absolute ethyl alcohol as a dispersing agent, and mixture powder is obtained after drying;
then placing the mixture powder into an oven, and drying for 10-20 hours at 80-125 ℃ to obtain a dried sample;
finally, the dried sample is put into a tube furnace, the temperature is raised to 480 ℃ at the speed of 2 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 300ml/min), the temperature is raised to 725 ℃ at the speed of 2 ℃/min for roasting for 20h, the temperature is naturally lowered to room temperature, the material is taken out and ground and sieved, and the dual-action modified high-nickel anode material LiNi of the lithium ion battery is obtained0.8Co0.15Al0.05O2。
The modified lithium ion battery high nickel anode material LiNi with double functions0.8Co0.15Al0.05O2Electrochemical performance tests show that the positive electrode material still has high specific discharge capacity and excellent cycling stability, the constant current charge-discharge multiplying power is 0.5C at the room temperature of 25 +/-1 ℃, the charge-discharge cutoff voltage is 2.8-4.3V, the first specific discharge capacity of the positive electrode material reaches 183.4mAh/g, the specific discharge capacity reaches 176.8mAh/g after 100 cycles, and the capacity is keptThe rate was 96.4%. At the high temperature of 50 +/-1 ℃, the constant current charge-discharge multiplying power is 0.5C, and when the charge-discharge cutoff voltage is 2.8-4.3V, the initial discharge specific capacity of the anode material reaches 188.5mAh/g, the discharge specific capacity after 100 cycles reaches 181.9mAh/g, and the capacity retention rate is 96.5%.
Comparative example
More specifically, the undoped coated parent positive electrode material LiNi0.8Co0.15Al0.05O2The preparation process specifically comprises the following steps: 0.9231g of LiOH. H were weighed out in a molar ratio of 10% excess of the lithium source2Dissolving O in 10ml of deionized water, adding 1.8448g of precursor, fully and uniformly grinding to obtain mixed slurry, adding absolute ethyl alcohol as a dispersing agent, continuously and fully and uniformly grinding in an agate mortar, drying to obtain mixture powder, and drying in an oven (drying at 90-120 ℃ for 10-12 hours); finally, the dried sample is put into a tube furnace to be preheated for 6h at the speed of 2 ℃/min to 480 ℃ under the oxygen atmosphere (the oxygen flow rate is 300ml/min), then the temperature is raised to 725 ℃ at the speed of 2 ℃/min to be roasted for 20h, then the temperature is naturally reduced to room temperature, the material is taken out and ground and sieved, and the undoped and coated high-nickel parent positive electrode material LiNi is obtained0.8Co0.15Al0.05O2。
For the parent cathode material LiNi which is ground and sieved and is not doubly modified0.8Co0.15Al0.05O2Performing electrochemical test, and undoped cladding double modified high nickel parent positive electrode material LiNi under the room temperature of 25 +/-1 ℃ and the charge-discharge cut-off voltage of 2.8-4.3V0.8Co0.15Al0.05O2The first discharge specific capacity under the charge-discharge rate of 0.5C is only 185.3mAh/g, the first-circle coulombic efficiency is only 77.8%, and the capacity retention rate is only 88.7% after 100 circles of circulation; under 50 +/-1 ℃, when the charge-discharge cutoff voltage is 2.8-4.3V, the material has the first discharge specific capacity of 203.9mAh/g under the charge-discharge multiplying power of 0.5C, the first-turn coulombic efficiency of 89.2 percent, and the capacity retention rate of only 85.4 percent after 100 cycles;
therefore, in the embodiment, the lithium ion battery modified by the dual functions of zirconium metaphosphate doping and coatingHigh nickel anode material LiNi0.8Co0.15Al0.05O2The electrochemical performance of the catalyst is comprehensively superior to that of a comparative example, and the catalyst is more obvious particularly at high temperature.
Example 6
This example provides a dual-function modified high-nickel positive electrode material for lithium ion batteries, which is synthesized from a main phase and a dopant, wherein the main phase is LiNi0.8Co0.1Mn0.1O2The doping agent is zirconium metaphosphate, the molar ratio of the main phase to the doping agent is (1-x), x and x are 0.005; the high-nickel cathode material of the lithium ion battery specifically comprises the following steps:
0.9231g of LiOH H are weighed according to the measurement2Dissolving O in 10ml of deionized water, adding 0.0407g of zirconium metaphosphate, and uniformly mixing to obtain mixed slurry;
1.8444g of Ni were added to the mixed slurry0.8Co0.1Mn0.1(OH)2The precursor is continuously and fully ground uniformly in an agate mortar by using absolute ethyl alcohol as a dispersing agent, and mixture powder is obtained after drying;
then placing the mixture powder into an oven, and drying for 10-20 hours at 80-125 ℃ to obtain a dried sample;
finally, the dried sample is put into a tube furnace, the temperature is raised to 480 ℃ at the speed of 2 ℃/min for pre-sintering for 6h under the oxygen atmosphere (the oxygen flow rate is 300ml/min), the temperature is raised to 720 ℃ at the speed of 2 ℃/min for roasting for 20h, the temperature is naturally lowered to the room temperature, the material is taken out and ground and sieved, and the dual-action modified high-nickel anode material LiNi of the lithium ion battery is obtained0.8Co0.1Mn0.1O2。
The modified lithium ion battery high nickel anode material LiNi with double functions0.8Co0.1Mn0.1O2Electrochemical performance tests show that the positive electrode material still has high specific discharge capacity and excellent cycling stability, the constant current charge-discharge multiplying power is 0.2C at the room temperature of 25 +/-1 ℃, the charge-discharge cutoff voltage is 2.8-4.3V, the first specific discharge capacity of the positive electrode material reaches 189.5mAh/g, the first coulombic efficiency reaches 86.5%, and the discharge capacity after 100 cycles is achievedThe amount was still 180.6mAh/g, and the capacity retention rate was 95.3%. At the high temperature of 50 +/-1 ℃, the constant current charge-discharge multiplying power is 0.2C, and when the charge-discharge cutoff voltage is 2.8-4.3V, the initial discharge specific capacity of the anode material reaches 193.5mAh/g, the initial coulombic efficiency reaches 88.8%, the capacity retention rate reaches 187.3mAh/g after 100 cycles, and the capacity retention rate is 96.8%.
Comparative example
More specifically, the undoped coated parent positive electrode material LiNi0.8Co0.1Mn0.1O2The preparation process specifically comprises the following steps: 0.9231g of LiOH. H were weighed out in a molar ratio of 10% excess of the lithium source2Dissolving O in 10ml of deionized water, adding 1.8479g of precursor, fully and uniformly grinding to obtain mixed slurry, adding absolute ethyl alcohol as a dispersing agent, continuously and fully and uniformly grinding in an agate mortar, drying to obtain mixture powder, and drying in an oven (drying at 90-120 ℃ for 10-12 hours); finally, the dried sample is put into a tube furnace to be preheated for 6h at the speed of 2 ℃/min to 480 ℃ under the oxygen atmosphere (the oxygen flow rate is 300ml/min), then the temperature is raised to 720 ℃ at the speed of 2 ℃/min to be roasted for 20h, then the temperature is naturally reduced to room temperature, the material is taken out and ground and sieved, and the undoped and coated high-nickel parent positive electrode material LiNi is obtained0.8Co0.1Mn0.1O2。
For the parent cathode material LiNi which is ground and sieved and is not doubly modified0.8Co0.1Mn0.1O2Performing electrochemical test, and undoped cladding double modified high nickel parent positive electrode material LiNi under the room temperature of 25 +/-1 ℃ and the charge-discharge cut-off voltage of 2.8-4.3V0.8Co0.1Mn0.1O2The first discharge specific capacity is 192.3mAh/g under the charge-discharge rate of 0.2C, the first-turn coulombic efficiency is 85.8%, and the capacity retention rate is only 75.2% after 100 cycles; when the charge-discharge cutoff voltage is 2.8-4.3V at 50 +/-1 ℃, the first discharge specific capacity of the material reaches 201.8mAh/g under the charge-discharge rate of 0.2C, the first-turn coulombic efficiency is 89.5%, but the capacity retention rate is only 75.4% after 100 cycles.
As can be seen, the zirconium metaphosphate doped in the present exampleLithium ion battery high-nickel anode material LiNi coated with dual-action modification0.8Co0.1Mn0.1O2The electrochemical performance of the composite material is comprehensively superior to that of a comparative example, and the composite material is more remarkable particularly at high temperature.
While the invention has been described with reference to specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.
Claims (8)
1. The high-nickel cathode material for the lithium ion battery is characterized by being synthesized by a main phase and a dopant, wherein the main phase is a high-nickel-cobalt binary cathode material, a high-nickel NCA ternary cathode material or a high-nickel NCM ternary cathode material, the dopant is zirconium metaphosphate, and the molar ratio of the main phase to the dopant is (1-x): x, x ═ 0.001-0.05.
2. The dual action modified high nickel positive electrode material of lithium ion battery as claimed in claim 1, wherein said main phase is LiNi0.9Co0.1O2、LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2。
3. The dual action modified high nickel positive electrode material of lithium ion battery as claimed in claim 1, wherein the main phase is LiNi0.9Co0.1O2The preparation method of the dual-action modified high-nickel cathode material for the lithium ion battery comprises the following steps of:
step 1, dissolving a lithium source raw material in deionized water, adding zirconium metaphosphate, and uniformly mixing to obtain mixed slurry;
step 2, adding Ni into the mixed slurry obtained in the step 10.9Co0.1(OH)2The precursor is absolute ethyl alcoholDispersing agent, grinding uniformly and drying to obtain mixture powder;
step 3, putting the mixture powder obtained in the step 2 into an oven for drying to obtain a dried sample;
and 4, putting the dried sample obtained in the step 3 into a tubular furnace, heating to 450-650 ℃ at the speed of 2-3 ℃/min for pre-sintering for 6-15 h in an oxygen atmosphere, heating to 700-950 ℃ at the speed of 2-3 ℃/min for roasting for 15-25 h, and naturally cooling to room temperature to obtain the dual-action modified high-nickel cathode material for the lithium ion battery.
4. The dual action modified high nickel positive electrode material of lithium ion battery as claimed in claim 1, wherein the main phase is LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2The preparation method of the dual-action modified high-nickel cathode material for the lithium ion battery comprises the following steps of:
step 1, dissolving a lithium source raw material in deionized water, adding zirconium metaphosphate, and uniformly mixing to obtain mixed slurry;
step 2, adding Ni into the mixed slurry obtained in the step 10.8Co0.15Al0.05(OH)2Precursor or Ni0.8Co0.1Mn0.1(OH)2The precursor is ground uniformly by using absolute ethyl alcohol as a dispersing agent and then dried to obtain mixture powder;
step 3, putting the mixture powder obtained in the step 1 into an oven for drying to obtain a dried sample;
and 4, putting the dried sample obtained in the step 3 into a tubular furnace, heating to 400-650 ℃ at the speed of 1-10 ℃/min for pre-sintering for 6-15 h in an oxygen atmosphere, heating to 700-950 ℃ at the speed of 1-10 ℃/min for roasting for 15-25 h, and naturally cooling to room temperature to obtain the dual-action modified high-nickel cathode material for the lithium ion battery.
5. The dual-action modified high-nickel cathode material for the lithium ion battery as claimed in claim 3 or 4, wherein the molar ratio of the lithium source raw material, zirconium metaphosphate and precursor is 1.10: x (1-x), wherein x is 0.001-0.05.
6. The dual action modified lithium ion battery high nickel positive electrode material of claim 3 or 4, wherein the lithium source material is at least one of lithium carbonate, lithium nitrate, lithium acetate, lithium chloride and lithium hydroxide.
7. The dual-action modified high-nickel cathode material for the lithium ion battery according to claim 3 or 4, wherein the temperature of the oven is as follows: and (3) drying at the temperature of 80-125 ℃ for the following time: 10 to 20 hours.
8. The dual-action modified high-nickel cathode material for the lithium ion battery as claimed in claim 3 or 4, wherein the flow rate of oxygen in the oxygen atmosphere is 100-1000 ml/min.
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