Solid-state sodium-ion battery electrolyte film and preparation method and application thereof

Abstract

The application provides a solid-state sodium-ion battery electrolyte film and a preparation method and application thereof, the preparation method uses zirconium source vapor, silicon source vapor, phosphorus source vapor and sodium source vapor in sequence for atomic layer deposition, and water vapor treatment is performed after each atomic layer deposition, the obtained solid-state sodium-ion battery electrolyte film is a sodium superionic conductor film, the sodium superionic conductor film can realize accurate control of nanoscale thickness, the obtained solid-state sodium-ion battery electrolyte film is dense and free of pinholes, can effectively inhibit the formation of sodium dendrites, improve the safety performance of a sodium-ion battery, and compared with other solid-state electrolyte materials, the sodium superionic conductor can provide higher sodium ion conductivity, and when used in a sodium-ion battery, the sodium-ion battery has excellent electrochemical performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of batteries, and relates to a battery film, in particular to a solid-state sodium ion battery electrolyte film and a preparation method and application thereof. BACKGROUND

[0002] Lithium ion batteries have the advantages of high energy density, low self-discharge and long service life, and are widely used in technical fields such as electronic devices and electric vehicles. With the increasing use of lithium ion batteries, the price of battery-grade lithium carbonate is also rising, and the cost problem has become an important factor restricting the further development of lithium ion batteries.

[0003] Sodium has properties close to lithium, but is lower in cost, and therefore, sodium metal batteries are recognized as one of the most promising alternatives to lithium ion batteries. Compared with liquid electrolyte sodium ion batteries, solid-state sodium batteries (SSNB) have high energy density, high power density and excellent safety, and have lower manufacturing and maintenance costs.

[0004] The solid-state electrolyte film is a key component of the solid-state sodium metal battery, and therefore, the preparation of an electrolyte material with high ionic conductivity is a key to the development of solid-state sodium batteries. At present, common methods for preparing solid-state electrolyte films include vacuum evaporation, magnetron sputtering, chemical vapor deposition and polymer extrusion calendaring. However, the above methods are relatively complicated, and the films prepared therefrom are often based on the surface of a flat and smooth substrate, and have poor coverage of the surface of the electrode material. Moreover, the thickness of the solid-state electrolyte film cannot be accurately controlled, and a solid-state electrolyte film with a nanoscale thickness and being dense and free of pinholes cannot be obtained.

[0005] For example, CN115411358A discloses a sodium ion solid-state electrolyte film with a penetrating structure and a preparation method thereof. A mixture is obtained by mixing a metal organic framework, a polymer chain segment PEO and a sodium salt, an acetonitrile solution is added to the mixture and ultrasonic treatment is performed, then ultrasonic stirring is performed to obtain a mixed solution; then the mixed solution is poured into a mold and dried in a vacuum drying box to obtain a sodium ion solid-state electrolyte film.

[0006] CN110165290A discloses a solid-state sodium ion electrolyte, a preparation method and application thereof. The preparation method comprises: using an electrospinning technology to spray a high molecular solution onto a selected receiving surface to form a continuous two-dimensional or three-dimensional structure, and performing pressure treatment on the two-dimensional or three-dimensional structure to densify the structure to obtain a continuous organic phase; and then impregnating the continuous organic phase with a sodium salt electrolyte solution to make the sodium salt electrolyte enter the high molecular fiber and the pores in the continuous organic phase to form a solid-state sodium ion electrolyte.

[0007] CN110690495A discloses a preparation method of a composite gel polymer solid electrolyte, comprising: preparing a spinning solution comprising an aluminum salt, a sodium salt and a first high molecular polymer; electrostatically spinning the spinning solution to obtain a precursor film; calcining the precursor film to obtain a fiber film; providing an impregnating solution comprising a second high molecular polymer; coating the impregnating solution in the fiber film to obtain a fiber / polymer composite film containing the second high molecular polymer; and placing the fiber / polymer composite film in an organic electrolyte solution, which is adsorbed in the fiber / polymer composite film to obtain a composite gel polymer solid electrolyte.

[0008] Therefore, in order to realize the preparation of a solid electrolyte film with nanoscale thickness and no pinholes, it is necessary to provide a solid sodium ion battery electrolyte film and a preparation method and application thereof. SUMMARY

[0009] In view of the deficiencies of the prior art, the purpose of the present application is to provide a solid sodium ion battery electrolyte film and a preparation method and application thereof. The solid sodium ion battery electrolyte film is a nanoscale pinhole-free sodium superionic conductor film, which can overcome the problems of complex process and thick finished film in the traditional solid film preparation method, and provides more feasibility for the safety, high energy density and fast charging of all-solid-state batteries.

[0010] To achieve this purpose, the present application adopts the following technical solutions:

[0011] In a first aspect, the present application provides a preparation method of a solid sodium ion battery electrolyte film, comprising the following steps:

[0012] (1) using a zirconium source vapor to perform atomic layer deposition on a deposition substrate, and then performing a first purge; then introducing water vapor, and then performing a second purge;

[0013] (2) using a silicon source vapor to continue atomic layer deposition, and then performing a third purge; then introducing water vapor, and then performing a fourth purge;

[0014] (3) using a phosphorus source vapor to continue atomic layer deposition, and then performing a fifth purge; then introducing water vapor, and then performing a sixth purge;

[0015] (4) using a sodium source vapor to continue atomic layer deposition, and then performing a seventh purge; then introducing water vapor, and then performing an eighth purge;

[0016] Steps (1) to (4) are cycled until a solid sodium ion battery electrolyte film with the desired thickness is obtained.

[0017] The deposition substrate in step (1) of the present application includes any one of a silicon wafer, a positive electrode wafer or a negative electrode wafer, and the present application does not make specific limitations, and those skilled in the art can reasonably select according to the needs.

[0018] The preparation method provided by the present application adopts an atomic layer deposition method to prepare a solid-state sodium ion battery electrolyte film. The atomic layer deposition method alternately introduces gas phase reactants to cause a chemical reaction on the surface of a deposition substrate, and realizes single-layer cumulative deposition, so that the thickness of the solid-state sodium ion battery electrolyte film obtained in a single cycle is about 0.1 nm, thereby realizing the preparation of a nanoscale or even sub-nanoscale solid-state sodium ion battery electrolyte film. Moreover, the solid-state sodium ion battery electrolyte film obtained by the present application has very good shape retention, and the surface is dense and free of pinholes.

[0019] Moreover, the solid-state sodium ion battery electrolyte film obtained by the preparation method of the present application is a sodium superionic conductor Na3Zr2Si2PO 12 The film can effectively inhibit the formation of sodium dendrites, thereby improving the safety performance of the sodium ion battery.

[0020] The atomic layer deposition is performed under vacuum conditions, and the zirconium source vapor, the silicon source vapor, the phosphorus source vapor and the sodium source vapor are independently generated under vacuum conditions; the absolute vacuum degree of the vacuum condition is ≤5×10 -3 Pa, and the present application does not make specific limitations on the specific conditions for generating vacuum, as long as the absolute vacuum degree when the vapor is generated meets the requirements.

[0021] The present application does not make specific limitations on the flow rates of the zirconium source vapor, the silicon source vapor, the phosphorus source vapor and the sodium source vapor, as long as they meet the formula amount of the sodium superionic conductor Na3Zr2Si2PO 12 .

[0022] Preferably, the zirconium source vapor in step (1) includes tetrakis(dimethylamino)zirconium and / or tert-butyl zirconium.

[0023] Preferably, the temperature of the zirconium source vapor in step (1) is 80-85℃, for example, it can be 80℃, 81℃, 82℃, 83℃, 84℃ or 85℃, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0024] Preferably, the introduction time of the zirconium source vapor in step (1) is 8-12s, for example, it can be 8s, 9s, 10s, 11s or 12s, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0025] Preferably, the first purging in step (1) is performed using a protective gas.

[0026] Preferably, the flow rate of the first purge of step (1) is 25-35 mL / min, and the temperature is 95-105 °C, and the time is 45-55 s.

[0027] The flow rate of the first purge of the present application is 25-35 mL / min, for example, it can be 25 mL / min, 27 mL / min, 28 mL / min, 30 mL / min, 32 mL / min, or 35 mL / min, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0028] The temperature of the first purge of the present application is 95-105 °C, for example, it can be 95 °C, 96 °C, 98 °C, 100 °C, 102 °C, or 105 °C, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0029] The time of the first purge of the present application is 45-55 s, for example, it can be 45 s, 48 s, 50 s, 52 s, 54 s, or 55 s, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0030] Preferably, the time of the water vapor of step (1) is 8-12 s, for example, it can be 8 s, 9 s, 10 s, 11 s, or 12 s, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0031] Preferably, the flow rate of the water vapor of step (1) is 120-130 mL / min, for example, it can be 120 mL / min, 122 mL / min, 125 mL / min, 126 mL / min, 128 mL / min, or 130 mL / min, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0032] Preferably, the second purge of step (1) is performed using a protective gas.

[0033] Preferably, the flow rate of the second purge of step (1) is 25-35 mL / min, and the temperature is 95-105 °C, and the time is 45-55 s.

[0034] The flow rate of the second purge of the present application is 25-35 mL / min, for example, it can be 25 mL / min, 27 mL / min, 28 mL / min, 30 mL / min, 32 mL / min, or 35 mL / min, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0035] The temperature of the second purge is 95-105°C, for example, it can be 95°C, 96°C, 98°C, 100°C, 102°C or 105°C, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0036] The time of the second purge is 45-55s, for example, it can be 45s, 48s, 50s, 52s, 54s or 55s, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0037] Preferably, the silicon source vapor in step (2) comprises ethyl silicate vapor and / or methyl orthosilicate vapor.

[0038] Preferably, the temperature of the silicon source vapor in step (2) is 75-80°C, for example, it can be 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0039] Preferably, the time of the silicon source vapor in step (2) is 8-12s, for example, it can be 8s, 9s, 10s, 11s or 12s, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0040] Preferably, the third purge in step (2) is performed using a protective gas.

[0041] Preferably, the flow rate of the third purge in step (2) is 25-35mL / min, the temperature is 95-105°C, and the time is 45-55s.

[0042] The flow rate of the third purge is 25-35mL / min, for example, it can be 25mL / min, 27mL / min, 28mL / min, 30mL / min, 32mL / min or 35mL / min, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0043] The temperature of the third purge is 95-105°C, for example, it can be 95°C, 96°C, 98°C, 100°C, 102°C or 105°C, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0044] The time of the third purge is 45-55s, for example, it can be 45s, 48s, 50s, 52s, 54s or 55s, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0045] Preferably, the time for the water vapor to pass in step (2) is 8-12 s, for example, it can be 8 s, 9 s, 10 s, 11 s or 12 s, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0046] Preferably, the flow rate of the water vapor in step (2) is 120-130 mL / min, for example, it can be 120 mL / min, 122 mL / min, 125 mL / min, 126 mL / min, 128 mL / min or 130 mL / min, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0047] Preferably, the fourth purge in step (2) is performed using a protective gas.

[0048] Preferably, the flow rate of the fourth purge in step (2) is 25-35 mL / min, the temperature is 95-105℃, and the time is 45-55 s.

[0049] The flow rate of the fourth purge in the present application is 25-35 mL / min, for example, it can be 25 mL / min, 27 mL / min, 28 mL / min, 30 mL / min, 32 mL / min or 35 mL / min, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0050] The temperature of the fourth purge in the present application is 95-105℃, for example, it can be 95℃, 96℃, 98℃, 100℃, 102℃ or 105℃, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0051] The time of the fourth purge in the present application is 45-55 s, for example, it can be 45 s, 48 s, 50 s, 52 s, 54 s or 55 s, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0052] Preferably, the phosphorus source vapor in step (3) includes trimethyl phosphate vapor and / or tetramethyl methylenediphosphonate vapor;

[0053] Preferably, the temperature of the phosphorus source vapor in step (3) is 40-60℃, for example, it can be 40℃, 45℃, 50℃, 55℃ or 60℃, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0054] Preferably, the time for the phosphorus source vapor to pass in step (3) is 4-6 s, for example, it can be 4 s, 4.5 s, 5 s, 5.5 s or 6 s, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0055] Preferably, the fifth purge of step (3) is performed using a protective gas.

[0056] Preferably, the fifth purge of step (3) has a flow rate of 25-35 mL / min, a temperature of 95-105 °C, and a time of 45-55 s.

[0057] The flow rate of the fifth purge of the present application is 25-35 mL / min, for example, it can be 25 mL / min, 27 mL / min, 28 mL / min, 30 mL / min, 32 mL / min, or 35 mL / min, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0058] The temperature of the fifth purge of the present application is 95-105 °C, for example, it can be 95 °C, 96 °C, 98 °C, 100 °C, 102 °C, or 105 °C, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0059] The time of the fifth purge of the present application is 45-55 s, for example, it can be 45 s, 48 s, 50 s, 52 s, 54 s, or 55 s, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0060] Preferably, the time of the water vapor of step (3) is 4-6 s, for example, it can be 4 s, 4.5 s, 5 s, 5.5 s, or 6 s, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0061] Preferably, the flow rate of the water vapor of step (3) is 120-130 mL / min, for example, it can be 120 mL / min, 122 mL / min, 125 mL / min, 126 mL / min, 128 mL / min, or 130 mL / min, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0062] Preferably, the sixth purge of step (3) is performed using a protective gas.

[0063] Preferably, the sixth purge of step (3) has a flow rate of 25-35 mL / min, a temperature of 95-105 °C, and a time of 45-55 s.

[0064] The flow rate of the sixth purge of the present application is 25-35 mL / min, for example, it can be 25 mL / min, 27 mL / min, 28 mL / min, 30 mL / min, 32 mL / min, or 35 mL / min, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0065] The temperature of the sixth purge according to the present application is 95-105℃, for example, it can be 95℃, 96℃, 98℃, 100℃, 102℃ or 105℃, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0066] The time of the sixth purge according to the present application is 45-55s, for example, it can be 45s, 48s, 50s, 52s, 54s or 55s, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0067] Preferably, the sodium source vapor in step (4) comprises sodium tert-butoxide vapor and / or sodium hexamethyldisilazide vapor.

[0068] Preferably, the temperature of the sodium source vapor in step (4) is 70-75℃, for example, it can be 70℃, 71℃, 72℃, 73℃, 74℃ or 75℃, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0069] Preferably, the time of the sodium source vapor in step (4) is 8-12s, for example, it can be 8s, 9s, 10s, 11s or 12s, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0070] Preferably, the seventh purge in step (4) is performed using a protective gas.

[0071] Preferably, the flow rate of the seventh purge in step (4) is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s.

[0072] The flow rate of the seventh purge according to the present application is 25-35mL / min, for example, it can be 25mL / min, 27mL / min, 28mL / min, 30mL / min, 32mL / min or 35mL / min, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0073] The temperature of the seventh purge according to the present application is 95-105℃, for example, it can be 95℃, 96℃, 98℃, 100℃, 102℃ or 105℃, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0074] The time of the seventh purge according to the present application is 45-55s, for example, it can be 45s, 48s, 50s, 52s, 54s or 55s, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0075] Preferably, the time for the water vapor to pass in step (4) is 8-12s, for example, it can be 8s, 9s, 10s, 11s or 12s, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0076] Preferably, the flow rate of the water vapor in step (4) is 120-130mL / min, for example, it can be 120mL / min, 122mL / min, 125mL / min, 126mL / min, 128mL / min or 130mL / min, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0077] Preferably, the eighth purge in step (4) is performed using a protective gas.

[0078] Preferably, the flow rate of the eighth purge in step (4) is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s.

[0079] The flow rate of the eighth purge according to the present application is 25-35mL / min, for example, it can be 25mL / min, 27mL / min, 28mL / min, 30mL / min, 32mL / min or 35mL / min, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0080] The temperature of the eighth purge according to the present application is 95-105℃, for example, it can be 95℃, 96℃, 98℃, 100℃, 102℃ or 105℃, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0081] The time of the eighth purge according to the present application is 45-55s, for example, it can be 45s, 48s, 50s, 52s, 54s or 55s, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0082] Preferably, the protective gas includes nitrogen and / or an inert gas.

[0083] Preferably, the deposition substrate in step (1) is placed in a thermostat with a temperature of 140-160℃, for example, it can be 140℃, 145℃, 150℃, 155℃ or 160℃, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0084] As a preferred technical solution of the preparation method according to the first aspect of the present application, the preparation method comprises the following steps:

[0085] (1) the deposition substrate is placed in a constant temperature part with a temperature of 140-160℃, atomic layer deposition is carried out on the deposition substrate using zirconium source steam with a temperature of 80-85℃ for 8-12s, and then a first purging is carried out using nitrogen; then water vapor is introduced at a flow rate of 120-130mL / min for 8-12s, and then a second purging is carried out using nitrogen; the flow rate of the first purging is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s; the flow rate of the second purging is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s;

[0086] (2) atomic layer deposition is continued using silicon source steam with a temperature of 75-80℃ for 8-12s, and then a third purging is carried out using nitrogen; then water vapor is introduced at a flow rate of 120-130mL / min for 8-12s, and then a fourth purging is carried out using nitrogen; the flow rate of the third purging is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s; the flow rate of the fourth purging is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s;

[0087] (3) atomic layer deposition is continued using phosphorus source steam with a temperature of 40-60℃ for 4-6s, and then a fifth purging is carried out using nitrogen; then water vapor is introduced at a flow rate of 120-130mL / min for 8-12s, and then a sixth purging is carried out using nitrogen; the flow rate of the fifth purging is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s; the flow rate of the sixth purging is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s;

[0088] (4) atomic layer deposition is continued using sodium source steam with a temperature of 70-75℃ for 8-12s, and then a seventh purging is carried out using nitrogen; then water vapor is introduced at a flow rate of 120-130mL / min for 8-12s, and then an eighth purging is carried out using nitrogen; the flow rate of the seventh purging is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s; the flow rate of the eighth purging is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s;

[0089] Steps (1) to (4) are cycled until a solid-state sodium ion battery electrolyte film with a desired thickness is obtained.

[0090] In a second aspect, the present application provides a solid-state sodium ion battery electrolyte film, which is obtained by the preparation method of the first aspect.

[0091] In a third aspect, the present application provides a sodium ion battery, which comprises the solid-state sodium ion battery electrolyte film according to the second aspect.

[0092] The numerical ranges recited herein are inclusive of the endpoints and also include any other ranges derived from the aforementioned ranges by combining the lower limit of one range or sub-range with the upper limit of another range or sub-range. For ranges containing explicit values, the explicit values are included in the range. For ranges containing upper and lower limits, the range includes the upper and lower limits.

[0093] Compared with the prior art, the present application has the following beneficial effects:

[0094] (1) The preparation method provided by the present application uses an atomic layer deposition method to prepare a solid-state sodium ion battery electrolyte film. The atomic layer deposition method alternately introduces gas-phase reactants, which chemically react on the surface of a deposition substrate to realize single-layer cumulative deposition, thereby realizing the preparation of a nanoscale or even sub-nanoscale solid-state sodium ion battery electrolyte film. Moreover, the solid-state sodium ion battery electrolyte film obtained by the present application has very good shape retention and a dense surface without pinholes.

[0095] (2) The solid-state sodium ion battery electrolyte film obtained by the preparation method of the present application is a sodium superionic conductor Na3Zr2Si2PO 12 The solid-state sodium ion battery electrolyte film can effectively inhibit the formation of sodium dendrites, thereby improving the safety performance of the sodium ion battery. DETAILED DESCRIPTION

[0096] The technical solutions of the present application will be further described below through specific embodiments.

[0097] In the specific embodiments of the present application, the atomic layer deposition is carried out under vacuum conditions, and the zirconium source vapor, the silicon source vapor, the phosphorus source vapor and the sodium source vapor are independently generated under vacuum conditions; the absolute vacuum degree of the vacuum conditions is ≤5×10 -3 Pa.

[0098] In the specific embodiments of the present application, the thickness of the solid-state sodium ion battery electrolyte film is measured by a step meter.

[0099] Example 1

[0100] The present embodiment provides a preparation method of a solid-state sodium ion battery electrolyte film, which comprises the following steps:

[0101] (1) The deposition substrate is placed on a thermostatic table with a temperature of 150°C, and the deposition substrate is subjected to atomic layer deposition for 10 s using tetrakis(dimethylamino)zirconium vapor with a temperature of 82°C, and then a first purging is performed using nitrogen; then water vapor is introduced at a flow rate of 125 mL / min for 10 s, and then a second purging is performed using nitrogen; the flow rate of the first purging is 30 mL / min, the temperature is 100°C, and the time is 50 s; the flow rate of the second purging is 30 mL / min, the temperature is 100°C, and the time is 50 s;

[0102] (2) The atomic layer deposition is continued for 10 s using ethyl silicate vapor with a temperature of 78°C, and then a third purging is performed using nitrogen; then water vapor is introduced at a flow rate of 125 mL / min for 10 s, and then a fourth purging is performed using nitrogen; the flow rate of the third purging is 30 mL / min, the temperature is 100°C, and the time is 50 s; the flow rate of the fourth purging is 30 mL / min, the temperature is 100°C, and the time is 50 s;

[0103] (3) The atomic layer deposition is continued for 5 s using phosphonium trimethyl ester vapor with a temperature of 50°C, and then a fifth purging is performed using nitrogen; then water vapor is introduced at a flow rate of 125 mL / min for 5 s, and then a sixth purging is performed using nitrogen; the flow rate of the fifth purging is 30 mL / min, the temperature is 100°C, and the time is 50 s; the flow rate of the sixth purging is 30 mL / min, the temperature is 100°C, and the time is 50 s;

[0104] (4) The atomic layer deposition is continued for 10 s using sodium tert-butoxide vapor with a temperature of 72°C, and then a seventh purging is performed using nitrogen; then water vapor is introduced at a flow rate of 125 mL / min for 10 s, and then an eighth purging is performed using nitrogen; the flow rate of the seventh purging is 30 mL / min, the temperature is 100°C, and the time is 50 s; the flow rate of the eighth purging is 30 mL / min, the temperature is 100°C, and the time is 50 s;

[0105] The thickness of the solid-state sodium ion battery electrolyte film obtained in one cycle is 0.1 nm; steps (1) to (4) are cycled until a solid-state sodium ion battery electrolyte film with a thickness of 200 nm is obtained.

[0106] Example 2

[0107] The present embodiment provides a preparation method of a solid-state sodium ion battery electrolyte film, which comprises the following steps:

[0108] (1) The deposition substrate was placed on a temperature-controlled stage at 140 °C, and atomic layer deposition was performed on the deposition substrate using tetrakis(dimethylamino)zirconium vapor at a temperature of 80 °C for 12 s, followed by a first purge using nitrogen. Then water vapor was introduced at a flow rate of 120 mL / min for 8 s, followed by a second purge using nitrogen. The flow rate of the first purge was 25 mL / min, the temperature was 95 °C, and the time was 55 s. The flow rate of the second purge was 25 mL / min, the temperature was 95 °C, and the time was 55 s.

[0109] (2) Atomic layer deposition was continued using ethyl silicate vapor at a temperature of 75 °C for 12 s, followed by a third purge using nitrogen. Then water vapor was introduced at a flow rate of 120 mL / min for 8 s, followed by a fourth purge using nitrogen. The flow rate of the third purge was 25 mL / min, the temperature was 95 °C, and the time was 55 s. The flow rate of the fourth purge was 25 mL / min, the temperature was 95 °C, and the time was 55 s.

[0110] (3) Atomic layer deposition was continued using trimethyl phosphate vapor at a temperature of 40 °C for 6 s, followed by a fifth purge using nitrogen. Then water vapor was introduced at a flow rate of 120 mL / min for 4 s, followed by a sixth purge using nitrogen. The flow rate of the fifth purge was 25 mL / min, the temperature was 95 °C, and the time was 55 s. The flow rate of the sixth purge was 25 mL / min, the temperature was 95 °C, and the time was 55 s.

[0111] (4) Atomic layer deposition was continued using sodium tert-butoxide vapor at a temperature of 70 °C for 12 s, followed by a seventh purge using nitrogen. Then water vapor was introduced at a flow rate of 120 mL / min for 8 s, followed by an eighth purge using nitrogen. The flow rate of the seventh purge was 25 mL / min, the temperature was 95 °C, and the time was 55 s. The flow rate of the eighth purge was 25 mL / min, the temperature was 95 °C, and the time was 55 s.

[0112] The thickness of the solid-state sodium-ion battery electrolyte thin film obtained in one cycle was 0.1 nm. Steps (1) to (4) were repeated until a solid-state sodium-ion battery electrolyte thin film with a thickness of 200 nm was obtained.

[0113] Example 3

[0114] The present embodiment provides a method for preparing a solid-state sodium-ion battery electrolyte thin film, which comprises the following steps:

[0115] (1) The deposition substrate was placed on a constant temperature table with a temperature of 160°C, atomic layer deposition was carried out on the deposition substrate using tetrakis (dimethylamino) zirconium vapor with a temperature of 85°C for 8s, and then a first purging was carried out using nitrogen; then water vapor was introduced at a flow rate of 130 mL / min for 12s, and then a second purging was carried out using nitrogen; the flow rate of the first purging was 35 mL / min, the temperature was 105°C, and the time was 45s; the flow rate of the second purging was 35 mL / min, the temperature was 105°C, and the time was 45s;

[0116] (2) Atomic layer deposition was continued using ethyl silicate vapor with a temperature of 80°C for 8s, and then a third purging was carried out using nitrogen; then water vapor was introduced at a flow rate of 130 mL / min for 12s, and then a fourth purging was carried out using nitrogen; the flow rate of the third purging was 35 mL / min, the temperature was 105°C, and the time was 45s; the flow rate of the fourth purging was 35 mL / min, the temperature was 105°C, and the time was 45s;

[0117] (3) Atomic layer deposition was continued using trimethyl phosphate vapor with a temperature of 60°C for 4s, and then a fifth purging was carried out using nitrogen; then water vapor was introduced at a flow rate of 130 mL / min for 6s, and then a sixth purging was carried out using nitrogen; the flow rate of the fifth purging was 35 mL / min, the temperature was 105°C, and the time was 45s; the flow rate of the sixth purging was 35 mL / min, the temperature was 105°C, and the time was 45s;

[0118] (4) Atomic layer deposition was continued using sodium tert-butoxide vapor with a temperature of 75°C for 8s, and then a seventh purging was carried out using nitrogen; then water vapor was introduced at a flow rate of 120 mL / min for 8s, and then an eighth purging was carried out using nitrogen; the flow rate of the seventh purging was 35 mL / min, the temperature was 105°C, and the time was 45s; the flow rate of the eighth purging was 35 mL / min, the temperature was 105°C, and the time was 45s;

[0119] The thickness of the solid-state sodium ion battery electrolyte film obtained in one cycle was 0.1 nm; steps (1) to (4) were cycled until a solid-state sodium ion battery electrolyte film with a thickness of 200 nm was obtained.

[0120] Example 4

[0121] The present example provides a method for preparing a solid-state sodium ion battery electrolyte film, which is the same as example 1 except that the zirconium source vapor is tert-butyl zirconium vapor.

[0122] Example 5

[0123] The embodiment provides a preparation method of a solid-state sodium ion battery electrolyte film, and the preparation method is the same as that in the embodiment 1 except that the phosphorus source vapor is tetramethyl methylenediphosphonate vapor.

[0124] Embodiment 6

[0125] The embodiment provides a preparation method of a solid-state sodium ion battery electrolyte film, and the preparation method is the same as that in the embodiment 1 except that the sodium source vapor is hexamethyldisilazane sodium vapor.

[0126] Embodiment 7

[0127] The embodiment provides a preparation method of a solid-state sodium ion battery electrolyte film, and the preparation method is the same as that in the embodiment 1 except that the temperature of the constant-temperature table is 135 DEG C.

[0128] Embodiment 8

[0129] The embodiment provides a preparation method of a solid-state sodium ion battery electrolyte film, and the preparation method is the same as that in the embodiment 1 except that the temperature of the constant-temperature table is 165 DEG C.

[0130] Comparative example 1

[0131] The comparative example provides a preparation method of a solid-state sodium ion battery electrolyte film, and the preparation method is the same as that in the embodiment 1 except that the step (1) of the preparation method is that the deposition substrate is placed on a constant-temperature table with a temperature of 150 DEG C, and the deposition substrate is subjected to atomic layer deposition for 10 s by using tetrakis (dimethylamino) zirconium vapor with a temperature of 82 DEG C, and then first and second purging are performed by using nitrogen; the flow rate of the first purging is 30 mL / min, the temperature is 100 DEG C, and the time is 50 s; the flow rate of the second purging is 30 mL / min, the temperature is 100 DEG C, and the time is 50 s.

[0132] The rest is the same as in the embodiment 1.

[0133] Comparative example 2

[0134] The comparative example provides a preparation method of a solid-state sodium ion battery electrolyte film, and the preparation method is the same as that in the embodiment 1 except that the step (2) of the preparation method is that atomic layer deposition is continuously performed for 10 s by using ethyl silicate vapor with a temperature of 78 DEG C, and then third and fourth purging are performed by using nitrogen; the flow rate of the third purging is 30 mL / min, the temperature is 100 DEG C, and the time is 50 s; the flow rate of the fourth purging is 30 mL / min, the temperature is 100 DEG C, and the time is 50 s.

[0135] The rest is the same as in the embodiment 1.

[0136] Comparative example 3

[0137] The comparative example 1 provides a preparation method of a solid-state sodium-ion battery electrolyte film, wherein step (3) of the preparation method is that: the atomic layer deposition is continued for 5 s using trimethyl phosphate vapor with a temperature of 50 °C, and then the fifth and sixth purges are performed using nitrogen; the flow rate of the fifth purge is 30 mL / min, the temperature is 100 °C, and the time is 50 s; the flow rate of the sixth purge is 30 mL / min, the temperature is 100 °C, and the time is 50 s.

[0138] The rest are the same as in example 1.

[0139] Comparative example 4

[0140] The comparative example 1 provides a preparation method of a solid-state sodium-ion battery electrolyte film, wherein step (3) of the preparation method is that: the atomic layer deposition is continued for 5 s using trimethyl phosphate vapor with a temperature of 50 °C, and then the fifth and sixth purges are performed using nitrogen; the flow rate of the fifth purge is 30 mL / min, the temperature is 100 °C, and the time is 50 s; the flow rate of the sixth purge is 30 mL / min, the temperature is 100 °C, and the time is 50 s.

[0141] The rest are the same as in example 1.

[0142] Performance test

[0143] The ion conductivity and cycle stability of the solid-state sodium-ion battery electrolyte films provided by examples 1-8 and comparative examples 1-4 are tested, and the results are shown in Table 1.

[0144] The test method of the ion conductivity is that: the resistance of the prepared solid-state sodium-ion battery electrolyte film is measured by a four-probe tester, and after the thickness and the surface area are known, the ion conductivity is obtained according to the ion conductivity calculation formula.

[0145] The test method of the cycle stability is that: Na3V2(PO4)3 is used as a positive electrode, a sodium sheet is used as a negative electrode, and a battery is assembled with the prepared solid-state sodium-ion battery electrolyte film; at a temperature of 25 °C, the battery is first charged at 0.1C to a voltage of 4.0V, and then discharged at 0.1C to a voltage of 2.0V after constant current charging; further, the battery is charged at 0.5C to a voltage of 4.0V, and then discharged at 0.5C to a voltage of 2.0V, which is one charge and discharge cycle process; the discharge capacity at the 100th cycle is detected according to the above method, and the ratio of the discharge capacity at the 100th cycle to the discharge capacity at the 1st cycle is the cycle capacity retention rate.

[0146] Table 1

[0147]

[0148]

[0149] In summary, the preparation method provided by the application adopts an atomic layer deposition method to prepare a solid-state sodium ion battery electrolyte film; the atomic layer deposition method alternately introduces gas-phase reactants, chemical reactions occur on the surface of a deposition substrate, single-layer cumulative deposition is achieved, and the preparation of a nanoscale or even sub-nanoscale solid-state sodium ion battery electrolyte film is achieved; moreover, the solid-state sodium ion battery electrolyte film obtained by the application has very good shape retention, and the surface is dense and free of pinholes; the solid-state sodium ion battery electrolyte film obtained by the preparation method of the application is a sodium superionic conductor Na3Zr2Si2PO 12 The solid-state sodium ion battery electrolyte film can effectively inhibit the formation of sodium dendrites, thereby improving the safety performance of the sodium ion battery.

[0150] The above-described specific embodiments further specifically describe the purposes, technical solutions and beneficial effects of the application, and it should be understood that the above-described embodiments are only specific embodiments of the application and are not intended to limit the application, and any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the application should be included in the protection scope of the application.

Claims

1. A method for preparing a solid-state sodium-ion battery electrolyte film, characterized in that, The preparation method comprises the following steps: (1) using zirconium source vapor to perform atomic layer deposition on a deposition substrate, and then performing first purging; then water vapor is introduced, followed by second purging; (2) using silicon source vapor to continue atomic layer deposition, and then performing third purging; then water vapor is introduced, followed by fourth purging; (3) using phosphorus source vapor to continue atomic layer deposition, and then performing fifth purging; then water vapor is introduced, followed by sixth purging; (4) using sodium source vapor to continue atomic layer deposition, and then performing seventh purging; then water vapor is introduced, followed by eighth purging; Steps (1) to (4) are cycled until a solid-state sodium-ion battery electrolyte film of a desired thickness is obtained; The solid-state sodium-ion battery electrolyte thin film is a sodium superionic conductor Na3Zr2Si2PO 12 Thin film; The atomic layer deposition is performed under vacuum conditions; The first purging to the eighth purging are all performed using a protective gas.

2. The production method according to claim 1, characterized by, The zirconium source vapor in step (1) comprises tetrakis(dimethylamino)zirconium and / or tert-butyl zirconium.

3. The preparation method according to claim 1, characterized in that, The temperature of the zirconium source vapor in step (1) is 80-85℃.

4. The method of claim 1, wherein, The introduction time of the zirconium source vapor in step (1) is 8-12s.

5. The preparation method according to claim 1, characterized in that, The flow rate of the first purging in step (1) is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s.

6. The method of claim 1, wherein, The introduction time of the water vapor in step (1) is 8-12s.

7. The preparation method according to claim 1, characterized in that, The flow rate of the water vapor in step (1) is 120-130mL / min.

8. The method of claim 1, wherein, The flow rate of the second purging in step (1) is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s.

9. The method of claim 1, wherein, The silicon source vapor in step (2) comprises ethyl silicate vapor and / or methyl orthosilicate vapor.

10. The method of claim 1, wherein, The temperature of the silicon source vapor in step (2) is 75-80℃.

11. The method of claim 1, wherein, The introduction time of the silicon source vapor in step (2) is 8-12s.

12. The method of claim 1, wherein, The flow rate of the third purging in step (2) is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s.

13. The method of claim 1, wherein, The introduction time of the water vapor in step (2) is 8-12s.

14. The method of claim 1, wherein, The flow rate of the water vapor in step (2) is 120-130mL / min.

15. The method of claim 1, wherein, The flow rate of the fourth purging in step (2) is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s.

16. The method of claim 1, wherein, The phosphorus source vapor in step (3) comprises trimethyl phosphate vapor and / or tetramethyl methylenediphosphonate vapor.

17. The method of claim 1, wherein, The temperature of the phosphorus source vapor in step (3) is 40-60℃.

18. The method of claim 1, wherein, The introduction time of the phosphorus source vapor in step (3) is 4-6s.

19. The method of claim 1, wherein, The flow rate of the fifth purging in step (3) is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s.

20. The method of claim 1, wherein, The introduction time of the water vapor in step (3) is 4-6s.

21. The method of claim 1, wherein, The flow rate of the water vapor in step (3) is 120-130mL / min.

22. The method of claim 1, wherein, The flow rate of the sixth purging in step (3) is 25-35mL / min, the temperature is 95-105℃, and the time is 45-55s.

23. The method of claim 1, wherein, The sodium source vapor in step (4) comprises sodium tert-butoxide vapor and / or sodium hexamethyldisilazide vapor.

24. The method of claim 1, wherein, The temperature of the sodium source vapor in step (4) is 70-75℃.

25. The method of claim 1, wherein, The sodium source vapor is introduced for 8-12 s.

26. The method of claim 1, wherein, The seventh purging in step (4) has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s.

27. The method of claim 1, wherein, The water vapor is introduced for 8-12 s in step (4).

28. The method of claim 1, wherein, The water vapor is introduced at a flow rate of 120-130 mL / min in step (4).

29. The method of claim 1, wherein, The eighth purging in step (4) has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s.

30. The method of claim 1, wherein, The protective gas comprises nitrogen and / or inert gas.

31. The method of claim 1, wherein, The deposition substrate in step (1) is placed in a constant temperature part with a temperature of 140-160 ℃.

32. The method of claim 1, wherein, The preparation method comprises the following steps: (1) The deposition substrate is placed in a constant temperature part with a temperature of 140-160 ℃, and the deposition substrate is subjected to atomic layer deposition using a zirconium source vapor with a temperature of 80-85 ℃ for 8-12 s, and then subjected to first purging using nitrogen; then water vapor is introduced at a flow rate of 120-130 mL / min for 8-12 s, and then subjected to second purging using nitrogen; the first purging has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s; the second purging has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s; (2) The atomic layer deposition is continued using a silicon source vapor with a temperature of 75-80 ℃ for 8-12 s, and then subjected to third purging using nitrogen; then water vapor is introduced at a flow rate of 120-130 mL / min for 8-12 s, and then subjected to fourth purging using nitrogen; the third purging has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s; the fourth purging has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s; (3) The atomic layer deposition is continued using a phosphorus source vapor with a temperature of 40-60 ℃ for 4-6 s, and then subjected to fifth purging using nitrogen; then water vapor is introduced at a flow rate of 120-130 mL / min for 8-12 s, and then subjected to sixth purging using nitrogen; the fifth purging has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s; the sixth purging has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s; (4) The atomic layer deposition is continued using a sodium source vapor with a temperature of 70-75 ℃ for 8-12 s, and then subjected to seventh purging using nitrogen; then water vapor is introduced at a flow rate of 120-130 mL / min for 8-12 s, and then subjected to eighth purging using nitrogen; the seventh purging has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s; the eighth purging has a flow rate of 25-35 mL / min, a temperature of 95-105 ℃, and a time of 45-55 s; Steps (1) to (4) are cycled until a solid-state sodium ion battery electrolyte film with a desired thickness is obtained.

33. A solid-state sodium-ion battery electrolyte film, characterized in that, The solid-state sodium-ion battery electrolyte film is obtained by the method of any one of claims 1-32.

34. A sodium-ion battery, characterized in that, The sodium-ion battery comprises the solid-state sodium-ion battery electrolyte film of claim 33.

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