CN113328088B - Controllable method for realizing surface modification of electrode material - Google Patents

Controllable method for realizing surface modification of electrode material Download PDF

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CN113328088B
CN113328088B CN202110534278.7A CN202110534278A CN113328088B CN 113328088 B CN113328088 B CN 113328088B CN 202110534278 A CN202110534278 A CN 202110534278A CN 113328088 B CN113328088 B CN 113328088B
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electrode material
stirring
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ethanol
complexing agent
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CN113328088A (en
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杨秀康
刘淇文
曹安民
孙勇刚
陈曼芳
舒洪波
王先友
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Xiangtan University
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Abstract

The invention discloses a controllable method for realizing surface modification of an electrode material, which comprises the following steps: (1) adding soluble metal salt into ethanol, and uniformly stirring to obtain a solution A; (2) adding an organic complexing agent with at least two adjacent phenolic hydroxyl groups into a mixed solvent formed by ethanol and alcohol or an alcohol polymer with at least two hydroxyl groups, and uniformly stirring to obtain a non-aqueous complexing agent solution B; (3) adding the electrode material into the nonaqueous complexing agent solution B, and uniformly stirring to obtain a suspension C; (4) adding the solution A into the suspension C, uniformly stirring, and carrying out solid-liquid separation, washing and drying to obtain an electrode material with the surface uniformly coated with the metal ion complex layer; (5) and calcining the electrode material with the surface uniformly coated with the metal ion complex layer to obtain the surface modified electrode material. The invention can realize the uniform coating or doping of the surface of the electrode material and endow the electrode material with better performance.

Description

Controllable method for realizing surface modification of electrode material
Technical Field
The invention relates to a controllable method for realizing surface modification of an electrode material, in particular to a controllable method for realizing uniform doping or coating of the surface of the electrode material, and belongs to the technical field of energy materials and electrochemistry.
Background
In recent years, the double harvest of the new energy automobile output and sales volume in China drives the rapid development of the whole upstream and downstream industry chains, and particularly the demand for lithium ion power batteries is continuously increased. Most of the existing lithium ion batteries do not have the advantages of high specific capacity, high charging efficiency and long cycle life, and the actual capacity is far from the theoretical capacity, so the technical innovation is very urgent, and the development of a novel lithium ion battery electrode material with excellent performance is the direction of important effort required by researchers at present.
The structural stability, the service cycle life, the voltage attenuation and other problems of the anode material still need to be further improved. Because the surface problems of transition metal ion dissolution, generation of a passivation layer on the surface of an electrode material and the like in the circulating process are not negligible in the research of the anode material, surface coating and doping are common modification means at present, and although the atomic deposition (ALD) technology can realize accurate and controllable thickness deposition, the ALD technology has certain selectivity on a substrate, the process is complex, and equipment is expensive.
The lithium ion battery cathode material is developed towards the direction of high specific capacity, long cycle life and low cost, and the cathode material comprising a metal base (Sn-based material and Si-based material), lithium titanate, a carbon material (carbon nano tube, graphene and the like) and the like has the remarkable advantages of small volume change, long cycle life, good safety, specific surface area, high conductivity, chemical stability and the like. However, the drop-off due to the volume change during the charge and discharge processes and the side reaction between the electrode interface and the electrolyte may cause the cycle performance to be degraded and the capacity to be degraded. At present, the research on the interface stability, the structural stability, the electronic conductivity, the dispersibility and the like of the surface coating and doping materials are obviously improved.
The surface coating modification creates a surface layer as a buffer region to avoid direct contact between the active material and the electrolyte solvent, while allowing lithium ions to migrate between the solution and the active material to slow the release of oxygen and the dissolution of transition metal ions. In addition, the ion doping is carried out on the surface of the electrode, which is not only beneficial to stabilizing the surface structure, reducing the side reaction of the active material and the electrolyte interface, and improving the electrochemical performance, but also avoids the capacity loss caused by the substitution of non-electrochemical active ions. However, the uniformity of surface modification, the controllability of the amount of coating and dopant, the selectivity of the substrate, the simplicity of the process, and the cost of the equipment remain significant challenges.
Therefore, the surface modification method which is uniform in doping or coating, accurate and controllable in amount, high in safety, simple to operate, low in cost and strong in substrate applicability is developed, and has important practical significance for the development of lithium ion batteries and related industries.
Disclosure of Invention
In order to solve the problems existing in the surface modification process of the existing electrode material, the invention aims to provide a controllable method for realizing the surface modification of the electrode material, which has simple and controllable process and strong substrate applicability and can realize the uniform coating or doping of the surface of the electrode material.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a controllable method for realizing surface modification of an electrode material comprises the following steps:
(1) adding soluble metal salt into ethanol, and uniformly stirring to obtain a solution A;
(2) adding an organic complexing agent with at least two adjacent phenolic hydroxyl groups into a mixed solvent formed by ethanol and alcohol or an alcohol polymer with at least two hydroxyl groups, and uniformly stirring to obtain a non-aqueous complexing agent solution B;
(3) adding the electrode material into the nonaqueous complexing agent solution B, and uniformly stirring to obtain a suspension C;
(4) adding the solution A into the suspension C, uniformly stirring, and carrying out solid-liquid separation, washing and drying to obtain an electrode material with the surface uniformly coated with the metal ion complex layer;
(5) and calcining the electrode material with the surface uniformly coated with the metal ion complex layer to obtain the surface modified electrode material.
Preferably, in step (1), the soluble metal salt is at least one selected from soluble metal salts containing group IIA-VIA, IB-VIIB and VIII metal elements, for example, soluble metal salts of metals such as aluminum, iron, magnesium, molybdenum and tin.
Preferably, in the step (2), the organic complexing agent is at least one selected from tannic acid, epicatechin gallate, epigallocatechin, and gallocatechin gallate.
Preferably, in the step (2), the alcohol or alcohol polymer having at least two hydroxyl groups is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, ethylene glycol, and α -propylene glycol.
Preferably, in the step (3), the electrode material is a positive electrode material or a negative electrode material;
the positive electrode material comprises an oxide positive electrode material (such as a lithium-rich manganese-based positive electrode material Li) of a lithium ion battery1.2Mn0.54Ni0.13Co0.13O2(ii) a High-nickel ternary positive electrode material LiNi0.8Co0.1Mn0.1O2(ii) a LiCoO as positive electrode material of cobalt-containing layered oxide2) Sodium ion battery oxide positive electrode material (e.g., Na)0.44MnO2) Potassium ion battery oxide positive electrode material (e.g. K)5/9Mn7/9Ti2/9O2) Lithium-based solid electrolyte oxide, sodium-based solid electrolyte, or potassium-based solid electrolyte oxide;
the negative electrode material includes Sn-based negative electrode material, Si-based negative electrode material, lithium titanate, or carbon negative electrode material (e.g., carbon nanotube, graphene, silicon carbide fiber, etc.).
Preferably, in the step (5), the calcining temperature is not lower than 300 ℃, and more preferably 400-800 ℃; the calcination time is not less than 2 hours, and more preferably 2 to 12 hours.
It should be noted that, in the invention, because the specific complexation degrees of different organic complexing agents and different metal ions are different, the invention does not make special requirements on the specific dosage of the complexing agent, and can be determined according to the type of the organic complexing agent and the metal ions selected in the actual reaction process; meanwhile, the requirements for doping or coating of different electrode materials are different, so that the dosage of the electrode material substrate and the soluble metal salt can be adjusted according to the specific requirements for doping or coating of different electrode materials; the speed and the difficulty degree of the complex reaction between different metal ions and the organic complexing agent are different, if the metal ions in the third period are more active, the viscosity of the mixed solution can be increased to slow down the reaction rate, the metal ions in the fifth period are more stable, the complex speed is mild, and the viscosity can be reduced, so that the volume ratio of the ethanol in the mixed solvent to the alcohol or the alcohol polymer with at least two hydroxyl groups is not specially required, and the method is determined according to the actual reaction process.
The principle and the advantages are as follows:
the inventor finds that an organic matter with at least two adjacent phenolic hydroxyl groups is used as a complexing agent, wherein the two adjacent phenolic hydroxyl groups can form a stable chelate with metal ions in the form of oxygen anions, and the excessive two or more phenolic hydroxyl groups do not participate in the complexation but can promote the dissociation of the two adjacent phenolic hydroxyl groups, thereby promoting the formation and the stabilization of the complex. However, such complexing agents rapidly complex with metal ions in aqueous solution and cannot be deposited on the surface of a substrate in a mild and controllable manner.
According to the invention, the organic complexing agent with at least two adjacent phenolic hydroxyl groups is added into the mixed solvent formed by ethanol and alcohol or alcohol polymer with at least two hydroxyl groups to obtain the non-aqueous complexing agent solution, and the alcohol or alcohol polymer with at least two hydroxyl groups can be well compatible with the ethanol, has good dispersibility and viscosity higher than that of the ethanol, so that the dispersibility and viscosity of the mixed solution can be increased, the complexing rate of the complexing agent and metal ions can be effectively slowed down, and the hydroxyl groups in the solvent can also promote the dissociation of the adjacent hydroxyl groups of the complexing agent, so that the complexing reaction can be controllably carried out at a milder rate. In addition, the complexing process is carried out in a non-aqueous system, so that the metal ion complex can be uniformly and controllably deposited on the surface of a substrate sensitive to water, and the electrode material with uniformly doped or coated surface is obtained by calcining, so that the controllable surface coating or doping is realized, and the electrode material has better performance.
Drawings
FIG. 1 shows Li in example 11.2Mn0.54Ni0.13Co0.13O2(1) Surface-coated tannic acid-aluminum complex coating layer1.2Mn0.54Ni0.13Co0.13O2@ TA-Al-12nm (2) and Li formed by uniformly doping Al element surface after calcination1.2Mn0.54Ni0.13Co0.13O2-X-ray diffraction (XRD) pattern of Al (3).
FIG. 2 shows Li in example 11.2Mn0.54Ni0.13Co0.13O2(1) And Li of different tannin-aluminum complex coating layer thicknesses synthesized in examples 1(3), 3(2) and 4(4)1.2Mn0.54Ni0.13Co0.13O2Scanning Electron Microscope (SEM) picture of @ TA-Al.
FIG. 3 shows Li in example 11.2Mn0.54Ni0.13Co0.13O2(1) And Li of different tannin-aluminum complex coating layer thicknesses synthesized in examples 1(3), 3(2) and 4(4)1.2Mn0.54Ni0.13Co0.13O2A Transmission Electron Microscope (TEM) image of @ TA-Al.
FIG. 4 shows Li in example 11.2Mn0.54Ni0.13Co0.13O2(1) Li uniformly doped on Al element surface synthesized in example 11.2Mn0.54Ni0.13Co0.13O2Al-12(2) and surface Al synthesized in example 32O3Uniformly coated Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3(3) High resolution (HR-TEM) images of transmission electron microscopy.
FIG. 5 shows that the Al element synthesized in example 1 is uniformly doped with Li on the surface1.2Mn0.54Ni0.13Co0.13O2-an X-ray energy spectral surface scan (EDS) map of Al-12;
FIG. 6 shows Li in example 11.2Mn0.54Ni0.13Co0.13O2Al element synthesized in example 1 was surface-uniformly doped with Li1.2Mn0.54Ni0.13Co0.13O2Al-12 and surface Al synthesized in example 32O3Uniformly coated Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3Cycling performance plot at 0.5C magnification.
FIG. 7 shows Li in example 11.2Mn0.54Ni0.13Co0.13O2Al element synthesized in example 1 was surface-uniformly doped with Li1.2Mn0.54Ni0.13Co0.13O2Al-12 and surface Al synthesized in example 32O3Uniformly coated Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3Graph of median change in discharge for cycles at 0.5C rate.
FIG. 8 shows Li in example 11.2Mn0.54Ni0.13Co0.13O2Al element synthesized in example 1 was surface-uniformly doped with Li1.2Mn0.54Ni0.13Co0.13O2-Al-12 and practiceExample 3 surface Al synthesized2O3Uniformly coated Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3Graph of rate performance in the interval 0.1C,0.2C,0.5C,1C,2C and 5C.
FIG. 9 shows LiNi with a tannin-aluminum complex coating layer synthesized in example 90.8Co0.1Mn0.1O2@ TA-Al (1) and LiCoO having tannin-aluminum complex coating layer synthesized in example 102A Transmission Electron Microscope (TEM) image of @ TA-Al (2).
FIG. 10 shows PS @ TA-Al-EtOH + Macrogol-400(3), PS @ TA-Al-EtOH + Macrogol-200(4), PS @ TA-Al-EtOH + PPG-400(5), PS @ TA-Al-EtOH +1,2-PG (6), PS @ TA-Al-H, synthesized in ethanol and polyethylene glycol (400) mixed solvent, ethanol and polyethylene glycol (200) mixed solvent, ethanol and polypropylene glycol (400) mixed solvent, ethanol and alpha-propylene glycol mixed solvent, water and ethanol, respectively, for examples 11 to 14 and comparative examples 1 to 22Transmission Electron Microscopy (TEM) images of O (1) and PS @ TA-Al-EtOH (2).
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be only illustrative of the specific embodiments of the present invention and should not be construed as limiting the scope of the invention.
It should be noted that examples 11-14 and comparative examples 1-2 in the present invention use non-metal organic polymer Polystyrene (PS) commonly used in the art as a substrate for modification attempts to observe the modification effect of different solvents; while examples 15-18 used Polystyrene (PS) as the substrate for the modification attempt to demonstrate the modification effect with different organic complexing agents.
Example 1
(1) Mixing AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride solution A with the concentration of 0.8 mmol/L; mixing 5.5X 10-3Adding Tannin (TA) mmol into 25mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:10), stirring to dissolve to obtain nonaqueous complexing agent solution B, and adding 500mg Li1.2Mn0.54Ni0.13Co0.13O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the lithium-rich cathode material with the surface uniformly coated with the TA-Al complex layer, wherein the lithium-rich cathode material is named as Li1.2Mn0.54Ni0.13Co0.13O2@TA-Al-12nm；
(4) In the air atmosphere, the material obtained in the step (3) is heated to 700 ℃ at the heating rate of 3 ℃/min, is kept warm for 2h and is cooled to room temperature, and the lithium-rich cathode material with the Al element surface uniformly doped is obtained, and is named as Li1.2Mn0.54Ni0.13Co0.13O2-Al-12。
From the analysis of the XRD diagram in figure 1, the trace Al element doping on the surface of the non-aqueous liquid phase coating and the high-temperature sintering has no damage to the crystal structure of the raw material; from the SEM image analysis of FIG. 2, it can be seen that the surface morphology of the material is not significantly changed during the non-aqueous liquid phase coating process and the high temperature sintering; from the analysis of the TME chart of FIG. 3, the method can achieve uniform surface coating of the TA-Al complex layer, with a coating thickness of about 12 nm; from the HR-TEM image of FIG. 4, it is seen that the surface crystal structure is not significantly changed after the surface is doped with Al; from the EDS diagram of fig. 5, it is seen that Al is uniformly distributed on the surface of the particles, indicating that this method achieves uniform doping of Al on the surface of the lithium-rich cathode material.
Battery assembly and electrochemical performance testing: li prepared as described above1.2Mn0.54Ni0.13Co0.13O2Mixing Al-12 with a binder polyvinylidene fluoride (PVDF) and a conductive agent Super-P according to a mass ratio of 8:1:1, adding a proper amount of solvent N-methylpyrrolidone (NMP), preparing slurry, taking an aluminum foil as a current collector, uniformly coating the slurry on the aluminum foil, and drying in vacuum at 100 ℃ for 12 hours to obtain Li1.2Mn0.54Ni0.13Co0.13O2-Al-12 composite positive electrode. Subsequently, the prepared composite positive electrode, the diaphragm, the electrolyte (EC/DEC (1: 1 by volume) solution of 1M LiPF 6), the lithium negative electrode, the positive electrode case, and the negative electrode case were assembled into a button lithium ion battery. And finally, performing constant-current charge and discharge test on the battery at 25 ℃ and in a voltage range of 2-4.6V. FIG. 6 is the above Li1.2Mn0.54Ni0.13Co0.13O2Cycle performance diagram of 100 cycles at 0.5C (1C-200 mA/g) rate for a cell with-Al-12 composite positive electrode as the positive electrode, Li1.2Mn0.54Ni0.13Co0.13O2The capacity retention of the base material after 100 cycles at a current density of 0.5C is only 68.4%, while Li1.2Mn0.54Ni0.13Co0.13O2The capacity retention rate of the-Al-12 doped modified material under the same test condition is improved to 80.1%, which shows that the lithium-rich cathode material uniformly doped on the surface of the Al element can remarkably improve the cycle stability of the battery, and fig. 7 shows that Li is used as the Li1.2Mn0.54Ni0.13Co0.13O2Graph of change in median voltage during 100 cycles of discharge at 0.5C (1C-200 mA/g) rate for a cell with an — Al-12 composite positive electrode as the positive electrode, Li1.2Mn0.54Ni0.13Co0.13O2After 100 cycles the voltage decayed 0.5395V, while Li1.2Mn0.54Ni0.13Co0.13O2The voltage attenuation of the Al-12 modified material is only 0.3908V, which shows that the discharge median voltage attenuation of the lithium-rich cathode material uniformly doped on the surface of Al element is relieved to a certain extent, and Li shown in FIG. 81.2Mn0.54Ni0.13Co0.13O2The multiplying power performance diagram of the battery taking the Al-12 composite positive electrode as the positive electrode in the ranges of 0.1C,0.2C,0.5C,1C,2C and 5C shows that the multiplying power performance of the lithium-rich positive electrode material uniformly doped on the surface of the Al element is obviously improved.
Example 2
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 0.8 mmol/L; mixing 5.5X 10-3Adding Tannin (TA) mmol to 25mL solution containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol)(400) 15:10) to obtain a nonaqueous complexing agent solution B, and dissolving 500mg of Li in the mixed solvent to obtain a nonaqueous complexing agent solution B1.2Mn0.54Ni0.13Co0.13O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the lithium-rich cathode material with the surface uniformly coated with the TA-Al complex layer, wherein the lithium-rich cathode material is named as Li1.2Mn0.54Ni0.13Co0.13O2@TA-Al-12nm；
(4) In the air atmosphere, the material obtained in the step (3) is heated to 400 ℃ at the heating rate of 3 ℃/min, is kept warm for 2h and is cooled to room temperature, and the Al of the invention is obtained2O3The lithium-rich cathode material with the surface uniformly coated is named as Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3。
As seen from the HR-TEM image of FIG. 4, the surface of the low-temperature heat-treated material had Al2O3The crystal structure of the back surface is not obviously changed;
battery assembly and electrochemical performance testing: li prepared as described above1.2Mn0.54Ni0.13Co0.13O2@Al2O3Mixing with polyvinylidene fluoride (PVDF) as a binder and a Super-P as a conductive agent in a mass ratio of 8:1:1, adding a proper amount of N-methylpyrrolidone (NMP) as a solvent to prepare slurry, uniformly coating the slurry on an aluminum foil by taking the aluminum foil as a current collector, and drying for 12 hours in vacuum at 100 ℃ to obtain Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3And (3) a composite positive electrode. Subsequently, the prepared composite positive electrode, the diaphragm, the electrolyte (EC/DEC (1: 1 by volume) solution of 1M LiPF 6), the lithium negative electrode, the positive electrode case, and the negative electrode case were assembled into a button lithium ion battery. Finally, the voltage of the battery is controlled within the range of 2-4.6V at 25 DEG CAnd carrying out constant current charge and discharge test. FIG. 6 is the above Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3Cycle performance plot of 100 cycles at 0.5C (1C ═ 200mA/g) rate for a battery with composite positive electrode as the positive electrode, Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3The capacity retention rate of the material is 80.3% after the material is cycled for 100 circles, which shows that the lithium-rich cathode material uniformly doped on the surface of the Al element can obviously improve the cycling stability of the battery. FIG. 7 is the above Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3Graph of change in median voltage during 100 cycles at 0.5C (1C ═ 200mA/g) rate for a battery with composite positive electrode as the positive electrode, Li1.2Mn0.54Ni0.13Co0.13O2@Al2O3The corresponding median voltage decayed only 0.3482V after 100 cycles, indicating Al2O3The discharge median voltage attenuation of the lithium-rich cathode material uniformly coated on the surface is relieved to a certain extent. Li as shown in FIG. 81.2Mn0.54Ni0.13Co0.13O2@Al2O3The multiplying power performance chart of the battery taking the composite anode as the anode in the intervals of 0.1C,0.2C,0.5C,1C,2C and 5C shows that Al2O3The rate capability of the lithium-rich cathode material with the uniformly coated surface is obviously improved.
Example 3
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 0.6 mmol/L; mixing 1.12X 10-2Adding Tannin (TA) mmol into 25mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio of 15:10), stirring to dissolve to obtain nonaqueous complexing agent solution B, and adding 500mg Li1.2Mn0.54Ni0.13Co0.13O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the lithium-rich cathode material with the surface uniformly coated with the TA-Al complex layer, wherein the lithium-rich cathode material is named as Li1.2Mn0.54Ni0.13Co0.13O2@TA-Al-3nm；
(4) In the air atmosphere, the material obtained in the step (3) is heated to 700 ℃ at the heating rate of 3 ℃/min, is kept warm for 2h and is cooled to room temperature, and the lithium-rich cathode material with the Al element surface uniformly doped is obtained, and is named as Li1.2Mn0.54Ni0.13Co0.13O2-Al-3。
The material is subjected to surface topography, and the material performance is not obviously changed after the TA-Al complex layer is uniformly coated on the surface, as shown in a figure 2 (2); meanwhile, as shown by TME diagram analysis in fig. 3(2), the TA-Al complex layer is about 3nm, which illustrates that compared with example 1, by simply reducing the addition amount of tannic acid, the thickness of the TA-Al complex coating layer on the surface of the material can be reduced, so that the doping amount of surface-doped Al element can be adjusted and controlled.
Example 4
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Tannin (TA) mmol into 25mL mixed solution containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:10), stirring to dissolve to obtain nonaqueous complexing agent solution B, and adding 500mg Li1.2Mn0.54Ni0.13Co0.13O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the lithium-rich cathode material with the surface uniformly coated with the TA-Al complex layer, wherein the lithium-rich cathode material is named as Li1.2Mn0.54Ni0.13Co0.13O2@TA-Al-20nm；
(4) In the air atmosphere, the material obtained in the step (3) is heated to 700 ℃ at the heating rate of 3 ℃/min, is kept warm for 2h and is cooled to room temperature, and the lithium-rich cathode material with the Al element surface uniformly doped is obtained, and is named as Li1.2Mn0.54Ni0.13Co0.13O2-Al-20。
The material is subjected to surface topography, and the performance of the material is not obviously changed after the TA-Al complex layer is uniformly coated on the surface, as shown in a figure 2 (4); meanwhile, as seen from the TEM images in fig. 3(4), the TA-Al complex layer is about 20nm, which illustrates that compared with examples 1 and 2, the thickness of the TA-Al complex coating layer on the surface of the material can be increased by simply increasing the addition amount of the tannic acid, so that the doping amount of the surface-doped Al element can be adjusted.
Example 5
(1) Stoichiometric FeCl3·6H2Dissolving O in 40mL of ethanol, and stirring to obtain a clear ferric chloride salt solution A with the concentration of 1.2 mmol/L; will be 1.6X 10-2Adding Tannin (TA) mmol into 25mL mixed solution containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:10), stirring to dissolve to obtain nonaqueous complexing agent solution B, and adding 500mg Li1.2Mn0.54Ni0.13Co0.13O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the lithium-rich cathode material with the surface uniformly coated with the TA-Fe complex coating layer, which is named as Li1.2Mn0.54Ni0.13Co0.13O2@TA-Fe-18nm；
(4) In the air atmosphere, heating the material obtained in the step (3) to 700 ℃ at the heating rate of 3 ℃/min, preserving the temperature for 2h, and cooling to room temperature to obtain the lithium-rich cathode material with the Fe element surface uniformly doped, wherein the lithium-rich cathode material is named as Li1.2Mn0.54Ni0.13Co0.13O2-Fe-18。
And carrying out structural and morphological characterization on the prepared cathode material. The TEM shows that the TA-Fe complex coating layer with a uniform surface is obtained, and the thickness of the coating layer is about 18nm, which shows that the method can still realize the uniform surface coating of the Fe complex coating layer, and further realize the uniform surface doping of the Fe element.
Example 6
(1) Stoichiometric MgCl2Dissolving in 40mL ethanol, and stirring to obtain a clear magnesium chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Tannin (TA) mmol into 20mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:5), stirring to dissolve to obtain nonaqueous complexing agent solution B, and adding LiMn 500mg0.54Ni0.13Co0.13O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain a lithium-rich cathode material with the surface uniformly coated with a TA-Mg complex coating layer, wherein the lithium-rich cathode material is named as Li1.2Mn0.54Ni0.13Co0.13O2@TA-Mg-15nm；
(4) In the air atmosphere, heating the material obtained in the step (3) to 700 ℃ at the heating rate of 3 ℃/min, preserving the temperature for 2h, and cooling to room temperature to obtain a lithium-rich cathode material with the Mg element surface uniformly doped, wherein the lithium-rich cathode material is named as Li1.2Mn0.54Ni0.13Co0.13O2-Mg-15。
And carrying out structural and morphological characterization on the prepared cathode material. The result of TEM shows that a TA-Mg complex coating layer with a uniform surface is obtained, the thickness of the coating layer is about 15nm, and the method shows that the complexation reaction rate of tannic acid and Mg ions can be controllably adjusted in a non-aqueous solvent by adjusting the proportion of ethanol and polyethylene glycol, so that the uniform surface coating of the Mg complex coating layer can be realized, and the uniform surface doping of Mg element can be realized.
Example 7
(1) Stoichiometric MoCl5Dissolving in 40mL ethanol, and stirring to obtain a clear molybdenum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Tannin (TA) mmol into 20mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:5), stirring to dissolve to obtain nonaqueous complexing agent solution B, and adding 500mg Li1.2Mn0.54Ni0.13Co0.13O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the lithium-rich cathode material with the surface uniformly coated with the TA-Mo complex coating layer, which is named as Li1.2Mn0.54Ni0.13Co0.13O2@TA-Mo-15nm；
(4) In the air atmosphere, heating the material obtained in the step (3) to 700 ℃ at the heating rate of 3 ℃/min, preserving the temperature for 2h, and cooling to room temperature to obtain the lithium-rich cathode material with the Mo element uniformly doped on the surface, wherein the lithium-rich cathode material is named as Li1.2Mn0.54Ni0.13Co0.13O2-Mo-15。
And carrying out structural and morphological characterization on the prepared cathode material. The TEM shows that the TA-Mo complex coating layer with a uniform surface is obtained, and the thickness of the coating layer is about 15nm, which indicates that the method can realize the uniform surface coating of the Mo complex coating layer and further realize the uniform surface doping of Mo element.
Example 8
(1) Adding stoichiometric SnCl4Dissolving in 40mL ethanol, and stirring to obtain a clear stannic chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Tannin (TA) mmol into 20mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) at volume ratio of 20:1), stirring and dissolvingHydrolyzing to obtain a non-aqueous complexing agent solution B, and adding 500mg of Li1.2Mn0.54Ni0.13Co0.13O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the lithium-rich anode material with the surface uniformly coated with the TA-Sn complex coating layer, which is named as Li1.2Mn0.54Ni0.13Co0.13O2@TA-Sn-12nm；
(4) In an air atmosphere, heating the material obtained in the step (3) to 700 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a lithium-rich cathode material with the Sn element surface uniformly doped, wherein the lithium-rich cathode material is named as Li1.2Mn0.54Ni0.13Co0.13O2-Sn-12。
And carrying out structural and morphological characterization on the prepared cathode material. The TEM shows that the TA-Sn complex coating layer with the uniform surface is obtained, and the thickness of the coating layer is about 12nm, which shows that the method can realize the uniform surface coating of the Sn complex coating layer and further realize the uniform surface doping of Sn element.
Example 9
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Tannin (TA) mmol into 25mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:10), stirring to dissolve to obtain nonaqueous complexing agent solution B, and adding LiNi 500mg0.8Co0.1Mn0.1O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2)Drying the anode material in a blast drying oven at 80 ℃ for 12 hours to obtain the high-nickel anode material with the surface uniformly coated with the TA-Al complex coating layer, which is named LiNi0.8Co0.1Mn0.1O2@TA-Al；
(4) In the air atmosphere, heating the material obtained in the step (3) to 700 ℃ at the heating rate of 3 ℃/min, preserving the temperature for 2h, and cooling to room temperature to obtain the high-nickel anode material with the Al element surface uniformly doped, wherein the high-nickel anode material is named as LiNi0.8Co0.1Mn0.1O2-Al。
For the preparation of LiNi0.8Co0.1Mn0.1O2And carrying out structural and morphological characterization on the positive electrode material. It is found from the TEM in fig. 9(1) that a TA-Al complex coating layer with a uniform surface is obtained, and the thickness of the coating layer is about 5nm, which indicates that the method can achieve uniform coating of the Al complex coating on the surface of the high-nickel ternary material of the lithium ion battery, and then achieve uniform doping of the surface of the Al element.
Example 10
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Tannin (TA) mmol into 25mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:10), stirring to dissolve to obtain non-aqueous complexing agent solution B, and adding 500mg LiCoO2Adding the materials into the suspension, uniformly stirring and ultrasonically treating the mixture to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain a lithium cobaltate positive electrode material with the surface uniformly coated with a TA-Al complex coating layer, wherein the lithium cobaltate positive electrode material is named as LiCoO2@TA-Al；
(4) In the air atmosphere, heating the material obtained in the step (3) to 700 ℃ at the heating rate of 3 ℃/min, preserving the temperature for 2h, and cooling to room temperature to obtain the lithium cobaltate cathode material with the Al element surface uniformly doped, wherein the lithium cobaltate cathode material is named as LiCoO2-Al。
For the preparation of LiCoO2And carrying out structural and morphological characterization on the positive electrode material. The TEM of fig. 9(2) shows that a TA-Al complex coating with a uniform surface is obtained, and the thickness of the coating is about 7nm, which indicates that the method can achieve uniform deposition of an Al complex on the surface of lithium layered cobaltate cathode material particles of a lithium ion battery, and then achieve uniform doping of the surface of Al element.
Example 11
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding mmol Tannic Acid (TA) into 20mL of mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) (Macrogol 400) volume ratio is 15:5), stirring and dissolving to obtain a non-aqueous complexing agent solution B, adding 10mg of Polystyrene (PS) material, stirring uniformly, and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain a material with the surface coated with the TA-Al complex, wherein the material is named as PS @ TA-Al-EtOH + Macrogol-400;
and carrying out structural and morphological characterization on the prepared PS @ TA-Al-EtOH + Macrogol-400. It is concluded from the TEM of FIG. 10(3) that a more uniform deposition of TA-Al complex on PS beads can be achieved in a mixed solution of ethanol and polyethylene glycol at a volume ratio of 15: 5.
Example 12
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding mmol Tannic Acid (TA) into 25mL of mixed solvent containing ethanol and polyethylene glycol (200) (ethanol: polyethylene glycol (200) (Macrogol 200) volume ratio is 15:10), stirring and dissolving to obtain nonaqueous complexing agent solution B, adding 10mg of Polystyrene (PS) material, stirring uniformly, and performing ultrasonic treatment to obtain suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain a material with the surface coated with the TA-Al complex, wherein the material is named as PS @ TA-Al-EtOH + Macrogol-200;
and carrying out structural and morphological characterization on the prepared PS @ TA-Al-EtOH + Macrogol-200. It is concluded from the TEM of FIG. 10(4) that a more uniform deposition of TA-Al complex on PS beads can be achieved in a mixed solution of ethanol and polyethylene glycol 200 at a volume ratio of 15: 10.
Example 13
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding mmol Tannic Acid (TA) into 20mL of mixed solvent containing ethanol and Polypropylene glycol (400) (Polypropylene glycol 400) (the volume ratio of ethanol to Polypropylene glycol (400) is 15:5), stirring and dissolving to obtain a non-aqueous complexing agent solution B, adding 10mg of Polystyrene (PS) material, stirring uniformly, and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain a material with the surface coated with the TA-Al complex, wherein the material is named as PS @ TA-Al-EtOH + PPG-400;
and carrying out structural and morphological characterization on the prepared PS @ TA-Al-EtOH + PPG-400. It is shown by TEM of FIG. 10(5) that relatively uniform deposition of TA-Al complex on PS beads can be achieved in a mixed solution of ethanol and polypropylene glycol 400 at a volume ratio of 15: 10.
Example 14
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2mmol of Tannic Acid (TA) was added to 20mL of a mixed solvent containing ethanol and α -propanediol (1,2-PG) (ethanol: α -propanediol in a volume ratio of 1:1)Stirring and dissolving to obtain a nonaqueous complexing agent solution B, adding 10mg of Polystyrene (PS) material, uniformly stirring, and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain a material with the surface coated with the TA-Al complex, wherein the material is named as PS @ TA-Al-EtOH +1, 2-PG;
and carrying out structural and morphological characterization on the prepared PS @ TA-Al-EtOH +1, 2-PG. It is concluded from the TEM of FIG. 10(6) that a more uniform deposition of TA-Al complex on PS beads can be achieved in a mixed solution of ethanol and α -propylene glycol at a volume ratio of 1: 1.
Comparative example 1
(1) Stoichiometric AlCl3Dissolved in 40mL of water (H)2O), stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding mmol Tannic Acid (TA) into 25mL of water, stirring and dissolving to obtain a complexing agent aqueous solution B, adding 10mg of Polystyrene (PS) material, stirring uniformly, and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain a material with the surface coated with the TA-Al complex, which is named as PS @ TA-Al-H2O；
For preparation of PS @ TA-Al-H2And O, carrying out structural and morphological characterization. It is shown by the TEM of FIG. 10(1) that TA-Al complex coating on PS beads is not achieved in aqueous solution.
Comparative example 2
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding mmol Tannic Acid (TA) into 25mL ethanol (EtOH), stirring to dissolve to obtain complexing agent ethanol solution B, and adding 1Adding 0mg of Polystyrene (PS) material, uniformly stirring and ultrasonically treating to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain a material with the surface coated with the TA-Al complex, wherein the material is named as PS @ TA-Al-EtOH;
and carrying out structural and morphological characterization on the prepared PS @ TA-Al-EtOH. It is shown by TEM of FIG. 10(2) that partial adsorption of TA-Al complex on PS beads was achieved in ethanol solution, but the TA-Al complex was not deposited on PS relatively uniformly.
Example 15
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding mmol Epicatechin (EC) into 25mL of mixed solvent containing ethanol and polyethylene glycol (400) (the volume ratio of the ethanol to the polypropylene glycol (400) is 15:10), stirring and dissolving to obtain a nonaqueous complexing agent solution B, adding 10mg of Polystyrene (PS) material, stirring uniformly, and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension B under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) and (3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the material with the surface coated with the EC-Al complex, which is named as PS @ EC-Al.
Example 16
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Epicatechin Gallate (EG) mmol into 25mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polypropylene glycol (400) volume ratio is 15:10), stirring to dissolve to obtain nonaqueous complexing agent solution B, adding Polystyrene (PS) 10mg, stirring, and dissolvingHomogenizing and ultrasonically treating to obtain a suspension C;
(2) dropwise adding the solution A into the suspension B under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) and (3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the material with the surface coated with the EG-Al complex, which is named as PS @ EG-Al.
Example 17
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding mmol Epigallocatechin (EGC) into 25mL mixed solvent containing ethanol and polyethylene glycol (400) (the volume ratio of ethanol to polypropylene glycol (400) is 15:10), stirring and dissolving to obtain a nonaqueous complexing agent solution B, adding 10mg of Polystyrene (PS) material, stirring uniformly, and performing ultrasound treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension B under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) and (3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in an air-blast drying oven at 80 ℃ for 12 hours to obtain the material with the surface coated with the EGC-Al complex, which is named as PS @ EGC-Al.
Example 18
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding mmol Gallocatechin gallate (GCG) into 25mL of mixed solvent containing ethanol and polyethylene glycol (400) (the volume ratio of ethanol to polypropylene glycol (400) is 15:10), stirring and dissolving to obtain nonaqueous complexing agent solution B, adding 10mg of Polystyrene (PS) material, stirring uniformly, and performing ultrasound treatment to obtain suspension C;
(2) dropwise adding the solution A into the suspension B under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) and (3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the material with the surface coated with the GCG-Al complex, wherein the material is named as PS @ GCG-Al.
Example 19
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Tannic Acid (TA) mmol to 25mL of mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:10), stirring to dissolve to obtain nonaqueous complexing agent solution B, and adding 500mg Na0.44MnO2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the sodium ion battery anode material with the surface uniformly coated with the TA-Al complex coating layer, wherein the name of the sodium ion battery anode material is Na0.44MnO2@TA-Al；
(4) In the air atmosphere, heating the material obtained in the step (3) to 700 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the sodium-ion battery anode material with the Al element surface uniformly doped, wherein the name of the sodium-ion battery anode material is Na0.44MnO2-Al。
Example 20
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Tannin (TA) mmol into 25mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:10), stirring to dissolve to obtain nonaqueous complexing agent solution B, and adding 500mgK5/ 9Mn7/9Ti2/9O2Adding the mixture into the solution, stirring the mixture evenly and performing ultrasonic treatment to obtain suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) will step withCentrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the potassium ion battery anode material with the surface uniformly coated with the TA-Al complex coating layer, which is named as K5/ 9Mn7/9Ti2/9O2@TA-Al；
(4) In the air atmosphere, heating the material obtained in the step (3) to 700 ℃ at the heating rate of 3 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain the potassium ion battery anode material with the Al element surface uniformly doped, wherein the name of the potassium ion battery anode material is K5/9Mn7/9Ti2/9O2。
Example 21
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding mmol Tannic Acid (TA) into 25mL of mixed solvent containing ethanol and polyethylene glycol (400) (the volume ratio of ethanol to polyethylene glycol (400) is 15:10), stirring and dissolving to obtain a non-aqueous complexing agent solution B, adding 10mg of carbon nanotubes, stirring uniformly, and performing ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a forced air drying oven at 80 ℃ for 12 hours to obtain the carbon nano tube with the surface uniformly coated with the TA-Al complex coating layer, wherein the name of the carbon nano tube is C @ TA-Al;
(4) and (3) under an air atmosphere, heating the material obtained in the step (3) to 700 ℃ at a heating rate of 3 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain the carbon nano tube with the Al element surface uniformly doped, wherein the carbon nano tube is named as C-Al.
Example 22
(1) Stoichiometric AlCl3Dissolving in 40mL of ethanol, and stirring to obtain a clear aluminum chloride salt solution A with the concentration of 1.2 mmol/L; mixing 1.6X 10-2Adding Tannin (TA) mmol into 25mL mixed solvent containing ethanol and polyethylene glycol (400) (ethanol: polyethylene glycol (400) volume ratio is 15:10), stirring and dissolving to obtain nonaqueous complexing agent solution B, and mixingAdding 10mg of silicon carbide fiber (SiCf) into the solution, uniformly stirring the solution and carrying out ultrasonic treatment to obtain a suspension C;
(2) dropwise adding the solution A into the suspension C under the condition of continuous stirring at room temperature, and continuously stirring for 10min after dropwise adding;
(3) centrifugally separating and washing the turbid liquid after the reaction in the step (2), and drying the turbid liquid in a blast drying oven at 80 ℃ for 12 hours to obtain the silicon carbide fiber with the surface uniformly coated with the TA-Al complex coating layer, wherein the silicon carbide fiber is named as SiCf @ TA-Al;
(4) and (3) under an air atmosphere, heating the material obtained in the step (3) to 700 ℃ at a heating rate of 3 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain the silicon carbide fiber with the Al element surface uniformly doped, wherein the silicon carbide fiber is named as SiCf-Al.

Claims (5)

1. A controllable method for realizing surface modification of an electrode material is characterized by comprising the following steps:
(1) adding soluble metal salt into ethanol, and uniformly stirring to obtain a solution A; the soluble metal salt is at least one of soluble metal salts containing IIA-VIA, IB-VIIB and VIII group metal elements;
(2) adding an organic complexing agent with at least two adjacent phenolic hydroxyl groups into a mixed solvent formed by ethanol and alcohol or an alcohol polymer with at least two hydroxyl groups, and uniformly stirring to obtain a non-aqueous complexing agent solution B; the organic matter complexing agent is at least one selected from tannic acid, epicatechin gallate, epigallocatechin and gallocatechin gallate;
(3) adding the electrode material into the nonaqueous complexing agent solution B, and uniformly stirring to obtain a suspension C;
(4) adding the solution A into the suspension C, uniformly stirring, and carrying out solid-liquid separation, washing and drying to obtain an electrode material with the surface uniformly coated with the metal ion complex layer;
(5) and calcining the electrode material with the surface uniformly coated with the metal ion complex layer to obtain the surface modified electrode material.
2. A controllable method for realizing surface modification of electrode material according to claim 1, characterized in that: in the step (2), the alcohol or alcohol polymer having at least two hydroxyl groups is at least one selected from polyethylene glycol, polypropylene glycol, ethylene glycol, and α -propylene glycol.
3. The controllable method for realizing the surface modification of the electrode material according to claim 1, characterized in that: in the step (3), the electrode material is a positive electrode material or a negative electrode material;
the anode material comprises a lithium ion battery oxide anode material, a sodium ion battery oxide anode material, a potassium ion battery oxide anode material, a lithium solid electrolyte oxide, a sodium solid electrolyte or a potassium solid electrolyte oxide;
the negative electrode material comprises Sn-based negative electrode material, Si-based negative electrode material, lithium titanate or carbon negative electrode material.
4. A controllable method for realizing surface modification of electrode material according to claim 1, characterized in that: in the step (5), the calcining temperature is not lower than 300 ℃, and the calcining time is not lower than 2 h.
5. A controllable method for realizing surface modification of electrode material according to claim 4, characterized in that: in the step (5), the calcining temperature is 400-800 ℃, and the calcining time is 2-12 h.
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