Preparation method and application of glass-based sodium ion all-solid-state battery

Abstract

The invention discloses a preparation method and application of a glass-based sodium ion all-solid-state battery, and belongs to the technical field of battery material preparation, and the preparation method comprises the following steps: based on a Sb2O3-B2O3-P2O5 glass system, replacing Sb2O3 with Fe2O3 to carry out component regulation and control so as to prepare an oxide glass electrode; preparing a Fe-based modified NASICON glass ceramic solid electrolyte, and further adjusting a heat treatment process to improve the ionic conductivity of the NASICON glass ceramic solid electrolyte; the oxide glass electrode and the NASICON glass ceramic electrolyte are simultaneously modified by the Fe2O3 component and are assembled into the all-solid-state sodium ion battery, so that the structural matching property and compatibility of an electrode / electrolyte interface are effectively improved, and the electrochemical performance and the safety performance of the battery are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of battery material preparation technology, and in particular to a method for preparing and applying a glass-based sodium-ion all-solid-state battery. Background Technology

[0002] Oxide-based sodium-ion all-solid-state batteries are considered a safer, more robust, and more sustainable alternative to traditional lithium-ion batteries. However, challenges remain in their manufacturing, particularly in electrode active materials and electrolytes. + The ionic radius (0.102 nm) is significantly larger than that of Li. + The 0.076 nm diameter leads to slow electrode reaction kinetics. Traditional hard carbon, due to its extremely low sodium intercalation potential, faces the risk of sodium dendrite formation at high rates. Alloyed materials suffer from high volume expansion. Therefore, it is crucial to prepare sodium-ion electrode materials with efficient ion transport networks and to construct stable cycling structures.

[0003] Another important factor affecting sodium-ion all-solid-state batteries is the development of solid-state electrolytes. NASICON solid-state electrolytes possess a three-dimensional network structure, allowing sodium ions to move rapidly and exhibiting high ionic conductivity. NASICON glass-ceramic solid-state electrolytes, prepared through heat treatment, are non-porous, highly dense, and prevent sodium dendrites from growing through pores or cracks, thus avoiding battery short circuits. Therefore, NASICON glass-ceramic solid-state electrolytes exhibit excellent safety performance. However, NASICON glass-ceramic solid-state electrolytes still have relatively low ionic conductivity, which needs improvement.

[0004] The commercialization of sodium-ion solid-state batteries remains hampered by the solid-solid interface problem. Typically, the electrodes and electrolytes are two different solid materials with distinct structures and compositions. Structurally, the differences in morphology and crystal structure between the electrodes and electrolytes can easily lead to physical mismatches, resulting in defects such as contact gaps, poor local contact, and lattice mismatch. This causes a significant increase in ion transport resistance, consequently affecting the battery's rate performance and cycle stability. On the other hand, excessive compositional differences can lead to additional interfacial reactions, causing structural distortions and rapid deterioration of the battery's state, resulting in poor cycle performance. Therefore, there is an urgent need to develop a glass-based sodium-ion all-solid-state battery that optimizes interfacial compatibility and improves electrochemical performance based on both structural and compositional dimensions to address the problems associated with electrode materials and solid electrolytes in sodium-ion all-solid-state batteries. Summary of the Invention

[0005] The purpose of this invention is to construct a glass-based sodium-ion all-solid-state battery with a compatible interface based on the compositional and structural similarities of glass electrodes and solid-state electrolytes. High-performance Fe-based oxide glass electrode materials and Fe₂O₃-doped NASICON glass-ceramic solid-state electrolytes were prepared by component control, and then assembled into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery. Oxide glass electrode materials with high cycle stability and capacity retention were prepared under air atmosphere. Appropriate heat treatment processes were used to improve the ionic conductivity, increase density, and reduce porosity of the NASICON glass-ceramic solid-state electrolyte, preventing sodium dendrite growth along the pores. Assembling the high-performance Fe-based oxide glass electrode material prepared by component control with the Fe-modified NASICON glass-ceramic solid-state electrolyte prepared by component doping into a glass-based sodium-ion all-solid-state battery significantly improves the electrochemical and safety performance of the energy storage device.

[0006] To achieve the above objectives, this invention provides a method for preparing a glass-based sodium-ion all-solid-state battery. This method involves controlling the molar ratio of Sb₂O₃ to Fe₂O₃ to prepare a high-performance Fe-based oxide glass electrode, and controlling the molar percentage of Fe₂O₃ to TiO₂ to prepare a Fe-based doped and modified NASICON glass-ceramic solid electrolyte. The method specifically includes the following steps: Step S1: Prepare Fe-based oxide glass electrode material; weigh out different molar percentages of Sb2O3, Fe2O3, B2O3 and P2O5, mix them evenly in a mortar, melt them into glass liquid under air atmosphere, anneal and grind them to prepare a series of Fe2O3-Sb2O3-B2O3-P2O5 system glasses, and obtain Fe-based oxide glass electrode material. Step S2: Preparation of glass-ceramic solid electrolyte; Weigh different molar percentages of Na2CO3, Fe2O3, TiO2 and NH4H2PO4, melt them into glass liquid in air atmosphere, cool and grind them, and further heat treat them to prepare Fe-based doped modified NASICON glass-ceramic solid electrolyte. Step S3: Prepare the Fe-based oxide glass electrode material obtained in step S1 as a Fe-based oxide glass electrode, and assemble the Fe-based oxide glass electrode and the Fe-based doped and modified NASICON glass ceramic solid electrolyte obtained in step S2 to obtain a glass-based sodium-ion all-solid-state battery with high electrochemical performance.

[0007] Preferably, step S1 specifically includes: Step S11: Weigh out 10-50 mol% Sb₂O₃, 0-40 mol% Fe₂O₃, 30 mol% B₂O₃, and 20 mol% P₂O₅; all the above oxides are analytical grade raw materials with a purity greater than 99.95%. Mix them evenly in a mortar and pour them into an alumina crucible. Step S12: Melt in air atmosphere to form molten glass; Step S13: Pour molten glass onto a preheated copper plate in an air atmosphere for annealing to prepare oxide glass; Step S14: Grind the oxide glass in an air atmosphere using a mortar and pestle for 30-60 minutes.

[0008] Preferably, in step S12, the melting temperature is 1200℃ and the holding time is 30min.

[0009] Preferably, step S2 specifically comprises: Step S21: Weigh out 15.00~22.50 mol% Na2CO3, 2.5~10.00 mol% Fe2O3, 30.00~45.00 mol% TiO2 and 25~37.50 mol% NH4H2PO4, mix them evenly in a mortar, and then pour them into an alumina crucible; Step S22: Melt in air atmosphere to form molten glass; Step S23: In an air atmosphere, pour molten glass into water for rapid cooling without annealing to prepare oxide glass; Step S24: Grind the oxide glass into powder, press it into a cylinder in a mold, and transfer it to a muffle furnace; Step S25: The pressed cylinder is subjected to high-temperature heat treatment at 100-400℃ above the crystallization initiation temperature to prepare Fe-based doped modified NASICON glass-ceramic solid electrolyte. Step S26: Polish the surface of the prepared Fe-based doped NASICON glass-ceramic solid electrolyte using a polishing machine to prepare it for assembly with the oxide glass electrode prepared in step S1 into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery.

[0010] Preferably, in step S22, the melting temperature is 1450°C under an air atmosphere, and the temperature is maintained for 30 minutes.

[0011] Preferably, in step S25, the heat treatment time is 1-10 hours in an air atmosphere.

[0012] Preferably, in step S3, the Fe-based oxide glass electrode includes an active material, a conductive agent, a binder, and a current collector; the preparation method of the Fe-based oxide glass electrode is to place the active material, conductive agent, binder, and current collector into a ball mill jar with N-methylpyrrolidone in a certain proportion and ball mill to obtain a slurry, coat the slurry onto a copper foil, dry it under high temperature and vacuum conditions, and after natural cooling, take it out and cut it into electrode sheets with a diameter of 12 mm using a punching machine to obtain the Fe-based oxide glass electrode.

[0013] Preferably, the active material is the Fe-based oxide glass electrode material prepared in step S1, the conductive agent is acetylene black, the binder is polyvinylidene fluoride, and the current collector is copper foil.

[0014] Preferably, the mass ratio of the active material, conductive agent, and binder is 7:2:1.

[0015] This invention provides an application of the glass-based sodium-ion all-solid-state battery obtained by the preparation method described above, which is used in energy storage devices.

[0016] Therefore, the present invention employs the above-described method for preparing and applying a glass-based sodium-ion all-solid-state battery, with the following beneficial effects: (1) Based on the design concept of interface compatibility caused by composition and structural similarity, this invention prepares high-performance Fe-based oxide glass sodium battery electrode materials by means of composition regulation and doping modification, achieving a performance of 100 mA g. -1 After 1000 stable cycles at the current density, the capacity is 120.3 mA hg. -1 This breakthrough overcomes the performance bottleneck of sodium-ion glass electrodes. Furthermore, a Fe-based modified NASICON-type solid electrolyte material was prepared, achieving a capacity of 3.44 × 10⁻⁶ ppm at room temperature. -4 mS / cm. The obtained high-performance Fe-based oxide glass electrode material was assembled with a Fe-modified NASICON glass-ceramic solid electrolyte obtained through component doping to form a sodium-ion solid-state battery. The sodium-ion solid-state battery exhibited good interfacial compatibility at 100 mA g. -1 After 1000 stable cycles at current density, it still maintains a high capacity of 84.4 mA hg. -1 .

[0017] (2) This invention obtains a high-performance Fe-based oxide glass electrode material through component control. The resulting product not only has excellent cycle stability but also outstanding performance in rate performance and sodium ion reaction kinetics, which can effectively improve the application scenarios of glass-based sodium-ion all-solid-state batteries.

[0018] (3) The Fe-based modified NASICON glass-ceramic solid electrolyte prepared by component doping in this invention is prepared by a one-step melting method followed by rapid cooling of the melt in water under air atmosphere to prepare a precursor glass; then, a NASICON glass-ceramic solid electrolyte with high ionic conductivity is prepared by a suitable heat treatment process under air atmosphere; due to the synergistic effect of the crystal and glass phase, the solid electrolyte prepared by this method is not only conducive to the rapid transport of sodium ions, but also increases the density between crystals, which significantly improves the interface. This reduces the battery short circuit phenomenon caused by dendrite problems.

[0019] (4) The production process of this invention is simple and adopts a one-step melting preparation method, which has low cost. The raw materials are widely available, inexpensive and environmentally friendly, with broad application prospects and excellent development prospects.

[0020] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0021] Figure 1 This is a flowchart illustrating the preparation method and application examples of a glass-based sodium-ion all-solid-state battery according to the present invention. Figure 2 The X-ray diffraction pattern of the Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5 prepared by component control in this invention is shown. Figure 3 Differential scanning calorimetry (DSC) image of the high-performance Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5 prepared by component control according to the present invention. Figure 4 This is the X-ray diffraction pattern of Fe-based modified NASICON glass-ceramic solid electrolyte NF0.6TP prepared based on component doping in Example 3 of the present invention; Figure 5 This is a differential scanning calorimeter of Fe-based modified NASICON glass-ceramic solid electrolyte NF0.6TP prepared based on component doping in Example 3 of the present invention; Figure 6 The electrochemical performance cycling curves of a high-performance glass-based sodium-ion all-solid-state battery are shown. The high-performance Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5 prepared in Example 3 of this invention is used as the electrode and assembled with Fe-based modified NASICON glass ceramic solid electrolyte NF0.6TP. Detailed Implementation

[0022] To better understand the above technical solutions, a detailed description of the solutions will be provided below in conjunction with the accompanying drawings and specific embodiments. Obviously, the described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0023] The terminology used in the embodiments of this invention is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms “a,” “the,” and “the” as used in the embodiments of this invention and the appended claims are also intended to include the plural forms, and “multiple” generally includes at least two unless the context clearly indicates otherwise.

[0024] It should also be noted that the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that an article or device that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such an article or device. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the article or device that includes said element.

[0025] Example 1 like Figure 1 As shown, a method for preparing a glass-based sodium-ion all-solid-state battery includes the following steps: Step S1: Prepare Fe-based oxide glass electrode material; Step S11: After mixing Sb2O3 25 mol%, Fe2O3 25 mol%, B2O3 30 mol%, and P2O5 20 mol% evenly in a mortar, pour the mixture into an alumina crucible. Step S12: Melt in air atmosphere at a melting temperature of 1200℃ for 30 minutes to form molten glass. Step S13: Pour the molten glass liquid into a preheated copper plate under an air atmosphere for annealing to prepare the Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5.

[0026] Step S2: Prepare glass-ceramic solid electrolyte; Step S21: Weigh out Na₂CO₃ 15.00 mol%, Fe₂O₃ 2.50 mol%, TiO₂ 45.00 mol%, and NH₄H₂PO₄ 37.50 mol%, mix them thoroughly in a mortar, and then pour them into an alumina crucible; Step S22: Melt in air at a temperature of 1450°C for 30 minutes to form molten glass. Step S23: Rapidly cool the molten glass in an air atmosphere to prepare the glass-ceramic solid electrolyte NFe0.2TP; Step S24: Grind NFe0.2TP into powder, press it into a cylinder in a mold, and transfer it to a muffle furnace; Step S25: Heat-treat at 900°C for 2 hours in air atmosphere to prepare Fe-based doped modified glass-ceramic solid electrolyte; Step S26: Polish the surface of the prepared Fe-based doped glass-ceramic solid electrolyte using a polishing machine to prepare it for assembly with the oxide glass electrode prepared in step S1 into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery.

[0027] Example 2 A method for preparing a glass-based sodium-ion all-solid-state battery includes the following steps: Step S1: Prepare Fe-based oxide glass electrode material; Step S11: After mixing Sb2O3 25 mol%, Fe2O3 25 mol%, B2O3 30 mol%, and P2O5 20 mol% evenly in a mortar, pour the mixture into an alumina crucible. Step S12: Melt in air atmosphere at a melting temperature of 1200℃ for 30 minutes to form molten glass. Step S13: Pour the molten glass liquid into a preheated copper plate under an air atmosphere for annealing to prepare the Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5.

[0028] Step S2: Prepare glass-ceramic solid electrolyte; Step S21: Weigh out Na₂CO₃ 17.50 mol%, Fe₂O₃ 5.00 mol%, TiO₂ 40.00 mol%, and NH₄H₂PO₄ 37.50 mol%, mix them thoroughly in a mortar, and then pour them into an alumina crucible; Step S22: Melt in air at a temperature of 1450°C for 30 minutes to form molten glass. Step S23: Rapidly cool the molten glass in an air atmosphere to prepare the glass-ceramic solid electrolyte NFe0.4TP; Step S24: Grind NFe0.4TP into powder, press it into a cylinder in a mold, and transfer it to a muffle furnace; Step S25: Heat-treat at 900°C for 2 hours in air atmosphere to prepare Fe-based doped modified glass-ceramic solid electrolyte; Step S26: Polish the surface of the prepared Fe-based doped glass-ceramic solid electrolyte using a polishing machine to prepare it for assembly with the oxide glass electrode prepared in step S1 into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery.

[0029] Example 3 A method for preparing a glass-based sodium-ion all-solid-state battery includes the following steps: Step S1: Prepare Fe-based oxide glass electrode material; Step S11: After mixing Sb2O3 25 mol%, Fe2O3 25 mol%, B2O3 30 mol%, and P2O5 20 mol% evenly in a mortar, pour the mixture into an alumina crucible. Step S12: Melt in air atmosphere at a melting temperature of 1200℃ for 30 minutes to form molten glass. Step S13: Pour the molten glass liquid into a preheated copper plate under an air atmosphere for annealing to prepare the Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5.

[0030] Step S2: Prepare glass-ceramic solid electrolyte; Step S21: Weigh out Na₂CO₃ 20.00 mol%, Fe₂O₃ 7.50 mol%, TiO₂ 35.00 mol%, and NH₄H₂PO₄ 37.50 mol%, mix them thoroughly in a mortar, and then pour them into an alumina crucible; Step S22: Melt in air at a temperature of 1450°C for 30 minutes to form molten glass. Step S23: Rapidly cool the molten glass in an air atmosphere to prepare the glass-ceramic solid electrolyte NFe0.6TP; Step S24: Grind NFe0.6TP into powder, press it into a cylinder in a mold, and transfer it to a muffle furnace; Step S25: Heat-treat at 900°C for 2 hours in air atmosphere to prepare Fe-based doped modified glass-ceramic solid electrolyte; Step S26: Polish the surface of the prepared Fe-based doped glass-ceramic solid electrolyte using a polishing machine to prepare it for assembly with the oxide glass electrode prepared in step S1 into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery.

[0031] Example 4 A method for preparing a glass-based sodium-ion all-solid-state battery includes the following steps: Step S1: Prepare Fe-based oxide glass electrode material; Step S11: After mixing Sb2O3 25 mol%, Fe2O3 25 mol%, B2O3 30 mol%, and P2O5 20 mol% evenly in a mortar, pour the mixture into an alumina crucible. Step S12: Melt in air atmosphere at a melting temperature of 1200℃ for 30 minutes to form molten glass. Step S13: Pour the molten glass liquid into a preheated copper plate under an air atmosphere for annealing to prepare the Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5.

[0032] Step S2: Prepare glass-ceramic solid electrolyte; Step S21: Weigh out Na₂CO₃ 22.50 mol%, Fe₂O₃ 10.00 mol%, TiO₂ 30.00 mol%, and NH₄H₂PO₄ 37.50 mol%, mix them thoroughly in a mortar, and then pour them into an alumina crucible; Step S22: Melt in air at a temperature of 1450°C for 30 minutes to form molten glass. Step S23: Rapidly cool the molten glass in an air atmosphere to prepare the glass-ceramic solid electrolyte NFe0.8TP; Step S24: Grind NFe0.8TP into powder, press it into a cylinder in a mold, and transfer it to a muffle furnace; Step S25: Heat-treat at 900°C for 2 hours in air atmosphere to prepare Fe-based doped modified glass-ceramic solid electrolyte; Step S26: Polish the surface of the prepared Fe-based doped glass-ceramic solid electrolyte using a polishing machine to prepare it for assembly with the oxide glass electrode prepared in step S1 into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery.

[0033] Example 5 A method for preparing a glass-based sodium-ion all-solid-state battery includes the following steps: Step S1: Prepare Fe-based oxide glass electrode material; Step S11: After mixing Sb2O3 25 mol%, Fe2O3 25 mol%, B2O3 30 mol%, and P2O5 20 mol% evenly in a mortar, pour the mixture into an alumina crucible. Step S12: Melt in air atmosphere at a melting temperature of 1200℃ for 30 minutes to form molten glass. Step S13: Pour the molten glass liquid into a preheated copper plate under an air atmosphere for annealing to prepare the Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5.

[0034] Step S2: Prepare glass-ceramic solid electrolyte; Step S21: Weigh out Na₂CO₃ 20.00 mol%, Fe₂O₃ 7.50 mol%, TiO₂ 35.00 mol%, and NH₄H₂PO₄ 37.50 mol%, mix them thoroughly in a mortar, and then pour them into an alumina crucible; Step S22: Melt in air at a temperature of 1450°C for 30 minutes to form molten glass. Step S23: Rapidly cool the molten glass in an air atmosphere to prepare the glass-ceramic solid electrolyte NFe0.6TP; Step S24: Grind NFe0.6TP into powder, press it into a cylinder in a mold, and transfer it to a muffle furnace; Step S25: Heat-treat at 950°C for 2 hours in air atmosphere to prepare Fe-based doped modified glass-ceramic solid electrolyte; Step S26: Polish the surface of the prepared Fe-based doped glass-ceramic solid electrolyte using a polishing machine to prepare it for assembly with the oxide glass electrode prepared in step S1 into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery.

[0035] Example 6 A method for preparing a glass-based sodium-ion all-solid-state battery includes the following steps: Step S1: Prepare Fe-based oxide glass electrode material; Step S11: After mixing Sb2O3 25 mol%, Fe2O3 25 mol%, B2O3 30 mol%, and P2O5 20 mol% evenly in a mortar, pour the mixture into an alumina crucible. Step S12: Melt in air atmosphere at a melting temperature of 1200℃ for 30 minutes to form molten glass. Step S13: Pour the molten glass liquid into a preheated copper plate under an air atmosphere for annealing to prepare the Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5.

[0036] Step S2: Prepare glass-ceramic solid electrolyte; Step S21: Weigh out Na₂CO₃ 20.00 mol%, Fe₂O₃ 7.50 mol%, TiO₂ 35.00 mol%, and NH₄H₂PO₄ 37.50 mol%, mix them thoroughly in a mortar, and then pour them into an alumina crucible; Step S22: Melt in air at a temperature of 1450°C for 30 minutes to form molten glass. Step S23: Rapidly cool the molten glass in an air atmosphere to prepare the glass-ceramic solid electrolyte NFe0.6TP; Step S24: Grind NFe0.6TP into powder, press it into a cylinder in a mold, and transfer it to a muffle furnace; Step S25: Heat-treat at 1000℃ for 2 hours in air atmosphere to prepare Fe-based doped modified glass-ceramic solid electrolyte; Step S26: Polish the surface of the prepared Fe-based doped glass-ceramic solid electrolyte using a polishing machine to prepare it for assembly with the oxide glass electrode prepared in step S1 into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery.

[0037] Example 7 A method for preparing a glass-based sodium-ion all-solid-state battery includes the following steps: The Fe-based doped modified glass-ceramic solid electrolyte NF0.6TP prepared in Example 3 was polished using a polishing machine in preparation for assembling with the Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5 prepared in step S13 into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery.

[0038] Assemble a high-electrochemical-performance glass-based sodium-ion all-solid-state battery: Fe-based oxide glass electrode material 25Fe2O3-25Sb2O3-30B2O3-20P2O5 powder, acetylene black and polyvinylidene fluoride (PVDF) were placed in a 50mL ball mill jar with 2ml of N-methylpyrrolidone in a mass ratio of 7:2:1 and ball milled at 400r / min for 4.5h. The slurry was then coated onto copper foil.

[0039] Dry under vacuum at 110℃ for 10 hours, and after natural cooling, remove and cut into electrode sheets with a diameter of 12mm using a punching machine.

[0040] Assemble the battery in the following order: positive electrode shell - electrode sheet - glass ceramic solid electrolyte - sodium sheet - nickel mesh - electrode shell. Then seal the battery with a sealing machine to obtain a high electrochemical performance glass-based sodium-ion all-solid-state battery (25Fe2O3-25Sb2O3-30B2O3-20P2O5 / NF0.6TP / Na).

[0041] The high electrochemical performance glass-based sodium-ion all-solid-state battery (25Fe2O3-25Sb2O3-30B2O3-20P2O5 / NF0.6TP / Na) prepared in this embodiment was tested for charge and discharge using the Blue Electricity testing system. With a cutoff voltage of 0.01-2.0V and a g of 100mA -1 A constant current charge-discharge cycle test was conducted on a high-electrochemical-performance glass-based sodium-ion all-solid-state battery (25Fe2O3-25Sb2O3-30B2O3-20P2O5 / NF0.6TP / Na) at a given current density. Figure 3 As shown, the discharge specific capacity in the first cycle is 621.3 mA hg. -1 After 1000 cycles, the specific capacity is 84.8 mA hg. -1 It has a high capacity.

[0042] Therefore, this invention employs the aforementioned method for preparing and applying a glass-based sodium-ion all-solid-state battery. Based on the design concept of interface compatibility due to component and structural similarity, a high-performance Fe-based oxide glass sodium battery electrode material is prepared through component regulation and doping modification, achieving a performance of 100 mA g. -1 After 1000 stable cycles at the current density, the capacity is 120.3 mA hg. -1 This breakthrough overcomes the performance bottleneck of sodium-ion glass electrodes. Furthermore, a Fe-based modified NASICON-type solid electrolyte material was prepared, achieving a capacity of 3.44 × 10⁻⁶ ppm at room temperature. -4 mS / cm. The obtained high-performance Fe-based oxide glass electrode material was assembled with a Fe-modified NASICON glass-ceramic solid electrolyte obtained through component doping to form a sodium-ion solid-state battery. The sodium-ion solid-state battery exhibited good interfacial compatibility at 100 mA g. -1 After 1000 stable cycles at current density, it still maintains a high capacity of 84.4 mA hg. -1This method is based on the similar structure of the electrode and the solid electrolyte, and effectively improves the interface compatibility between the electrode and the solid electrolyte by using the same oxide modification as the core. A new oxide glass system was prepared as a sodium-ion battery electrode by adjusting the ratio of Fe2O3 to Sb2O3 through component control, overcoming the technical bottleneck of low cycle capacity of oxide glass electrodes in sodium-ion batteries. Furthermore, a NASICON glass-ceramic system modified with Fe2O3 was prepared through component doping. The ionic conductivity of the NASICON glass-ceramic solid electrolyte was improved by enhancing the heat treatment process, increasing density, reducing porosity, and preventing sodium dendrite growth along the pores. Finally, the high-performance Fe-based glass electrode prepared by component control was combined with the Fe-based modified NASICON glass-ceramic solid electrolyte prepared by component doping to prepare a glass-based sodium-ion all-solid-state battery, significantly improving the electrochemical performance and safety performance of the energy storage device. In addition, the production process of this invention is simple, and the components are widely available, inexpensive, and environmentally friendly, showing excellent development prospects.

[0043] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a glass-based sodium-ion all-solid-state battery, characterized in that, High-performance Fe-based oxide glass electrodes were prepared by adjusting the molar ratio of Sb₂O₃ to Fe₂O₃, and Fe-based doped NASICON glass-ceramic solid electrolytes were prepared by adjusting the molar percentage of Fe₂O₃ to TiO₂. The specific steps include: Step S1: Prepare Fe-based oxide glass electrode material; weigh out different molar percentages of Sb2O3, Fe2O3, B2O3 and P2O5, mix them evenly in a mortar, melt them into glass liquid under air atmosphere, anneal and grind them to prepare a series of Fe2O3-Sb2O3-B2O3-P2O5 system glasses, and obtain Fe-based oxide glass electrode material. Step S2: Preparation of glass-ceramic solid electrolyte; Weigh different molar percentages of Na2CO3, Fe2O3, TiO2 and NH4H2PO4, melt them into glass liquid in air atmosphere, cool and grind them, and further heat treat them to prepare Fe-based doped modified NASICON glass-ceramic solid electrolyte. Step S3: Prepare the Fe-based oxide glass electrode material obtained in step S1 as a Fe-based oxide glass electrode, and assemble the Fe-based oxide glass electrode and the Fe-based doped and modified NASICON glass ceramic solid electrolyte obtained in step S2 to obtain a glass-based sodium-ion all-solid-state battery with high electrochemical performance.

2. The method for preparing a glass-based sodium-ion all-solid-state battery according to claim 1, characterized in that, Step S1 specifically involves: Step S11: Weigh out 10-50 mol% Sb2O3, 0-40 mol% Fe2O3, 30 mol% B2O3 and 20 mol% P2O5; all the above oxides are analytical grade raw materials with a purity greater than 99.95%; mix them evenly in a mortar and pour them into an alumina crucible. Step S12: Melt in air atmosphere to form molten glass; Step S13: Pour molten glass onto a preheated copper plate in an air atmosphere for annealing to prepare oxide glass; Step S14: Grind the oxide glass in an air atmosphere using a mortar and pestle for 30-60 minutes.

3. The method for preparing a glass-based sodium-ion all-solid-state battery according to claim 2, characterized in that, In step S12, the melting temperature is 1200℃ and the holding time is 30min.

4. The method for preparing a glass-based sodium-ion all-solid-state battery according to claim 1, characterized in that, Step S2 specifically involves: Step S21: Weigh out 15.00~22.50 mol% Na2CO3, 2.5~10.00 mol% Fe2O3, 30.00~45.00 mol% TiO2 and 25~37.50 mol% NH4H2PO4, mix them evenly in a mortar, and then pour them into an alumina crucible; Step S22: Melt in air atmosphere to form molten glass; Step S23: In an air atmosphere, pour molten glass into water for rapid cooling without annealing to prepare oxide glass; Step S24: Grind the oxide glass into powder, press it into a cylinder in a mold, and transfer it to a muffle furnace; Step S25: The pressed cylinder is subjected to high-temperature heat treatment at 100-400℃ above the crystallization initiation temperature to prepare Fe-based doped modified NASICON glass-ceramic solid electrolyte. Step S26: Polish the surface of the prepared Fe-based doped NASICON glass-ceramic solid electrolyte using a polishing machine to prepare it for assembly with the oxide glass electrode prepared in step S1 into a high-electrochemical-performance glass-based sodium-ion all-solid-state battery.

5. The method for preparing a glass-based sodium-ion all-solid-state battery according to claim 4, characterized in that, In step S22, the melting temperature is 1450℃ under air atmosphere, and the temperature is maintained for 30 minutes.

6. The method for preparing a glass-based sodium-ion all-solid-state battery according to claim 4, characterized in that, In step S25, the heat treatment time is 1-10 hours in an air atmosphere.

7. The method for preparing a glass-based sodium-ion all-solid-state battery according to claim 1, characterized in that, In step S3, the Fe-based oxide glass electrode includes an active material, a conductive agent, a binder, and a current collector. The Fe-based oxide glass electrode is prepared by placing the active material, conductive agent, binder, and current collector in a ball mill with N-methylpyrrolidone in a ball mill jar to obtain a slurry, coating the slurry onto a copper foil, drying it under high temperature and vacuum conditions, and then taking it out after natural cooling and cutting it into electrode sheets with a diameter of 12 mm using a punching machine to obtain the Fe-based oxide glass electrode.

8. The method for preparing a glass-based sodium-ion all-solid-state battery according to claim 7, characterized in that, The active material is the Fe-based oxide glass electrode material prepared in step S1, the conductive agent is acetylene black, the binder is polyvinylidene fluoride, and the current collector is copper foil.

9. The method for preparing a glass-based sodium-ion all-solid-state battery according to claim 7, characterized in that, The mass ratio of the active material, conductive agent, and binder is 7:2:

1.

10. An application of a glass-based sodium-ion all-solid-state battery obtained by the preparation method of the glass-based sodium-ion all-solid-state battery according to any one of claims 1-9, characterized in that, It is used in energy storage devices.

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