CN115976494A - Sodium-ion battery positive electrode material and preparation method and application thereof - Google Patents
Sodium-ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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- CN115976494A CN115976494A CN202211649978.1A CN202211649978A CN115976494A CN 115976494 A CN115976494 A CN 115976494A CN 202211649978 A CN202211649978 A CN 202211649978A CN 115976494 A CN115976494 A CN 115976494A
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Abstract
The invention provides a sodium ion battery anode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: placing an inner core of the positive electrode material of the sodium-ion battery in an atomic layer deposition reaction cavity, and introducing an aluminum source gas-phase precursor, a sodium source gas-phase precursor and water vapor into the reaction cavity to carry out atomic layer deposition so as to finish a deposition process; repeatedly introducing reactants to realize the circulation of the primary deposition process, and obtaining the sodium ion battery anode material with the surface coated with sodium metaaluminate; according to the preparation method, the atomic layer deposition is adopted for coating modification, a water phase is not involved, and compared with other coating methods, the uniformity of the obtained coating layer and the bonding strength of the coating layer and the kernel are high, so that the cycle performance of the sodium-ion battery anode material can be remarkably improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a sodium-ion battery positive electrode material, and a preparation method and application thereof.
Background
The sodium ion battery is similar to the lithium ion battery in working principle, and is a rocking chair type secondary battery which depends on the reciprocating de-intercalation of ions between a positive electrode and a negative electrode. Compared with lithium resources, the sodium resource is quite abundant in reserve, the sodium content in the crust is four hundred times of that of lithium, and the crust has the advantages of low cost and stability; in the aspect of performance, although the energy density of the sodium ion battery is lower than that of the lithium ion battery, the sodium ion battery has unique advantages in the aspects of charge-discharge rate and low-temperature performance, 80% of electric quantity can be achieved after charging for 15 minutes at normal temperature, and when the sodium ion battery works in an environment at-20 ℃, the energy conservation rate of the sodium ion battery is close to 90%. Therefore, the application potential of the sodium ion battery in the fields of new energy power batteries and large-scale energy storage is of great concern.
The anode material is one of key materials of the sodium ion battery, which greatly influences the energy density and power density of the battery, namely, the layered transition metal oxide (Na) x T m O 2 ) The material is a main anode material of a sodium ion battery at present, however, sodium ions can be removed and water can be embedded when the material is exposed in the air, sodium hydroxide formed by removing the sodium ions on the surface has extremely strong water absorption, and can further react with carbon dioxide to form an alkaline insulating layer, so that the cycle and rate performance of the battery are reduced, and the structure of the material is seriously damaged, therefore, the surface of the sodium ion layered anode material needs to be coated and modified to solve the problems. However, since the layered oxide material of the sodium ion battery is very easy to absorb water and decompose and oxidize, the coating modification cannot be realized in the post-treatment modes of the material such as water washing and the like and the coating process involving the aqueous solution.
Based on the above research, it is desirable to provide a preparation method of a sodium-ion battery cathode material, which avoids the damage of a water phase coating method to the sodium-ion battery cathode material, and the obtained coating layer is compact and uniform, has high thickness controllability, can effectively alleviate the problem of water absorption on the surface of the material while not affecting the desorption of sodium ions, and improves the cycle stability of the sodium-ion battery.
Disclosure of Invention
The invention aims to provide a sodium ion battery anode material and a preparation method and application thereof, the preparation method adopts atomic layer deposition for coating modification, does not relate to a water phase, can accurately control the thickness of a coating on a nanometer level, has high uniformity of the obtained coating and high bonding strength with a kernel compared with other coating methods, and can be used as an effective means for coating modification of the sodium ion battery anode material to remarkably improve the cycle performance of the sodium ion battery anode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a positive electrode material of a sodium ion battery, wherein the preparation method comprises the following steps:
(1) Placing an inner core of the positive electrode material of the sodium-ion battery in an atomic layer deposition reaction cavity, and introducing an aluminum source gas-phase precursor, a sodium source gas-phase precursor and water vapor into the reaction cavity to carry out atomic layer deposition so as to finish a deposition process;
(2) And (2) repeatedly introducing reactants to realize the circulation of the primary deposition process in the step (1) and obtain the sodium ion battery cathode material with the surface coated with sodium metaaluminate.
The method adopts the atomic layer deposition method to coat the sodium metaaluminate on the surface of the positive electrode material of the sodium-ion battery in situ, the whole coating process is carried out in gas phase, the method is simple and controllable, green and pollution-free, the thickness of the coating layer can be precisely controlled on a nanometer level, the damage of a water phase coating method to the positive electrode material of the sodium-ion battery is avoided, the obtained coating layer has high density and good uniformity, and is tightly combined with the inner core, a series of side reactions when the material is exposed in the air are effectively avoided, the water absorption problem on the surface of the material is effectively relieved while the de-intercalation of sodium ions is not influenced, the contact between the electrode material and electrolyte is isolated in the circulation process, and the circulation performance of the battery is improved.
The inner core of the invention comprises Na x TMO 2 TM comprises a transition metal, which may be, for example, any one or a group of at least two of Ti, V, cr, mn or CuX.ltoreq.1, for example 1, 0.8, 0.6, 0.4 or 0.2, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable.
Preferably, the atomic layer deposition reaction chamber of step (1) has a temperature of 210-250 ℃, for example, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃ or 250 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
The temperature of the atomic layer deposition reaction cavity influences the deposition effect, and if the temperature of the atomic layer deposition reaction cavity is too high, the deposition coating can be decomposed; if the temperature of the atomic deposition reaction chamber is too low, the temperature of the deposition reaction is too low, which is not favorable for generating a coating layer, and a coating with ideal components cannot be prepared.
Preferably, the core of step (1) comprises a layered transition metal oxide.
Preferably, in the step (1), the introduction sequence is that an aluminum source gas-phase precursor is introduced first, then a sodium source gas-phase precursor is introduced, and finally water vapor is introduced.
According to the invention, the water vapor is introduced finally, so that the damage of the water vapor to the core material can be avoided, the water molecules are prevented from being embedded into the core, and the gas is introduced according to the sequence to promote the in-situ generation of the sodium metaaluminate, so that the bonding strength of the coating layer and the core is improved.
Preferably, in the step (1), before the gas is introduced into the reaction chamber, vacuum is firstly pumped.
Preferably, after the aluminum source gas-phase precursor is introduced in the step (1), purging is performed, and then the sodium source gas-phase precursor is introduced.
Preferably, after the sodium source gas-phase precursor is introduced in the step (1), purging is performed, and then steam is introduced.
Preferably, the step (1) is also purged after the steam is introduced.
The method provided by the invention has the advantages that the purging is carried out after the reaction gas is introduced every time, the coating uniformity can be further improved, and the cycle performance of the battery is further improved.
Preferably, the purge gas employed for the purge comprises nitrogen.
Preferably, the purge gas has a flow rate of 40 to 70sccm, such as 40sccm, 45sccm, 50sccm, 55sccm, 60sccm, or 70sccm, but is not limited to the recited values, and other unrecited values within the range of values are equally applicable.
The flow of the purge gas influences the deposition effect of the coating layer, if the flow of the purge gas is too small, the precursor source cannot be purged completely, and the reaction of the next precursor source is interfered; if the flow rate of the purge gas is too large, the gas is wasted.
Preferably, the purge time is 20-40s, for example 20s, 25s, 30s, 35s or 40s, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
Preferably, the steam of step (1) is obtained by heating with pure water at 98-105 deg.C, such as 98 deg.C, 100 deg.C or 105 deg.C, but not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the water vapor is introduced in step (1) for a period of time ranging from 1 to 3 seconds, for example 1s, 1.5s, 2s, 2.5s or 3s, but not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the steam is introduced into the step (1) at a flow rate of 20-40sccm, such as 20sccm, 30sccm or 40sccm, but not limited to the values listed, and other values not listed in the range of values are also applicable.
The water vapor participates in the reaction of the coating layer, and the introduction time of the water vapor also influences the coating effect and the stability of the material.
Preferably, the aluminum source vapor phase precursor in step (1) is obtained by heating an aluminum source at 20 to 40 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the aluminium source comprises trimethylaluminium and/or dimethylaluminium isopropoxide.
Preferably, the period of time for which the aluminum source vapor phase precursor is passed in step (1) is in the range of 0.5 to 2s, for example, 0.5s, 1s, 1.5s or 2s, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the aluminum source vapor phase precursor in step (1) is introduced at a flow rate of 20 to 40sccm, such as 20sccm, 30sccm or 40sccm, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the sodium source vapor phase precursor of step (1) is obtained by heating a sodium source at 160-180 ℃, for example, 160 ℃, 165 ℃, 170 ℃, 175 ℃ or 180 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the sodium source comprises sodium tert-butoxide/sodium acetoacetate.
Preferably, the sodium source vapor phase precursor is introduced in step (1) for a period of time in the range of 1 to 3 seconds, such as 1 second, 1.5 seconds, 2 seconds, 2.5 seconds, or 3 seconds, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the flow rate of the sodium source gas phase precursor in the step (1) is 20-40sccm, such as 20sccm, 30sccm or 40sccm, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the thickness of the positive electrode material of the sodium-ion battery in the step (2) is 15-60nm, such as 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm or 60nm, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
The number of the circulation in the step (2) is not particularly limited, and the number of the circulation can be adaptively adjusted according to the thickness of the coating layer.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
(1) Heating an aluminum source at the temperature of 20-40 ℃ to obtain an aluminum source gas-phase precursor; heating a sodium source at 160-180 ℃ to obtain a sodium source gas-phase precursor; heating pure water at 98-105 deg.C to obtain water vapor;
(2) Placing an inner core of the positive electrode material of the sodium-ion battery in an atomic layer deposition reaction cavity at the temperature of 210-250 ℃, vacuumizing, then introducing an aluminum source gas phase precursor into the reaction cavity at the flow rate of 20-40sccm for 0.5-2s, and introducing nitrogen at the flow rate of 40-70sccm for purging for 20-40s;
(3) After the purging in the step (2) is finished, introducing the sodium source gas-phase precursor for 1-3s at the flow rate of 20-40sccm, and then introducing nitrogen at the flow rate of 40-70sccm for purging for 20-40s;
(4) After the purging in the step (3) is finished, introducing water vapor for 1-3s at the flow rate of 20-40sccm, and then introducing nitrogen for purging for 20-40s at the flow rate of 40-70sccm to finish a primary deposition process;
(5) And (5) repeatedly introducing reactants to realize the circulation of the primary deposition process in the step (4) and obtain the sodium ion battery cathode material with the surface coated with sodium metaaluminate.
In a second aspect, the invention provides a positive electrode material of a sodium-ion battery, which is prepared by the preparation method of the first aspect.
In a third aspect, the invention provides a sodium-ion battery comprising the sodium-ion battery positive electrode material of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through an atomic layer deposition technology, gas-phase atmosphere coating is realized, the damage of a water-phase coating method to the sodium ion battery anode material is avoided, the whole deposition process is simple and controllable, the controllability is high, the method is green and pollution-free, the thickness of the coating layer can be regulated and controlled on a nanometer level, the quality of the prepared sodium metaaluminate coating layer is more excellent, the uniformity and the compactness degree are high, compared with the traditional alumina coating layer, the prepared sodium metaaluminate coating layer has higher conductivity, mechanical protection can be provided for material particles under the condition of not influencing the surface de-intercalation of sodium ions, the sodium ions in the material are prevented from being removed and embedded in water, and the cycle performance of the material is improved.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The core of the positive electrode material for sodium-ion batteries described in the following examples and comparative examples is NaMnO 2 The description of the kernel is only for more complete illustration of the technical solution of the present invention, and should not be regarded as a specific limitation of the present invention.
Example 1
The embodiment provides a preparation method of a sodium-ion battery cathode material, which comprises the following steps:
(1) Heating trimethylaluminum at 25 ℃ to obtain a trimethylaluminum gas phase precursor; heating sodium tert-butoxide at 170 ℃ to obtain a sodium tert-butoxide gas-phase precursor; heating pure water at 100 deg.C to obtain water vapor;
(2) Placing the inner core of the positive electrode material of the sodium-ion battery in an atomic layer deposition reaction cavity with the temperature of 235 ℃, vacuumizing, introducing a trimethylaluminum gas phase precursor into the reaction cavity for 1s at the flow rate of 30sccm, and introducing nitrogen for purging for 30s at the flow rate of 60 sccm;
(3) After the purging in the step (2) is finished, introducing a sodium tert-butoxide gas-phase precursor for 2s at the flow rate of 30sccm, and then introducing nitrogen at the flow rate of 60sccm to purge for 30s;
(4) After the purging in the step (3) is finished, introducing water vapor for 2s at the flow rate of 30sccm, and then introducing nitrogen for purging for 30s at the flow rate of 60sccm to finish a primary deposition process;
(5) And (5) repeatedly introducing reactants to realize the circulation of the primary deposition process in the step (4) until the surface is coated with sodium metaaluminate with the thickness of 30nm to obtain the sodium-ion battery anode material.
Example 2
The embodiment provides a preparation method of a sodium-ion battery cathode material, which comprises the following steps:
(1) Heating isopropanol dimethyl aluminum at 40 ℃ to obtain an isopropanol dimethyl aluminum gas phase precursor; heating sodium acetoacetate at 180 ℃ to obtain a sodium acetoacetate gas-phase precursor; heating pure water at 105 deg.C to obtain water vapor;
(2) Placing an inner core of the positive electrode material of the sodium-ion battery in an atomic layer deposition reaction cavity at the temperature of 250 ℃, vacuumizing, then introducing an isopropanol dimethyl aluminum gas phase precursor into the reaction cavity at the flow rate of 20sccm for 2s, and introducing nitrogen at the flow rate of 70sccm for purging for 20s;
(3) After the purging in the step (2) is finished, introducing a sodium acetoacetate gas-phase precursor for 1s at the flow rate of 30sccm, and then introducing nitrogen at the flow rate of 40sccm to purge for 40s;
(4) After the purging in the step (3) is finished, introducing water vapor for 3s at the flow rate of 20sccm, and then introducing nitrogen for purging for 20s at the flow rate of 70sccm to complete a primary deposition process;
(5) And (4) repeatedly introducing reactants, and realizing the circulation of the primary deposition process in the step (4) until the surface is coated with sodium metaaluminate with the thickness of 60nm to obtain the sodium-ion battery anode material.
Example 3
The embodiment provides a preparation method of a positive electrode material of a sodium-ion battery, which comprises the following steps:
(1) Heating trimethylaluminum at 20 ℃ to obtain a trimethylaluminum gas-phase precursor; heating sodium tert-butoxide at 160 ℃ to obtain a sodium tert-butoxide gas-phase precursor; heating pure water at 98 deg.C to obtain water vapor;
(2) Placing the inner core of the positive electrode material of the sodium-ion battery in an atomic layer deposition reaction cavity with the temperature of 210 ℃, vacuumizing, introducing a trimethylaluminum gas phase precursor into the reaction cavity at the flow rate of 30sccm for 0.5s, and introducing nitrogen at the flow rate of 40sccm for purging for 40s;
(3) After the purging in the step (2) is finished, introducing a sodium tert-butoxide gas-phase precursor for 3s at the flow rate of 40sccm, and then introducing nitrogen at the flow rate of 70sccm to purge for 20s;
(4) After the purging in the step (3) is finished, introducing water vapor for 1s at the flow rate of 40sccm, and then introducing nitrogen for purging for 40s at the flow rate of 40sccm to finish a deposition process;
(5) And (4) repeatedly introducing reactants, and realizing the circulation of the primary deposition process in the step (4) until the surface is coated with sodium metaaluminate with the thickness of 15nm to obtain the sodium-ion battery anode material.
Example 4
This example provides a method for preparing a positive electrode material for a sodium-ion battery, which is the same as that of example 1 except that the temperature of the ald reaction chamber in step (2) is 200 ℃.
Example 5
The embodiment provides a preparation method of a positive electrode material of a sodium-ion battery, which is the same as the embodiment 1 except that the temperature of the atomic layer deposition reaction chamber in the step (2) is 260 ℃.
Example 6
This example provides a method for preparing a positive electrode material for a sodium ion battery, which is the same as that of example 1 except that the flow rate of nitrogen gas at the time of purging was 30 sccm.
Example 7
This example provides a method for preparing a positive electrode material for a sodium ion battery, which is the same as that of example 1 except that the flow rate of nitrogen gas at the time of purging was 80 sccm.
Example 8
This example provides a method for producing a positive electrode material for a sodium-ion battery, which is the same as that of example 1 except that purging is not performed in both step (2) and step (3).
Example 9
This example provides a method for producing a positive electrode material for a sodium ion battery, which is the same as that of example 1 except that purging is not performed in any of steps (2) to (4).
Example 10
The embodiment provides a preparation method of a sodium-ion battery cathode material, which is the same as that in embodiment 1 except that a trimethyl aluminum gas-phase precursor, a sodium tert-butoxide gas-phase precursor and water vapor are introduced into a reaction cavity together, and purging is performed after all reactants are introduced.
Example 11
The embodiment provides a preparation method of a sodium-ion battery cathode material, which is the same as that in embodiment 1 except that water vapor is firstly introduced into an atomic layer deposition reaction chamber, and then a trimethylaluminum gas-phase precursor in step (2) and a sodium tert-butoxide gas-phase precursor in step (3) are introduced.
Comparative example 1
The comparative example provides a preparation method of a positive electrode material of a sodium-ion battery, comprising the following steps:
(1) Heating sodium metaaluminate at 235 ℃ to obtain sodium metaaluminate gas;
(2) Placing the inner core of the positive electrode material of the sodium-ion battery in an atomic layer deposition reaction cavity at 235 ℃, vacuumizing, introducing sodium metaaluminate gas into the reaction cavity for 5s, and introducing nitrogen at the flow of 60sccm to purge for 30s to complete a deposition process;
(3) And (3) repeatedly introducing reactants, and realizing the circulation of the primary deposition process in the step (2) until the surface is coated with sodium metaaluminate with the thickness of 30nm to obtain the sodium-ion battery anode material.
Comparative example 2
The comparative example provides a preparation method of a sodium-ion battery cathode material, which comprises the following steps:
mixing the inner core of the positive electrode material of the sodium-ion battery, sodium metaaluminate and water according to the formula amount, and then filtering and drying to obtain the positive electrode material of the sodium-ion battery.
Preparing the positive electrode material of the sodium-ion battery obtained in the above embodiment and comparative example into a positive electrode plate, then preparing the positive electrode plate and a sodium plate into the sodium-ion battery, and testing the cycle retention rate of 200 circles of the sodium-ion battery, wherein the test results are shown in the following table; the test method of the cycle performance comprises the following steps: at the temperature of 25 ℃, charging the battery to the voltage of 4.0V by a constant current of 0.1C, charging to the current of 0.05C by a constant voltage, and then discharging to the voltage of 2.0V by a constant current of 0.1C; further charging with a constant current of 0.5C to a voltage of 4.0V, and then discharging with a constant current of 0.5C to a voltage of 2.0V, which is a charge-discharge cycle process; and (4) cycling and charging 200 times according to the method, detecting the discharge capacity when the cycle is 200 times, and dividing the discharge capacity by the first discharge capacity to obtain the capacity retention rate.
TABLE 1
From the above table it can be seen that:
from the embodiment 1 and the comparative example 1, the sodium metaaluminate coating layer is prepared by in-situ deposition, compared with the method of directly depositing by taking sodium metaaluminate as a precursor, the obtained coating layer is more uniform and compact, the stability of the coating layer is higher, and the phase structure is good, so that the cycle performance of the obtained battery is excellent; as can be seen from the example 1 and the comparative example 2, compared with liquid phase coating, the atomic layer deposition coating method of the present invention does not damage the structural stability of the positive electrode material of the sodium ion battery, and the obtained battery has excellent cycle performance; from the embodiment 1 and the embodiments 4 to 7, it can be known that the temperature of the atomic layer deposition reaction chamber and the flow rate of the nitrogen purging affect the atomic layer deposition process, thereby affecting the deposition uniformity and the bonding strength between the coating layer and the core; from the embodiment 1 and the embodiments 8-9, the invention can improve the deposition effect by nitrogen purging after the reaction gas is introduced, thereby improving the cycle performance of the battery; it can be seen from examples 1 and 10-11 that the sequence of the introduction of the gaseous reactants according to the present invention also affects the deposition effect.
In conclusion, the preparation method adopts atomic layer deposition for coating modification, does not relate to a water phase, can accurately control the thickness of a coating on a nanometer level, has high uniformity of the obtained coating and high bonding strength with a kernel compared with other coating methods, and can remarkably improve the cycle performance of the sodium-ion battery cathode material.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The preparation method of the positive electrode material of the sodium-ion battery is characterized by comprising the following steps of:
(1) Placing an inner core of the positive electrode material of the sodium-ion battery in an atomic layer deposition reaction cavity, and introducing an aluminum source gas-phase precursor, a sodium source gas-phase precursor and water vapor into the reaction cavity to carry out atomic layer deposition so as to finish a deposition process;
(2) And (2) repeatedly introducing reactants to realize the circulation of the primary deposition process in the step (1) and obtain the sodium ion battery cathode material with the surface coated with sodium metaaluminate.
2. The method for preparing the atomic layer deposition reaction chamber according to the claim 1, wherein the temperature of the atomic layer deposition reaction chamber in the step (1) is 210-250 ℃;
preferably, the introducing sequence in the step (1) is to introduce an aluminum source gas phase precursor, introduce a sodium source gas phase precursor and finally introduce water vapor;
preferably, in the step (1), before the gas is introduced into the reaction chamber, vacuum is firstly pumped.
3. The production method according to claim 1 or 2, characterized in that, after the aluminum source vapor phase precursor is introduced in step (1), purging is performed, and then a sodium source vapor phase precursor is introduced;
preferably, after the sodium source gas-phase precursor is introduced in the step (1), purging is performed, and then steam is introduced;
preferably, purging is also performed after the steam is introduced in the step (1).
4. The production method according to claim 3, wherein the purge gas used for the purge includes nitrogen;
preferably, the flow rate of the purge gas is 40-70sccm;
preferably, the time for purging is 20-40s.
5. The production method according to any one of claims 1 to 4, wherein the water vapor in step (1) is obtained by heating with pure water at 98 to 105 ℃;
preferably, the water vapor in the step (1) is introduced for 1 to 3s at a flow rate of 20 to 40sccm.
6. The production method according to any one of claims 1 to 5, wherein the vapor phase precursor of the aluminum source in the step (1) is obtained by heating an aluminum source at 20 to 40 ℃;
preferably, the aluminium source comprises trimethylaluminium and/or dimethylaluminium isopropoxide;
preferably, the introducing time of the aluminum source gas phase precursor in the step (1) is 0.5-2s, and the introducing flow rate is 20-40sccm.
7. The production method according to any one of claims 1 to 6, wherein the sodium source gas phase precursor in step (1) is obtained by heating a sodium source at 160 to 180 ℃;
preferably, the sodium source comprises sodium tert-butoxide/sodium acetoacetate;
preferably, the sodium source gas-phase precursor is introduced for 1 to 3s in the step (1), and the introduction flow rate is 20 to 40sccm.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) Heating an aluminum source at the temperature of 20-40 ℃ to obtain an aluminum source gas-phase precursor; heating a sodium source at 160-180 ℃ to obtain a sodium source gas-phase precursor; heating pure water at 98-105 deg.C to obtain water vapor;
(2) Placing an inner core of the sodium-ion battery anode material in an atomic layer deposition reaction cavity with the temperature of 210-250 ℃, vacuumizing, then introducing an aluminum source gas phase precursor into the reaction cavity at the flow rate of 20-40sccm for 0.5-2s, and introducing nitrogen at the flow rate of 40-70sccm for purging for 20-40s;
(3) After the purging in the step (2) is finished, introducing the sodium source gas-phase precursor for 1-3s at the flow rate of 20-40sccm, and then introducing nitrogen at the flow rate of 40-70sccm for purging for 20-40s;
(4) After the purging in the step (3) is finished, introducing water vapor for 1-3s at the flow rate of 20-40sccm, and then introducing nitrogen for purging for 20-40s at the flow rate of 40-70sccm to finish a primary deposition process;
(5) And (4) repeatedly introducing reactants, and realizing the circulation of the primary deposition process in the step (4) to obtain the sodium ion battery anode material with the surface coated with sodium metaaluminate.
9. The positive electrode material for the sodium-ion battery, which is prepared by the preparation method of any one of claims 1 to 8.
10. A sodium-ion battery, characterized in that the sodium-ion battery comprises the sodium-ion battery positive electrode material according to claim 9.
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