Sodium-based high-entropy sulfide solid electrolyte and preparation method and application thereof

Abstract

The invention discloses a sodium-based high-entropy sulfide solid electrolyte as well as a preparation method and application thereof, and belongs to the technical field of solid electrolyte materials. Through high-entropy design and in combination with process innovation: microwave rapid sintering and interface / coating collaborative process optimization, high ionic conductivity (gt; 8 * 10 <-3 > S / cm), and long cycle stability (gt; and the grain boundary impedance is reduced by 72%. In the preparation method of the sodium-based high-entropy sulfide solid electrolyte, volatilization of sulfur is avoided through high-energy ball milling and microwave rapid sintering; a 5T superconducting magnetic field is used for inducing oriented growth; crystal grains are preferentially arranged along a crystal face, so that the ion transmission anisotropy is improved; interface engineering processing is carried out, and interface impedance is reduced; and the interface wettability and the mechanical strength are improved by adopting dynamic coating.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid electrolyte materials, and in particular relates to a sodium-based high-entropy sulfide solid electrolyte and a preparation method and application thereof. Background Art

[0002] Traditional oxide solid electrolytes (such as Na-β-Al2O3) have low ionic conductivity (10 -4 ~10 -3 S / cm), while sulfide electrolytes (such as Na3PS4) have high conductivity (10 -3 ~10 -2 S / cm), but there are problems such as poor chemical / electrochemical stability, high interfacial impedance, and easy reaction with sodium metal.

[0003] Currently, in the solid electrolyte industry, high entropy design (ΔS ≥ 1.5R) can improve the structural stability and ionic conductivity of materials, but existing technologies have the following problems:

[0004] (1) The sintering process is complex (traditional hot sintering easily leads to sulfur volatilization and low phase purity);

[0005] (2) poor interfacial compatibility (solid-solid contact leads to high interfacial resistance);

[0006] (3) Insufficient mechanical properties (difficult to inhibit sodium dendrite penetration);

[0007] (4) Lithium sulfide dependence: Li2S accounts for over 60% of the cost of traditional sulfide electrolytes (650 / kg), and its preparation requires high-temperature annealing (>10 hours);

[0008] (5) Bottleneck of sodium-based materials: low sodium ion mobility (conductivity < 3×10 -3 S / cm), high interface impedance (>100Ω·cm 2 ). Summary of the Invention

[0009] The purpose of the present invention is to provide a method for preparing a sodium-based high-entropy sulfide solid electrolyte, which achieves high ionic conductivity (>8×10 -3 S / cm), long cycle stability (>1000 times), and a 72% reduction in grain boundary resistance.

[0010] The present invention is achieved through the following technical solutions:

[0011] A sodium-based high entropy sulfide solid electrolyte, the chemical formula of the solid electrolyte is: Na 10- x Li 0.20 K0.15 Ca 0.15 Y 0.15 SnP2S 12 -ySe3O2, where 0.8≤x≤1.0, 0.45≤y≤0.55, and the cation entropy value ΔS≥1.5R.

[0012] Among them, 0.8≤x≤1.0 refers to the regulation of ion mobility by Na vacancies; 0.45≤y≤0.55 refers to the optimization of S vacancy concentration by Se / O dual doping; and the cation entropy value ΔS≥1.5R refers to the high entropy effect of Li / K / Ca / Y / Sn quinary.

[0013] A method for preparing a sodium-based high-entropy sulfide solid electrolyte comprises the following steps:

[0014] S1. High energy ball milling:

[0015] The raw material precursors: sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are selected, mixed, and a solvent is added to mix. The mixture is then placed in a high-energy ball mill, and grinding balls are added. The mixture is subjected to high-energy ball milling treatment in an argon / hydrogen sulfide mixed gas atmosphere to obtain a nano-mixed powder.

[0016] S2. Microwave sintering:

[0017] The nano-mixed powder is placed in a multi-mode microwave sintering device for microwave sintering to obtain a material with a gradient grain boundary structure;

[0018] S3, superconducting magnetic field assisted deposition: placing the gradient grain boundary structure material in a superconducting magnetic field to induce grain growth along the crystal plane to obtain a sodium-based high entropy sulfide solid electrolytic interface;

[0019] S4. Interface engineering treatment:

[0020] MXene treatment: Ti3AlC2 was etched with a 40% NH4HF2 aqueous solution at 50-60°C for 20-24 hours, and sulfur passivated to obtain Ti3C2S2;

[0021] MoS2 quantum dot loading: (NH4)2MoS4 was mixed with 0.1M ethanol solution to obtain a precursor, which was decomposed by CVD method and then MoS2 quantum dots were loaded on the surface of graphene / MXene support;

[0022] S5, dynamic covering layer:

[0023] The dynamic coating is obtained by mixing and cross-linking polyethylene glycol diacrylate, vinylene carbonate and tetrahydrofuran-γ-butyrolactone;

[0024] The dynamic coating coating is coated on the sodium-based high-entropy sulfide solid electrolyte interface after interface engineering treatment to obtain a sodium-based high-entropy sulfide solid electrolyte.

[0025] Preferably, in S1, the mass concentrations of sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are 99.9wt%, 99.5wt%, 99wt%, 99wt%, 99.99wt%, and 99.9wt%;

[0026] Molar ratio: 4.55 mol of sodium sulfide, 0.10 mol of lithium sulfide, 1.0 mol of phosphorus pentasulfide, 0.5 mol of tin disulfide, 1.5 mol of selenium, and 0.0375 mol of yttrium oxide.

[0027] Preferably, in S1, the grinding balls are ZrO2 grinding balls, the ball milling speed is 800 rpm, and the ball-to-material ratio is 20:1;

[0028] The argon / hydrogen sulfide mixed gas atmosphere is mixed in a volume ratio of 9:1, wherein the H2S partial pressure is 0.1 MPa;

[0029] The high-energy ball milling time is 10 to 12 hours, with forward and reverse rotations alternating every 30 minutes;

[0030] The particle size of the nano-mixed powder is no more than 200 nm.

[0031] Preferably, in S2, the multimode microwave sintering device is a 2.45 GHz microwave field;

[0032] The microwave sintering process is as follows: raising the temperature gradient from 200° C. to 645-655° C. and then keeping the temperature for 40-45 seconds.

[0033] Preferably, in S3, in a 5T superconducting magnetic field, the grains are induced to grow along the crystal plane within a temperature range of 300-500°C;

[0034] The grain aspect ratio is 3:1.

[0035] Preferably, in S4, the interlayer spacing of the MXene treatment is expanded to 0.98±0.02 nm;

[0036] The particle size of the MoS2 quantum dots is 3 to 5 nm.

[0037] Preferably, in S5, the mass concentration of polyethylene glycol diacrylate is 80 wt %, and the mass concentration of vinylene carbonate is 20 wt %;

[0038] The volume ratio of tetrahydrofuran to gamma-butyrolactone was 3:1, and the amount added was 14 wt% of the total solution volume;

[0039] The coating is carried out by combining a dipping and pulling method with a UV curing method;

[0040] The dipping and pulling speed is 2 mm / s; UV curing is performed using a 365 nm ultraviolet lamp for 10 minutes;

[0041] The coating thickness is 360-365 nm and the coating time is 8-10 min;

[0042] The pore size after coating is 30 to 50 nm.

[0043] Application of a sodium-based high-entropy sulfide solid electrolyte in the preparation of high-energy-density solid-state sodium batteries.

[0044] Compared with the prior art, the present invention has at least the following technical effects:

[0045] The present invention provides a method for preparing a sodium-based high-entropy sulfide solid electrolyte. Through high-entropy design, combined with process innovation: microwave rapid sintering + interface / coating synergistic process optimization, high ionic conductivity (>8×10 -3 S / cm), long cycle stability (>1000 times), and a 72% reduction in grain boundary resistance.

[0046] In the preparation method of this sodium-based high-entropy sulfide solid electrolyte, sulfur volatilization is avoided through high-energy ball milling and microwave rapid sintering; microwave rapid sintering (less than 1 minute) is completed simultaneously with magnetic field-assisted grain growth, avoiding the intermittent performance loss of segmented processing; 5T superconducting magnetic field is used to induce oriented growth: the grains are preferentially arranged along the crystal plane, improving the anisotropy of ion transport; interface engineering treatment is performed to reduce interface impedance; and dynamic coating is used to improve interface wettability and mechanical strength. DETAILED DESCRIPTION

[0047] The embodiments of the present invention will be described in detail below with reference to the examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. Specific conditions not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used without indicating the manufacturer are all conventional products that can be purchased commercially.

[0048] The technical solution of a specific embodiment of the present invention is:

[0049] A sodium-based high entropy sulfide solid electrolyte, the chemical formula of the solid electrolyte is: Na 10- x Li 0.20 K 0.15 Ca 0.15 Y 0.15 SnP2S 12-ySe3O2, where 0.8≤x≤1.0, 0.45≤y≤0.55, and the cation entropy value ΔS≥1.5R.

[0050] A method for preparing a sodium-based high-entropy sulfide solid electrolyte comprises the following steps:

[0051] S1. High energy ball milling:

[0052] The raw material precursors: sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are selected, mixed, and a solvent is added to mix. The mixture is then placed in a high-energy ball mill, and grinding balls are added. The mixture is subjected to high-energy ball milling treatment in an argon / hydrogen sulfide mixed gas atmosphere to obtain a nano-mixed powder.

[0053] The mass concentrations of the sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are 99.9wt%, 99.5wt%, 99wt%, 99wt%, 99.99wt%, and 99.9wt%;

[0054] Molar ratio: sodium sulfide 4.55 mol, lithium sulfide 0.10 mol, phosphorus pentasulfide 1.0 mol, tin disulfide 0.5 mol, selenium 1.5 mol, yttrium oxide 0.0375 mol;

[0055] The grinding balls are ZrO2 grinding balls, the ball milling speed is 800 rpm, and the ball-to-material ratio is 20:1;

[0056] In the atmosphere of argon / hydrogen sulfide mixed gas, the volume ratio is 9:1, wherein the H2S partial pressure is 0.1 MPa;

[0057] The high-energy ball milling time is 10 to 12 hours, with forward and reverse rotations alternating every 30 minutes;

[0058] The particle size of the nano-mixed powder is not greater than 200nm.

[0059] S2. Microwave sintering:

[0060] The nano-mixed powder is placed in a multi-mode microwave sintering device for microwave sintering to obtain a material with a gradient grain boundary structure;

[0061] The multimode microwave sintering device is a 2.45GHz microwave field;

[0062] The microwave sintering process is as follows: raising the temperature gradient from 200°C to 645-655°C and then keeping it at that temperature for 40-45s.

[0063] S3, superconducting magnetic field assisted deposition: placing the gradient grain boundary structure material in a superconducting magnetic field to induce grain growth along the crystal plane to obtain a sodium-based high entropy sulfide solid electrolytic interface;

[0064] In a 5T superconducting magnetic field, the grains are induced to grow along the crystal planes within the temperature range of 300-500°C;

[0065] The grain aspect ratio is 3:1.

[0066] S4. Interface engineering treatment:

[0067] MXene treatment: Ti3AlC2 was etched with a 40% NH4HF2 aqueous solution at 50-60°C for 20-24 hours, and sulfur passivated to obtain Ti3C2S2;

[0068] MoS2 quantum dot loading: (NH4)2MoS4 was mixed with 0.1M ethanol solution to obtain a precursor, which was decomposed by CVD method and then MoS2 quantum dots were loaded on the surface of graphene / MXene support;

[0069] The interlayer spacing of MXene treatment expanded to 0.98 ± 0.02 nm;

[0070] The particle size of the MoS2 quantum dots is 3 to 5 nm.

[0071] S5, dynamic covering layer:

[0072] The dynamic coating is obtained by mixing and cross-linking polyethylene glycol diacrylate, vinylene carbonate and tetrahydrofuran-γ-butyrolactone;

[0073] The dynamic coating coating is coated on the sodium-based high-entropy sulfide solid electrolyte interface after interface engineering treatment to obtain a sodium-based high-entropy sulfide solid electrolyte.

[0074] The mass concentration of polyethylene glycol diacrylate is 80 wt %, and the mass concentration of vinylene carbonate is 20 wt %;

[0075] The volume ratio of tetrahydrofuran to gamma-butyrolactone was 3:1, and the amount added was 14 wt% of the total solution volume;

[0076] The coating is carried out by combining the dipping and pulling method with the UV curing method;

[0077] The dipping and pulling speed is 2 mm / s; UV curing is performed using a 365 nm ultraviolet lamp for 10 minutes;

[0078] The coating thickness is 360-365 nm and the coating time is 8-10 min;

[0079] The pore size after coating is 30 to 50 nm.

[0080] Example 1:

[0081] The general chemical formula of solid electrolyte is: Na 10-x Li 0.20 K0.15 Ca 0.15 Y 0.15 SnP2S 12 -ySe3O2, where 0.8≤x≤1.0, 0.45≤y≤0.55, and the cation entropy value ΔS≥1.5R.

[0082] When x = 0.9, y = 0.5:

[0083] A method for preparing a sodium-based high-entropy sulfide solid electrolyte comprises the following steps:

[0084] S1. High energy ball milling:

[0085] The raw material precursors: sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are selected, mixed, and a solvent is added to mix. The mixture is then placed in a high-energy ball mill, and grinding balls are added. The mixture is subjected to high-energy ball milling treatment in an argon / hydrogen sulfide mixed gas atmosphere to obtain a nano-mixed powder.

[0086] The mass concentrations of the sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are 99.9wt%, 99.5wt%, 99wt%, 99wt%, 99.99wt%, and 99.9wt%;

[0087] Molar ratio: sodium sulfide 4.55 mol, lithium sulfide 0.10 mol, phosphorus pentasulfide 1.0 mol, tin disulfide 0.5 mol, selenium 1.5 mol, yttrium oxide 0.0375 mol;

[0088] The grinding balls are ZrO2 grinding balls, the ball milling speed is 800 rpm, and the ball-to-material ratio is 20:1;

[0089] In the atmosphere of argon / hydrogen sulfide mixed gas, the volume ratio is 9:1, wherein the H2S partial pressure is 0.1 MPa;

[0090] The high-energy ball milling time was 12 h, with forward and reverse rotations alternating every 30 min;

[0091] The particle size of the nano-mixed powder is not greater than 200nm.

[0092] S2. Microwave sintering:

[0093] The nano-mixed powder is placed in a multi-mode microwave sintering device for microwave sintering to obtain a material with a gradient grain boundary structure;

[0094] The multimode microwave sintering device is a 2.45GHz microwave field;

[0095] The microwave sintering process is as follows: the temperature gradient is increased from 200°C to 650°C and then kept at this temperature for 45 seconds.

[0096] S3, superconducting magnetic field assisted deposition: placing the gradient grain boundary structure material in a superconducting magnetic field to induce grain growth along the crystal plane to obtain a sodium-based high entropy sulfide solid electrolytic interface;

[0097] In a 5T superconducting magnetic field, the grains were induced to grow along the crystal plane within 500°C;

[0098] The grain aspect ratio is 3:1.

[0099] S4. Interface engineering treatment:

[0100] MXene treatment: Ti3AlC2 was etched with a 40% NH4HF2 aqueous solution at 60°C for 24 h, and sulfur passivated to obtain Ti3C2S2;

[0101] MoS2 quantum dot loading: (NH4)2MoS4 was mixed with 0.1M ethanol solution to obtain a precursor, which was decomposed by CVD method and then MoS2 quantum dots were loaded on the surface of graphene / MXene support;

[0102] The interlayer spacing of MXene treatment expanded to 0.98 ± 0.02 nm;

[0103] The particle size of the MoS2 quantum dots is 3 to 5 nm.

[0104] S5, dynamic covering layer:

[0105] The dynamic coating is obtained by mixing and cross-linking polyethylene glycol diacrylate, vinylene carbonate and tetrahydrofuran-γ-butyrolactone;

[0106] The dynamic coating coating is coated on the sodium-based high-entropy sulfide solid electrolyte interface after interface engineering treatment to obtain a sodium-based high-entropy sulfide solid electrolyte.

[0107] The mass concentration of polyethylene glycol diacrylate is 80 wt %, and the mass concentration of vinylene carbonate is 20 wt %;

[0108] The volume ratio of tetrahydrofuran to gamma-butyrolactone was 3:1, and the amount added was 14 wt% of the total solution volume;

[0109] The coating is carried out by combining the dipping and pulling method with the UV curing method;

[0110] The dipping and pulling speed is 2 mm / s; UV curing is performed using a 365 nm ultraviolet lamp for 10 minutes;

[0111] The coating thickness is 365 nm and the coating time is 10 min;

[0112] The pore size after coating is 50 nm.

[0113] The ionic conductivity of the sodium-based high-entropy sulfide solid electrolyte was 8.3×10 -3 S / cm; interface resistance: 4.8Ω·cm 2 ; Critical current density: 2.1mA / cm 2 .

[0114] Comparative Example 1:

[0115] The general chemical formula of solid electrolyte is: Na 10-x Li 0.20 K 0.15 Ca 0.15 Y 0.15 SnP2S 12 -ySe3O2, no high entropy design, x=y=0:

[0116] A method for preparing a sodium-based high-entropy sulfide solid electrolyte comprises the following steps:

[0117] S1. High energy ball milling:

[0118] The raw material precursors: sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are selected, mixed, and a solvent is added to mix. The mixture is then placed in a high-energy ball mill, and grinding balls are added. The mixture is subjected to high-energy ball milling treatment in an argon / hydrogen sulfide mixed gas atmosphere to obtain a nano-mixed powder.

[0119] The mass concentrations of the sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are 99.9wt%, 99.5wt%, 99wt%, 99wt%, 99.99wt%, and 99.9wt%;

[0120] Molar ratio: sodium sulfide 4.55 mol, lithium sulfide 0.10 mol, phosphorus pentasulfide 1.0 mol, tin disulfide 0.5 mol, selenium 1.5 mol, yttrium oxide 0.0375 mol;

[0121] The grinding balls are ZrO2 grinding balls, the ball milling speed is 800 rpm, and the ball-to-material ratio is 20:1;

[0122] In the atmosphere of argon / hydrogen sulfide mixed gas, the volume ratio is 9:1, wherein the H2S partial pressure is 0.1 MPa;

[0123] The high-energy ball milling time was 12 h, with forward and reverse rotations alternating every 30 min;

[0124] The particle size of the nano-mixed powder is not greater than 200nm.

[0125] S2. Microwave sintering:

[0126] The nano-mixed powder is placed in a multi-mode microwave sintering device for microwave sintering to obtain a material with a gradient grain boundary structure;

[0127] The multimode microwave sintering device is a 2.45GHz microwave field;

[0128] The microwave sintering process is as follows: the temperature gradient is increased from 200°C to 650°C and then kept at this temperature for 45 seconds.

[0129] S3, superconducting magnetic field assisted deposition: placing the gradient grain boundary structure material in a superconducting magnetic field to induce grain growth along the crystal plane to obtain a sodium-based high entropy sulfide solid electrolytic interface;

[0130] In a 5T superconducting magnetic field, the grains were induced to grow along the crystal plane within 500°C;

[0131] The grain aspect ratio is 3:1.

[0132] S4. Interface engineering treatment:

[0133] MXene treatment: Ti3AlC2 was etched with a 40% NH4HF2 aqueous solution at 60°C for 24 h, and sulfur passivated to obtain Ti3C2S2;

[0134] MoS2 quantum dot loading: (NH4)2MoS4 was mixed with 0.1M ethanol solution to obtain a precursor, which was decomposed by CVD method and then MoS2 quantum dots were loaded on the surface of graphene / MXene support;

[0135] The interlayer spacing of MXene treatment expanded to 0.98 ± 0.02 nm;

[0136] The particle size of the MoS2 quantum dots is 3 to 5 nm.

[0137] S5, dynamic covering layer:

[0138] The dynamic coating is obtained by mixing and cross-linking polyethylene glycol diacrylate, vinylene carbonate and tetrahydrofuran-γ-butyrolactone;

[0139] The dynamic coating coating is coated on the sodium-based high-entropy sulfide solid electrolyte interface after interface engineering treatment to obtain a sodium-based high-entropy sulfide solid electrolyte.

[0140] The mass concentration of polyethylene glycol diacrylate is 80 wt %, and the mass concentration of vinylene carbonate is 20 wt %;

[0141] The volume ratio of tetrahydrofuran to gamma-butyrolactone was 3:1, and the amount added was 14 wt% of the total solution volume;

[0142] The coating is carried out by combining the dipping and pulling method with the UV curing method;

[0143] The dipping and pulling speed is 2 mm / s; UV curing is performed using a 365 nm ultraviolet lamp for 10 minutes;

[0144] The coating thickness is 365 nm and the coating time is 10 min;

[0145] The pore size after coating is 50 nm.

[0146] The ionic conductivity of the sodium-based high-entropy sulfide solid electrolyte was 8.3×10 -3 S / cm; interface resistance: 4.8Ω·cm 2 ; Critical current density: 2.1mA / cm 2 .

[0147] The ionic conductivity of the sodium-based high-entropy sulfide solid electrolyte was 5.2×10 -3 S / cm; interface resistance: 15.6Ω·cm 2 ; Critical current density: 0.8mA / cm 2 .

[0148] Product performance test standards:

[0149] Test items method Eligibility criteria Ionic conductivity (25℃) EIS (0.1-1 MHz, blocked electrode) <![CDATA[≥8.0×10 - 3S / cm]]> activation energy Arrhenius fitting (25-100℃) ≤0.20eV Critical current density Constant current polarization (Li / Na-HESS / Li symmetric battery) <![CDATA[≥2.0mA / cm 2 (No short circuit)]]> Cycling stability 0.5C charge and discharge (NVP / Na-HESS / Na) 1000 times capacity retention rate ≥90%

[0150] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A sodium-based high-entropy sulfide solid electrolyte, characterized in that: The chemical formula of the solid electrolyte is: Na 10- x Li 0.20 K 0.15 Ca 0.15 Y 0.15 SnP2S 12 -ySe3O2, where 0.8≤x≤1.0, 0.45≤y≤0.55, and the cation entropy value ΔS≥1.5R.

2. A method for preparing the sodium-based high-entropy sulfide solid electrolyte according to claim 1, characterized in that: The steps include: S1. High energy ball milling: The raw material precursors: sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are selected, mixed, and a solvent is added to mix. The mixture is then placed in a high-energy ball mill, and grinding balls are added. The mixture is subjected to high-energy ball milling treatment in an argon / hydrogen sulfide mixed gas atmosphere to obtain a nano-mixed powder. S2. Microwave sintering: The nano-mixed powder is placed in a multi-mode microwave sintering device for microwave sintering to obtain a material with a gradient grain boundary structure; S3, superconducting magnetic field assisted deposition: placing the gradient grain boundary structure material in a superconducting magnetic field to induce grain growth along the crystal plane to obtain a sodium-based high entropy sulfide solid electrolytic interface; S4. Interface engineering treatment: MXene treatment: Ti3AlC2 was etched with a 40% NH4HF2 aqueous solution at 50-60°C for 20-24 hours, and sulfur passivated to obtain Ti3C2S2; MoS2 quantum dot loading: (NH4)2MoS4 was mixed with 0.1M ethanol solution to obtain a precursor, which was decomposed by CVD method and then MoS2 quantum dots were loaded on the surface of graphene / MXene support; S5, dynamic covering layer: The dynamic coating is obtained by mixing and cross-linking polyethylene glycol diacrylate, vinylene carbonate and tetrahydrofuran-γ-butyrolactone; The dynamic coating coating is coated on the sodium-based high-entropy sulfide solid electrolyte interface after interface engineering treatment to obtain a sodium-based high-entropy sulfide solid electrolyte.

3. The method for preparing a sodium-based high-entropy sulfide solid electrolyte according to claim 2, characterized in that: In S1, the mass concentrations of sodium sulfide, lithium sulfide, phosphorus pentasulfide, tin disulfide, selenium, and yttrium oxide are 99.9wt%, 99.5wt%, 99wt%, 99wt%, 99.99wt%, and 99.9wt% respectively; Molar ratio: 4.55 mol of sodium sulfide, 0.10 mol of lithium sulfide, 1.0 mol of phosphorus pentasulfide, 0.5 mol of tin disulfide, 1.5 mol of selenium, and 0.0375 mol of yttrium oxide.

4. The method for preparing a sodium-based high-entropy sulfide solid electrolyte according to claim 3, characterized in that: In S1, the grinding balls are ZrO2 grinding balls, the ball milling speed is 800 rpm, and the ball-to-material ratio is 20:1; The argon / hydrogen sulfide mixed gas atmosphere is mixed in a volume ratio of 9:1, wherein the H2S partial pressure is 0.1 MPa; The high-energy ball milling time is 10 to 12 hours, with forward and reverse rotations alternating every 30 minutes; The particle size of the nano-mixed powder is no more than 200 nm.

5. The method for preparing a sodium-based high-entropy sulfide solid electrolyte according to claim 2, characterized in that: In said S2, the multimode microwave sintering device is a 2.45 GHz microwave field; The microwave sintering process is as follows: raising the temperature gradient from 200° C. to 645-655° C. and then keeping the temperature for 40-45 seconds.

6. The method for preparing a sodium-based high-entropy sulfide solid electrolyte according to claim 2, characterized in that: In said S3, in a 5T superconducting magnetic field, inducing the growth of grains along the crystal plane within a temperature range of 300-500°C; The grain aspect ratio is 3:

1.

7. The method for preparing a sodium-based high-entropy sulfide solid electrolyte according to claim 2, wherein: In the S4, the interlayer spacing after MXene treatment expanded to 0.98 ± 0.02 nm; The particle size of the MoS2 quantum dots is 3 to 5 nm.

8. The method for preparing a sodium-based high-entropy sulfide solid electrolyte according to claim 2, characterized in that: In said S5, the mass concentration of polyethylene glycol diacrylate is 80 wt %, and the mass concentration of vinylene carbonate is 20 wt %; The volume ratio of tetrahydrofuran to gamma-butyrolactone was 3:1, and the amount added was 14 wt% of the total solution volume; The coating is carried out by combining a dipping and pulling method with a UV curing method; The dipping and pulling speed is 2 mm / s; UV curing was performed using a 365 nm UV lamp for 10 min; The coating thickness is 360-365 nm and the coating time is 8-10 min; The pore size after coating is 30 to 50 nm.

9. Use of the sodium-based high-entropy sulfide solid electrolyte according to claim 1 in preparing a high-energy-density solid-state sodium battery.