CN111009645A - graphene-based/AlPO4Method for compositely coating modified high-nickel ternary cathode material - Google Patents

graphene-based/AlPO4Method for compositely coating modified high-nickel ternary cathode material Download PDF

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CN111009645A
CN111009645A CN201911182734.5A CN201911182734A CN111009645A CN 111009645 A CN111009645 A CN 111009645A CN 201911182734 A CN201911182734 A CN 201911182734A CN 111009645 A CN111009645 A CN 111009645A
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nickel ternary
alpo
graphene
cathode material
coating
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张萍
邓孝龙
范未峰
邓敏
颜华
张郑
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Yibin Libao New Materials Co Ltd
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Abstract

The invention discloses a graphene-based/AlPO4A method for preparing a composite coating modified high-nickel ternary cathode material comprises the step of preparing graphene oxide/AlPO (aluminum oxide/aluminum oxide) from graphene oxide, deionized water, an aluminum salt solution and a phosphoric acid solution4Taking the in-situ composite solution as a coating material to coat the high-nickel ternary cathode material by washing to obtain the graphene-based/AlPO4The composite coating modified high nickel ternary anode material. In the invention, the graphene oxide solution and the trivalent aluminum ion solution are mixed at the molecular level, and then aluminum phosphate grows in situ on the surface of the graphene oxide,to obtain graphene-based/AlPO with uniform dispersion4Graphene oxide/AlPO of composite structure4In-situ compounding solution to avoid AlPO on the surface of high-nickel ternary material in the conventional coating method4Formation of island-like structures, monolithic graphene oxide/AlPO4The compound is tightly and firmly coated on the surface of the high-nickel ternary cathode material, the coating layer is not easy to fall off, and the activity and the residual lithium content of the surface of the high-nickel ternary cathode material are effectively reduced.

Description

graphene-based/AlPO4Method for compositely coating modified high-nickel ternary cathode material
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to graphene-based/AlPO4A method for compounding and coating a modified high-nickel ternary cathode material.
Background
Currently, among the commercial lithium ion battery positive electrode materials, LiCoO2Has the problems of safety and overcharge resistance, Co belongs to a rare resource, is expensive, and metal cobalt easily causes pollution to the environment, and LiMn2O4The crystal transformation, the dissolution of manganese ions and the Jahn-Teller effect easily occur in the circulating process, the capacity of the battery is reduced, and LiFePO4Can be called as a zero-pollution anode material, is paid more attention due to the advantages of low price and high safety, but has low conductivity and small tap density, and the application field of the material is still greatly limitedxMnyCozO2(x + y + z ═ 1) as a positive electrode material for lithium ion batteries, and LiCoO was synthesized2，LiNiO2，LiMnO2The advantages of the three lithium ion battery anode materials are widely applied to the fields of communication, electric tools, electric bicycles, electric automobile power batteries and the like. For the production method of the lithium nickel cobalt manganese oxide material, the mainstream synthesis method in the prior art is a high-temperature solid phase method, namely, solid compounds such as lithium oxide or carbonic acid are selected and uniformly mixed with hydroxide (ternary precursor) of nickel, cobalt and manganese, and the mixture is burnt at high temperature to react to generate the lithium nickel cobalt manganese oxide material.
LiNi of nickel cobalt lithium manganate materialxMnyCozO2In (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 requirement on the energy density of a power battery and the coming of a subsidy and energy density hook policy, the application and development of the high-nickel ternary cathode material are greatly promoted, but the improvement of the nickel content can also cause a series of influences on the performance of the material, and the high-nickel ternary cathode material Ni is used as a Ni-based cathode material2+/Li+The mixed discharge is serious, and the circulation and the rate type performance of the material are influenced; and the high-nickel ternary cathode material has high residual lithium content and high activity on the surface, so that the electrolyte is easy to react, and the cycle performance and the safety performance are obviously reduced. The surface coating modification is an ideal solution for improving the cycle performance at present, the coating can reduce the contact area between the material and the outside, improve the storage performance and protect the material from being corroded by electrolyte in the charging and discharging processes, for example, the Chinese patent application with the publication number of CN109244428A discloses a coating modification method of a high-nickel ternary material, which mixes the prefabricated high-nickel ternary material powder and pyrophosphate powder and then sinters the mixture in an oxygen atmosphere to obtain the pyrophosphate-coated high-nickel ternary material; then adding the pyrophosphate-coated high-nickel ternary material into a polymerization system for polymerization to obtain pyrophosphate and polymer-coated high-nickel ternary material, wherein the polymer coating part of the obtained coating is distributed in a gap between the phosphate coating and the high-nickel ternary material, the storage performance is improved by further reducing the side reaction caused by the contact of the high-nickel ternary cathode material and external electrolyte, and the problem that the high-nickel ternary cathode material Ni is not solved2+/Li+The problem of cycle and rate performance reduction caused by serious mixed arrangement; and the phosphate-coated high-nickel ternary positive electrode material is easy to form a phosphate island-shaped structure coating layer on the surface, and the coating layer is not firm and is easy to fall off along with the de-intercalation of Li ions between the positive electrode and the negative electrode, so that the circulation is influenced.
Disclosure of Invention
The invention is to solve the technical problemThe technical problem is to provide the graphene-based/AlPO4The method for compositely coating the modified high-nickel ternary cathode material solves the problem of Ni in the high-nickel ternary cathode material in the prior art2+/Li+Serious mixed discharge and high surface activity and residual lithium quantity, which affect the cycle and rate performance of the material.
The technical scheme adopted by the invention for solving the technical problems is as follows: graphene-based/AlPO4A method for preparing a composite coating modified high-nickel ternary cathode material comprises the step of preparing graphene oxide/AlPO (aluminum oxide/aluminum oxide) from graphene oxide, deionized water, an aluminum salt solution and a phosphoric acid solution4Taking the in-situ composite solution as a coating material to coat the high-nickel ternary cathode material by washing to obtain the graphene-based/AlPO4The composite coating modified high nickel ternary anode material.
The invention carries out ultrasonic dispersion treatment on graphene oxide and an aluminum salt solution to obtain the positively charged Al3+Attracting with the negative-charged graphene oxide group, adding phosphoric acid, and reacting phosphate radical with Al3+The ions are subjected to a precipitation reaction in situ on the surface of the graphene oxide to generate AlPO4The crystal is in-situ nucleated and grows on the graphene oxide lamella, and then graphene oxide/AlPO is obtained4Composite of AlPO thus formed on graphene oxide sheets4The particles are fine and can be uniformly coated in the subsequent coating process; in the coating process, graphene oxide provides a template, then a high-nickel ternary positive electrode material is added, and the graphene oxide/AlPO are stirred to ensure that the graphene oxide/AlPO are mixed4The compound is uniformly dispersed into the high-nickel ternary material, and then secondary sintering is carried out in an inert atmosphere to obtain surface AlPO4Coated and graphene-modified high-nickel ternary positive electrode material AlPO4The coating reduces the activity and residual lithium content of the surface of the high-nickel ternary material, and the graphene greatly reduces the contact resistance among the particles of the high-nickel ternary material, so that the conductivity of the material is enhanced.
The graphene oxide solution and the trivalent aluminum ion solution are mixed at the molecular level, aluminum phosphate grows in situ on the surface of the graphene oxide, and then the high-nickel ternary material is added, so that the graphene base/AlPO with uniform dispersion is favorably obtained4The composite structure avoids the AlPO on the surface of the high-nickel ternary material in the conventional coating method4Due to the fact that the aluminum phosphate is loaded on the surface of the graphene oxide, the aluminum phosphate and the graphene oxide form a whole, and agglomeration among the graphene oxide can be prevented.
Preferably, the structural formula of the high-nickel ternary cathode material is LixNiyCozMn1-y-zO2Wherein x is more than or equal to 0.95 and less than or equal to 1.1, y is more than or equal to 0.6 and less than or equal to 0.95, and z is more than or equal to 0.05 and less than or equal to 0.25.
Preferably, the high-nickel ternary cathode material is in a single crystal, quasi-single crystal or quasi-spherical form, and D50 is 2-20 μm.
Preferably, the graphene oxide is added into deionized water for ultrasonic dispersion, then an aluminum salt solution is added into the solution for stirring, and then a phosphoric acid solution is added for stirring to obtain the graphene oxide/AlPO4Compounding the solution in situ.
Preferably, the ultrasonic dispersion time is 2-5 h, and the ultrasonic dispersion power is 1000-5000W; adding the aluminum salt solution, stirring for 5-30 min, adding the phosphoric acid solution, and stirring for 5-20 min to obtain the graphene oxide/AlPO4Compounding the solution in situ.
Firstly, adding an aluminum salt solution into a graphene solution to obtain positively charged Al3+Attracting with the surface group of the negatively charged graphene oxide, adding phosphoric acid, and then adding PO43-With Al3+In-situ formation of AlPO on the surface of graphene oxide4Precipitation, if aluminum phosphate is directly added for coating, only physical simple mixing is adopted, the coated particles are easy to agglomerate, island-shaped coating is formed on the surface of the ternary material, and the coating effect is poor; al (Al)3+Can exist stably in the pH range of the graphene oxide solution, and can form AlPO after a certain amount of phosphoric acid is added4And (4) precipitating.
Preferably, the addition amount of the deionized water is 0.5-2 times of the mass of the high-nickel ternary cathode material, and the addition amount of the graphene oxide is 0.1-2% of the mass of the high-nickel ternary cathode material.
Preferably, the aluminum salt in the aluminum salt solution is selected from one of aluminum nitrate, aluminum chloride, aluminum sulfate and alum, the molar ratio of aluminum element to phosphate radical in the aluminum salt solution and the phosphoric acid solution is 1: 1-3, and the mass ratio of the high-nickel ternary cathode material to the aluminum element in the aluminum salt solution is 1: 0.0001 to 0.01.
Preferably, the ultrasonic dispersion time is 2-5 h, and the ultrasonic dispersion power is 1000-5000W; adding the aluminum salt solution, stirring for 5-30 min, adding the phosphoric acid solution, and stirring for 5-20 min to obtain the graphene oxide/AlPO4Compounding the solution in situ.
Preferably, the water washing coating process is to add the high-nickel ternary cathode material into the graphene oxide/AlPO4Stirring the in-situ composite solution, wherein the water washing temperature is 10-100 ℃, and the washing time is 5-60 min; after the water washing is finished, filter pressing and vacuum drying are carried out, and then secondary sintering, crushing, sieving and iron removal are carried out under the inert gas atmosphere to obtain the graphene-based/AlPO4The composite coating modified high nickel ternary anode material.
The main synthesis process of the high-nickel ternary cathode material comprises the following steps: mixing materials, primary sintering, crushing, washing and coating, drying and secondary sintering, wherein the primary sintering is a high-temperature synthesis reaction, the secondary sintering is used for optimizing a crystal structure, and the washing is mainly used for reducing residual alkali on the surface of a high-nickel material.
Preferably, the temperature of the secondary sintering is 200-900 ℃, and the sintering time is 3-12 h; the filter pressing time is 0.5-2 h, and the vacuum drying time is 2-5 h.
Preferably, the concentration of the aluminum salt solution is 0.1-1 mol/L, and the concentration of the phosphoric acid solution is 0.1-10 mol/L.
The inert gas is nitrogen, argon or a mixed gas of nitrogen and argon.
The invention has the beneficial effects that: according to the method, a graphene oxide solution and a trivalent aluminum ion solution are mixed at a molecular level, and then aluminum phosphate grows on the surface of graphene oxide in situ to obtain uniformly dispersed graphene-based/AlPO4Graphene oxide/AlPO of composite structure4In-situ compounding solution to avoid AlPO on the surface of high-nickel ternary material in the conventional coating method4Formation of island-like structure due to aluminum phosphateAfter the aluminum phosphate is loaded on the surface of the graphene oxide, the aluminum phosphate and the graphene oxide form a whole, so that agglomeration among the graphite oxides can be prevented, and meanwhile, the whole graphene oxide/AlPO4The compound is tightly and firmly coated on the surface of the high-nickel ternary cathode material, the coating layer is not easy to fall off, and the activity and the residual lithium content of the surface of the high-nickel ternary cathode material are effectively reduced; and graphene oxide/AlPO4The graphene on the compound greatly reduces the contact resistance among the particles of the high-nickel ternary positive electrode material, thereby improving the conductivity of the material, greatly improving the cycle performance and rate capability of the material, and reducing Ni2+/Li+The influence of serious mixed discharge on the circulation and multiplying power performance; the invention has simple process and easy control, and adopts the simplest coating method to obtain the ternary cathode material which has high specific capacity, good cycle performance and excellent rate performance and is suitable for the application field of power batteries.
Drawings
FIG. 1 shows the graphene-based/AlPO obtained in example 14SEM picture of composite coating modified high nickel ternary cathode material;
FIG. 2 shows the graphene-based/AlPO obtained in example 24XRD pattern of the composite coating modified high nickel ternary anode material;
FIG. 3 is the graphene-based/AlPO obtained in example 34The charge-discharge curves of the lithium ion battery taking the composite coating modified high-nickel ternary positive electrode material as the positive electrode material under different multiplying powers are obtained;
FIG. 4 shows the graphene-based/AlPO obtained in example 34The lithium ion battery taking the composite coating modified high-nickel ternary cathode material as the cathode material has a normal-temperature cycle performance curve at a multiplying power of 1C.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1:
taking high-nickel ternary positive electrode material LiNi0.83Co0.11Mn0.06O2Sample 20Kg for graphene-based/AlPO4Composite coating modification test by adding graphene oxideCarrying out ultrasonic dispersion in deionized water for 3 hours, wherein the addition of the graphene oxide is 0.5 percent of the mass of the high-nickel ternary cathode material, the mass ratio of the addition of the deionized water to the high-nickel ternary cathode material is 0.6:1, and the ultrasonic dispersion power is 2000W;
after the ultrasonic dispersion is finished, adding an aluminum chloride solution into a graphene oxide solution, stirring for 10min, adding aluminum chloride according to the mass ratio of aluminum element to the high-nickel ternary positive electrode material of 0.001:1, then adding a phosphoric acid solution, stirring for 5min, adding phosphoric acid according to the molar ratio of aluminum element to phosphate radical in aluminum chloride and phosphoric acid of 1:1.0, and obtaining graphene oxide/AlPO4And (3) a complex solution. Wherein the concentration of the aluminum chloride solution is 0.5mol/L, and the concentration of the phosphoric acid solution is 5 mol/L.
Adding a high-nickel ternary cathode material into graphene oxide/AlPO4Washing the composite solution with water, stirring for 10min, then performing pressure filtration for 1.5h, performing vacuum drying treatment at 110 ℃ for 4h, and performing secondary sintering at 500 ℃ in nitrogen atmosphere for 8h to obtain graphene-based/AlPO4And compounding the high-nickel ternary cathode material. Referring to fig. 1, an SEM image of the material obtained in this example 1 shows that the material in the SEM image has good sphericity and intact particles, and no cracking phenomenon is found, and graphene is uniformly dispersed among the high-nickel ternary cathode materials and no agglomeration occurs.
Example 2:
taking high-nickel ternary positive electrode material LiNi0.83Co0.11Mn0.06O2Sample 20Kg for graphene-based/AlPO4In the composite coating modification test, graphene oxide is added into deionized water for ultrasonic dispersion for 5 hours, wherein the addition amount of the graphene oxide is 1.0% of the mass of the high-nickel ternary material, the mass ratio of the addition amount of the deionized water to the high-nickel ternary cathode material is 1.5:1, and the ultrasonic dispersion power is 3000W;
after the ultrasonic dispersion is finished, adding an aluminum sulfate solution into the graphene oxide solution, stirring for 30min, wherein the adding amount of the aluminum sulfate solution is 0.008:1 according to the mass ratio of aluminum to the high-nickel ternary positive electrode material, then adding a phosphoric acid solution, stirring for 20min, and the adding amount of the phosphoric acid solution is aluminum sulfate and phosphorusThe molar ratio of the aluminum element to the phosphate radical in the acid is 1:1.2, and the graphene oxide/AlPO is obtained4And (3) a complex solution. The concentration of the aluminum sulfate solution is 1mol/L, and the concentration of the phosphoric acid solution is 10 mol/L.
Adding a high-nickel ternary cathode material into graphene oxide/AlPO4Washing the composite solution with water, stirring for 30min, then performing pressure filtration for 1.5h, performing vacuum drying treatment at 110 ℃ for 4h, performing secondary sintering at 700 ℃ in argon atmosphere for 8h to obtain graphene-based/AlPO4And compounding the high-nickel ternary cathode material. Referring to fig. 2, the XRD pattern of the material obtained in this example 2 is relatively sharp, and has good crystallinity, and no impurity peak is found, which indicates that the material has no impurity.
Example 3:
taking high-nickel ternary positive electrode material LiNi0.83Co0.11Mn0.06O2Sample 20Kg for graphene-based/AlPO4In the composite coating modification test, graphene oxide is added into deionized water and then subjected to ultrasonic dispersion for 4 hours, wherein the addition amount of the graphene oxide is 0.8% of the mass of the high-nickel ternary material, the mass ratio of the addition amount of the deionized water to the high-nickel ternary cathode material is 1:1, and the ultrasonic dispersion power is 3000W;
after the ultrasonic dispersion is finished, adding an aluminum nitrate solution into a graphene oxide solution, stirring for 20min, adding the aluminum nitrate solution according to the mass ratio of aluminum to the high-nickel ternary positive electrode material of 0.002:1, then adding a phosphoric acid solution, stirring for 10min, and adding the phosphoric acid solution according to the molar ratio of aluminum elements in aluminum nitrate and phosphoric acid to phosphate radicals of 1:1.1 to obtain the graphene oxide/AlPO4And (3) a complex solution. The concentration of the aluminum nitrate solution is 0.2mol/L, and the concentration of the phosphoric acid solution is 2 mol/L.
Adding a high-nickel ternary cathode material into graphene oxide/AlPO4Washing the composite solution with water, stirring for 20min, then performing pressure filtration for 1.5h, performing vacuum drying treatment at 110 ℃ for 4h, performing secondary sintering at 600 ℃ in a nitrogen atmosphere for 6h to obtain graphene-based/AlPO4Composite high-nickel ternary positive electrodeA material. The charge and discharge curves of the lithium ion battery using the material obtained in example 3 as the cathode material at different multiplying factors are shown in fig. 3. The discharge specific capacities at 0.1C, 0.2C, 0.5C, 1C and 2C are respectively maintained to be above 207.6mAh/g, 203.6mAh/g, 194.9mAh/g, 189.1mAh/g and 183.8mAh/g, and higher discharge capacity and excellent rate capability are shown. The cycle performance curve of the button cell using the material obtained in this embodiment 3 as the positive electrode material at 1C rate is shown in fig. 4, the charge-discharge voltage range of the button cell is 3.0-4.3V, and the capacity retention rate of the button cell at 1C rate after 50 cycles at normal temperature is 95.5%, which shows excellent cycle performance.
Comparative example 1:
high nickel ternary positive electrode material LiNi0.83Co0.11Mn0.06O2And adding 20Kg of primary sintered material into deionized water, washing and stirring for 30min, wherein the mass ratio of the added amount of the deionized water to the high-nickel ternary cathode material is 1:1, then carrying out filter pressing for 1.5h, carrying out vacuum drying treatment at 110 ℃ for 4h, and then carrying out secondary sintering in a nitrogen atmosphere, wherein the sintering temperature is 500 ℃, and the heat preservation time is 6h, thus obtaining the high-nickel ternary cathode material.
Comparative example 2:
high nickel ternary positive electrode material LiNi0.83Co0.11Mn0.06O2Adding 20Kg of primary sintered material of a sample into deionized water, washing and stirring for 30min, wherein the mass ratio of the added amount of the deionized water to the high-nickel ternary cathode material is 1:1, then carrying out filter pressing for 1.5h, carrying out vacuum drying treatment at 110 ℃ for 4h, and then carrying out AlPO4Dry coating of AlPO4The adding amount of the aluminum-nickel ternary positive electrode material is 0.002:1 by mass ratio, and the AlPO is obtained by secondary sintering in nitrogen atmosphere at the sintering temperature of 600 ℃ for 6 hours4And (3) a coated high-nickel ternary cathode material.
Comparative example 3:
taking high-nickel ternary positive electrode material LiNi0.83Co0.11Mn0.06O2A sample of 20Kg is tested, graphene oxide is added into deionized water for ultrasonic dispersion for 4 hours to obtain graphene oxide dispersion liquid, wherein the graphene oxide dispersion liquid is oxidizedThe addition amount of the graphene is 1.0% of the mass of the high-nickel ternary material, the mass ratio of the addition amount of the deionized water to the high-nickel ternary positive electrode material is 1:1, and the ultrasonic dispersion power is 3000W.
Adding the high-nickel ternary cathode material into the graphene oxide dispersion liquid, washing and stirring for 30min, then carrying out filter pressing for 1.5h, carrying out vacuum drying treatment for 4h at 110 ℃, and then carrying out secondary sintering at 600 ℃ for 6h in a nitrogen atmosphere to obtain the graphene composite high-nickel ternary cathode material.
Comparative example 4:
taking high-nickel ternary positive electrode material LiNi0.83Co0.11Mn0.06O2Sample 20Kg for graphene/AlPO4In the composite coating modification test, graphene oxide is added into deionized water, ultrasonic dispersion is carried out for 3 hours, the addition amount of the graphene oxide is 0.5 percent of the mass of the high-nickel ternary cathode material, the mass ratio of the addition amount of the deionized water to the mass of the high-nickel ternary cathode material is 0.6:1, then an aluminum phosphate solution is added into the graphene oxide solution and stirred for 30 minutes, and the addition amount of the aluminum phosphate solution is 0.001:1 according to the mass ratio of aluminum element to the high-nickel ternary cathode material, so that graphene oxide/AlPO is obtained4And (3) a complex solution. Wherein the concentration of the aluminum phosphate solution is 1mol/L, and the ultrasonic dispersion power is 3000W.
Adding the high-nickel three-positive-electrode-element material into graphene oxide/AlPO4Washing the composite solution with water, stirring for 10min, then performing pressure filtration for 1.5h, performing vacuum drying treatment at 110 ℃ for 4h, and performing secondary sintering at 500 ℃ in nitrogen atmosphere for 8h to obtain graphene-based/AlPO4And compounding the high-nickel ternary cathode material.
The high-nickel ternary positive electrode materials obtained in the above examples 1-3 and comparative examples 1-4 are made into button cells, and electrochemical performance test is performed, wherein the button cells are manufactured into 2025 type cells under the following test conditions:
anodal pole: SP: PVDF: 90: 5,
Negative electrode: metallic lithium,
Electrolyte solution: new Zhou nation (M10),
The charging and discharging voltage range is 3.0-4.3V,
the test results are shown in tables 1 and 2, wherein the rate performance in the process of returning to the 0.1C rate and the normal-temperature cycle performance retention rate at the 1C rate are mainly tested after the charge and discharge are carried out for 1 time respectively at different rates of 0.1C, 0.2C, 0.5C, 1C and 2C.
TABLE 1 Rate Performance
0.1C 0.2C 0.5 C 1C 2C 0.1C
Example 1 208.2 204.3 195.6 189.2 183.6 207.8
Example 2 205.1 201.8 193.3 187.8 183.0 204.3
Example 3 207.6 203.6 194.9 189.1 184.3 207.2
Comparative example 1 208.1 203.9 194.7 187.5 182.1 203.5
Comparative example 2 207.1 203.2 194.1 187.1 181.2 205.9
Comparative example 3 207.3 203.7 195.1 189.2 184.2 204.3
Comparative example 4 205.5 202.6 193.6 187.2 182.5 203.9
TABLE 2 cycling stability
Figure BDA0002291700340000061
Figure BDA0002291700340000071

Claims (10)

1. graphene-based/AlPO4The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: preparing graphene oxide/AlPO from graphene oxide, deionized water, aluminum salt solution and phosphoric acid solution4Taking the in-situ composite solution as a coating material to coat the high-nickel ternary cathode material by washing to obtain the graphene-based/AlPO4The composite coating modified high nickel ternary anode material.
2. The graphene-based/AlPO according to claim 14The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: the structural formula of the high-nickel ternary cathode material is represented by LixNiyCozMn1-y-zO2Wherein x is more than or equal to 0.95 and less than or equal to 1.1, y is more than or equal to 0.6 and less than or equal to 0.95, and z is more than or equal to 0.05 and less than or equal to 0.25.
3. The graphene-based/AlPO according to claim 1 or 24The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: the high-nickel ternary positive electrode material is in a single crystal, single-crystal-like or spherical-like form, and D50 is 2-20 mu m.
4. The graphene-based/AlPO according to claim 14The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: adding graphene oxide into deionized water for ultrasonic dispersion, then adding an aluminum salt solution into the solution for stirring, then adding a phosphoric acid solution for stirring to obtain graphene oxide/AlPO4Compounding the solution in situ.
5. The graphene-based/AlPO according to claim 1 or 44The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: the addition amount of the deionized water is 0.5-2 times of the mass of the high-nickel ternary cathode material, and the addition amount of the graphene oxide is 0.1-2% of the mass of the high-nickel ternary cathode material.
6. The graphene-based/AlPO according to claim 1 or 44The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: the aluminum salt in the aluminum salt solution is selected from one of aluminum nitrate, aluminum chloride, aluminum sulfate and alum, the molar ratio of aluminum element to phosphate radical in the aluminum salt solution and the phosphoric acid solution is 1: 1-3, and the mass ratio of the high-nickel ternary positive electrode material to the aluminum element in the aluminum salt solution is 1: 0.0001 to 0.01.
7. The graphene-based/AlPO according to claim 44The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: the ultrasonic dispersion time is 2-5 h, and the ultrasonic dispersion power is 1000-5000W; adding the aluminum salt solution, stirring for 5-30 min, adding the phosphoric acid solution, and stirring for 5-20 min to obtain the graphene oxide/AlPO4Compounding the solution in situ.
8. The graphene-based/AlPO according to claim 14The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: the washing coating process is to add the high-nickel ternary cathode material into the graphene oxide/AlPO4In situ composite solutionStirring, wherein the water washing temperature is 10-100 ℃, and the washing time is 5-60 min; after the water washing is finished, filter pressing and vacuum drying are carried out, and then secondary sintering, crushing, sieving and iron removal are carried out under the inert gas atmosphere to obtain the graphene-based/AlPO4The composite coating modified high nickel ternary anode material.
9. The graphene-based/AlPO according to claim 84The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: the temperature of the secondary sintering is 200-900 ℃, and the sintering time is 3-12 h; the filter pressing time is 0.5-2 h, and the vacuum drying time is 2-5 h.
10. The graphene-based/AlPO according to claim 64The method for compositely coating the modified high-nickel ternary cathode material is characterized by comprising the following steps of: the concentration of the aluminum salt solution is 0.1-1 mol/L, and the concentration of the phosphoric acid solution is 0.1-10 mol/L.
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