All-solid-state sodium battery
Patent Information
- Application Number
- PCT/CN2025/095013
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2025-03-27
- Filing Date
- 2025-05-15
- Publication Date
- 2026-10-01
Smart Images
Figure CN2025095013_01102026_PF_FP_ABST
Abstract
Description
A type of all-solid-state sodium battery Technical Field
[0001] This invention belongs to the field of solid-state sodium batteries, and specifically relates to an all-solid-state sodium battery. Background Technology
[0002] Sodium-ion batteries have gained widespread attention in recent years due to their low cost and abundant resources, showing promising applications in low-speed electric vehicles, start-stop power supplies, residential energy storage, and large-scale energy storage. While sodium-ion batteries offer improved safety compared to lithium-ion batteries due to their lower energy density, the use of organic electrolytes still presents safety risks. In particular, layered cathodes, under extreme conditions such as compression, puncture, and short circuits, still pose a risk of thermal runaway, challenging their suitability even in the previously well-suited low-speed vehicle market. One effective solution to the safety issues of sodium-ion batteries is to replace organic electrolytes with solid-state electrolytes, assembling all-solid-state sodium batteries. Similar to solid-state lithium-ion batteries, solid-state sodium-ion batteries also face challenges such as low conductivity and a narrow electrochemical window, which can easily trigger interfacial side reactions, leading to high interfacial resistance, hindering interfacial charge transport and causing battery performance degradation, ultimately resulting in battery failure. Summary of the Invention
[0003] The purpose of this invention is to overcome the shortcomings of existing technologies and provide an all-solid-state sodium battery. This all-solid-state sodium battery possesses both excellent safety performance and a long cycle life.
[0004] Another object of the present invention is to provide a method for preparing the all-solid-state sodium battery.
[0005] To achieve the above objectives, the present invention employs the following technical solution:
[0006] A solid-state sodium battery comprises, in sequence, a negative electrode layer, an intermediate layer, a solid electrolyte layer, and a positive electrode layer;
[0007] The intermediate layer is selected from β”-Al2O3; the solid electrolyte layer is selected from amorphous sulfur-doped halides, the general chemical formula of which is Na. 1+x TaCl n A 6-x-n S x In the formula, A is a mixture of at least one of Br, I, and F, 0 <x≤0.5,5≤n≤5.5。
[0008] In this invention, using β”-Al2O3 as an intermediate layer can effectively suppress the interfacial reaction between the solid electrolyte layer and the negative electrode, and suppress sodium dendrite formation. Simultaneously, Na… 1+x TaCl n A 6-x-n Sx Furthermore, β”-Al2O3 exhibits low interfacial resistance, which promotes sodium ion transport at the interface and more effectively suppresses sodium dendrite formation. β”-Al2O3 also demonstrates good interfacial stability with both the negative electrode layer and the solid electrolyte layer. 1+x TaCl n A 6-x-n S x It has good interfacial stability with the positive electrode layer.
[0009] Preferably, the ionic conductivity of the β”-Al2O3 is greater than 1×10 -4 S / cm.
[0010] Preferably, the average particle size of the β”-Al2O3 is 50 to 500 nanometers.
[0011] Preferably, the ionic conductivity of the amorphous sulfur-doped halide is greater than 1×10⁻⁶. -3 S / cm.
[0012] In this invention, the negative electrode layer can be selected from metallic sodium, sodium alloy or carbon material, the sodium alloy is selected from sodium-tin alloy, sodium-antimony alloy, sodium-phosphorus alloy or sodium-bismuth alloy, and the carbon material is selected from soft carbon, hard carbon, soft / hard carbon composite material or phosphorus-carbon composite material.
[0013] Preferably, adjacent layers are bonded together with an adhesive.
[0014] Preferably, the adhesive is selected from polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polycarbonate, polyethylene oxide, or polybutene.
[0015] More preferably, the binder is polytetrafluoroethylene (PTFE). PTFE can undergo shear dispersion and fibrosis to achieve dry film formation.
[0016] Preferably, the thickness of the intermediate layer is 1 to 10 μm.
[0017] Preferably, the thickness of the solid electrolyte layer is 10–100 μm.
[0018] The preparation method of the all-solid-state sodium battery includes the following steps:
[0019] S1. Prepare the negative electrode layer;
[0020] S2. Mix β”-Al2O3 with binder evenly, roll and press into a film, and press onto the surface of the negative electrode layer to form an intermediate layer;
[0021] S3. The amorphous sulfur-doped halide is mixed evenly with the binder and rolled into a film, which is then pressed onto the surface of the intermediate layer to form a solid electrolyte layer.
[0022] S4. The positive electrode active material, binder, conductive agent, and the amorphous sulfur-doped halide mentioned in S3 are sheared and dispersed, and then rolled to obtain a positive electrode film; the positive electrode film is pressed onto the surface of the solid electrolyte layer to form a positive electrode layer;
[0023] S5. Encapsulation process to obtain the all-solid-state sodium battery.
[0024] Preferably, the negative electrode layer comprises a negative electrode material and a binder. More preferably, the weight ratio of the negative electrode material to the binder is 100:0.1 to 5.
[0025] Preferably, in the intermediate layer, the weight ratio of β”-Al2O3 to the binder is 100:0.1-5.
[0026] Preferably, in the solid electrolyte layer, the weight ratio of amorphous sulfur-doped halide to binder is 100:0.1-5.
[0027] Preferably, the amorphous sulfur-doped halide is prepared by ball milling. More specifically, it can be prepared by ball milling a mixture of LiA, Li2S, and TaCl5 in stoichiometric ratio as a precursor. 1+x TaCl n A 6-x-n S x .
[0028] More preferably, the ball milling time is 5 to 40 hours.
[0029] More preferably, the rotational speed of the ball mill is 400-600 rpm.
[0030] Preferably, in the positive electrode layer, the positive electrode active material is selected from commercially available layered oxides, polyanionic materials, or Prussian blue materials.
[0031] Preferably, in the positive electrode layer, the conductive agent is selected from at least one of graphene, fullerene, acetylene black, Super P, carbon nanotubes, and carbon nanofibers.
[0032] Preferably, in the positive electrode layer, the positive electrode active material, binder, conductive agent, and amorphous sulfur-doped Na are present. 1+x TaCl n A 6-x-n S x The weight ratio is 80-92:0.1-5:1-10:1-20.
[0033] Compared with the prior art, the present invention has the following beneficial effects:
[0034] In the all-solid-state sodium battery disclosed in this invention, the β”-Al2O3 interlayer effectively suppresses the interfacial reaction between the solid electrolyte layer and the negative electrode, and also suppresses sodium dendrite formation. The amorphous sulfur-doped halide solid electrolyte Na… 1+x TaCl n A 6-x-n S x It possesses high sodium ion conductivity and high voltage resistance, which is beneficial for suppressing interfacial reactions at the cathode and ion exchange. 1+x TaCl n A 6-x-n S x The β”-Al2O3 interlayer exhibits good interfacial stability, thereby suppressing interfacial reactions and reducing interfacial resistance, resulting in the all-solid-state sodium battery of the present invention having excellent safety performance and long cycle life. Attached Figure Description
[0035] Figure 1 shows the impedance spectrum of the solid electrolyte prepared in Example 1;
[0036] Figure 2 is a schematic diagram of the structure of the all-solid-state sodium battery prepared in Example 1;
[0037] Figure 3 shows the charge-discharge curves of the all-solid-state sodium battery prepared in Example 1;
[0038] Figure 4 shows the cycle life of the all-solid-state sodium battery prepared in Example 1;
[0039] Figure 5 shows the charge-discharge curves of the all-solid-state sodium battery prepared in Comparative Example 1.
[0040] Figure 6 shows the cycle life of the all-solid-state sodium battery prepared in Comparative Example 1. Detailed Implementation
[0041] The present invention will be further described in detail below with reference to specific embodiments. These embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods; the materials and reagents used are commercially available unless otherwise specified.
[0042] Example 1
[0043] S1. A negative electrode layer is obtained by rolling metallic sodium, and the thickness of the negative electrode layer is 50 micrometers.
[0044] S2. β”-Al2O3 and polytetrafluoroethylene are mixed at a weight ratio of 100:2, and then sheared, dispersed, and rolled to obtain a β”-Al2O3 film with a thickness of 5 micrometers. This film is then pressed onto the surface of the negative electrode layer to obtain an intermediate layer, wherein the ionic conductivity of β”-Al2O3 is 1.5 × 10⁻⁶. -4 S / cm, with an average particle size of 200 nanometers.
[0045] S3. Using NaCl, Na₂S, NaBr, and TaCl₅ as precursors, they were mixed in a molar ratio of 0.2:0.1:0.7:1 and ball-milled to prepare Na₂S. 1.1 TaCl 5.2 Br 0.7 S 0.1 The ball milling speed was 500 rpm, and the milling time was 20 hours. After testing, Na... 1.1 TaCl 5.2 Br 0.7 S 0.1 Its ionic conductivity is 1.8 × 10⁻⁶. -3 S / cm, see Figure 1.
[0046] Will Na 1.1 TaCl 5.2 Br 0.7 S 0.1 Na is mixed with polytetrafluoroethylene at a weight ratio of 100:2, and then sheared, dispersed, and rolled to obtain a Na film with a thickness of 60 micrometers. 1.1 TaCl 5.2 Br 0.7 S 0.1 A membrane is formed, and then the membrane is pressed onto the surface of the intermediate layer to obtain a solid electrolyte layer.
[0047] S4. Commercial NaNi 1 / 3 Fe 1 / 3 Mn 1 / 3 O2 cathode, polytetrafluoroethylene, carbon nanotubes, Na 1.1 TaCl 5.2 Br 0.7 S 0.1 The mixture is prepared by weight ratio of 82:2:3:13, and after shearing, dispersion and rolling, a positive electrode film with a thickness of 100 micrometers is obtained. The positive electrode film is then pressed onto the surface of the solid electrolyte layer to obtain the positive electrode layer.
[0048] S5. Aluminum foil current collectors were placed on the positive and negative electrode sides of the above-mentioned laminated material. After isostatic pressing, the material was packaged and assembled into an all-solid-state sodium battery. The battery structure is shown in Figure 2. The battery was charged and discharged at 2–4V, 0.1C (1C is defined as 150mA / g), and room temperature. The discharge capacity was 120.7mAh / g, as shown in Figure 3. After 200 cycles at 1C, the capacity retention rate was 94.4%, as shown in Figure 4. The cycled battery was disassembled and tested. No sodium dendrites were found in the solid electrolyte layer.
[0049] Example 2
[0050] S1. Na 15 Sn4 is rolled to obtain the negative electrode layer, and the thickness of the negative electrode layer is 70 micrometers.
[0051] S2. β”-Al2O3 and polytetrafluoroethylene are mixed at a weight ratio of 100:2, and after shear dispersion and rolling, a β”-Al2O3 film with a thickness of 8 micrometers is obtained. This film is then pressed onto the surface of the negative electrode layer to obtain the intermediate layer, wherein the ionic conductivity of β”-Al2O3 is 1.5 × 10⁻⁶. -4 S / cm, with an average particle size of 200 nanometers.
[0052] S3. Using NaCl, Na₂S, and TaCl₅ as precursors, they were mixed in a molar ratio of 0.8:0.2:1 and ball-milled to prepare Na₂S. 1.2 TaCl 5.8 S 0.2 The ball milling speed was 500 rpm, and the milling time was 20 hours. After testing, Na... 1.2 TaCl 5.8 S 0.2 Its ionic conductivity is 1.5 × 10⁻⁶. -3 S / cm. Na 1.2 TaCl 5.8 S 0.2 Na was mixed with polytetrafluoroethylene at a weight ratio of 100:2.5, and then sheared, dispersed, and rolled to obtain a Na film with a thickness of 55 micrometers. 1.2 TaCl 5.8 S 0.2 A membrane is formed, and then the membrane is pressed onto the surface of the intermediate layer to obtain a solid electrolyte layer.
[0053] S4. Combining commercial Na3V2(PO4)3 cathode, polytetrafluoroethylene, carbon nanofibers, and Na... 1.2 TaCl 5.8 S 0.2 The mixture was prepared by mixing ingredients in a weight ratio of 83:1.5:2.5:13, followed by shearing, dispersion, and rolling to obtain a positive electrode film with a thickness of 90 micrometers. The positive electrode film was then pressed onto the surface of the solid electrolyte layer to obtain the positive electrode layer.
[0054] S5. Aluminum foil current collectors are placed on the positive and negative electrode sides of the above-mentioned laminated material. After isostatic pressing, the material is packaged and assembled into an all-solid-state sodium battery. The battery was charged and discharged at 2.5–3.7V, 0.1C (1C is defined as 110mA / g), and room temperature. The discharge capacity was 105.3mAh / g, and the capacity retention rate was 95.2% after 200 cycles at 1C. The cycled battery was disassembled and tested, and no sodium dendrites were found in the solid electrolyte layer.
[0055] Example 3
[0056] S1. Hard carbon and polytetrafluoroethylene are mixed at a weight ratio of 100:2, and the mixture is sheared, dispersed and rolled to obtain a negative electrode layer with a thickness of 60 micrometers.
[0057] S2. β”-Al2O3 and polytetrafluoroethylene are mixed at a weight ratio of 100:2, and after shear dispersion and rolling, a β”-Al2O3 film with a thickness of 7 micrometers is obtained. This film is then pressed onto the surface of the negative electrode layer to obtain the intermediate layer, wherein the ionic conductivity of β”-Al2O3 is 1.5 × 10⁻⁶. -4 S / cm, with an average particle size of 200 nanometers.
[0058] S3. Using NaCl, NaI, NaBr, Na2S, and TaCl5 as precursors, mixed in a molar ratio of 0.5:0.05:0.4:0.05:1, and ball-milled to prepare Na 1.05 TaCl 5.5 Br 0.4 I 0.05 S 0.05 The ball milling speed was 500 rpm, and the milling time was 20 hours. After testing, Na... 1.05 TaCl 5.5 Br 0.4 I 0.05 S 0.05 The ionic conductivity is 2.0 × 10⁻⁶. -3 S / cm. Na 1.05 TaCl 5.5 Br 0.4 I 0.05 S 0.05 Na was mixed with polytetrafluoroethylene at a weight ratio of 100:1.5, and then sheared, dispersed, and rolled to obtain a Na film with a thickness of 65 micrometers. 1.05 TaCl 5.5 Br 0.4 I 0.05 S 0.05 A membrane is formed, and then the membrane is pressed onto the surface of the intermediate layer to obtain a solid electrolyte layer.
[0059] S4. Commercial Na2Fe 0.5 Mn 0.5 [Fe(CN)6] cathode, polytetrafluoroethylene, graphene, Na 1.05 TaCl 5.5 Br 0.4 I 0.05 S 0.05 The mixture is prepared by mixing in a weight ratio of 84:2.5:3:10.5, followed by shearing, dispersion, and rolling to obtain a positive electrode film with a thickness of 80 micrometers. The positive electrode film is then pressed onto the surface of the solid electrolyte layer to obtain the positive electrode layer.
[0060] S5. Aluminum foil current collectors are placed on the positive and negative electrode sides of the above-mentioned laminated material. After isostatic pressing, the material is packaged and assembled into an all-solid-state sodium battery. The battery was charged and discharged at 1.8–3.7V, 0.1C (1C is defined as 150mA / g), and room temperature. The discharge capacity was 123.3mAh / g, and the capacity retention rate was 92.1% after 200 cycles at 1C. The cycled battery was disassembled and tested, and no sodium dendrites were found in the solid electrolyte layer.
[0061] Example 4
[0062] S1. A negative electrode layer is obtained by rolling metallic sodium, and the thickness of the negative electrode layer is 65 micrometers.
[0063] S2. β”-Al2O3 and polytetrafluoroethylene are mixed at a weight ratio of 100:2, and after shear dispersion and rolling, a β”-Al2O3 film with a thickness of 6 micrometers is obtained. This film is then pressed onto the surface of the negative electrode layer to obtain the intermediate layer, wherein the ionic conductivity of β”-Al2O3 is 1.5 × 10⁻⁶. -4 S / cm, with an average particle size of 200 nanometers.
[0064] S3. Using NaBr, Na2S, and TaCl5 as precursors, they were mixed in a molar ratio of 0.5:0.5:1 and ball-milled to prepare Na 1.5 TaCl5Br 0.5 S 0.5 The ball milling speed was 500 rpm, and the milling time was 20 hours. After testing, Na... 1.5 TaCl5Br 0.5 S 0.5 Its ionic conductivity is 1.3 × 10⁻⁶. -3 S / cm. Na 1.5 TaCl5Br 0.5 S 0.5 Na is mixed with polytetrafluoroethylene at a weight ratio of 100:2, and then sheared, dispersed, and rolled to obtain a Na film with a thickness of 70 micrometers. 1.5 TaCl5Br 0.5 S 0.5 A membrane is formed, and then the membrane is pressed onto the surface of the intermediate layer to obtain a solid electrolyte layer.
[0065] S4. Commercial positive electrode NaNi 0.4 Fe 0.2 Mn 0.4 O2, polytetrafluoroethylene, Super P, Na 1.5 TaCl5Br 0.5 S 0.5 The components were mixed in a weight ratio of 84.5:2:3.5:10, and after shearing, dispersion and rolling, a positive electrode film with a thickness of 95 micrometers was obtained. The positive electrode film was then pressed onto the surface of the solid electrolyte layer to obtain the positive electrode layer.
[0066] S5. Aluminum foil current collectors are placed on the positive and negative electrode sides of the above-mentioned laminated material. After isostatic pressing, the material is packaged and assembled into an all-solid-state sodium battery. The battery was charged and discharged at 2-4V, 0.1C (1C is defined as 150mA / g), and room temperature. The discharge capacity was 122.4mAh / g, and the capacity retention rate was 93.2% after 200 cycles at 1C. The cycled battery was disassembled and tested, and no sodium dendrites were found in the solid electrolyte layer.
[0067] Comparative Example 1
[0068] The fabrication process of the all-solid-state sodium battery is the same as in Example 1, except that in step S3, the molar ratio of the amorphous sulfur-doped halide raw materials is adjusted so that the prepared amorphous sulfur-doped halide is NaTaCl. 5.2 Br 0.8 This means that no sulfur doping was performed. Testing showed that this NaTaCl... 5.2 Br 0.8 Its ionic conductivity is 0.4 × 10⁻⁶. -3 S / cm.
[0069] The prepared all-solid-state sodium battery exhibited a discharge capacity of 103.1 mAh / g at 2–4 V and 0.1 C (Figure 5), and a capacity retention of 78.9% after 200 cycles at 1 C (Figure 6). Disassembly and testing of the cycled battery revealed the presence of sodium dendrites in the solid electrolyte layer.
[0070] Comparative Example 2
[0071] The fabrication process of the all-solid-state sodium battery is the same as in Example 1, except that in step S3, the molar ratio of the amorphous sulfur-doped halide raw materials is adjusted so that the prepared amorphous sulfur-doped halide is Na. 1.6 TaCl 5.2 Br 0.2 S 0.6 This means the amount of sulfur doping is too high. Testing revealed that the Na... 1.6 TaCl 5.2 Br 0.2 S 0.6 The ionic conductivity is 0.2 × 10⁻⁶. -3 S / cm.
[0072] The prepared all-solid-state sodium battery exhibited a discharge capacity of 100.7 mAh / g at 2–4V and 0.1C, and retained 79.3% of its capacity after 200 cycles at 1C. Upon disassembly and testing of the cycled battery, sodium dendrites were observed in the solid electrolyte layer.
[0073] Comparative Example 3
[0074] The fabrication process of the all-solid-state sodium battery is the same as in Example 1, except that in step S3, the molar ratio of the amorphous sulfur-doped halide raw materials is adjusted so that the prepared solid electrolyte is Na. 1.1 TaBr 5.9 S 0.1 That is, replacing TaCl5 with TaBr5 and NaCl with NaBr, the ionic conductivity of this electrolyte was tested to be 0.3 × 10⁻⁶. -4 S / cm.
[0075] The prepared all-solid-state sodium battery exhibited a discharge capacity of 81.2 mAh / g at 2–4V and 0.1C, and retained 69.4% of its capacity after 200 cycles at 1C. Upon disassembly and testing of the cycled battery, sodium dendrites were observed in the solid electrolyte layer.
[0076] Comparative Example 4
[0077] The fabrication process of the all-solid-state sodium battery is as described in Example 1, except that there is no intermediate layer, that is, the solid electrolyte layer is directly pressed onto the surface of the negative electrode layer.
[0078] The prepared all-solid-state sodium battery exhibited a discharge capacity of 107.7 mAh / g at 2–4V and 0.1C, and retained 82.1% of its capacity after 200 cycles at 1C. Upon disassembly and testing of the cycled battery, sodium dendrites were observed in the solid electrolyte layer.
[0079] Comparative Example 5
[0080] The fabrication process of the all-solid-state sodium battery is as described in Example 1, except that β-Al₂O₃ is replaced with β-Al₂O₃ in the intermediate layer, wherein the ionic conductivity of β-Al₂O₃ is 1.1 × 10⁻⁶. -5 S / cm, with an average particle size of 200 nanometers.
[0081] The prepared all-solid-state sodium battery exhibited a discharge capacity of 109.5 mAh / g at 2–4V and 0.1C, and retained 82.8% of its capacity after 200 cycles at 1C. Upon disassembly and testing of the cycled battery, sodium dendrites were observed in the solid electrolyte layer.
[0082] Comparative Example 6
[0083] The fabrication process of the all-solid-state battery is as described in Example 1, except that the intermediate layer is made of commercially available Na3Zr2Si2PO4. 12 Replace β”-Al2O3, where Na3Zr2Si2PO 12 Its ionic conductivity is 5.0 × 10⁻⁶. -4 S / cm, with an average particle size of 200 nanometers.
[0084] The prepared all-solid-state sodium battery exhibited a discharge capacity of 111.3 mAh / g at 2–4V and 0.1C, and retained 84.3% of its capacity after 200 cycles at 1C. Disassembly and testing of the cycled battery revealed the presence of sodium dendrites in the solid electrolyte layer.
[0085] Comparative Example 7
[0086] The fabrication process of the all-solid-state battery is as described in Example 1, except that the intermediate layer is replaced with commercial Na3PS4 instead of β”-Al2O3, wherein the ionic conductivity of Na3PS4 is 2.2 × 10 -4 S / cm, with an average particle size of 200 nanometers.
[0087] The prepared all-solid-state sodium battery exhibited a discharge capacity of 112.1 mAh / g at 2–4 V and 0.1 C, and retained 85.1% of its capacity after 200 cycles at 1 C. Upon disassembly and testing of the cycled battery, sodium dendrites were observed in the solid electrolyte layer.
[0088] Comparative Example 8
[0089] The fabrication process of the all-solid-state battery is as described in Example 1, except that Na is not used. 1.1 TaCl 5.2 Br 0.7 S 0.1 A solid electrolyte was prepared, meaning the positive electrode film was directly pressed onto the surface of the intermediate layer without preparing a solid electrolyte layer. Experiments revealed that this battery could not function properly.
[0090] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.
Claims
1. An all-solid-state sodium battery, characterized by, The negative electrode layer, the intermediate layer, the solid-state electrolyte layer and the positive electrode layer are sequentially arranged. The intermediate layer is selected from the group consisting of β"-Al2O3; the solid-state electrolyte layer is selected from the group consisting of amorphous sulfur-doped halides, the chemical general formula of the amorphous sulfur-doped halides being Na 1+x TaCl n A 6-x-n S x , wherein A is a mixture of at least one of Br, I, F, 0 < x ≤ 0.5, 5 ≤ n ≤ 5.
5.
2. The all-solid-state sodium battery according to claim 1, characterized in that, The ion conductivity of the β"-Al2O3 is greater than 1 x 10 -4 S / cm.
3. The all-solid-state sodium battery according to claim 1 or 2, characterized in that, The average particle size of the β''-Al2O3 is 50-500 nm.
4. The all-solid-state sodium battery of claim 1, wherein, The amorphous sulfur-doped halide is prepared by mixing LiA, Li2S and TaCl5 in stoichiometric ratio as a precursor and ball milling.
5. The all-solid-state sodium battery of claim 1, wherein, The non-crystalline sulfur-doped halide has an ionic conductivity greater than 1 x 10 -3 S / cm.
6. The all-solid-state sodium battery of claim 1, wherein, The adjacent two layers are bonded by a bonding agent.
7. The all-solid-state sodium battery according to claim 6, characterized in that, The bonding agent is selected from polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polycarbonate, polyethylene oxide or polybutylene.
8. The all-solid-state sodium battery of claim 1, wherein, The thickness of the intermediate layer is 1-10 μm.
9. The all-solid-state sodium battery of claim 1, wherein, The thickness of the solid-state electrolyte layer is 10-100 μm.
10. The method of producing an all-solid-state sodium battery according to any one of claims 1 to 9, characterized by, The method comprises the following steps: S1. Preparing a negative electrode layer; S2. Mixing the β''-Al2O3 with a bonding agent, uniformly rolling into a film and pressing on the surface of the negative electrode layer to form an intermediate layer; S3. Mixing the amorphous sulfur-doped halide with a bonding agent, uniformly rolling into a film and pressing on the surface of the intermediate layer to form a solid-state electrolyte layer; S4. Shearing and dispersing the positive electrode active material, the bonding agent, the conductive agent and the amorphous sulfur-doped halide of S3, then rolling to obtain a positive electrode film; pressing the positive electrode film on the surface of the solid-state electrolyte layer to form a positive electrode layer; S5. Packaging to obtain the full-solid-state sodium battery.