CN115425296A - All-solid-state sodium ion battery and preparation method thereof - Google Patents

All-solid-state sodium ion battery and preparation method thereof Download PDF

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CN115425296A
CN115425296A CN202211099205.0A CN202211099205A CN115425296A CN 115425296 A CN115425296 A CN 115425296A CN 202211099205 A CN202211099205 A CN 202211099205A CN 115425296 A CN115425296 A CN 115425296A
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陈本
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    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H—ELECTRICITY
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Abstract

The invention relates to an all-solid-state sodium ion battery and a preparation method thereof, wherein the battery comprises a sodium metal cathode, a solid electrolyte and an anode, wherein: the sodium metal cathode is deposited on the metal foil through physical vapor deposition, and a sodium layer with the thickness of 0.5-10 mu m is formed on the surface of the metal foil through controlling at least one of deposition time, deposition temperature or voltage; the preparation method of the solid electrolyte comprises the following steps: mixing a polymer, a sodium salt, an adhesive and water, casting the obtained mixed solution on a plate, and then carrying out vacuum drying; the positive electrode is an active material containing sodium ions. The preparation method of the all-solid-state sodium ion battery provided by the invention is easy to realize industrial production, and the prepared all-solid-state sodium ion battery has excellent cycle performance, energy density and power density, is improved in safety and has a good market application prospect.

Description

All-solid-state sodium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of surface coating and the technical field of new energy materials, in particular to an all-solid-state sodium ion battery and a preparation method thereof.
Background
Of fossil fuel consumptionThe increase has led to a pressing crisis of energy insecurity and climate change. Cost-effective and reliable energy storage technologies are key contributors to achieving seamless integration of fluctuating intermittent renewable energy sources to offset fossil fuel consumption. As a feasible substitute of the ubiquitous lithium ion battery, the sodium ion battery has abundant and cheap sodium resources, various sodium-based solid phases and ultrahigh theoretical capacity (1165 mA h g) -1 ) And low electrode potential (-2.714v vs. she), and is therefore considered to be an ideal choice for large-scale, low-cost energy storage systems.
Sodium ion batteries using sodium metal cathodes can achieve energy densities comparable to the most advanced lithium ion batteries at present. However, practical application of Na metal anodes is hampered by two major challenges related to cyclability and safety, mainly due to their high chemical reactivity and large volume expansion, which ultimately leads to uncontrolled growth of Na dendrites. At the same time, the preparation of Na metal foil is also crucial. Unlike Li metal, na metal foil is not commercially available. Pure metallic sodium is very reactive and must be stored in mineral oil or under an inert gas atmosphere. It can quickly react with O in air 2 And H 2 And forming a passivation layer by O reaction, wherein the high resistance of the passivation layer on the surface of the Na metal is not favorable for the electrochemical performance of the Na metal anode.
At present, the preparation of Na metal anode mostly adopts scraping and polishing Na cube. After rolling the Na cube into a foil using a polyethylene rod or block, the Na metal anode was obtained by stamping the Na foil.
The PVD coating technology is effectively applied to various surface treatments and preparation of thin film materials, such as protective coatings on the surfaces of parts, coatings on the surfaces of dies, conductive light-transmitting coatings, hard coatings on the surfaces of dies and the like. The coating prepared by PVD has uniform surface thickness, controllable coating thickness, safety and high efficiency, and is suitable for large-scale production.
However, sodium metal is difficult to ensure safety due to its extremely strong reactivity, so that a sodium layer is not deposited directly on a metal substrate at present. In the prior art, the application of the PVD technique for depositing a sodium layer is also known, but a mixed transition layer of a negative electrode active material and a conductive agent must be formed on a substrate layer (e.g., aluminum foil) in advance, and then the deposition of the sodium layer is performed, and the sodium layer only serves as a compensation function of a positive electrode material. As in the prior patents: chinese patent application CN 108336301a proposes to deposit a layer of sodium metal on the surface of a negative electrode plate active material by a physical vapor deposition method, in the process, the negative electrode plate active material (such as hard carbon, soft carbon, amorphous carbon, etc.) and a conductive agent are mixed and then coated on a negative current collector aluminum foil, and then a layer of sodium metal is deposited on the surface by a PVD technique, the purpose of depositing a sodium layer is to release ions of the sodium layer, so as to reduce the loss of active sodium ions in the positive electrode material and improve the first coulombic efficiency of a sodium ion battery. The above method is complicated in steps and high in process cost, and the negative electrode active material is not sodium metal.
Disclosure of Invention
The invention aims to overcome the problems in the preparation of the existing sodium cathode material and provide an all-solid-state sodium ion battery, wherein the all-solid-state sodium ion battery adopts physical vapor deposition to attach a sodium layer on the surface of a metal foil matrix, and simultaneously combines the advantages of a flexible solid electrolyte, including excellent film forming property and thermal stability, and utilizes a solid electrolyte film to replace two parts of an electrolyte and a diaphragm of a conventional sodium ion battery, thereby reducing the volume and the quality of a battery finished product and obviously improving the energy and the power density.
On the other hand, the sodium ion solid-state battery system formed by the polymer electrolyte and the sodium metal negative electrode can effectively buffer the volume expansion of the sodium negative electrode in circulation, and the safety of the battery system is ensured.
The specific scheme is as follows:
a method of making an all-solid-state sodium ion battery comprising a sodium metal negative electrode, a solid-state electrolyte, and a positive electrode, wherein:
the sodium metal cathode is deposited on the metal foil through physical vapor deposition, and a sodium layer with the thickness of 0.5-10 mu m is formed on the surface of the metal foil through controlling at least one of deposition time, deposition temperature or voltage;
the preparation method of the solid electrolyte comprises the following steps: mixing a polymer, a sodium salt, a binder and water, casting the obtained mixed solution on a plate, and then performing vacuum drying to obtain the film-shaped solid electrolyte;
the positive electrode is an active material containing sodium ions.
Further, the physical vapor deposition mode is vacuum evaporation coating, vacuum magnetron sputtering coating or vacuum ion coating, preferably vacuum ion coating;
optionally, the metal foil is subjected to surface cleaning before physical vapor deposition, the metal foil is subjected to ultrasonic cleaning for 10-60min under the condition of 10-40kHz in distilled water, then is subjected to ultrasonic cleaning for 10-60min under the condition of 10-40kHz in absolute alcohol, and then is subjected to drying treatment.
Furthermore, the vacuum degree of the vacuum evaporation coating is 1 multiplied by 10 -3 Pa to 9X 10 -3 Pa, and the evaporation temperature is 100-1000 ℃.
Furthermore, the vacuum degree of the vacuum magnetron sputtering coating is 1 multiplied by 10 -2 Pa to 9X 10 -1 Pa, heating to 50-100 ℃, under the condition of plasma, bombarding the surface of the target by positive ions formed after inert gas is ionized, plating a film on the surface of the metal foil by adopting magnetron sputtering, wherein the sputtering voltage is selected to be between 100V and 800V, and sodium forms a film on the surface of the metal foil.
Further, the vacuum degree of the vacuum ion plating film is 1 multiplied by 10 -3 Pa to 9X 10 -3 Pa, starting the metal target, and injecting inert gas to make the vacuum degree at 1X 10 -2 Pa to 9X 10 -1 Within the range of Pa; loading bias voltage, and coating a film on the surface of the metal foil, wherein the film coating time is 10-1000min, the loading bias voltage is 10V-200V, and the duty ratio is 20% to 80%; preferably, the coating time is 10-1000min, the loading bias voltage is 10-200V, and the duty ratio is 40-60%;
optionally, before coating, glow cleaning is carried out for 100-1000s under the conditions that the hydrogen flow is 100-1000sccm, the loading bias voltage is 300-500V, the duty ratio is 40-60 percent and the time is 100-1000.
Further, the preparation method of the positive electrode comprises the following steps: mixing Na 3 V 2 (PO 4 ) 3 Mixing the conductive agent and the adhesive according to the mass ratio of 7-10, 1-2:1-2, then adding a solvent to obtain positive electrode slurry, then coating the positive electrode slurry on a positive electrode current collector, and drying in vacuum to obtain the positive electrode;
preferably, the conductive agent is at least one of acetylene black, ketjen black, carbon nanotubes, carbon nanofibers and graphene; the adhesive is at least one of sodium carboxymethylcellulose, polyvinylidene fluoride, polytetrafluoroethylene, fluorinated rubber, polyurethane, polyacrylic acid, sodium polyacrylate, polyvinyl alcohol, alginic acid, sodium alginate and styrene butadiene rubber; the solvent is at least one of N-methyl pyrrolidone, dimethyl formamide and dimethyl sulfoxide solvent.
Further, in the preparation method of the solid electrolyte, the polymer is at least one of polyethylene oxide, polyvinylidene fluoride, poly (vinylidene fluoride hexafluoropropylene) and polyethylene glycol;
optionally, the sodium salt is NaClO 4 At least one of sodium hexafluorophosphate or sodium bis (fluorosulfonyl) imide;
optionally, the binder is sodium carboxymethylcellulose.
Further, the mass ratio of the polymer, the sodium salt and the binder is 80-90;
optionally, the temperature of the vacuum drying is 40-100 ℃, and the time is 12-48 h, so that the solid electrolyte with the thickness of 10-120 microns is obtained.
The invention also provides the all-solid-state sodium ion battery prepared by the preparation method of the all-solid-state sodium ion battery.
Furthermore, the energy density of the all-solid-state sodium ion battery is 370-390 wh/kg, the capacity retention rate is 85-97% after 100 cycles of charge and discharge under 1C; preferably, the all-solid-state sodium ion battery is charged and discharged for 100 times at 1C, and the capacity retention rate is 96.6%; the capacity retention rate is 91.36% after charging and discharging for 300 times under 1C; the capacity retention rate is 85.1% after charging and discharging 500 times at 1C.
Has the beneficial effects that:
in the invention, the sodium metal cathode is deposited on the metal foil through physical vapor deposition, and the sodium layer with the thickness of 0.5-10 mu m is formed on the surface of the metal foil by controlling at least one of deposition time, deposition temperature or voltage, so that the formed film layer can be ensured to be stable and not easy to fall off.
In the invention, the sodium metal negative electrode is connected with Na with NASICON structure 3 V 2 (PO 4 ) 3 The full cell composed of the positive electrode and the low-cost full-solid polymer electrolyte can provide excellent electrochemical performance. The sodium metal negative electrode with the thickness of 0.5-10 mu m effectively reduces the quality of the negative electrode side, and can improve the energy density and the power density of the solid-state sodium ion battery.
Furthermore, a sodium ion solid-state battery system formed by the polymer electrolyte and the sodium metal negative electrode can effectively buffer the volume expansion of the sodium negative electrode in circulation, improve the circulation performance and effectively inhibit the growth of sodium negative electrode dendrites.
In a word, the preparation method of the all-solid-state sodium ion battery provided by the invention is easy to realize industrial production, and the prepared all-solid-state sodium ion battery has excellent cycle performance, energy density and power density, is improved in safety and has a good market application prospect.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings will be briefly introduced, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not limiting to the present invention.
Fig. 1 is a charge-discharge cycle diagram of a battery 1C according to an embodiment 1 of the present invention.
Detailed Description
Definitions for some of the terms used in the present invention are given below, and other terms not described have definitions and meanings known in the art:
the all-solid-state sodium ion battery comprises a sodium metal negative electrode, a solid electrolyte and a positive electrode, wherein:
the sodium metal cathode is deposited on the metal foil through physical vapor deposition, and a sodium layer with the thickness of 0.5-10 mu m is formed on the surface of the metal foil through controlling at least one of deposition time, deposition temperature or voltage;
the preparation method of the solid electrolyte comprises the following steps: mixing a polymer, a sodium salt, a binder and water, casting the obtained mixed solution on a plate, and then performing vacuum drying to obtain the film-shaped solid electrolyte;
the positive electrode is an active material containing sodium ions.
The metal foil may be an aluminum foil or a copper foil, and has a thickness of 1 to 100 μm, preferably, 50 μm. The following description will be made by taking an aluminum foil as an example.
The physical vapor deposition method of the present invention is not particularly limited, and the physical vapor deposition method may be vacuum evaporation coating, vacuum sputtering coating, or vacuum ion coating, and preferably is vacuum ion coating.
If vacuum evaporation coating is adopted, a vacuum evaporation system is used, and the aluminum foil metal matrix and the sodium metal block to be coated are both placed in the vacuum evaporation system. The vacuum degree of the aluminum foil is 1 multiplied by 10 -3 Pa to 9X 10 -3 Pa, and putting the sodium metal block to be plated in an evaporation boat. The evaporation voltage is adjusted to heat the evaporation boat to the evaporation temperature of the evaporation metal, such as 100-1000 ℃. The deposition of the sodium-plated metal film on the surface of the aluminum foil is realized, and then the aluminum foil is annealed under the protection of inert gas such as argon.
If vacuum sputtering coating is adopted, the vacuum degree of the aluminum foil is controlled to be 1 multiplied by 10 -2 Pa to 9X 10 -1 Heating to 50-100 ℃ within Pa range. Under the condition of plasma, positive ions formed after argon is ionized bombard the surface of a target material, magnetron sputtering is adopted to plate a film on the surface of an aluminum foil, the sputtering voltage is selected to be between 100V and 800V, and metal sodium forms a film on the surface of the aluminum foil.
If vacuum ion plating is adopted, the aluminum foil metal matrix and the sodium metal block to be plated are both placed in a vacuum evaporation system. The vacuum degree of the aluminum foil is 1 multiplied by 10 -3 Pa to 9X 10 -3 Pa. Starting the metal target and injecting gas to make the vacuum degree at 1X 10 -2 Pa to 9X 10 -1 In the Pa range. And (5) loading bias voltage and plating a film on the surface of the aluminum foil. Wherein the coating time is 10-1000min. Loaded bias voltage10V to 200V, and a duty cycle of 20% to 80%, where in the present invention "duty cycle" refers to the ratio of the time taken by the pulses to the total time during which the device is in continuous operation.
The sodium metal negative electrode of the invention is an ultrathin negative electrode, comprising: the aluminum foil comprises an aluminum foil substrate and a sodium metal physical vapor deposition layer uniformly attached to the surface of the aluminum foil substrate, wherein the thickness of a sodium metal film is 0.5-10 mu m. The thickness of the aluminum foil is 10-30 μm.
The invention provides an all-solid-state sodium ion battery, which comprises the ultrathin anode material, a solid electrolyte and Na 3 V 2 (PO 4 ) 3 And (4) a positive electrode. The preparation process of the solid electrolyte comprises the following steps: mixing polymer such as polyethylene oxide (PEO), sodium salt such as NaClO 4 And binder such as sodium carboxymethylcellulose (Na-CMC), respectively, by mixing in warm water at certain ratio. Wherein Na-CMC is used as an electrode binder and an electrolyte additive, which is beneficial to optimizing the interface contact of an electrode/electrolyte. Stirring at 80-90 deg.C until a clear and homogeneous liquid solution is obtained. The film is formed by casting a hot homogeneous solution on a polytetrafluoroethylene plate, putting the hot homogeneous solution into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to a preset temperature and keeping the preset temperature for a preset time so as to obtain the solid electrolyte film; the preset time range is 12-48 h; the preset temperature range is 40-100 ℃, and the thickness of the film is 10-120 mu m.
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1:
and ultrasonically washing an aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute alcohol for 30min by using distilled water under the condition of 25kHz, and wiping and cleaning the surface of the aluminum foil substrate. After cleaning, drying at 100 ℃.
And (3) coating by adopting a vacuum ion coating mode, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. The glow cleaning is carried out firstly under the conditions of hydrogen flow of 300sccm, loading bias of 400V, duty ratio of 50% and duration of 500 s. The vacuum degree of the aluminum foil is 5 multiplied by 10 -3 Heating under the condition of Pa, and adjusting the temperature in the furnace to 80 ℃. Placing the metal block to be plated with sodium in an evaporation boat, adjusting the target current to 20A, injecting protective argon to ensure that the vacuum degree is 5 multiplied by 10 -1 Pa, gas flow of 130sccm, loading bias voltage of 100V, duty ratio of 50%, depositing for 30min, and depositing sodium film on the surface of the aluminum foil, wherein the thickness of the sodium film cathode is 0.5 μm.
Mixing polyethylene oxide (PEO), naClO 4 And sodium carboxymethylcellulose (Na-CMC) in a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Mixing acetylene black and polyvinylidene fluoride according to a mass ratio of 8.
Assembling the battery: and cutting the prepared cathode, the solid electrolyte film and the anode plate into proper sizes in a glove box, preparing a solid sodium-ion battery cell in a lamination mode, and packaging to obtain the sodium-ion battery.
The sodium ion battery prepared in example 1 is tested, fig. 1 shows the cycle performance of an all-solid-state sodium ion battery 1C, and the capacity retention rate is 96.6% after 100 times of charge and discharge at 1C; the capacity retention rate is 91.36% after charging and discharging for 300 times under 1C; the capacity retention rate is 85.1% after charging and discharging 500 times at 1C.
Example 2:
and ultrasonically washing an aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute alcohol for 30min by using distilled water under the condition of 25kHz, and wiping and cleaning the surface of the aluminum foil substrate. After cleaning, drying at 100 ℃.
And (3) coating by adopting a vacuum ion coating mode, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. The glow cleaning is carried out firstly under the conditions of hydrogen flow of 300sccm, loading bias of 400V, duty ratio of 50% and duration of 500 s. The vacuum degree of the aluminum foil is 5 multiplied by 10 -3 Heating under Pa, and regulating the temperature in the furnace to 80 ℃. Placing the metal block to be plated in an evaporation boat, adjusting the target current to 20A, injecting protective argon gas to ensure that the vacuum degree is 5 multiplied by 10 -1 Pa, gas flow rate of 130sccm, loading bias voltage of 100V, duty ratio of 50%, depositing for 300min, and depositing sodium film on the surface of the aluminum foil, wherein the thickness of the sodium film cathode is 5 mu m.
Mixing polyethylene oxide (PEO), naClO 4 And sodium carboxymethylcellulose (Na-CMC) in a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time so as to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Mixing acetylene black and polyvinylidene fluoride according to a mass ratio of 8.
Assembling the battery: and cutting the prepared cathode, the solid electrolyte film and the anode plate into proper sizes in a glove box, preparing a solid sodium-ion battery cell in a lamination mode, and packaging to obtain the sodium-ion battery.
Example 3:
and ultrasonically washing an aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute alcohol for 30min by using distilled water under the condition of 25kHz, and wiping and cleaning the surface of the aluminum foil substrate. After cleaning, drying at 100 ℃.
Coating by vacuum evaporation, adjusting vacuum degree to 5 × 10 -3 Pa, argon gas was injected at a flow rate of 70sccm. Then glow cleaning is carried out for 180s; injecting oxygen at a flow rate of 60sccm to reach a vacuum degree of 4 × 10 -1 And Pa, starting a sodium target for 90s, and evaporating for 30min under the condition that the evaporation current is 800A to form a sodium film cathode with the thickness of 5 mu m, wherein the sodium film is positioned on the surface layer of the aluminum foil.
Mixing polyethylene oxide (PEO), naClO 4 And sodium carboxymethylcellulose (Na-CMC) in a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Acetylene black and polyvinylidene fluoride are mixed according to the mass ratio of 8.
And finally, stacking the positive plate, the solid electrolyte membrane and the negative plate prepared in the steps in sequence, wherein the flexible solid electrolyte membrane is positioned between the positive plate and the negative plate to play a role in isolation, and meanwhile, the flexible solid electrolyte membrane can reinforce a sodium membrane layer deposited on the aluminum foil on the negative side and can effectively prevent the sodium membrane layer from falling off.
Example 4:
and ultrasonically washing an aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute alcohol for 30min by using distilled water under the condition of 25kHz, and wiping and cleaning the surface of the aluminum foil substrate. After cleaning, drying at 100 ℃.
And (3) coating by adopting a vacuum sputtering coating mode, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. Glow cleaning is carried out under the conditions of 300sccm of hydrogen flow, 400V of loading bias voltage, 50% duty ratio and 500s of time. Controlling the vacuum degree in the vacuum place of the coating chamber to be 5 multiplied by 10 -1 Pa, heating to 80 ℃, introducing protective argon, adjusting the magnetic field to 500Gs, adjusting the target current, starting a power supply, and carrying out bombardment treatment on the surface of the product for minutes. And after the process is finished, introducing working gas nitrogen into the film coating chamber, turning on a power supply, applying bias voltage to the workpiece to be coated, controlling the bias voltage to be 200V, starting a target source, and starting film coating when the target material is sodium metal. And (3) coating time, wherein the coating time is 50min, and the thickness of the obtained sodium film is 2 mu m.
Mixing polyethylene oxide (PEO), naClO 4 And sodium carboxymethylcellulose (Na-CMC) in a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Mixing acetylene black and polyvinylidene fluoride according to a mass ratio of 8.
Assembling the battery: and cutting the prepared cathode, the solid electrolyte film and the anode plate into proper sizes in a glove box, preparing a solid sodium ion battery cell in a lamination mode, and packaging to obtain the sodium ion battery.
Example 5:
and ultrasonically washing the aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute ethyl alcohol for 30min by using distilled water under the condition of 25kHz, and wiping the surface of the aluminum foil substrate to clean. After cleaning, drying at 100 ℃.
And (3) adopting a vacuum ion plating mode to plate the film, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. The glow cleaning is carried out firstly under the conditions of hydrogen flow of 300sccm, loading bias of 400V, duty ratio of 50% and duration of 500 s. The vacuum degree of the aluminum foil is 5 multiplied by 10 -3 Heating under Pa, and regulating the temperature in the furnace to 80 ℃. Placing the metal block to be plated in an evaporation boat, adjusting the target current to 20A, injecting protective argon gas to ensure that the vacuum degree is 5 multiplied by 10 -1 Pa, gas flow rate of 130sccm, loading bias voltage of 100V, duty ratio of 50%, depositing for 300min, and depositing sodium film on the surface of the aluminum foil, wherein the thickness of the sodium film cathode is 5 mu m.
Mixing polyethylene glycol (PEG), naClO 4 And sodium carboxymethylcellulose (Na-CMC) in a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Acetylene black and polyvinylidene fluoride are mixed in a mass ratio of 8And drying to obtain the positive plate.
Assembling the battery: and cutting the prepared cathode, the solid electrolyte film and the anode plate into proper sizes in a glove box, preparing a solid sodium-ion battery cell in a lamination mode, and packaging to obtain the sodium-ion battery.
Example 6:
and ultrasonically washing an aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute alcohol for 30min by using distilled water under the condition of 25kHz, and wiping and cleaning the surface of the aluminum foil substrate. After cleaning, drying at 100 ℃.
And (3) coating by adopting a vacuum ion coating mode, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. The glow cleaning is carried out firstly under the conditions of hydrogen flow of 300sccm, loading bias of 400V, duty ratio of 50% and duration of 500 s. Aluminum foil with vacuum degree of 5X 10 -3 Heating under the condition of Pa, and adjusting the temperature in the furnace to 80 ℃. Placing the metal block to be plated with sodium in an evaporation boat, adjusting the target current to 20A, injecting protective argon to ensure that the vacuum degree is 5 multiplied by 10 -1 Pa, gas flow rate of 130sccm, loading bias voltage of 100V, duty ratio of 50%, depositing for 300min, and depositing sodium film on the surface of the aluminum foil, wherein the thickness of the sodium film cathode is 5 mu m.
Polyvinylidene fluoride (PVDF), naClO 4 And sodium carboxymethylcellulose (Na-CMC) in a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Acetylene black and polyvinylidene fluoride are mixed in a mass ratio of 8Drying the foil in a vacuum drying oven at 80 ℃ to obtain the positive plate.
Assembling the battery: and cutting the prepared cathode, the solid electrolyte film and the anode plate into proper sizes in a glove box, preparing a solid sodium ion battery cell in a lamination mode, and packaging to obtain the sodium ion battery.
Example 7:
and ultrasonically washing an aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute alcohol for 30min by using distilled water under the condition of 25kHz, and wiping and cleaning the surface of the aluminum foil substrate. After cleaning, drying at 100 ℃.
And (3) coating by adopting a vacuum ion coating mode, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. The glow cleaning is carried out firstly under the conditions of hydrogen flow of 300sccm, loading bias of 400V, duty ratio of 50% and duration of 500 s. The vacuum degree of the aluminum foil is 5 multiplied by 10 -3 Heating under the condition of Pa, and adjusting the temperature in the furnace to 80 ℃. Placing the metal block to be plated with sodium in an evaporation boat, adjusting the target current to 20A, injecting protective argon to ensure that the vacuum degree is 5 multiplied by 10 -1 Pa, gas flow rate of 130sccm, loading bias voltage of 100V, duty ratio of 50%, depositing for 300min, and depositing sodium film on the surface of the aluminum foil, wherein the thickness of the sodium film cathode is 5 mu m.
Poly (vinylidene fluoride hexafluoropropylene) (PVDF HFP), naClO 4 And sodium carboxymethylcellulose (Na-CMC) in a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Acetylene black and polyvinylidene fluoride are mixed in a mass ratio of 8And coating the anode slurry on an aluminum foil of a positive electrode current collector with the thickness of 15 mu m, and drying in a vacuum drying oven at 80 ℃ to obtain the positive electrode plate.
Assembling the battery: and cutting the prepared cathode, the solid electrolyte film and the anode plate into proper sizes in a glove box, preparing a solid sodium ion battery cell in a lamination mode, and packaging to obtain the sodium ion battery.
Example 8:
and ultrasonically washing an aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute alcohol for 30min by using distilled water under the condition of 25kHz, and wiping and cleaning the surface of the aluminum foil substrate. After cleaning, drying at 100 ℃.
And (3) coating by adopting a vacuum ion coating mode, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. The glow cleaning is carried out firstly under the conditions of hydrogen flow of 300sccm, loading bias of 400V, duty ratio of 50% and duration of 500 s. The vacuum degree of the aluminum foil is 5 multiplied by 10 -3 Heating under the condition of Pa, and adjusting the temperature in the furnace to 80 ℃. Placing the metal block to be plated in an evaporation boat, adjusting the target current to 20A, injecting protective argon gas to ensure that the vacuum degree is 5 multiplied by 10 -1 Pa, gas flow rate of 130sccm, loading bias voltage of 100V, duty ratio of 50%, depositing for 30min, and depositing sodium film on the surface of the aluminum foil, wherein the thickness of the sodium film cathode is 0.5 μm.
Mixing polyethylene oxide (PEO), naPF 6 And sodium carboxymethylcellulose (Na-CMC) in a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Acetylene black was mixed with polyvinylidene fluoride in a mass ratio of 8And (3) uniformly stirring the pyrrolidone to obtain positive electrode slurry, then coating the positive electrode slurry on a positive electrode current collector aluminum foil with the thickness of 15 microns, and drying in a vacuum drying oven at 80 ℃ to obtain the positive electrode plate.
Assembling the battery: and cutting the prepared cathode, the solid electrolyte film and the anode plate into proper sizes in a glove box, preparing a solid sodium ion battery cell in a lamination mode, and packaging to obtain the sodium ion battery.
Example 9:
and ultrasonically washing the aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute ethyl alcohol for 30min by using distilled water under the condition of 25kHz, and wiping the surface of the aluminum foil substrate to clean. After cleaning, drying at 100 ℃.
And (3) adopting a vacuum ion plating mode to plate the film, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. The glow cleaning is carried out firstly under the conditions of hydrogen flow of 300sccm, loading bias of 400V, duty ratio of 50% and duration of 500 s. The vacuum degree of the aluminum foil is 5 multiplied by 10 -3 Heating under the condition of Pa, and adjusting the temperature in the furnace to 80 ℃. Placing the metal block to be plated in an evaporation boat, adjusting the target current to 20A, injecting protective argon gas to ensure that the vacuum degree is 5 multiplied by 10 -1 Pa, gas flow of 130sccm, loading bias voltage of 100V, duty ratio of 50%, depositing for 30min, and depositing sodium film on the surface of the aluminum foil, wherein the thickness of the sodium film cathode is 0.5 μm.
Polyethylene oxide (PEO), naFSI and sodium carboxymethylcellulose (Na-CMC) were thoroughly mixed in warm water at a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time so as to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Acetylene black is mixed with polyvinylidene fluoride in a mass ratio of 8Dissolving the compound into a small amount of N-methyl pyrrolidone, uniformly stirring to obtain anode slurry, then coating the anode slurry on an anode current collector aluminum foil with the thickness of 15 mu m, and drying in a vacuum drying oven at 80 ℃ to obtain an anode plate.
Assembling the battery: and cutting the prepared cathode, the solid electrolyte film and the anode plate into proper sizes in a glove box, preparing a solid sodium ion battery cell in a lamination mode, and packaging to obtain the sodium ion battery.
Comparative example 1:
and ultrasonically washing an aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute alcohol for 30min by using distilled water under the condition of 25kHz, and wiping and cleaning the surface of the aluminum foil substrate. After cleaning, drying at 100 ℃.
And (3) coating by adopting a vacuum ion coating mode, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. The glow cleaning is carried out firstly under the conditions of hydrogen flow of 300sccm, loading bias of 400V, duty ratio of 50% and duration of 500 s. The vacuum degree of the aluminum foil is 5 multiplied by 10 -3 Heating under the condition of Pa, and adjusting the temperature in the furnace to 80 ℃. Placing the metal block to be plated in an evaporation boat, adjusting the target current to 20A, injecting protective argon gas to ensure that the vacuum degree is 5 multiplied by 10 -1 Pa, gas flow of 130sccm, loading bias voltage of 100V, duty ratio of 50%, depositing for 30min, and depositing sodium film on the surface of the aluminum foil, wherein the thickness of the sodium film cathode is 0.5 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Mixing acetylene black and polyvinylidene fluoride according to a mass ratio of 8.
The positive plate, the glass fiber filter membrane and the negative plate are assembled into the battery in a lamination mode, wherein 1mol/L ethylene carbonate/diethyl carbonate (volume ratio 1:1) is used as electrolyte in the electrolyte, and the sodium ion battery is obtained after encapsulation.
Comparative example 2:
and ultrasonically washing an aluminum foil with the thickness of 15 mu m for 30min by using distilled water under the condition of 25kHz, ultrasonically washing the aluminum foil with absolute alcohol for 30min by using distilled water under the condition of 25kHz, and wiping and cleaning the surface of the aluminum foil substrate. After cleaning, drying at 100 ℃.
And (3) coating by adopting a vacuum ion coating mode, and placing the aluminum foil matrix and the metal to be plated with sodium in a vacuum evaporation system. The glow cleaning is carried out firstly under the conditions of hydrogen flow of 300sccm, loading bias of 400V, duty ratio of 50% and duration of 500 s. The vacuum degree of the aluminum foil is 5 multiplied by 10 -3 Heating under the condition of Pa, and adjusting the temperature in the furnace to 80 ℃. Placing the metal block to be plated in an evaporation boat, adjusting the target current to 20A, injecting protective argon gas to ensure that the vacuum degree is 5 multiplied by 10 -1 Pa, gas flow rate of 130sccm, loading bias voltage of 100V, duty ratio of 50%, depositing for 15min, and depositing sodium film on the surface of the aluminum foil, wherein the thickness of the sodium film cathode is only 0.2 μm.
Mixing polyethylene oxide (PEO), naClO 4 And sodium carboxymethylcellulose (Na-CMC) in a mass ratio of 82. Followed by stirring at 80 ℃ until a clear homogeneous mixed liquid solution is obtained. Casting the hot homogeneous solution on a polytetrafluoroethylene plate, putting the polytetrafluoroethylene plate into a vacuum drying oven, and then adjusting the temperature in the vacuum drying oven to 25 ℃ and keeping the temperature for a preset time so as to obtain a solid electrolyte membrane; the preset time range is 24h. The thickness of the prepared solid electrolyte film was 95 μm.
Mixing Na 3 V 2 (PO 4 ) 3 Mixing acetylene black and polyvinylidene fluoride according to a mass ratio of 8.
Assembling the battery: and cutting the prepared cathode, the solid electrolyte film and the anode plate into proper sizes in a glove box, preparing a solid sodium ion battery cell in a lamination mode, and packaging to obtain the sodium ion battery.
Test example:
the negative electrodes prepared in examples and comparative examples were assembled into a battery and tested. The sodium ion batteries prepared in examples 1 to 9 and comparative examples 1 to 2 were subjected to constant current charge and discharge tests under the conditions that the current densities of 0.1C and 1C were 2.5 to 4.0V using a lap CT2001A type battery test system of wuhan blue electronics ltd, and the cycle was more than 100 cycles, and the test results are shown in table 1. The test results show that the energy density of the all-solid-state sodium-ion battery prepared by the method is more than 370wh/kg, and the capacity retention rate after 100 cycles is superior to that of the comparative example, so that the method can be effectively applied to the preparation of the all-solid-state sodium-ion battery with high energy density.
TABLE 1 Performance data sheet of all-solid-state Na-ion battery
Figure BDA0003838101120000131
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A preparation method of an all-solid-state sodium ion battery is characterized by comprising the following steps: the all-solid-state sodium ion battery comprises a sodium metal cathode, a solid electrolyte and an anode, wherein:
the sodium metal cathode is deposited on the metal foil through physical vapor deposition, and a sodium layer with the thickness of 0.5-10 mu m is formed on the surface of the metal foil through controlling at least one of deposition time, deposition temperature or voltage;
the preparation method of the solid electrolyte comprises the following steps: mixing a polymer, a sodium salt, a binder and water, casting the obtained mixed solution on a plate, and then performing vacuum drying to obtain the film-shaped solid electrolyte;
the positive electrode is an active material containing sodium ions.
2. The method for preparing an all-solid-state sodium-ion battery according to claim 1, characterized in that: the physical vapor deposition mode is vacuum evaporation coating, vacuum magnetron sputtering coating or vacuum ion coating, and preferably vacuum ion coating;
optionally, the metal foil is subjected to surface cleaning before physical vapor deposition, the metal foil is subjected to ultrasonic cleaning for 10-60min under the condition of 10-40kHz in distilled water, then is subjected to ultrasonic cleaning for 10-60min under the condition of 10-40kHz in absolute alcohol, and then is subjected to drying treatment.
3. The method for preparing an all-solid-state sodium-ion battery according to claim 2, characterized in that: the vacuum degree of the vacuum evaporation coating is 1 multiplied by 10 -3 Pa to 9X 10 -3 Pa, and the evaporation temperature is 100-1000 ℃.
4. The method for preparing an all-solid-state sodium-ion battery according to claim 2, characterized in that: the vacuum degree of the vacuum magnetron sputtering coating is 1 multiplied by 10 -2 Pa to 9X 10 -1 Pa, heating to 50-100 ℃, under the condition of plasma, bombarding the surface of the target by positive ions formed after inert gas is ionized, plating a film on the surface of the metal foil by adopting magnetron sputtering, wherein the sputtering voltage is selected to be between 100V and 800V, and sodium forms a film on the surface of the metal foil.
5. The all-solid-state sodion solution of claim 2The preparation method of the sub-battery is characterized by comprising the following steps: the vacuum degree of the vacuum ion plating film is 1 multiplied by 10 -3 Pa to 9X 10 -3 Pa, starting the metal target, and injecting inert gas to make the vacuum degree at 1X 10 -2 Pa to 9X 10 -1 Within the range of Pa; loading bias voltage, and coating a film on the surface of the metal foil, wherein the film coating time is 10-1000min, the loading bias voltage is 10V-200V, and the duty ratio is 20% to 80%; preferably, the coating time is 10-1000min, the loading bias voltage is 10-200V, and the duty ratio is 40-60%;
optionally, before coating, glow cleaning is carried out for 100-1000s under the conditions that the hydrogen flow is 100-1000sccm, the loading bias voltage is 300-500V, the duty ratio is 40-60 percent and the time is 100-1000.
6. The method for producing an all-solid-state sodium ion battery according to any one of claims 1 to 5, characterized in that: the preparation method of the positive electrode comprises the following steps: mixing Na 3 V 2 (PO 4 ) 3 Mixing the conductive agent and the adhesive according to the mass ratio of 7-10, 1-2:1-2, then adding a solvent to obtain positive electrode slurry, then coating the positive electrode slurry on a positive electrode current collector, and drying in vacuum to obtain the positive electrode;
preferably, the conductive agent is at least one of acetylene black, ketjen black, carbon nanotubes, carbon nanofibers and graphene; the adhesive is at least one of sodium carboxymethylcellulose, polyvinylidene fluoride, polytetrafluoroethylene, fluorinated rubber, polyurethane, polyacrylic acid, sodium polyacrylate, polyvinyl alcohol, alginic acid, sodium alginate and styrene butadiene rubber; the solvent is at least one of N-methyl pyrrolidone, dimethyl formamide and dimethyl sulfoxide solvent.
7. The method for producing an all-solid-state sodium ion battery according to any one of claims 1 to 5, characterized in that: in the preparation method of the solid electrolyte, the polymer is at least one of polyethylene oxide, polyvinylidene fluoride, poly (vinylidene fluoride hexafluoropropylene) and polyethylene glycol;
optionally, the sodium salt is NaClO 4 Sodium hexafluorophosphate or sodium bis (fluorosulfonyl) imideAt least one of (a);
optionally, the binder is sodium carboxymethylcellulose.
8. The method for preparing an all-solid-state sodium-ion battery according to claim 7, characterized in that: the mass ratio of the polymer, the sodium salt and the binder is (80-90);
optionally, the temperature of the vacuum drying is 40-100 ℃, and the time is 12-48 h, so that the solid electrolyte with the thickness of 10-120 microns is obtained.
9. The all-solid-state sodium ion battery prepared by the method for preparing the all-solid-state sodium ion battery according to any one of claims 1 to 8.
10. The all-solid-state sodium-ion battery of claim 9, wherein: the energy density of the all-solid-state sodium ion battery is 370-390 wh/kg, the battery is charged and discharged for 100 circles under 1C, and the capacity retention rate is 85-97%; preferably, the all-solid-state sodium ion battery is charged and discharged for 100 times at 1C, and the capacity retention rate is 96.6%; the capacity retention rate is 91.36 percent after 300 times of charge and discharge at 1C; the capacity retention rate is 85.1% after charging and discharging 500 times at 1C.
CN202211099205.0A 2022-09-08 2022-09-08 All-solid-state sodium ion battery and preparation method thereof Pending CN115425296A (en)

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