CN111883748A - Method for coating oxide film on surface of lithium ion battery anode powder material - Google Patents
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Abstract
The invention discloses a method for coating an oxide film on the surface of a lithium ion battery anode powder material. The method comprises the following steps: firstly, pre-coating a positive electrode powder material by using a vaporized precursor, then putting the positive electrode powder material into oxygen-containing plasma, and oxidizing oxygen active particles to form a metal oxide film; or directly introducing the vaporized precursor into oxygen-containing plasma, oxidizing and decomposing the precursor under the action of oxygen and the plasma, and depositing the precursor on the surface of the anode material to form an oxide film to finish coating. The oxide film prepared by the method is completely and uniformly coated and is tightly combined with the anode material, so that the electrochemical performance of the material can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of surface coating of powder materials, and particularly relates to a method for coating an oxide film on the surface of a lithium ion battery anode powder material.
Background
At present, lithium iron phosphate, lithium cobaltate, ternary lithium and the like are mainstream lithium ion battery anode materials in the market. The nickel-rich anode material in the ternary lithium has high energy density and relatively low production cost, and has great application prospect in power batteries and energy storage batteries. However, the nickel-rich material has insufficient cycle performance and safety, and the surface of the nickel-rich material is coated, so that the structure of the electrode material can be stabilized, the corrosion of electrolyte to the anode material is relieved, and the cycle life and the safety of the battery are improved.
The plasma is a fourth state of matter except solid, liquid and gaseous, has some special properties, is commonly used in the surface treatment process of materials, and can greatly reduce the temperature required by reaction, accelerate or simplify the treatment process, improve the treatment quality and the like.
For example, in chinese patent application publication No. CN 108258224 a, a ternary cathode material with a metal oxide coated on the surface and a preparation method thereof are disclosed, in which plasma assistance is mainly added on the basis of high-energy ball milling, and only one-step discharge ball milling is required, a metal oxide coating layer can be prepared on the surface of the ternary cathode material, thereby eliminating the step of further chemical reaction or heat treatment required by the conventional ball milling method. The metal oxide and the surface of the ternary material have stronger bonding force and more uniform and efficient coating through the synergistic effect of mechanical energy and plasma energy, but the metal oxide and the ternary material are still solid-phase coating in nature, and the coating uniformity and controllability are far inferior to those of liquid-phase coating and gas-phase coating.
For example, patent application publication No. CN 108615863a discloses an atomic layer coating method for a positive electrode material of a ternary lithium battery. Firstly, ball-milling and pressing an anode material into a sheet shape, ionizing metal-organic compound steam loaded by an air source into plasma under the action of microwaves, uniformly diffusing the plasma to an atomic level through high dispersibility of the argon plasma, combining the plasma with hydroxyl on the surface layer of the sheet-shaped ternary material to form an M1-O-M2-R structure, and then fluorinating a substituent R group to form the metal fluoride salt coated ternary anode material. The method is a method for assisting plasma on an atomic layer deposition method, is a high-precision surface coating technology, is still in a research stage in the surface modification of powder particles due to the self-limiting reaction characteristic, and is rarely reported. The method needs to use a precursor with very high reaction activity and high risk, has very strict requirements on the used equipment and has high production cost. Therefore, the method has very important significance for improving the surface coating uniformity of the anode material powder at lower cost.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a method for coating an oxide film on the surface of a lithium ion battery anode powder material, so as to overcome the defect that the uniformity and integrity of the coating on the surface of lithium ion battery anode powder particles are not easy to control in the prior art, and further effectively improve the electrochemical performance of the coated anode material.
The purpose of the invention is realized by the following technical scheme:
a method for coating an oxide film on the surface of a lithium ion battery anode powder material comprises the following steps:
in the first mode, the anode powder material of the lithium ion battery is in a motion state, a vaporized precursor is introduced, pretreatment is carried out for 5-100 min, the precursor is adsorbed on the surface of anode powder material particles, and then the precursor is oxidized into an oxide film in a plasma environment with the oxygen partial pressure of 5-100% and the temperature of 25-500 ℃, so that coating is completed;
wherein the precursor is a metal organic compound and/or silane, and the saturated vapor pressure of the precursor at 20 ℃ is lower than 10 torr;
or in the second mode, placing the lithium ion battery anode powder material in a moving state in a plasma environment with the oxygen partial pressure of 5-100% and the temperature of 25-500 ℃, introducing the vaporized precursor, decomposing and oxidizing the precursor under the action of oxygen and plasma, depositing the precursor on the surface of the anode powder material to form an oxide film, and finishing coating;
the precursor is a metal organic compound and/or silane, and the saturated vapor pressure of the precursor at 20 ℃ is higher than 10 torr.
The oxygen partial pressure refers to the pressure ratio of oxygen to the gas in the whole reaction chamber.
Preferably, the oxygen partial pressure is 50-100%; the temperature is 25-200 ℃. The upper limit of the temperature is related to the temperature resistance of the equipment materials used in the coating process.
Preferably, the discharge power of the plasma is 50-500W, and more preferably 150-300W; the discharge time is 10-150 min, more preferably 30-80 min, and most preferably 60 min.
Preferably, the plasma discharge mode is at least one of glow discharge, dielectric barrier discharge, corona discharge, sliding arc discharge and high-frequency discharge.
Preferably, the pretreatment time is 30-80 min.
Preferably, the mass ratio of the precursor to the lithium ion battery anode powder material is 1-10: 100, more preferably 1-3: 100, respectively; most preferably 1-2: 100.
preferably, the metal organic compound is at least one of an organic aluminum compound, an organic silicon compound, an organic titanium compound, an organic zinc compound and an organic zirconium compound; more preferably triethylaluminum, triisobutylaluminum, diethylaluminum chloride, di-sec-butoxyaluminum ethylacetoacetate, aluminum ethylacetoacetate, di-sec-butoxyaluminum acetylacetonate, triisopropylaluminate, distearoyloxyisopropylaluminate, ethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, triisostearoylisopropyl titanate, tetraoctyloxytitanium, stearyl titanate, diisopropoxybis-acetylacetonatotitanium, isopropoxytitanium, titanium lactate, dicyclopentadienyl titanium, diphenyl titanium, dimethylmagnesium, ethylethoxymagnesium, metallocenes, tetra-n-propylzirconate, alkoxytris (vinyl-ethoxy) zirconate, tetra (triethanolamine) zirconate, zirconium acetylacetonate, n-propoxide, zirconium n-butoxide, zirconium isopropoxide, biscyclopentadienyldimethylzirconium, dicyclopentadiene dihydride, dimethyl bis (tert-butylcyclopentadienyl) zirconium, At least one of zirconium tetraethoxide, diethyl zinc, di (pentamethylcyclopentadienyl) zinc, dimethyl zinc and monoethyl zinc; most preferred is at least one of butyl titanate and triisobutylaluminum.
Preferably, the silanes are all octamethylcyclotetrasiloxane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, vinyltrimethoxysilane, thiopropyltrimethoxysilane, trialkoxysilane, propenyl (chloromethyl) dimethylsilane, monosilane, disilane, octa (trimethylsiloxane) silsesquioxane, acetoxypropylmethyldichlorosilane, 1-dimethyl-1, 2-siloxaneoxane, dimethylethyloxyformyloxysilane, bis (methacryloyloxyethyloxy) diphenylsilane, acryloxymethyltrimethoxysilane, diphenylmethoxydiacetoxysilane, 2-dimethyl-1, 3,6,9,12, 15-hexaoxa-2-silaheptadecane, 1,1,1,3, 3-pentamethyl-3-acetoxydisiloxane, 1, 1-diethoxy-1-silacyclopentyl-3-ene, 3-trimethylsilane-1-propanol, 1, 1-dimethylsilyl-14-crown 5, 1,1,3, 3-tetramethyl-1, 3-disilacyclobutane, trimethylsilylpentamethylcyclopentadiene, 1, 3-divinyltetrakis (trimethylsiloxy) disiloxane, 3- (3-hydroxypropyl) heptamethyltrisiloxane, 1, 1-dimethylsila-11-crown-4, 1, 3-bis (3-methacryloyloxypropyl) tetrakis (trimethylsiloxy) disiloxane, a salt of a compound of formula (I), a salt of a compound of formula (II), a salt of a compound of formula (III, Methacryloxypentamethyldisiloxane, oxymethyltris (trimethylsiloxy) silane, p-ethylphenylethyl) trimethoxysilane, methylstyrenesilane, trimethylsilyl 3- (trimethylsilyl) propiolic acid, 1, 2-bis (methyldimethoxysilyl) ethane, tris (methoxyethoxy) propyloxysilane, 1- (tert-butyldimethylsiloxy) 2-propanone, 2-acryloyloxyethyltrimethylsilane, trimethylsilanolate, 1, 4-bis (trimethoxysilylmethyl) benzene, triethoxyphenylethoxycarboxysilane, phenylacetoxytrimethylsilane, phenyldiethoxysilane, 4- (trimethylsilylethynyl) benzoic acid, tert-butyldiphenylmethoxysilane, tert-butyltrimethylsilylacetic acid, and mixtures thereof, At least one of methylvinylphenylmethoxysilane, (4-methoxybenzyl) trimethylsilane, (4-methoxyphenylethynyl) trimethylsilane, 2-bis [ (4-trimethylsiloxy) phenyl ] propane, tetrakis (phenylethynyl) silane, tetraethylcyclotetrasiloxane and (Z) -2, 6-diphenylhexamethylcyclotetrasiloxane; more preferably hexamethyldisiloxane.
Preferably, the lithium ion battery anode powder material can be in a motion state by any one of turning, stirring, rotating and suspending, so as to ensure that a fresh surface of the powder is continuously exposed in a plasma environment.
More preferably, the turning and stirring modes can be realized by arranging a stirring paddle in a container, the rotating speed is controllable, the shape of the paddle is not limited as long as all powder in the container can be turned, the rotating mode can be realized by rotating the container filled with the powder in the surface treatment process, the rotating speed is controllable, the inner wall of the container can be provided with a groove to increase the turning amplitude of the powder or increase the roughness of the inner wall of the container as long as the powder can not slide when the container rotates, and the rotating speeds of the turning, stirring and container rotating are 5-50 rpm, preferably 10-30 rpm.
The lithium ion battery anode material powder is in a motion state in the pretreatment process, preferably, a suspension mode is adopted, the suspension mode can be realized through an air jet mill or high-speed dispersion, and the high-speed dispersion rotating speed is 1000-5000 rpm, and more preferably 2000-4000 rpm.
Preferably, the anode powder materials of the lithium ion battery are all Li1+xNiyCozMnsMtO2-rWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, t is more than or equal to 0 and less than or equal to 1, and r is more than or equal to 0 and; or LiMn2-xMxO4Wherein x is more than or equal to 0 and less than or equal to 0.5; or LiFe1- xMxPO4Wherein x is more than or equal to 0 and less than or equal to 1; more preferably at least one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium iron phosphate, lithium cobaltate, lithium manganate and lithium nickelate; more preferably LiCoO2、LiNiO2、LiMnO2、LiFePO4、LiMn2O4、LiNi0.5Mn0.2Co0.3、LiNi0.8Mn0.1Co0.1、LiNi0.85Co0.1Al0.05At least one of; most preferably LiNi0.8Co0.15Al0.05O2。
Preferably, the thickness of the oxide film is 1-100 nm, more preferably 5-20 nm, and most preferably 10-15 nm, so that the direct contact between the surface of the material and the electrolyte can be effectively prevented, and the negative influence on the ionic and electronic conductivity of the cathode material can be reduced.
Preferably, the oxide film is at least one of aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide, silicon oxide and zinc oxide film; more preferably at least one of titanium oxide, aluminum oxide and silicon oxide thin film.
Preferably, the surface of the lithium ion battery anode powder material can be coated with a single oxide film or a composite oxide film, or can be coated with more than one layer of oxide film.
The precursor has a saturated vapor pressure of less than 10torr (20 ℃) and is difficult to vaporize by conventional means such as low pressure, heating (<120 ℃).
The saturated vapor pressure of the precursor is higher than 10torr (20 ℃), and the precursor is easy to vaporize.
The lithium ion battery anode powder material is in a motion state in the pretreatment and plasma discharge treatment processes so as to ensure that a fresh surface of the powder is continuously exposed in a plasma environment.
The reaction-deposited coating layer in the present invention is a vapor coating. Compared with the liquid and solid coating methods, the gaseous coating method can improve the contact integrity between the coating material and the coated powder to the maximum extent, and the powder is in a continuous motion state in the treatment process, so that the coating conformality, uniformity and integrity are good.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention carries out coating on the surface of the anode material through the gas phase, and the coating integrity and uniformity are superior to those of liquid phase and solid phase coating. The method utilizes plasma discharge to decompose and oxidize metal organic compounds or silane, and grows a film on the surface of the anode material powder in a turning state in situ. Most metal oxides can finish the surface coating of the anode material in a second mode, namely in the one-step discharge treatment process, no additional high-temperature treatment step is needed, and the energy consumption is low; the obtained coating layer is tightly, uniformly and completely combined with the anode material; and in the second mode, the thickness of the coating layer can be controlled by adjusting parameters such as discharge power, discharge time, oxygen content and the like. The process is simple, low in energy consumption, environment-friendly, low in toxicity and wide in application range, realizes nanoscale uniform coating of particles of the positive electrode material for the lithium ion battery, and effectively improves the electrochemical performance of the positive electrode material.
Drawings
FIG. 1 is a schematic diagram of the deposition mechanism of example 3.
Figure 2 XRD pattern of example 1.
Figure 3 XRD pattern of example 2.
Figure 4 XRD pattern of example 3.
Figure 5 XRD pattern of comparative example 1.
Figure 6 XRD pattern of comparative example 2.
Figure 7 is a graph comparing XPS data Si2p for example 3 and comparative example 1.
Fig. 8 is a graph showing the first charge and discharge curves of example 3 and comparative examples 1 and 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
The plasma discharge modes in the examples and comparative examples of the present application were glow discharge.
Example 1
In the embodiment, the coating material is titanium oxide, the used precursor is butyl titanate, the molecular weight of the butyl titanate is 340.36, the boiling point of the butyl titanate is 310-314 ℃, the butyl titanate is difficult to vaporize at normal temperature, and the surface coating is carried out by adopting the first mode of the invention. The specific implementation steps are as follows:
firstly, anode powder material LiNi is adopted0.8Co0.15Al0.05O2(hereinafter referred to as NCA) was placed in a high-speed disperser, and the powder was suspended by a fly cutter rotating at 2000 rpm. And after 5min, carrying the butyl titanate into a high-speed dispersion machine by using a carrier gas, wherein the processing time is 30min, and the NCA powder is in full contact with vaporized butyl titanate, wherein the mass ratio of the butyl titanate to the NCA powder is 2: 100. The obtained NCA powder material having butyl titanate adsorbed on the surface was placed in a plasma reaction chamber, and the container in which the NCA was placed was rotated at a set rotation speed of 15 rpm. The reaction chamber is evacuated to less than 10Pa without additional heating, and then O is introduced at a flow rate of 40sccm2(i.e., oxygen partial pressure of 100%). After the gas pressure in the reaction chamber is stabilized, the plasma discharge power supply is turned on, and the plasma surface treatment can be started by setting the discharge power to 300W. By O in plasma2The generated high-energy particles oxidize the tetrabutyl titanate adsorbed on the surface of the anode material to form a titanium oxide film, and CO are generated2And the byproduct gas is pumped out of the reaction chamber. And (3) after the discharge time is 60min, the discharge power supply can be turned off, and the surface treatment process of the plasma is finished to obtain the NCA cathode material with the surface coated with the titanium oxide. The XRD pattern of the resulting sample is shown in FIG. 2, with all characteristic peaks still corresponding to α -NaFeO2Structural R3m space group. The coated sample is prepared into a power-on state, and the initial discharge specific capacity of the coated sample is tested to be 189.7mAhg at the speed of 0.1C at normal temperature through a blue test system-1。
Example 2
In this example, the coating material was alumina, triisobutylaluminum was used as a precursor, the molecular weight of the monomer was 198.33, the boiling point was 86 ℃, and the surface coating was performed by the second embodiment of the present invention.
Firstly, NCA powder material is put into a plasma reaction chamber, and NC is put into the plasma reaction chamberThe container for A was rotated, and the reaction chamber was evacuated to 10Pa or less at a rotation speed of 15rpm, with 50g of NCA powder placed therein, without additional heating. Then the flow rate was adjusted at 20 sccm: introducing O at a flow rate of 20sccm2And triisobutylaluminum (mass ratio of triisobutylaluminum to NCA is 1.2: 100, oxygen partial pressure is 50%), starting a plasma discharge power supply after the air pressure in the reaction chamber is stabilized, setting the discharge power to be 150W, starting plasma surface treatment, closing the discharge power supply after discharging for 60min, and ending the plasma surface treatment process to obtain the NCA cathode material with the surface coated with aluminum oxide. The XRD pattern of the resulting sample is shown in FIG. 3, with all characteristic peaks still corresponding to α -NaFeO2Structural R3m space group. The coated sample is prepared into a power-on state, and the initial discharge specific capacity of the coated sample is 193.4mAhg which is tested by a blue test system at the normal temperature at the speed of 0.1C-1。
Example 3
In this example, the coating material was silicon oxide, the precursor used was Hexamethyldisiloxane (HMDSO), the molecular weight of the monomer was 162.38, the boiling point was 99.5 ℃, and the monomer was vaporized at room temperature under low pressure, so surface coating was performed using the second embodiment of the present invention.
Firstly, 50g of NCA powder material is put into a plasma reaction chamber, wherein a container for placing the NCA can rotate, the rotating speed of the container for placing the NCA powder is set to be 15rpm, and the reaction chamber is vacuumized to be within 10Pa without additional heating. Then the flow rate was adjusted at 20 sccm: introducing O at a flow rate of 20sccm2And HMDSO (the mass ratio of the HMDSO to the NCA is 1: 100, the oxygen partial pressure is 50%), after the air pressure in the reaction chamber is stable, a plasma discharge power supply is turned on, the discharge power is set to be 150W, the plasma surface treatment can be started, the discharge power supply can be turned off after discharging for 60min, and the plasma surface treatment process is finished, so that the NCA cathode material with the surface coated with silicon oxide is obtained. The XRD pattern of the resulting sample is shown in FIG. 4, with all characteristic peaks still corresponding to α -NaFeO2Structural R3m space group. The XPS spectrum of example 3 in FIG. 7 shows that the peak position of Si2p is close to 103.5eV, and is in SiO2Chemical state of (a). The coated sample is prepared into a power-on state and is subjected to a blue light test system at normal temperatureThe initial specific discharge capacity of the material is 201.9mAhg when the rate of 0.1C is tested-1。
Example 4
In the same manner as in example 1, the surface of NCA particles was coated with a titanium oxide film, and then placed in a plasma chamber, followed by coating with a silicon oxide film in accordance with the procedure of example 2, to obtain a double-coated NCA positive electrode material.
Example 5
In the same manner as in example 3, the surface of NCA particles was coated with a silicon oxide film using HMDSO as a precursor. Then, the procedure is repeated, and the surface of the titanium oxide film is coated with ethyl titanate as a precursor, and the construction parameters are the same as those in example 3, so that the NCA positive electrode material with double coating layers can be obtained.
Comparative example 1
Similar to the operation of example 3, the surface of NCA material was coated with silicon oxide using hexamethyldisiloxane as a precursor, 50g of NCA powder material was placed in a plasma reaction chamber, the rotation speed of the container holding the NCA powder was set at 15rpm, and the reaction chamber was evacuated to within 10Pa without additional heating. Then the flow rate was measured at 1 sccm: flow rate ratio of 40sccm O2And HMDSO (the mass ratio of HMDSO to NCA is 1: 100, the oxygen partial pressure is 2.5%), after the air pressure in the reaction chamber is stable, the plasma discharge power supply is turned on, the discharge power is set to be 150W, the plasma surface treatment can be started, the discharge power supply can be turned off after discharging for 60min, and the plasma surface treatment process is finished. Because the oxygen content in the plasma discharge process is very low, the deposited film is difficult to be completely oxidized, and the carbon content of the prepared coating layer is greatly increased. The XRD pattern of the resulting sample is shown in FIG. 5, with all characteristic peaks still corresponding to α -NaFeO2R3m space group of the structure, SiO was not observed2Peaks are present. As shown in FIG. 7, the peak of Si2p for the sample prepared in example 3 was at 103.4eV, which is the chemical state of silicon oxide, while the peak of Si2p for the sample of comparative example was at 101.7eV, which is the chemical state of silicone. The density of the organic silicon is lower than that of silicon oxide, so that the coating layer prepared in the comparative example cannot well prevent the contact of the electrolyte and the anode material, and the improvement effect on the battery performance is not obvious. By coating the coated sampleThe product is prepared into a discharge circuit, and the initial discharge specific capacity of the product is 181.9mAhg when the product is tested at the speed of 0.1C by a blue light test system at normal temperature-1。
Comparative example 2
Similar to the operation of example 3, with hexamethyldisiloxane as a precursor, 50g of NCA powder material was placed in a plasma reaction chamber, the rotation speed of a container for placing NCA powder was set at 15rpm, the reaction chamber was evacuated to within 10Pa, and the temperature was heated to 600 ℃. Then the flow rate was adjusted at 20 sccm: flow rate ratio of 20sccm into O2And HMDSO (the mass ratio of HMDSO to NCA is 1: 100, the oxygen partial pressure is 50%), after the air pressure in the reaction chamber is stable, the plasma discharge power supply is turned on, the discharge power is set to be 150W, the plasma surface treatment can be started, the discharge power supply can be turned off after discharging for 60min, and the plasma surface treatment process is finished. The heating temperature is properly increased in the plasma surface treatment process, which is beneficial to the improvement of the crystallinity of the coating layer. However, the excessive temperature causes the lithium-nickel mixed discharging degree of the NCA material to be deepened, and the specific capacity of the material is reduced. As shown in Table 1, the ratio of I (003)/I (104) is 1.16, and generally, the ratio is larger than 1.2, so that the material has low degree of lithium-nickel segregation. The coated sample is prepared into a power-on state, and the initial discharge specific capacity of the coated sample is 155.9mAhg when the coated sample is tested at the speed of 0.1C under normal temperature by a blue light test system-1。
TABLE 1 table of I (003)/I (104) peak intensity ratios in XRD patterns of examples and comparative examples
| Sample (I) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| I(003)/I(104) | 1.32 | 1.34 | 1.32 | 1.31 | 1.33 | 1.33 | 1.16 |
TABLE 2 first Charge-discharge specific capacity tables of examples 1 to 3 and comparative examples 1 to 2
| Sample (I) | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Specific capacity of first discharge/mAhg-1 | 189.7 | 193.4 | 201.9 | 181.9 | 155.9 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for coating an oxide film on the surface of a lithium ion battery anode powder material is characterized by comprising the following steps:
enabling the lithium ion battery anode powder material to be in a motion state, introducing a vaporized precursor, pretreating for 5-100 min to enable the precursor to be adsorbed on the surface of anode powder material particles, and oxidizing the precursor into an oxide film in a plasma environment with the oxygen partial pressure of 5-100% and the temperature of 25-500 ℃ to finish coating;
or placing the lithium ion battery anode powder material in a moving state in a plasma environment with the oxygen partial pressure of 5-100% and the temperature of 25-500 ℃, introducing a vaporized precursor, decomposing and oxidizing the precursor under the action of oxygen and plasma, depositing the precursor on the surface of the anode powder material to form an oxide film, and finishing coating;
wherein the precursor is a metal organic compound and/or silane.
2. The method for coating the oxide film on the surface of the lithium ion battery anode powder material according to claim 1, wherein the saturated vapor pressure of the precursor at 20 ℃ in the first method is lower than 10torr, the saturated vapor pressure of the precursor at 20 ℃ in the second method is higher than 10torr, and the mass ratio of the precursor to the lithium ion battery anode powder material is 1-10: 100.
3. The method for coating the oxide film on the surface of the lithium ion battery anode powder material according to claim 1, wherein the oxygen partial pressure is 50-100%; the temperature is 25-200 ℃.
4. The method for coating the oxide film on the surface of the lithium ion battery anode powder material according to claim 1, wherein the discharge power of the plasma is 50-500W, and the discharge time is 10-150 min.
5. The method for coating the oxide film on the surface of the lithium ion battery anode powder material according to claim 1,2, 3 or 4, wherein the metal organic compound is at least one of an organic aluminum compound, an organic silicon compound, an organic titanium compound, an organic zinc compound and an organic zirconium compound;
the anode powder materials of the lithium ion battery are all Li1+xNiyCozMnsMtO2-rWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, t is more than or equal to 0 and less than or equal to 1, and r is more than or equal to 0 and; or LiMn2-xMxO4Wherein x is more than or equal to 0 and less than or equal to 0.5; or LiFe1-xMxPO4Wherein x is more than or equal to 0 and less than or equal to 1;
the oxide film is at least one of aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide, silicon oxide and zinc oxide film.
6. The method of claim 5, wherein the metal organic compound is triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, di-sec-butoxy aluminum ethyl acetoacetate, di-sec-butoxy aluminum acetyl acetonate, triisopropyl aluminate, distearoyl isopropyl aluminate, ethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, triisostearyl isopropyl titanate, tetraoctyloxy titanium, stearyl titanate, diisopropoxy bis-acetylacetonato titanium, isopropoxy titanium, titanium lactate, dicyclopentadienyl titanium, diphenyl titanium, dimethyl magnesium, ethyl ethoxy magnesium, dicyclopentadienyl magnesium, tetra-n-propyl zirconate, alkoxy tri (vinyl-ethoxy) zirconate, tetra (triethanolamine) zirconate, zirconium acetylacetonate, zirconium oxide, aluminum oxide, triisopropyl titanate, triisobutyl titanate, triisostearyl titanate, tetraoctyloxy titanium, stearyl titanate, diisopropoxy bis-acetylacetonato titanium, diisopropoxy titanium lactate, dicyclopentadienyl titanium, diphenyl titanium, dimethyl magnesium, at least one of zirconium n-propoxide, zirconium n-butoxide, zirconium isopropoxide, biscyclopentadienyldimethylzirconium, dicyclopentadiene zirconium dihydride, dimethylbis (tert-butylcyclopentadienyl) zirconium, tetraethoxyzirconium, diethylzinc, bis (pentamethylcyclopentadienylzinc, dimethylzinc and monoethylzinc;
the silanes are all octamethylcyclotetrasiloxane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, vinyltrimethoxysilane, thiopropyltrimethoxysilane, trialkoxysilane, propenyl (chloromethyl) dimethylsilane, monosilane, disilane, octa (trimethylsiloxane) silsesquioxane, acetoxypropylmethyldichlorosilane, 1-dimethyl-1, 2-siloxaneoxane, dimethylethyloxyformyloxysilane, bis (methacryloyloxyethyloxy) diphenylsilane, acryloxymethyltrimethoxysilane, diphenylmethoxydiacetoxysilane, 2-dimethyl-1, 3,6,9,12, 15-hexaoxa-2-silaheptadecane, 1,1,1,3, 3-pentamethyl-3-acetoxydisiloxane, 1, 1-diethoxy-1-silacyclopentyl-3-ene, 3-trimethylsilane-1-propanol, 1, 1-dimethylsilyl-14-crown 5, 1,1,3, 3-tetramethyl-1, 3-disilacyclobutane, trimethylsilylpentamethylcyclopentadiene, 1, 3-divinyltetrakis (trimethylsiloxy) disiloxane, 3- (3-hydroxypropyl) heptamethyltrisiloxane, 1, 1-dimethylsila-11-crown-4, 1, 3-bis (3-methacryloyloxypropyl) tetrakis (trimethylsiloxy) disiloxane, a salt of a compound of formula (I), a salt of a compound of formula (II), a salt of a compound of formula (III, Methacryloxypentamethyldisiloxane, oxymethyltris (trimethylsiloxy) silane, p-ethylphenylethyl) trimethoxysilane, methylstyrenesilane, trimethylsilyl 3- (trimethylsilyl) propiolic acid, 1, 2-bis (methyldimethoxysilyl) ethane, tris (methoxyethoxy) propyloxysilane, 1- (tert-butyldimethylsiloxy) 2-propanone, 2-acryloyloxyethyltrimethylsilane, trimethylsilanolate, 1, 4-bis (trimethoxysilylmethyl) benzene, triethoxyphenylethoxycarboxysilane, phenylacetoxytrimethylsilane, phenyldiethoxysilane, 4- (trimethylsilylethynyl) benzoic acid, tert-butyldiphenylmethoxysilane, tert-butyltrimethylsilylacetic acid, and mixtures thereof, At least one of methylvinylphenylmethoxysilane, (4-methoxybenzyl) trimethylsilane, (4-methoxyphenylethynyl) trimethylsilane, 2-bis [ (4-trimethylsiloxy) phenyl ] propane, tetrakis (phenylethynyl) silane, tetraethylcyclotetrasiloxane and (Z) -2, 6-diphenylhexamethylcyclotetrasiloxane;
the lithium ion battery anode powder material is at least one of nickel cobalt lithium manganate, nickel cobalt lithium aluminate, lithium iron phosphate, lithium cobaltate, lithium manganate and lithium nickelate;
the oxide film is at least one of titanium oxide, aluminum oxide and silicon oxide film.
7. The method for coating the oxide film on the surface of the lithium ion battery anode powder material according to claim 6, wherein the metal organic compound is at least one of butyl titanate and triisobutyl aluminum;
the anode powder material of the lithium ion battery is LiCoO2、LiNiO2、LiMnO2、LiFePO4、LiMn2O4、LiNi0.5Mn0.2Co0.3、LiNi0.8Mn0.1Co0.1、LiNi0.85Co0.1Al0.05At least one of;
the silane is hexamethyldisiloxane.
8. The method for coating the oxide film on the surface of the lithium ion battery anode powder material according to claim 5, wherein the pretreatment time is 30-80 min; the discharge power of the plasma is 150-300W; the discharge time is 30-80 min; the mass ratio of the precursor to the lithium ion battery anode powder material is 1-3: 100.
9. the method for coating the oxide film on the surface of the lithium ion battery anode powder material according to claim 5, wherein the thickness of the oxide film is 1-100 nm; the lithium ion battery anode powder material can be in a motion state by any one of turning, stirring, rotating and suspending; the rotation speed of the turning, stirring and container rotation is 5-50 rpm;
the lithium ion battery anode material powder is in a motion state in the pretreatment process and is realized in a suspension mode, the suspension mode can be realized through an air jet mill or high-speed dispersion, and the high-speed dispersion rotating speed is 1000-5000 rpm.
10. The method for coating the oxide film on the surface of the lithium ion battery anode powder material according to claim 5, wherein the plasma discharge mode is at least one of glow discharge, dielectric barrier discharge, corona discharge, sliding arc discharge and high-frequency discharge; the thickness of the oxide film is 5-20 nm.
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