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CN113437270A - Double-layer coating modified lithium ion battery anode material powder and preparation method thereof - Google Patents

Double-layer coating modified lithium ion battery anode material powder and preparation method thereof Download PDF

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CN113437270A
CN113437270A CN202110666675.XA CN202110666675A CN113437270A CN 113437270 A CN113437270 A CN 113437270A CN 202110666675 A CN202110666675 A CN 202110666675A CN 113437270 A CN113437270 A CN 113437270A
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coating
positive electrode
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ion battery
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陈益钢
费哲伟
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University of Shanghai for Science and Technology
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Abstract

本发明公开了一种双层包覆层改性锂离子电池正极材料粉体及其制备方法，基体材料为镍钴锰酸锂三元正极，第一层包覆层为导电的碳纳米球涂层，第二层包覆层为金属氧化物涂层。其中，所述第一层碳纳米球涂层由湿法分散‑烧结法制备；所述第二层金属氧化物涂层由磁控溅射法制备，最终形成碳纳米球/金属氧化物双层涂层。本发明所述的双层包覆层有效的解决的单层金属氧化物涂层导电性不佳的问题，同时还阻止了循环中电解液中少量的HF对正极材料的腐蚀作用，因此双层包覆后的正极材料具有高的倍率性能、高比容量以及良好的循环性能；同时，本发明方法简单、易于操作适合大规模产业化生产。

Figure 202110666675

The invention discloses a double-layer coating layer modified lithium ion battery positive electrode material powder and a preparation method thereof. The base material is nickel-cobalt lithium manganate ternary positive electrode, and the first coating layer is a conductive carbon nanosphere layer, and the second cladding layer is a metal oxide coating. Wherein, the first layer of carbon nanosphere coating is prepared by wet dispersion-sintering method; the second layer of metal oxide coating is prepared by magnetron sputtering method, and finally a carbon nanosphere/metal oxide double layer is formed coating. The double-layer coating layer of the present invention effectively solves the problem of poor electrical conductivity of the single-layer metal oxide coating, and also prevents the corrosive effect of a small amount of HF in the electrolyte on the positive electrode material during the cycle. The coated positive electrode material has high rate performance, high specific capacity and good cycle performance; meanwhile, the method of the invention is simple and easy to operate, and is suitable for large-scale industrial production.

Figure 202110666675

Description

Double-layer coating modified lithium ion battery anode material powder and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, particularly relates to a layered transition metal oxide ternary cathode material, and particularly relates to a double-coating-layer modified lithium ion battery cathode material powder and a preparation method thereof.
Background
With the rapid change of portable electronic devices and the accelerated popularization of new energy electric vehicles, lithium ion batteries with higher energy density and power density are required. However, the energy density of a lithium ion battery is largely determined by the cathode material. Among all positive electrode materials, ternary layered LiNixCoyMn1-x-yO2The material has the advantages of high capacity, low cost, low toxicity and the like, and becomes a positive electrode material with great potential.
However, the multi-layered positive electrode material LiNixCoyMn1-x-yO2The defects of low capacity retention rate, quick voltage attenuation, poor rate capability and the like in the circulation process limit the commercial application of the composite material, particularly in the field of new energy power automobiles. The reasons for this are the following:
1. the lithium-containing compound is easy to remain after the surface of the nickel-rich ternary laminar positive electrode material with high specific discharge capacity is sintered; the residual lithium compound is easy to react with carbon dioxide in the air and water to generate Li2CO3And LiOH, and affect the performance of the battery;
2. in the circulation process, trace HF in the electrolyte corrodes the surface of the anode material, so that metal ions are dissolved and the circulation performance of the battery is attenuated;
3. the cycle process of the nickel-rich ternary cathode material leads to further deepening of the lithium-nickel mixed-discharging degree, and the crystal structure of the material is accompanied by a layered structure
Figure BDA0003117703370000011
To spinel structure
Figure BDA0003117703370000012
Transforming;
4. the lithium intercalation/deintercalation behavior during the charge and discharge cycle of the material causes the expansion or contraction of the crystal structure of the material, and the subsequent microscopic stress causes the destruction of the material structure and the generation of microcracks.
The surface of the anode material is coated and modified, so that the dissolution of metal ions and the irreversible phase change of the structure caused by the corrosion of HF on the anode can be effectively prevented, and the high-activity Ni can be prevented in the state of high delithiation of the material4+Side reactions with the electrolyte and the precipitation of lattice oxygen inside the material.
In general, metal oxide coating has been shown to be effective in improving the surface stability of the battery material, thereby improving the cycling performance of the battery. But the insulating metal oxide coating causes a decrease in the capacity of the battery.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide a double-layer coating modified lithium ion battery anode material powder and a preparation method thereof. The double-layer coated modified lithium ion battery cathode material simultaneously shows high capacity, long cycle and high rate characteristics, has good conductivity, higher surface coverage rate and excellent chemical stability, and can effectively improve the cycle and rate performance of the cathode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a double-layer coating modified lithium ion battery anode material powder comprises an anode material substrate, a first coating layer coated on the surface of the anode material substrate and a second coating layer coated on the surface of the first coating layer; wherein the first coating layer is a carbon nanosphere coating layer; the second cladding layer is a metal oxide coating.
Preferably, the carbon nanosphere coating three-dimensional material adopts at least one of acetylene black, graphene and multi-wall fullerene. More preferably a multi-walled fullerene.
Preferably, the material of the metal oxide coating adopts at least one of aluminum oxide, zinc oxide, titanium oxide, magnesium oxide, tungsten oxide and zirconium oxide. More preferably at least one of alumina, zirconia and titania.
Preferably, the thickness of the carbon nanoball coating is 2-50 nm, and the particle size of the carbon nanoball is 5-100 nm. More preferably 8-20 nm.
Preferably, the thickness of the metal oxide coating is 2-50 nm. More preferably 5-30nm, most preferably 8-20 nm.
Preferably, the preparation method of the metal oxide coating includes, but is not limited to, any one method of vacuum evaporation deposition, magnetron sputtering deposition, pulsed laser deposition, chemical vapor deposition, metal organic chemical vapor deposition, molecular beam epitaxy deposition and atomic layer deposition.
Preferably, the carbon nanoball coating is prepared by a wet dispersion-sintering method.
Preferably, the metal oxide coating is prepared by a magnetron sputtering method.
Preferably, the molecular formula of the material of the cathode material matrix is Li1+xNiyCozMnsMnO2-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, and r is more than or equal to 0 and less than or equal to 0.1.
In addition, preferably, the molecular formula of the material of the cathode material matrix is LiMn2-xMxO4Wherein x is more than or equal to 0 and less than or equal to 0.5.
Also preferably, the molecular formula of the material of the cathode material matrix is LiFe1-xMxPO4Wherein x is more than or equal to 0 and less than or equal to 1.
Preferably, the molecular formula of the material of the cathode material matrix is LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiFePO4、LiMn2O4At least one of (1). Most preferably LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2One kind of (1).
The invention relates to a preparation method of double-layer coating modified lithium ion battery anode material powder, which comprises the following steps:
the method comprises the following steps: the mass ratio of the carbon nanospheres to the positive electrode material matrix is (0.1-5.0): dispersing 100 carbon nanospheres in absolute ethyl alcohol, adding the anode material powder, continuously stirring at the temperature of not less than 80 ℃ until the organic solvent is completely evaporated, finally putting the dried product into a muffle furnace, and sintering for 3-10 hours at the temperature of 200-450 ℃ in the air atmosphere to prepare the lithium ion battery anode material powder coated with the carbon nanosphere coating;
step two: placing the lithium ion battery anode material powder coated with the carbon nanosphere coating prepared in the step one in a magnetron sputtering coating device, enabling the lithium ion battery anode material powder to be in a motion state through a regularly vibrating sample disc, controlling the temperature to be 25-400 ℃ under the pressure condition that the air pressure is 0.1-5.0 Pa, and enabling the power density to be 1-6W/cm2And placing the mixture in an argon gas-oxygen volume ratio of (1-4): 1, coating a metal oxide coating on the surface of the anode material under the condition that the sputtering time is 5-15 min, and obtaining the double-layer coating modified lithium ion battery anode material powder.
Preferably, in the first step, the mass ratio of the carbon nanospheres to the cathode material substrate is (0.5-2.0): dispersing 100 carbon nanospheres in absolute ethyl alcohol, adding the anode material powder, continuously stirring at the temperature of not less than 80 ℃ until the organic solvent is completely evaporated, finally placing the dried product into a muffle furnace, and sintering for 5-8 hours at the temperature of 250-400 ℃ in the air atmosphere to prepare the lithium ion battery anode material powder coated with the carbon nanosphere coating. Effectively improving the bonding force of the carbon nanospheres and the aggregate.
Preferably, in the second step, the motion state is that the cathode material coated with the carbon nanoball moves by at least one of vibration, stirring, rotation and turning. The object is to keep the uncoated side of the material in the plasma, preferably vibrating.
Preferably, in the second step, the temperature is controlled to be 200-400 ℃ under the pressure condition that the air pressure is 0.5-2.0 Pa, and the power density is 2-5W/cm2And placing the mixture in an argon gas-oxygen volume ratio of (2-3): 1, coating a metal oxide coating on the surface of the anode material under the condition that the sputtering time is 8-12 min.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. according to the invention, the conductive carbon nanosphere coating and the metal oxide coating are coated on the surface of the anode material substrate in sequence through a two-step method, wherein the carbon nanosphere coating has good conductivity, and after coating, the conductivity of the composite coating can be integrally improved, electron transmission is promoted, and the rate capability of the material is improved; the metal oxide coating has stable chemical properties, can inhibit side reactions between the electrolyte and the surface of the matrix after coating, optimizes the interface electrochemical reaction environment and improves the cycle performance of the material;
2. the second layer of metal oxide coating is coated by using a magnetron sputtering method, so that the problem that the performance of the material is reduced due to the fact that transition metal elements in the ternary cathode material are easily reduced by a carbon material in the traditional process of preparing the metal oxide coating by high-temperature sintering is solved;
3. the double-coated coating prepared by the process method has good conductivity, higher surface coverage rate and excellent chemical stability, and can effectively improve the cycle and rate performance of the anode material.
Drawings
Fig. 1 is a graph comparing cycle performance curves of the positive electrode materials of example 1 of the present invention and comparative examples 1 and 2.
Fig. 2 is a graph comparing rate performance curves of the positive electrode materials of example 1 of the present invention and comparative examples 1 and 2.
Fig. 3 is a comparison of XRD patterns of the positive electrode materials of example 1 of the present invention and comparative example 1.
Detailed Description
In order to facilitate an understanding of the invention, the invention will now be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1
In this embodiment, a double-layer coating modified lithium ion battery cathode material powder includes a cathode material substrate, a first coating layer coated on the surface of the cathode material substrate, and a second coating layer coated on the surface of the first coating layer; wherein the first coating layer is a carbon nanosphere coating layer; the second cladding layer is a metal oxide coating.
A preparation method of the double-layer coating layer modified lithium ion battery anode material powder comprises the steps of firstly, using a wet method-sintering process to obtain LiNi serving as a lithium ion battery anode material0.5Co0.2Mn0.3O2The surface is coated with a multi-wall fullerene coating, and then a layer of aluminum oxide coating is coated by a radio frequency sputtering method to prepare the lithium ion battery anode material coated by the double-layer coating, and the specific implementation steps are as follows:
(1) weighing 0.05g of multi-wall fullerene, uniformly dispersing the multi-wall fullerene in 50mL of absolute ethyl alcohol, pouring 5g of anode material powder into the multi-wall fullerene, heating the absolute ethyl alcohol to 80 ℃, and continuously stirring to evaporate the absolute ethyl alcohol to obtain mixed powder;
(2) putting the mixed powder obtained in the step (1) into a muffle furnace, and sintering at 300 ℃ for 5h to prepare multi-wall fullerene coating-coated anode material powder;
(3) placing the positive electrode material powder coated by the multi-wall fullerene coating prepared in the step (2) on a sample table of a magnetron sputtering device, wherein the sample table has a vibration function and enables the material to be in a motion state; vacuumizing the sample cavity of the magnetron sputtering device until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to 350 ℃; closing the baffle, introducing argon gas of 30sccm, carrying out pre-sputtering with the power of 100W, the pre-sputtering pressure of 0.8Pa and the pre-sputtering time of 20 min; opening a baffle plate, respectively introducing 10sccm oxygen and 25sccm argon, setting the deposition pressure to be 1Pa, opening a radio frequency power supply, and setting the power density to be 4W/cm2And sputtering for 10min, wherein the thickness of the metal oxide coating continuously deposited on the surface of the multi-wall fullerene coating is 10nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
Example 2
This embodiment is substantially the same as the first embodiment, and is characterized in that:
a preparation method of the double-layer coating layer modified lithium ion battery anode material powder comprises the steps of firstly, using a wet method-sintering process to obtain LiNi serving as a lithium ion battery anode material0.5Co0.2Mn0.3O2The surface is coated with a multi-wall fullerene coating, and then a layer of zirconia coating is coated by a radio frequency sputtering method to prepare the lithium ion battery anode material powder coated by the double-layer coating, and the specific implementation steps are as follows:
(1) weighing 0.05g of multi-wall fullerene, uniformly dispersing the multi-wall fullerene in 50mL of absolute ethyl alcohol, pouring 5g of anode material powder into the multi-wall fullerene, heating the absolute ethyl alcohol to 80 ℃, and continuously stirring to evaporate the absolute ethyl alcohol to obtain mixed powder;
(2) putting the mixed powder obtained in the step (1) into a muffle furnace, and sintering at 300 ℃ for 5h to prepare multi-wall fullerene coating-coated anode material powder;
(3) placing the positive electrode material powder coated by the multi-wall fullerene coating prepared in the step (2)On a sample table of the magnetron sputtering device, the sample table has a vibration function, so that the powder is in a motion state; vacuumizing the sample cavity of the magnetron sputtering device until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to be 400 ℃; closing the baffle, introducing argon gas of 30sccm, carrying out pre-sputtering with the power of 100W, the pre-sputtering pressure of 0.8Pa and the pre-sputtering time of 20 min; opening a baffle plate, respectively introducing 10sccm of oxygen and 40sccm of argon, setting the deposition pressure to be 1.3Pa, and opening a radio frequency power supply to set the power density to be 4W/cm2And sputtering for 10min, wherein the thickness of the metal oxide coating continuously deposited on the surface of the multi-wall fullerene coating is 10nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
Example 3
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of the double-layer coating layer modified lithium ion battery anode material powder comprises the steps of firstly, using a wet method-sintering process to obtain LiNi serving as a lithium ion battery anode material0.5Co0.2Mn0.3O2The surface is coated with a multi-wall fullerene coating, and then a layer of titanium oxide coating is coated by a radio frequency sputtering method to prepare the lithium ion battery anode material powder coated by the double-layer coating, wherein the specific implementation steps are as follows:
(1) weighing 0.05g of multi-wall fullerene, uniformly dispersing the multi-wall fullerene in 50ml of absolute ethyl alcohol, pouring 5g of anode material powder into the multi-wall fullerene, heating the absolute ethyl alcohol to 80 ℃, and continuously stirring to evaporate the absolute ethyl alcohol to obtain mixed powder;
(2) putting the mixed powder obtained in the step (1) into a muffle furnace, and sintering at 300 ℃ for 5h to prepare multi-wall fullerene coating-coated anode material powder;
(3) placing the positive electrode material powder coated by the multi-wall fullerene coating prepared in the step (2) on a sample table of a magnetron sputtering device, wherein the sample table has a vibration function so as to enable the material powder to be in a motion state; vacuumizing the sample cavity of the magnetron sputtering device until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to be 400 ℃; the baffle is closed, and argon is introduced into the reactor at 30sccm, the pre-sputtering power is 100W, the pre-sputtering pressure is 0.8Pa, and the pre-sputtering time is 20 min; opening a baffle plate, respectively introducing 20sccm oxygen and 40sccm argon, setting the deposition pressure to be 1.4Pa, and opening a radio frequency power supply to set the power density to be 4W/cm2And sputtering for 10min, wherein the thickness of the metal oxide coating continuously deposited on the surface of the multi-wall fullerene coating is 10nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
Comparative example 1
Taking the ternary material LiNi in example 10.5Co0.2Mn0.3O2But without any coating treatment.
Comparative example 2
The preparation process of example 1 is repeated except that coating of the carbon nanoball coating is not performed:
(1) the uncoated positive electrode material LiNi0.5Co0.2Mn0.3O2The sample table is placed on a sample table of a magnetron sputtering machine, and the sample table has a vibration function and can enable the powder to be in a motion state;
(2) vacuumizing until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to 350 ℃; closing the baffle, introducing argon gas of 30sccm, carrying out pre-sputtering with the power of 100W, the pre-sputtering pressure of 0.8Pa and the pre-sputtering time of 20 min;
(3) opening a baffle plate, respectively introducing 10sccm oxygen and 25sccm argon, setting the deposition pressure to be 1Pa, opening a radio frequency power supply, and setting the power density to be 5W/cm2Sputtering for 10min, wherein the thickness of the deposited metal oxide coating is about 10nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
Electrical performance tests were performed on example 1 and comparative examples 1 and 2, wherein a lithium sheet was used as a negative electrode, positive electrode material powders prepared respectively were used as positive electrodes, a button cell was manufactured in an argon-filled glove box, and charging and discharging were performed at 0.1C and 1C in a voltage range of 2.75 to 4.3V, respectively, and the test results are shown in fig. 1 and 2.
As can be seen from the results of fig. 1, example 1 has the best capacity retention rate in the cycle test with the magnification of 1C, the capacity retention rate after 100 cycles is 79%, while comparative examples 1 and 2 are 43% and 65%, respectively, which shows that the double-layer coating treatment significantly improves the cycle performance of the cathode material;
from the results of fig. 2, it is seen that the specific discharge capacity of example 1 at 5C rate is 102mAh/g, while that of comparative examples 1 and 2 are 42mAh/g and 79mAh/g, respectively, in the rate performance test, and it is known that the rate performance of the double-layer coating-coated positive electrode material is the best.
XRD test was performed on example 1 and comparative examples 1 and 2, and the test results are shown in fig. 3.
As can be seen from the results of fig. 3, the XRD test results of example 1 and comparative examples 1 and 2 show that the positions of the diffraction peaks of the three groups of samples are kept consistent, and compared to comparative example 1, there is no new diffraction peak observable in both example 1 and comparative example 2, because the content of the metal oxide coating is too low.
Example 4
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of the double-layer coating layer modified lithium ion battery anode material powder comprises the steps of firstly, using a wet method-sintering process to obtain LiNi serving as a lithium ion battery anode material0.5Co0.2Mn0.3O2The surface is coated with a multi-wall fullerene coating, and then a layer of titanium oxide coating is coated by a radio frequency sputtering method to prepare the lithium ion battery anode material powder coated by the double-layer coating, wherein the specific implementation steps are as follows:
(1) weighing 0.1g of multi-wall fullerene, uniformly dispersing the multi-wall fullerene in 50ml of absolute ethyl alcohol, pouring 5g of anode material powder into the multi-wall fullerene, heating the absolute ethyl alcohol to 80 ℃, and continuously stirring to evaporate the absolute ethyl alcohol to obtain mixed powder;
(2) putting the mixed powder obtained in the step (1) into a muffle furnace, and sintering at 400 ℃ for 8h to prepare multi-wall fullerene coating-coated anode material powder;
(3) placing the positive electrode material powder coated by the multi-wall fullerene coating prepared in the step (2) on a sample table of a magnetron sputtering device, wherein the sample table has a vibration function so as to enable the material powder to be in a motion state; magnetic control sputteringVacuumizing the sample cavity of the injection device until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to be 200 ℃; closing the baffle, introducing argon gas of 30sccm, carrying out pre-sputtering with the power of 100W, the pre-sputtering pressure of 0.8Pa and the pre-sputtering time of 20 min; opening a baffle plate, respectively introducing 20sccm oxygen and 40sccm argon, setting the deposition pressure to be 2.0Pa, and opening a radio frequency power supply to set the power density to be 5W/cm2And sputtering for 15min, wherein the thickness of the metal oxide coating continuously deposited on the surface of the multi-wall fullerene coating is 20nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
To sum up, in the above embodiment, the preparation method of the lithium ion battery cathode material powder coated with the double-layer coating layer includes that the substrate material is a nickel cobalt lithium manganate ternary cathode, the first coating layer is a conductive carbon nanosphere coating, and the second coating layer is a metal oxide coating. Wherein the first layer of carbon nanosphere coating is prepared by a wet dispersion-sintering method; the second layer of metal oxide coating is prepared by a magnetron sputtering method, and finally the carbon nanosphere/metal oxide double-layer coating is formed. The double-layer coating layer effectively solves the problem of poor conductivity of the single-layer metal oxide coating, and simultaneously prevents a small amount of HF in circulating electrolyte from corroding the anode material, so that the anode material coated by the double-layer coating layer has high rate capability, high specific capacity and good circulating performance; meanwhile, the method of the embodiment is simple, is easy to operate and is suitable for large-scale industrial production.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention should be replaced with equivalents as long as the object of the present invention is met, and the technical principle and the inventive concept of the present invention are not departed from the scope of the present invention.

Claims (10)

1.一种双层包覆层改性锂离子电池正极材料粉体，其特征在于：包括正极材料基体、包覆于正极材料基体表面的第一包覆层和包覆于第一层包覆层表面的第二包覆层；其中，所述第一层包覆层为碳纳米球涂层；所述第二包覆层为金属氧化物涂层。1. a double-layer coating layer modified lithium ion battery positive electrode material powder, is characterized in that: comprise a positive electrode material matrix, be coated on the first coating layer on the surface of the positive electrode material matrix and be coated on the first layer coating The second cladding layer on the surface of the layer; wherein, the first cladding layer is a carbon nanosphere coating; the second cladding layer is a metal oxide coating. 2.根据权利要求1所述双层包覆层改性锂离子电池正极材料粉体，其特征在于：所述碳纳米球涂层三维材料采用乙炔黑、石墨烯和多壁富勒烯中的至少一种；2. The double-layer coating layer modified lithium-ion battery positive electrode material powder according to claim 1 is characterized in that: the three-dimensional material of the carbon nanosphere coating adopts acetylene black, graphene and multi-wall fullerenes. at least one; 或者，所述金属氧化物涂层的材料采用氧化铝、氧化锌、氧化钛、氧化镁、氧化钨、氧化锆中的至少一种。Alternatively, the material of the metal oxide coating is at least one of aluminum oxide, zinc oxide, titanium oxide, magnesium oxide, tungsten oxide, and zirconium oxide. 3.根据权利要求1所述双层包覆层改性锂离子电池正极材料粉体，其特征在于：碳纳米球涂层厚度为2～50nm，碳纳米球的粒径为5～100nm。3 . The double-layer coating layer modified lithium ion battery positive electrode material powder according to claim 1 , characterized in that: the thickness of the carbon nanosphere coating is 2-50 nm, and the particle size of the carbon nano-sphere is 5-100 nm. 4 . 4.根据权利要求1所述双层包覆层改性锂离子电池正极材料粉体，其特征在于：所述金属氧化物涂层的厚度为2～50nm。4 . The double-layer coating layer modified lithium ion battery positive electrode material powder according to claim 1 , wherein the thickness of the metal oxide coating is 2-50 nm. 5 . 5.根据权利要求1所述双层包覆层改性锂离子电池正极材料粉体，其特征在于：所述金属氧化物涂层的制备方法包括但不限于真空蒸发沉积、磁控溅射沉积、脉冲激光沉积、化学气相沉积、金属有机化学气相沉积、分子束外延沉积、原子层沉积中的任意一种方法；5. The double-layer coating layer modified lithium ion battery positive electrode material powder according to claim 1, wherein the preparation method of the metal oxide coating includes but is not limited to vacuum evaporation deposition, magnetron sputtering deposition , any one of pulsed laser deposition, chemical vapor deposition, metal organic chemical vapor deposition, molecular beam epitaxy deposition, atomic layer deposition; 或者，所述碳纳米球涂层采用湿法分散-烧结法制备而成；Alternatively, the carbon nanosphere coating is prepared by a wet dispersion-sintering method; 或者，所述金属氧化物涂层由磁控溅射法制备而成。Alternatively, the metal oxide coating is prepared by magnetron sputtering. 6.根据权利要求1所述双层包覆层改性锂离子电池正极材料粉体，其特征在于：所述正极材料基体的材料的分子式为Li1+xNiyCozMnsMnO2-r，其中0≤x≤1，0≤y≤1，0≤z≤1，0≤s≤1，0≤r≤0.1；6. The double-layer coating layer modified lithium ion battery positive electrode material powder according to claim 1, characterized in that: the molecular formula of the material of the positive electrode material matrix is Li 1+x Ni y Co z Mn s MnO 2- r , where 0≤x≤1, 0≤y≤1, 0≤z≤1, 0≤s≤1, 0≤r≤0.1; 或者，所述正极材料基体的材料的分子式为LiMn2-x’Mx’O4，其中0≤x’≤0.5；Alternatively, the molecular formula of the material of the cathode material matrix is LiMn 2-x' M x' O 4 , where 0≤x'≤0.5; 或者，所述正极材料基体的材料的分子式为LiFe1-x”Mx”PO4，其中0≤x”≤1。Alternatively, the molecular formula of the material of the cathode material matrix is LiFe 1-x" M x" PO 4 , where 0≤x"≤1. 7.根据权利要求1所述双层包覆层改性锂离子电池正极材料粉体，其特征在于：所述正极材料基体的材料的分子式为LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiFePO4、LiMn2O4中的至少一种。7 . The positive electrode material powder of double-layer coating layer modified lithium ion battery according to claim 1 , wherein: the molecular formula of the material of the positive electrode material matrix is LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.6 Co 0.2 At least one of Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiFePO 4 , and LiMn 2 O 4 . 8.一种权利要求1所述双层包覆层改性锂离子电池正极材料粉体的制备方法，其特征在于，包括以下步骤：8. A preparation method of the double-layer coating layer modified lithium ion battery positive electrode material powder according to claim 1, characterized in that, comprising the following steps: 步骤一：将碳纳米球与正极材料基体的质量比为(0.1～5.0)：100的碳纳米球分散于无水乙醇中，并加入正极材料粉体，然后在不低于80℃下持续搅拌直至有机溶剂完全蒸发，最后将干燥后的产物放入马弗炉中，在空气气氛下，在200～450℃条件下，烧结3～10h，制备得到碳纳米球涂层包覆的锂离子电池正极材料粉体；Step 1: Disperse the carbon nanospheres with a mass ratio of the carbon nanospheres to the positive electrode material matrix (0.1-5.0): 100 in absolute ethanol, add the positive electrode material powder, and continue stirring at a temperature not lower than 80 °C Until the organic solvent is completely evaporated, finally, the dried product is put into a muffle furnace, and sintered for 3 to 10 hours at 200 to 450 °C in an air atmosphere to prepare a carbon nanosphere coating-coated lithium-ion battery. Positive electrode material powder; 步骤二：将在所述步骤一中制备的碳纳米球涂层包覆的锂离子电池正极材料粉体置于磁控溅射镀膜装置中，通过规律震动的样品盘使其处于运动状态，在气压为0.1～5.0Pa的压力条件下，控制温度为25～400℃，使功率密度为1～6W/cm2，并置于氩气与氧气体积比为(1～4)：1的等离子体环境下，在溅射时间为5～15min的条件下，在正极材料表面再包覆一层金属氧化物涂层，得到双层包覆层改性锂离子电池正极材料粉体。Step 2: Place the lithium-ion battery positive electrode material powder coated with the carbon nanosphere coating prepared in the step 1 in a magnetron sputtering coating device, and make it in a moving state through the regularly vibrating sample disk, Under the pressure of 0.1-5.0Pa, the temperature is controlled to be 25-400°C, the power density is 1-6W/cm 2 , and the plasma is placed in a plasma whose volume ratio of argon to oxygen is (1-4):1 Under the environment, under the condition of sputtering time of 5-15 minutes, a layer of metal oxide coating is coated on the surface of the positive electrode material to obtain a double-layer coating layer modified lithium ion battery positive electrode material powder. 9.根据权利要求8所述双层包覆层改性锂离子电池正极材料粉体的制备方法，其特征在于：在所述步骤一中，将碳纳米球与正极材料基体的质量比为(0.5～2.0)：100的碳纳米球分散于无水乙醇中，并加入正极材料粉体，然后在不低于80℃下持续搅拌直至有机溶剂完全蒸发，最后将干燥后的产物放入马弗炉中，在空气气氛下，在250～400℃条件下，烧结5～8h，制备得到碳纳米球涂层包覆的锂离子电池正极材料粉体。9. the preparation method of double-layer coating layer modified lithium ion battery positive electrode material powder according to claim 8, is characterized in that: in described step 1, the mass ratio of carbon nanosphere and positive electrode material matrix is ( 0.5 ~ 2.0): 100 carbon nanospheres are dispersed in absolute ethanol, and the positive electrode material powder is added, and then continuously stirred at not lower than 80 ° C until the organic solvent is completely evaporated, and finally the dried product is put into the muffle In a furnace, under the condition of 250-400 DEG C., sintering for 5-8 hours in an air atmosphere to prepare a lithium-ion battery cathode material powder coated with a carbon nanosphere coating. 10.根据权利要求8所述双层包覆层改性锂离子电池正极材料粉体的制备方法，其特征在于：在所述步骤二中，所述运动状态为碳纳米球包覆的正极材料通过振动、搅拌、旋转、翻动中的至少一种方式实现运动；10 . The method for preparing a positive electrode material powder for a double-layer coating layer modified lithium ion battery according to claim 8 , wherein in the second step, the motion state is a positive electrode material coated with carbon nanospheres. 11 . Movement is achieved by at least one of vibration, stirring, rotation, and flipping; 或者，在所述步骤二中，在气压为0.5～2.0Pa的压力条件下，控制温度为200～400℃，使功率密度为2～5W/cm2，并置于氩气与氧气体积比为(2～3)：1的等离子体环境下，在溅射时间为8～12min的条件下，在正极材料表面再包覆一层金属氧化物涂层。Or, in the second step, under the pressure condition of the air pressure of 0.5-2.0Pa, the temperature is controlled to be 200-400°C, the power density is 2-5W/cm 2 , and the volume ratio of argon to oxygen is (2-3): In the plasma environment of 1, and under the condition that the sputtering time is 8-12 minutes, the surface of the positive electrode material is coated with a layer of metal oxide coating.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115304108A (en) * 2022-07-13 2022-11-08 合肥国轩电池材料有限公司 Preparation method and device of tungsten-coated ternary cathode material

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130224603A1 (en) * 2012-02-27 2013-08-29 Guorong Chen Lithium-ion cell having a high-capacity anode and a high-capacity cathode
CN103996832A (en) * 2014-05-16 2014-08-20 合肥工业大学 Carbon-metal oxide two-component cladding modified high-voltage positive material and cladding method
CN107275592A (en) * 2017-05-24 2017-10-20 江苏大学 A kind of lithium-rich manganese-based anode material of surface double-coating and preparation method thereof
CN107565112A (en) * 2017-08-29 2018-01-09 湖南长远锂科有限公司 A kind of preparation method of graphene coated lithium ion secondary battery anode material
CN109461892A (en) * 2017-12-26 2019-03-12 北京当升材料科技股份有限公司 A kind of composite anode material for lithium ion battery and preparation method thereof
CN109461927A (en) * 2017-12-21 2019-03-12 北京当升材料科技股份有限公司 A kind of compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation method thereof
CN109935803A (en) * 2018-11-28 2019-06-25 万向一二三股份公司 A kind of preparation method of lithium iron phosphate positive material
CN112436116A (en) * 2020-11-18 2021-03-02 合肥国轩高科动力能源有限公司 Aluminum-doped ZnO film-coated ternary positive electrode @ C composite microsphere and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130224603A1 (en) * 2012-02-27 2013-08-29 Guorong Chen Lithium-ion cell having a high-capacity anode and a high-capacity cathode
CN103996832A (en) * 2014-05-16 2014-08-20 合肥工业大学 Carbon-metal oxide two-component cladding modified high-voltage positive material and cladding method
CN107275592A (en) * 2017-05-24 2017-10-20 江苏大学 A kind of lithium-rich manganese-based anode material of surface double-coating and preparation method thereof
CN107565112A (en) * 2017-08-29 2018-01-09 湖南长远锂科有限公司 A kind of preparation method of graphene coated lithium ion secondary battery anode material
CN109461927A (en) * 2017-12-21 2019-03-12 北京当升材料科技股份有限公司 A kind of compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation method thereof
CN109461892A (en) * 2017-12-26 2019-03-12 北京当升材料科技股份有限公司 A kind of composite anode material for lithium ion battery and preparation method thereof
CN109935803A (en) * 2018-11-28 2019-06-25 万向一二三股份公司 A kind of preparation method of lithium iron phosphate positive material
CN112436116A (en) * 2020-11-18 2021-03-02 合肥国轩高科动力能源有限公司 Aluminum-doped ZnO film-coated ternary positive electrode @ C composite microsphere and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨静、李圆圆: "磁控溅射技术在微小颗粒表面涂层中的应用", 《真空》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115304108A (en) * 2022-07-13 2022-11-08 合肥国轩电池材料有限公司 Preparation method and device of tungsten-coated ternary cathode material
CN115304108B (en) * 2022-07-13 2023-10-27 合肥国轩电池材料有限公司 Preparation method and device of tungsten-coated ternary cathode material

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