Internally- and externally-improved sodium superionic conductor type solid electrolyte, and preparation method therefor and use thereof

Abstract

The present invention belongs to the field of solid electrolytes. Disclosed are a sodium superionic conductor type solid electrolyte, and a preparation method therefor and the use thereof. The sodium superionic conductor type solid electrolyte has the chemical general formula as represented below: Na1+x+2y+z-i+j[Zr2-y-z-h-i-jAII yAIII zAIV hAⅤ iBj]SixP3-xO12. By subjecting the sodium superionic conductor type solid electrolyte to doping modification, the ionic conductivity of the solid electrolyte is high, and the compactness thereof is also improved.

Description

A sodium superion conductor solid electrolyte with both internal and external improvements, as well as its preparation method and application Technical Field

[0001] The present invention belongs to the field of solid electrolytes, and more specifically, relates to a sodium superion conductor solid electrolyte with both internal and external improvements, a preparation method, and an application thereof. Background Art

[0002] The development of efficient secondary battery energy storage devices is of strategic importance for improving power balance, developing sustainable energy sources such as wind and solar, and promoting the development of new energy vehicles. Lithium-ion batteries, with their advantages of high specific energy and power, low self-discharge, and no memory effect, have gradually entered the fields of electric vehicles, rail transit, and large-scale energy storage. However, lithium-ion batteries are not the ideal energy storage device. Due to the scarcity of lithium resources, uneven geographical distribution, and high cost, the application of lithium-ion batteries in large-scale energy storage faces irreconcilable contradictions.

[0003] Sodium ions and lithium ions belong to the same main group, sharing similar chemical properties and intercalation mechanisms. Furthermore, sodium resources are abundant, making sodium-ion batteries (SIBs) complementary to lithium-ion batteries. The organic electrolytes used in SIBs are flammable and volatile, posing safety risks and limiting their energy density. Replacing organic liquid electrolytes with solid electrolytes offers the potential to address these safety issues. Currently, the most studied inorganic solid electrolytes for sodium ions include Na-β”-Al2O3, sodium superion conductors, and sulfides. Among these, sodium superion conductor solid electrolytes hold great potential for application in solid-state sodium-ion batteries due to their wide electrochemical window, high mechanical strength, air stability, and high ionic conductivity. However, their lower ionic conductivity compared to organic electrolytes limits their application in solid-state sodium batteries. Therefore, improving the ionic conductivity of SIBs would facilitate their application in energy storage.

[0004] Currently, researchers have discovered that by modifying sodium superion conductors with doping, they can produce solid electrolytes with high ionic conductivity. However, simply doping sodium superion conductor-type solid electrolytes only affects their ionic conductivity and does not significantly improve their ability to suppress sodium dendrites.

[0005] Therefore, it is urgent to propose a sodium superion conductor solid electrolyte with both internal and external advantages and a preparation method thereof.

[0006] Summary of the Invention

[0007] The present invention addresses the shortcomings of existing technologies by providing a sodium superionic conductor-type solid electrolyte with both internal and external improvements and a method for its preparation. The present invention provides a doping strategy for simultaneously bulk doping and grain boundary modification of the sodium superionic conductor-type solid electrolyte. By doping and modifying the sodium superionic conductor-type solid electrolyte, high ionic conductivity is achieved while simultaneously increasing its density.

[0008] In order to achieve the above-mentioned object, the first aspect of the present invention provides a sodium superionic conductor type solid electrolyte with both internal and external improvements, wherein the sodium superionic conductor type solid electrolyte has the chemical formula shown in formula (1): Na1+x+2y+z-i+j[Zr2-yzhi-jA Ⅱ y A Ⅲ z A Ⅳ h A Ⅴ i B j ]Si x P 3-x O 12 (1);

[0009] Wherein: x, y, z, h, i, j are the molar percentages of the corresponding elements, wherein 0≤x≤3, 0≤y≤0.5, 0≤z≤0.5, 0≤h≤0.5, 0≤i≤0.5, 0≤j≤0.5, 0 <y+z+h+i+j≤2;

[0010] A Ⅱ It is a +2 valence metal element doped and substituted in the Zr position;

[0011] A Ⅲ It is a +3 valence non-lanthanide metal element doped and substituted at the Zr position;

[0012] A Ⅳ It is a +4 valence metal element doped with Zr;

[0013] A Ⅴ It is a +5 valence metal element doped with Zr;

[0014] B is a +3 valent lanthanide metal element doped and substituted at the Zr position.

[0015] According to the present invention, preferably, the A Ⅱ It is at least one of Mg, Cd, Mn, Co, Ni and Zn.

[0016] According to the present invention, preferably, the A Ⅲ It is at least one of Al, In, Ga, Sc and Y.

[0017] According to the present invention, preferably, the A Ⅳ is at least one of Hf, Sn, Ge and Ti.

[0018] According to the present invention, preferably, the A Ⅴ It is at least one of Nb, Ta, As and Sb.

[0019] According to the present invention, preferably, the B is at least one of La, Ce, Pr, Nd, Eu, Yb and Lu.

[0020] The second aspect of the present invention provides a method for preparing the sodium superion conductor-type solid electrolyte with both internal and external improvements, and the preparation method is a solid-phase method.

[0021] According to the present invention, preferably, the preparation method comprises the following steps:

[0022] Doping element A Ⅱ 、A Ⅲ 、A Ⅳ 、A Ⅴ and mixing at least one precursor of B, a Na source, a P source, a Zr source, and a Si source, and sequentially subjecting the mixture to ball milling and calcination to obtain the powder of the sodium superionic conductor-type solid electrolyte with both internal and external improvements.

[0023] According to the present invention, preferably, the doping element A Ⅱ The precursor is at least one of ZnO, MgO, CdO, MnO, CoO and NiO.

[0024] According to the present invention, preferably, the doping element A Ⅲ The precursor is at least one of Al2O3, In2O3, Ga2O3, Sc2O3 and Y2O3.

[0025] According to the present invention, preferably, the doping element A Ⅳ The precursor is at least one of HfO2, SnO2, GeO2, and TiO2.

[0026] According to the present invention, preferably, the doping element A Ⅴ The precursor is at least one of Nb2O5, Ta2O5, As2O5 and Sb2O5.

[0027] According to the present invention, preferably, the precursor of the doping element B is at least one of Ce2O3, La2O3, Pr2O3, Nd2O3, Eu2O3, Yb2O3 and Lu2O3.

[0028] According to the present invention, preferably, the Na source is at least one of Na2CO3, NaHCO3, NaOH and Na2O.

[0029] According to the present invention, preferably, the P source is at least one of NH4H2PO4, (NH4)2HPO4, and P2O5.

[0030] According to the present invention, preferably, the Zr source is ZrO2 and / or Zr(OH)4, and the specification of the Zr source is nanometer level. Preferably, the specification of the Zr source is ≤100 nm.

[0031] According to the present invention, preferably, the Si source is SiO2 and / or Si(OH)4.

[0032] According to the present invention, preferably, the ball milling process includes: adding the doping element A Ⅱ 、A Ⅲ 、A Ⅳ 、A Ⅴ and at least one precursor of B, a Na source, a P source, a Zr source, a Si source and a solvent, and ball-milled, heating to evaporate the solvent, crushing and screening to obtain a mixed powder after ball-milling.

[0033] According to the present invention, preferably, the calcination treatment is divided into two stages, the calcination temperature of the first stage is 300-500°C, and the calcination time is 1-3 hours; the calcination temperature of the second stage is 900-1150°C, and the calcination time is 4-24 hours; the calcination atmosphere of the calcination treatment is at least one of air, oxygen, nitrogen and argon.

[0034] According to the present invention, preferably, the conditions of the ball milling treatment include:

[0035] The ball-to-material ratio is (3-5):1;

[0036] The ball milling temperature is room temperature, preferably 20-30°C;

[0037] The ball milling speed is 200-500 rpm;

[0038] Ball milling time is 6-24 hours;

[0039] The solvent is ethanol and / or isopropanol.

[0040] According to the present invention, preferably, the preparation method further includes mixing a portion of the powder of the sodium superionic conductor type solid electrolyte with both internal and external improvements with a binder, placing the mixture into a mold, and forming a green body by cold pressing; burying the green body in the remaining portion of the powder of the sodium superionic conductor type solid electrolyte with both internal and external improvements, and sintering at a high temperature to obtain the sodium superionic conductor type solid electrolyte sheet.

[0041] According to the present invention, preferably, the binder is a PVA aqueous solution with a concentration of 5%-20% and / or a PVB ethyl acetate solution with a concentration of 3%-10%.

[0042] According to the present invention, preferably, the high-temperature sintering is divided into two stages, the calcination temperature of the first stage is 200-400°C, and the calcination time is 1-3 hours; the calcination temperature of the second stage is 1200-1300°C, and the calcination time is 4-24 hours, and the calcination atmosphere of the high-temperature sintering is at least one of air, oxygen, nitrogen and argon.

[0043] The third aspect of the present invention provides the use of the sodium superionic conductor solid electrolyte with both internal and external improvements in the preparation of at least one device among sodium batteries, sodium-sulfur batteries, mixed electrolyte system batteries, new fuel cells and electrochemical sensors.

[0044] In the present invention, preferably, the sodium battery is a solid-state sodium battery or a sodium symmetric battery.

[0045] The beneficial effects of the technical solution of the present invention are as follows:

[0046] The present invention provides a doping strategy for simultaneously bulk doping and grain boundary modification ("internal and external modification") of sodium superionic conductor-type solid electrolytes. By doping and modifying the sodium superionic conductor-type solid electrolyte, high room-temperature ionic conductivity is achieved while simultaneously increasing its density.

[0047] The present invention achieves high room-temperature ionic conductivity through bulk doping. The introduction of lanthanide elements simultaneously achieves bulk doping and grain boundary modification. Grain boundary modification increases the density of the electrolyte, reduces its electronic conductivity, and thus enhances its ability to suppress sodium dendrites. Batteries and other devices prepared using the sodium superionic conductor solid electrolyte of the present invention exhibit good sodium dendrite suppression and excellent cycling stability.

[0048] The preparation method of the present invention has the advantages of simple preparation process, easy acquisition of raw materials, easy realization of batch preparation, and is suitable for large-scale production.

[0049] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] The above and other objects, features and advantages of the present invention will become more apparent through a more detailed description of exemplary embodiments of the present invention with reference to the accompanying drawings, wherein like reference numerals generally represent like components throughout the exemplary embodiments of the present invention.

[0051] FIG1 shows an XRD pattern of a sodium superionic conductor-type solid electrolyte with both internal and external improvements provided in Example 1 of the present invention (wherein, “Intensity” represents the diffraction peak intensity, “2Theta” represents the scanning angle, “Experimental” represents the experimental data, “Refined” represents the XRD refined data, “C2 / c” represents the monoclinic crystal structure, “Differences” represents the data difference between the experimental data and the PDF standard card, and “Rwp” represents the refinement accuracy, which is generally less than 10).

[0052] FIG2 shows a cross-sectional SEM image of a sodium superion conductor-type solid electrolyte with both internal and external improvements provided in Example 1 of the present invention.

[0053] Figure 3 shows the undoped sodium superion conductor solid electrolyte Na3Zr2Si2PO 12 AC impedance diagram (where "-Z" (Ω) is impedance, "Z' (Ω)" is impedance, and "NZSP-contrast" is the undoped sodium superion conductor type solid electrolyte Na3Zr2Si2PO 12 ).

[0054] FIG4 shows an AC impedance diagram of a sodium superionic conductor-type solid electrolyte with both internal and external improvements provided in Example 1 of the present invention.

[0055] Figure 5 shows a DC polarization diagram of a sodium superionic conductor-type solid electrolyte with both internal and external improvements provided in Example 1 of the present invention (wherein, "Current" is the current, "Time" is the time, and "Au|NZSP|Au" is the gold plating on the electrolyte wafer in Example 1).

[0056] FIG6 shows a Na|NZSP|Na cycle performance diagram of a sodium metal symmetric battery prepared using a sodium superionic conductor solid electrolyte with both internal and external improvements provided in Example 1 of the present invention (wherein “Voltage” is voltage).

[0057] Figure 7 shows a charge and discharge cycle diagram of a solid-state sodium battery prepared using a sodium superion conductor solid electrolyte with both internal and external improvements provided in Example 1 of the present invention (wherein "Specific capacity" is the discharge specific capacity, "Cycle number" is the number of cycles, and "Efficiency" is the Coulombic efficiency). DETAILED DESCRIPTION

[0058] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. Instead, these embodiments are provided to make the present invention more thorough and complete and to fully convey the scope of the present invention to those skilled in the art.

[0059] Example 1

[0060] This embodiment provides a sodium superion conductor solid electrolyte with both internal and external improvements, namely Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12 .

[0061] The preparation method of the above-mentioned superionic conductor type solid electrolyte is as follows:

[0062] (1) Mechanical ball milling: Precursors of sodium Na, phosphorus P, zirconium Zr, silicon Si, zinc Zn and cerium Ce are placed in a ball mill according to the molar ratio of Na, P, Zr, Si, Zn and Ce of 3.3:1:1.8:2:0.1:0.1 (wherein, Na2CO3, NH4H2PO4, nano-sized ZrO2, SiO2, ZnO and Ce2O3 are selected as raw materials, and Na2CO3 is in excess of 8wt% and NH4H2PO4 is in excess of 15wt%), anhydrous ethanol is added to obtain a mixture, and the mixture is ground using grinding balls; after the grinding is completed, the mixture is heated to evaporate the solvent, crushed and separated using a sieving instrument to obtain a mixed powder; the ball-to-material ratio is 5:1, the ball milling temperature is 25°C, the ball milling speed is 200 rpm, and the ball milling time is 12 hours.

[0063] (2) High-temperature calcination: The mixed powder is placed in a muffle furnace for two-stage calcination, and the calcined powder is crushed and sieved to obtain Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12 The first stage calcination temperature is 400°C, and the calcination time is 1 hour; the second stage calcination temperature is 1150°C, and the calcination time is 12 hours; the calcination atmosphere is air.

[0064] (3) Cold pressing sintering: a portion of Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12The powder was mixed with 10% PVA aqueous solution and placed in a custom mold. A green body was formed by cold pressing. The green body was buried in the remaining Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12 The powder undergoes a two-stage high-temperature sintering in a muffle furnace: the first stage at 400°C for one hour, and the second stage at 1250°C for 12 hours in an air atmosphere. After annealing, a sodium superion conductor solid electrolyte sheet is obtained. This is then polished into discs with a diameter of 10-12 mm and a thickness of 1-2 mm, resulting in a sodium superion conductor solid electrolyte with both internal and external improvements.

[0065] As shown in FIG1 , the sodium superion conductor solid electrolyte Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12 (NZSP) still maintains the monoclinic phase, and a second phase Na3Ce(PO4)2 is produced. The production of the second phase is beneficial to improving the electrolyte density and the ionic conductivity at the grain boundary.

[0066] As shown in FIG2 , the sodium superion conductor solid electrolyte Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12 The grains are in close contact with each other, with no apparent pores, indicating that the prepared solid electrolyte has a high density. Furthermore, the density of the prepared sodium superionic conductor-type solid electrolyte, which is both internally and externally improved, was measured using the Archimedean drainage method, and the average density of the prepared solid electrolyte was calculated to be 99.2%, consistent with the information presented in Figure 2.

[0067] The Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12 Gold electrodes were plated on both sides of the electrolyte disc and the conductivity test was carried out. The results are shown in Figure 4. At the same time, the undoped sodium superion conductor type solid electrolyte Na3Zr2Si2PO 12 The same conductivity test was carried out, and the results are shown in Figure 3. As can be seen from Figures 3 and 4, Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12The room temperature ionic conductivity of the electrolyte disc is 2.12 mS cm -1 , while the undoped sodium superion conductor solid electrolyte Na3Zr2Si2PO 12 The room temperature ionic conductivity is only 0.58 mS cm -1 This indicates that the ionic conductivity of sodium superionic conductor-type solid electrolytes can be improved through bulk doping and grain boundary modification, that is, a "both inside and outside" doping strategy.

[0068] As shown in FIG5 , the sodium superionic conductor solid electrolyte of this embodiment has a low electronic conductivity of 6.23×10 -8 S cm -1 , which is beneficial to inhibit the formation of sodium dendrites.

[0069] Preparation of sodium metal symmetric battery: In an inert atmosphere glove box with water oxygen value less than 0.1ppm, the sodium superionic conductor type solid electrolyte Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12 Sodium metal sheets are attached to both sides of the (NZSP) disc to form a symmetrical sodium metal battery. The structure of the symmetrical sodium metal battery is Na|NZSP|Na. The constant current charge and discharge test of the sodium metal symmetric battery is carried out. As shown in Figure 6, the Na|NZSP|Na battery has a current density of 0.3 mA cm -2 Under the conditions of , it can be stably cycled for 1000 hours without short circuit phenomenon. This result shows that the solid electrolyte of this embodiment has excellent sodium dendrite inhibition ability.

[0070] Preparation of solid-state sodium battery: Na3V2(PO4)3(NVP) positive electrode, conductive agent carbon black, and binder PVDF were mixed in a mass ratio of 8:1:1 to prepare positive electrode slurry. After magnetic stirring for 12 hours, the slurry was coated and placed in an 80℃ oven to dry to obtain NVP@C positive electrode sheet. In an inert atmosphere glove box with a water oxygen value of less than 0.1ppm, the sodium superionic conductor solid electrolyte Na 3.3 Zr 1.8 Zn 0.1 Ce 0.1 Si2PO 12 The (NZSP) disc was attached to the negative electrode side with a sodium sheet, and the positive electrode side was attached to the prepared NVP@C positive electrode sheet, and then packaged into a solid-state sodium battery. The electrochemical performance of the solid-state sodium battery was tested with a charge and discharge voltage range of 2.8 to 3.8 V. As shown in Figure 7, the solid-state sodium battery had an initial discharge capacity of 109.5 mAh g at a rate of 0.2C. -1The first-cycle coulombic efficiency is 96.2% and the capacity retention rate is 94.5% after 50 cycles, showing excellent cycle stability.

[0071] While various embodiments of the present invention have been described above, the above description is intended to be illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A sodium superionic conductor solid electrolyte with both internal and external improvements, characterized in that, The sodium superionic conductor solid electrolyte has a chemical general formula shown in formula (1): Na1+x+2y+z-i+j[Zr2-y-z-h-i-jA Ⅱ y A Ⅲ z A Ⅳ h A Ⅴ i B j Si x P 3-x O 12 (1); wherein: x, y, z, h, i, and j are respectively the molar percentages of the corresponding elements, where 0 ≤ x ≤ 3, 0 ≤ y ≤ 0.5, 0 ≤ z ≤ 0.5, 0 ≤ h ≤ 0.5, 0 ≤ i ≤ 0.5, 0 ≤ j ≤ 0.5, and 0 < y + z + h + i + j ≤ 2; A Ⅱ is a divalent metal element substituted by Zr-site doping; A Ⅲ is a +3 valence non-lanthanide metal element substituted by doping at the Zr site; A Ⅳ is a +4 valence metal element substituted by doping at the Zr site; A Ⅴ is a +5 valence metal element substituted by doping at the Zr position; B is a +3-valent lanthanide metal element substituted by doping at the Zr site.

2. The method for preparing the internally and externally cultivated sodium superionic conductor type solid electrolyte according to claim 1, wherein, The said A Ⅱ is at least one of Mg, Cd, Mn, Co, Ni and Zn; The said A Ⅲ is at least one of Al, In, Ga, Sc and Y; The said A Ⅳ is at least one of Hf, Sn, Ge, and Ti; The said A Ⅴ is at least one of Nb, Ta, As, and Sb; the B is at least one of La, Ce, Pr, Nd, Eu, Yb, and Lu.

3. The preparation method of the internally and externally cultivated sodium superionic conductor solid electrolyte according to claim 1 or 2, characterized in that, The preparation method is a solid-phase method.

4. The preparation method of the sodium superionic conductor solid electrolyte with both internal and external cultivation according to claim 3, wherein, The preparation method includes the following steps: Dope the element A Ⅱ 、A Ⅲ 、A Ⅳ 、A Ⅴ and at least one precursor of B, a Na source, P Mix the Na source, Zr source, and Si source and successively perform ball milling and calcination treatments to obtain the powder of the internally and externally cultivated sodium superionic conductor type solid electrolyte.

5. The method for preparing the internally and externally cultivated sodium superionic conductor type solid electrolyte according to claim 4, wherein, Doped element A Ⅱ The precursor of which is at least one of ZnO, MgO, CdO, MnO, CoO and NiO; Doping element A Ⅲ The precursor is at least one of Al2O3, In2O3, Ga2O3, Sc2O3, and Y2O3; Doping element A Ⅳ The precursor thereof is at least one of HfO2, SnO2, GeO2, and TiO2; Doping element A Ⅴ The precursor is at least one of Nb2O5, Ta2O5, As2O5, and Sb2O5; The precursor of the doping element B is at least one of Ce2O3, La2O3, Pr2O3, Nd2O3, Eu2O3, Yb2O3, and Lu2O3; the Na source is at least one of Na2CO3, NaHCO3, NaOH, and Na2O; the P source is at least one of NH4H2PO4, (NH4)2HPO4, and P2O5; the Zr source is ZrO2 and / or Zr(OH)4, and the specification of the Zr source is nanoscale. Preferably, the specification of the Zr source ≤ 100 nm; the Si source is SiO2 and / or Si(OH)4.

6. The method for preparing the internally and externally cultivated sodium superionic conductor type solid electrolyte according to claim 4, wherein, The ball milling treatment includes: mixing a precursor of at least one of doped element A Ⅱ , A Ⅲ , A Ⅳ , A Ⅴ and B, a Na source, a P source, a Zr source, a Si source and a solvent, and performing ball milling, heating and evaporating the solvent, pulverizing and sieving to obtain a mixed powder after ball milling treatment; The calcination treatment is divided into two stages. The calcination temperature in the first stage is 300 - 500 °C, and the calcination time is 1 - 3 hours; the calcination temperature in the second stage is 900 - 1150 °C, and the calcination time is 4 - 24 hours; the calcination atmosphere of the calcination treatment is at least one of air, oxygen, nitrogen, and argon.

7. The preparation method of the internally and externally cultivated sodium superionic conductor solid electrolyte according to claim 6, wherein, The conditions of the ball milling treatment include: The ball-to-material ratio is (3 - 5):1; The ball milling temperature is 20 - 30 °C; The ball milling speed is 200 - 500 revolutions per minute; The ball milling time is 6 - 24 hours; The solvent is ethanol and / or isopropanol.

8. The preparation method of the internally and externally cultivated sodium superionic conductor solid electrolyte according to claim 4, wherein, The preparation method further includes mixing a part of the powder of the internally and externally cultivated sodium superionic conductor type solid electrolyte with a binder, putting it into a mold, and forming a green body by cold pressing; burying the green body in the remaining powder of the internally and externally cultivated sodium superionic conductor type solid electrolyte, and performing high-temperature sintering to obtain the sodium superionic conductor type solid electrolyte sheet.

9. The method for preparing the internally and externally cultivated sodium superionic conductor type solid electrolyte according to claim 8, wherein, the binder is an aqueous PVA solution with a concentration of 5% - 20% and / or an ethyl acetate solution of PVB with a concentration of 3% - 10%; The high-temperature sintering is divided into two stages. The calcination temperature in the first stage is 200-400°C, and the calcination time is 1-3 hours; the calcination temperature in the second stage is 1200-1300°C, and the calcination time is 4-24 hours. The calcination atmosphere for the high-temperature sintering is at least one of air, oxygen, nitrogen, and argon.

10. Use of the internally and externally cultivated sodium superionic conductor solid electrolyte according to claim 1 or 2 in the preparation of at least one device among sodium batteries, sodium-sulfur batteries, mixed electrolyte system batteries, new fuel cells, and electrochemical sensors.

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