CN110620219A - Method for coating metal oxide film on surface of lithium ion anode material - Google Patents
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention relates to a method for coating a metal oxide film on the surface of a lithium ion anode material, which comprises the steps of carrying out constant-humidity treatment on the lithium ion anode material for 5-20h at room temperature to ensure that the surface of the lithium ion anode material naturally adsorbs water vapor to be balanced; dissolving a metal compound precursor in an organic solvent; dispersing the lithium ion cathode material powder treated by constant humidityCarrying out chemical liquid phase deposition reaction in the obtained organic solvent at 50-70 ℃ under the protection of inert gas or nitrogen, combining a metal compound precursor with adsorbed water on the surface of the lithium ion anode material, then directionally hydrolyzing, depositing on the surface of the lithium ion anode material, and heating and volatilizing the organic solvent; after the organic solvent is completely volatilized, drying the obtained powder in an oven, and drying the powder in a drying oven at 400-550oC, roasting for 3-5h to obtain a lithium ion anode material coated by a metal oxide film; the obtained material has good charge and discharge performance and circulation stability, and the method has the advantages of simple process, environmental friendliness, low input cost and suitability for popularization and application.
Description
Technical Field
The invention relates to the field of lithium ion anode materials, in particular to a method for coating a metal oxide film on the surface of a lithium ion anode material.
Background
With the rapid development of social economy, the problems of energy and environmental protection are increasingly prominent, and the problems become the main challenges faced by human at present; the development and utilization of renewable environment-friendly new energy are becoming more and more urgent, and a novel lithium ion battery belongs to clean energy, has the advantages of safety, high cyclicity, long service life, environmental friendliness and the like, and is regarded as one of the most effective electrochemical energy storage systems.
The energy density of lithium ion batteries mainly depends on the energy density of the cathode material, and the most widely used and studied cathode material at present is LiCoO2、LiMn2O4、LiFePO4(LFP) and the ternary material LiNixCoyMnzO2(NCM) or LiNixCoyAlzO2(NCA) and NMC materials are the current research hotspots due to high energy density, long service life and high safety performance.
The surface coating and modification are the most common means for improving the performance of the lithium ion battery anode material, and the effective coating can avoid the direct contact of an electrode active substance and electrolyte, inhibit the dissolution of transition metal, improve the mechanical strength of the anode material, and slow down the structure collapse phenomenon of the active material in the long-term charge and discharge process, thereby improving the electrochemical performance, the cycling stability and the rate capability of the material.
The coating method widely used at present generally utilizes a mode of fully mixing and then roasting the positive electrode material and a certain amount of solid particle substances, the method is not easy to achieve the uniform dispersion of coating substances on the surface of the positive electrode material, so that the optimal effect cannot be obtained with a smaller coating amount, and in addition, the mixing process (such as a ball milling method) and the high-temperature roasting process are easy to cause adverse effects such as the breakage of the positive electrode material particles, the structural damage and the like. Some novel methods such as Atomic Layer Deposition (ALD), Molecular Beam Epitaxy (MBE), Chemical Vapor Deposition (CVD), etc. can prepare a cathode material with a uniformly coated nanoscale thin film on the surface, but these methods are still limited to experimental level at present and are difficult to be applied in large scale, because the devices used in these methods are complex and expensive, and the process time is long, there are disadvantages such as low working efficiency, waste of resources, high cost, etc.
Disclosure of Invention
The invention aims to provide a method for coating a metal oxide film on the surface of a lithium ion positive electrode material, aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for coating a metal oxide film on the surface of a lithium ion anode material comprises the following steps:
1) carrying out constant-humidity treatment on the lithium ion positive electrode material for 5-20h at room temperature, so that water vapor is naturally adsorbed on the surface of the lithium ion positive electrode material until the surface is balanced;
2) dissolving a metal compound precursor in an organic solvent;
3) dispersing the lithium ion anode material powder treated by the constant humidity in the step 1) into the organic solvent obtained in the step 2), carrying out chemical liquid phase deposition reaction at 50-70 ℃ under the protection of inert gas or nitrogen, combining a metal compound precursor with the absorbed water on the surface of the lithium ion anode material, then directionally hydrolyzing, depositing on the surface of the lithium ion anode material, and heating and volatilizing the organic solvent;
4) and after the organic solvent is completely volatilized, drying the obtained powder in an oven, and roasting at the temperature of 400-550 ℃ for 3-5h to obtain the lithium ion cathode material coated by the metal oxide film.
In a further preferred embodiment, the lithium ion positive electrode material is any one of the following materials:
Li(NixCoyMn1-x-y)O2wherein 0 is<x<1，0<y<1；
LiNixCo1-xO2Wherein x is more than or equal to 0 and less than or equal to 1;
Li(NixCoyAl1-x-y)O2wherein 0 is<x<1，0<y<1；
xLi2MnO3·(1-x)LiMO2Wherein 0 is<x<1, M is at least one of Mn, Ni and Co;
LiNi0.5Mn1.5O4。
in a further preferred embodiment, the metal compound precursor is selected from one of triethyl aluminum, diethyl aluminum chloride, tetrabutyl titanate, titanium tetrachloride, ethyl orthosilicate, silicon tetrachloride, tetrabutyl zirconate, zirconium isopropoxide and zirconium tetrachloride.
In a further preferred embodiment, the metal oxide film is one of aluminum oxide, titanium dioxide, silicon dioxide and zirconium dioxide.
In a further preferred embodiment, the organic solvent is selected from one or more of cyclohexane, n-hexane, decalin and olefin.
Further preferably, the concentration of the metal compound precursor in the organic solvent in the step 2) is 2 to 15 g/L.
In a further preferable scheme, the concentration of the lithium ion cathode material powder in the organic solvent in the step 3) is 0.05-2.5 g/mL.
Further preferably, the thickness of the metal oxide film coated on the surface of the lithium ion cathode material is increased by repeating the operations from step 1) to step 4).
The invention has the beneficial effects that:
1. compared with the conventional mixing-roasting coating method, the method adopts a modified chemical liquid phase deposition method: through the constant humidity and deposition process, the metal compound precursor can be directionally hydrolyzed and deposited on the surface of the anode material to generate a more uniform metal oxide film, so that the contact between the anode material and the electrolyte is more effectively blocked, and the material structure is stabilized.
2. The method can accurately control the deposition amount and thickness of the oxide film on the surface of the lithium ion cathode material by adjusting the concentration of the metal compound precursor in the organic solvent and the times of repeating the operation steps according to different performance requirements.
3. Compared with the existing methods such as Atomic Layer Deposition (ALD), Molecular Beam Epitaxy (MBE), Chemical Vapor Deposition (CVD) and the like, the method provided by the invention is simple in process, environment-friendly, low in investment cost and suitable for popularization and application.
Drawings
FIG. 1 is a schematic view of a constant humidity apparatus used in an embodiment of the present invention;
FIG. 2 is a schematic view of a deposition apparatus used in an embodiment of the present invention;
wherein: 1-porcelain boat, 2-glass dryer, 3-heating stirrer, 4-water bath, 5-deposition flask, 6-protective gas inlet pipe, 7-condenser pipe and 8-organic solvent collection bottle.
Detailed Description
The invention will be further illustrated with reference to specific embodiments:
example 1
Preparation of Al2O3Coated LiNi0.8Co0.1Mn0.1O2
Referring to FIG. 1, 20g of LiNi, a ternary positive electrode material, was weighed0.8Co0.1Mn0.1O2Loading into a porcelain boat 1, placing in a glass drier 2 with saturated sodium chloride solution at the bottom, and maintaining constant humidity at room temperature for 5 hr to obtain LiNi0.8Co0.1Mn0.1O2The surface naturally adsorbs water vapor to equilibrium.
0.45g of triethylaluminum was dissolved in 200mL of cyclohexane (organic solvent), and LiNi was obtained after constant humidity0.8Co0.1Mn0.1O2The powder was added to the organic solvent and dispersed with stirring, and then poured into the deposition flask 5.
In the embodiment, a chemical liquid phase deposition reaction is carried out by the device shown in fig. 2, the heating stirrer 3 heats the water bath 4, the deposition flask 5 is placed in the water bath 4, the reaction temperature is set to 55 ℃, the deposition flask 5 is connected with the protective gas inlet pipe 6 and is used for introducing inert gas or nitrogen gas in the deposition reaction, the deposition flask 5 is simultaneously connected with the condensing pipe 7, and the condensing pipe 7 collects and recovers the organic solvent which is heated and continuously volatilized in the deposition reaction into the organic solvent collecting bottle 8.
After the organic solvent is completely volatilized, drying the obtained powder in an oven, and then roasting the powder in a muffle furnace at 450 ℃ for 3 hours to obtain Al2O3Ternary positive electrode material LiNi uniformly coated with film0.8Co0.1Mn0.1O2。
Example 2
Preparation of TiO2Coated LiNi0.8Co0.1Mn0.1O2
Weighing 20g of ternary cathode material LiNi0.8Co0.1Mn0.1O2Loading into ceramic boat, placing in glass drier with saturated sodium chloride solution at bottom, and maintaining constant humidity at room temperature for 5 hr to obtain LiNi0.8Co0.1Mn0.1O2Naturally adsorbing water vapor on the surface until the water vapor is balanced;
0.85g of tetrabutyl titanate was dissolved in 200mL of cyclohexane (organic solvent), and LiNi was obtained after constant humidity0.8Co0.1Mn0.1O2Adding the powder into an organic solvent, stirring and dispersing, carrying out chemical liquid phase deposition reaction by using a device shown in figure 2 as in example 1, wherein the reaction temperature is 55 ℃, continuously volatilizing the organic solvent under heating, cooling and collecting the organic solvent outside a reaction vessel through a condensing tube, drying the obtained powder in an oven after the solvent is completely volatilized, and then roasting the dried powder in a muffle furnace at 450 ℃ for 3 hours to obtain TiO2Ternary positive electrode material LiNi uniformly coated with film0.8Co0.1Mn0.1O2。
Example 3
SiO2Coated LiNi0.8Co0.1Mn0.1O2
Weighing 20g of ternary cathode material LiNi0.8Co0.1Mn0.1O2Loading into ceramic boat, placing in glass drier with saturated sodium chloride solution at bottom, and maintaining constant humidity at room temperature for 5 hr to obtain LiNi0.8Co0.1Mn0.1O2Naturally adsorbing water vapor on the surface until the water vapor is balanced;
take 0.69g of tetraethoxysilane was dissolved in 200mL of cyclohexane (organic solvent), and LiNi was obtained after constant humidity0.8Co0.1Mn0.1O2Adding the powder into an organic solvent, stirring and dispersing, carrying out chemical liquid phase deposition reaction by using a device shown in figure 2 as in example 1, wherein the reaction temperature is 55 ℃, continuously volatilizing the organic solvent under heating, cooling and collecting the organic solvent outside a reaction vessel through a condensing tube, drying the obtained powder in an oven after the solvent is completely volatilized, and then roasting the dried powder in a muffle furnace at 450 ℃ for 3 hours to obtain SiO2Ternary positive electrode material LiNi uniformly coated with film0.8Co0.1Mn0.1O2。
Example 4
ZrO2Coated LiNi0.8Co0.1Mn0.1O2
Weighing 20g of ternary cathode material LiNi0.8Co0.1Mn0.1O2Loading into ceramic boat, placing in glass drier with saturated sodium chloride solution at bottom, and maintaining constant humidity at room temperature for 5 hr to obtain LiNi0.8Co0.1Mn0.1O2Naturally adsorbing water vapor on the surface until the water vapor is balanced;
0.62g of tetrabutyl zirconate was dissolved in 200mL of cyclohexane (organic solvent), and LiNi was obtained after constant humidity0.8Co0.1Mn0.1O2Adding the powder into an organic solvent, stirring and dispersing, carrying out chemical liquid phase deposition reaction by using a device shown in figure 2 as in example 1, wherein the reaction temperature is 55 ℃, continuously volatilizing the organic solvent under heating, cooling and collecting the organic solvent outside a reaction container through a condensing tube, drying the obtained powder in an oven after the solvent is completely volatilized, and then roasting the powder in a muffle furnace at 450 ℃ for 3 hours to obtain ZrO2Ternary positive electrode material LiNi uniformly coated with film0.8Co0.1Mn0.1O2。
Ternary positive electrode material LiNi obtained in examples 1 to 4 and coated with different metal oxide films0.8Co0.1Mn0.1O2Making positive plate from the material, and making into 2032 type button in glove box by conventional methodThe battery was subjected to charge and discharge tests at different rates, wherein the charge and discharge specific capacities and the cycle performance of the different materials are shown in table 1.
Example 5
Preparation of TiO2Coated LiNi0.5Mn1.5O4
20g of LiNi serving as a positive electrode material is weighed0.5Mn1.5O4Loading in ceramic boat, placing in glass drier with saturated sodium chloride solution at bottom, and maintaining constant humidity at room temperature for 10 hr to obtain LiNi0.5Mn1.5O4Naturally adsorbing water vapor on the surface until the water vapor is balanced;
0.85g of tetrabutyl titanate is dissolved in 200mL of n-hexane (organic solvent), and the LiNi after constant humidity is obtained0.5Mn1.5O4Adding the powder into an organic solvent, stirring and dispersing, carrying out chemical liquid phase deposition reaction by using a device shown in figure 2 as in example 1, wherein the reaction temperature is 50 ℃, continuously volatilizing the organic solvent under heating, cooling and collecting the organic solvent outside a reaction container through a condensing tube, drying the obtained powder in an oven after the solvent is completely volatilized, and then roasting the dried powder in a muffle furnace at 400 ℃ for 3 hours to obtain TiO2Positive electrode material LiNi uniformly coated with thin film0.5Mn1.5O4。
Example 6
Preparation of TiO2Coated LiNi0.8Co0.2O2
20g of LiNi serving as a positive electrode material is weighed0.8Co0.2O2Loading into ceramic boat, placing in glass drier with saturated sodium chloride solution at bottom, and maintaining constant humidity at room temperature for 15 hr to obtain LiNi0.8Co0.2O2Naturally adsorbing water vapor on the surface until the water vapor is balanced;
0.85g of tetrabutyl titanate was dissolved in 200mL of decahydronaphthalene (organic solvent), and LiNi was obtained after constant humidity0.8Co0.2O2Adding the powder into organic solvent, stirring, dispersing, performing chemical liquid phase deposition reaction at 60 deg.C by using the device shown in FIG. 2, and volatilizing the organic solvent outside the reaction vesselCooling and collecting through a condensing tube, drying the obtained powder in an oven after the solvent is completely volatilized, and then roasting the dried powder in a muffle furnace at 500 ℃ for 3 hours to obtain TiO2Positive electrode material LiNi uniformly coated with thin film0.8Co0.2O2。
Example 7
Preparation of TiO2Coated LiNi0.85Co0.1Al0.05O2
20g of LiNi serving as a positive electrode material is weighed0.85Co0.1Al0.05O2Loading into ceramic boat, placing in glass drier with saturated sodium chloride solution at bottom, and maintaining constant humidity at room temperature for 20 hr to obtain LiNi0.85Co0.1Al0.05O2Naturally adsorbing water vapor on the surface until the water vapor is balanced;
0.85g of tetrabutyl titanate was dissolved in 200mL of decahydronaphthalene (organic solvent), and LiNi was obtained after constant humidity0.85Co0.1Al0.05O2Adding the powder into an organic solvent, stirring and dispersing, carrying out chemical liquid phase deposition reaction by using a device shown in figure 2 as in example 1, wherein the reaction temperature is 65 ℃, continuously volatilizing the organic solvent under heating, cooling and collecting the organic solvent outside a reaction vessel through a condensing tube, drying the obtained powder in an oven after the solvent is completely volatilized, and then roasting the dried powder in a muffle furnace at 550 ℃ for 4 hours to obtain TiO2Ternary positive electrode material LiNi uniformly coated with film0.85Co0.1Al0.05O2。
Example 8
Preparation of TiO2Coated Li1.2Ni0.15Mn0.55Co0.1O2
Weighing 20g of lithium-rich manganese-based positive electrode material Li1.2Ni0.15Mn0.55Co0.1O2Loading into porcelain boat, placing in glass drier with saturated sodium chloride solution at bottom, and maintaining constant humidity at room temperature for 15 hr to make Li1.2Ni0.15Mn0.55Co0.1O2Naturally adsorbing water vapor on the surface until the water vapor is balanced;
taking 0.85g of titanic acidTetrabutyl ester was dissolved in 200mL of decene (organic solvent), and Li was added after constant humidity1.2Ni0.15Mn0.55Co0.1O2Adding the powder into an organic solvent, stirring and dispersing, carrying out chemical liquid phase deposition reaction by using a device shown in figure 2 as in example 1, wherein the reaction temperature is 70 ℃, continuously volatilizing the organic solvent under heating, cooling and collecting the organic solvent outside a reaction container through a condensing tube, drying the obtained powder in an oven after the solvent is completely volatilized, and then roasting the dried powder in a muffle furnace at 550 ℃ for 3 hours to obtain TiO2Lithium-rich manganese-based cathode material Li uniformly coated by thin film1.2Ni0.15Mn0.55Co0.1O2。
Comparative example 1
LiNi which is not coated is taken as a positive electrode material0.8Co0.1Mn0.1O2The material was made into positive plate, and made into 2032 type button cell by conventional technique in glove box, and charge and discharge tests were performed at different multiplying power, and the results are shown in table 1.
Table 1:
as can be seen from table 1, the lithium ion cathode material coated with a metal oxide film prepared by the chemical liquid deposition method according to the present invention has improved battery capacity compared to the uncoated lithium ion cathode material.
Wherein TiO in example 22Coated LiNi0.8Co0.1Mn0.1O2The material has the best performance, the discharge capacity reaches 204.2 mA.h/g at 0.2C, and the LiNi which is not coated in the comparative example0.8Co0.1Mn0.1O2The initial specific discharge capacity of the battery made of the material is 197.8 mA.h/g, and the uncoated LiNi can be seen from the test result of 100-week cycle discharge of 1C0.8Co0.1Mn0.1O2The cycling efficiency of the cell made of the material was 95.9%, compared to the TiO in example 22Coated LiNi0.8Co0.1Mn0.1O2The material battery cycling efficiency is 98.3%.
The above results illustrate that: the method provided by the invention is a method capable of effectively modifying the electrochemical performance of the lithium ion anode material, the obtained material has better charge and discharge performance and cycle stability, and the method is simple in process, environment-friendly, low in investment cost and suitable for popularization and application.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (8)
1. A method for coating a metal oxide film on the surface of a lithium ion anode material is characterized by comprising the following steps: the method comprises the following steps:
1) carrying out constant-humidity treatment on the lithium ion positive electrode material for 5-20h at room temperature, so that water vapor is naturally adsorbed on the surface of the lithium ion positive electrode material until the surface is balanced;
2) dissolving a metal compound precursor in an organic solvent;
3) dispersing the lithium ion anode material powder treated by the constant humidity in the step 1) into the organic solvent obtained in the step 2), carrying out chemical liquid phase deposition reaction at 50-70 ℃ under the protection of inert gas or nitrogen, combining a metal compound precursor with the absorbed water on the surface of the lithium ion anode material, then directionally hydrolyzing, depositing on the surface of the lithium ion anode material, and heating and volatilizing the organic solvent;
4) after the organic solvent is completely volatilized, drying the obtained powder in an oven, and drying the powder in a drying oven at 400-550oAnd C, roasting for 3-5h to obtain the lithium ion anode material coated by the metal oxide film.
2. The method for coating the surface of the lithium ion cathode material with the metal oxide film according to claim 1, wherein the method comprises the following steps: the lithium ion positive electrode material is any one of the following materials:
Li(NixCoyMn1-x-y)O2wherein 0 is<x<1，0<y<1；
LiNixCo1-xO2Wherein x is more than or equal to 0 and less than or equal to 1;
Li(NixCoyAl1-x-y)O2wherein 0 is<x<1，0<y<1；
xLi2MnO3·(1-x)LiMO2Wherein 0 is<x<1, M is at least one of Mn, Ni and Co;
LiNi0.5Mn1.5O4。
3. the method for coating the surface of the lithium ion cathode material with the metal oxide film according to claim 1, wherein the method comprises the following steps: the metal compound precursor is selected from one of triethyl aluminum, diethyl aluminum chloride, tetrabutyl titanate, titanium tetrachloride, ethyl orthosilicate, silicon tetrachloride, tetrabutyl zirconate, zirconium isopropoxide and zirconium tetrachloride.
4. The method for coating the surface of the lithium ion cathode material with the metal oxide film according to claim 3, wherein the method comprises the following steps: the metal oxide film is one of aluminum oxide, titanium dioxide, silicon dioxide and zirconium dioxide.
5. The method for coating the surface of the lithium ion cathode material with the metal oxide film according to claim 1, wherein the method comprises the following steps: the organic solvent is selected from one or more of cyclohexane, n-hexane, decalin and olefin.
6. The method for coating the surface of the lithium ion cathode material with the metal oxide film according to claim 1, wherein the method comprises the following steps: the concentration of the metal compound precursor in the organic solvent in the step 2) is 2-15 g/L.
7. The method for coating the surface of the lithium ion cathode material with the metal oxide film according to claim 1, wherein the method comprises the following steps: the concentration of the lithium ion anode material powder in the organic solvent in the step 3) is 0.05-2.5 g/mL.
8. The method for coating the surface of the lithium ion cathode material with the metal oxide film according to claim 1, wherein the method comprises the following steps: and (4) increasing the thickness of the metal oxide film coated on the surface of the lithium ion cathode material by repeating the operations from the step 1) to the step 4).
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Cited By (3)
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|---|---|---|---|---|
| CN111430670A (en) * | 2020-04-13 | 2020-07-17 | 阮弟根 | Positive electrode plate, processing method thereof, application of positive electrode plate in preparation of lithium battery, and lithium battery |
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