A modified argyrodite sulfide solid-state electrolyte and a method for preparing the same

Abstract

The application provides a modified argyrodite sulfide solid electrolyte and a preparation method thereof, the preparation method comprising the following steps: (a) providing raw materials: Li2S, P2S5, LiCl and Ag2O; (b) weighing the raw materials according to a predetermined molar ratio of Li:Ag:P:S:O:Cl; (c) ball-milling and mixing the raw materials under an inert atmosphere to obtain a mixed powder; (d) sintering the mixed powder under an inert atmosphere at 550-650 DEG C for 5-12 hours to obtain the Ag-O cation-anion co-doped modified argyrodite sulfide solid electrolyte, which has a chemical general formula of Li 6‑y Ag y PS 5‑x O x Cl, wherein 0.1 <= x <= 0.5, y=2x. The application effectively solves the problems of poor cycle performance and unstable interface between the existing argyrodite sulfide solid electrolyte and a lithium metal negative electrode.

Description

Technical Field

[0001] This invention relates to the field of solid electrolyte materials technology, and in particular to a modified silver-germanium sulfide solid electrolyte with Ag-O dual doping of anions and cations for all-solid-state lithium batteries and its preparation method. Background Technology

[0002] All-solid-state lithium batteries are considered an ideal choice for next-generation energy storage systems due to their high safety and high energy density. Among various solid-state electrolytes, the silver-germanium sulfide solid-state electrolyte Li6PS5X (where X can be Cl, Br, or I) has attracted widespread attention in all-solid-state batteries due to its high room-temperature ionic conductivity, good cold-pressing performance, and low preparation temperature. In particular, Li6PS5Cl (often abbreviated as LPSC) is a typical silver-germanium sulfide solid-state electrolyte.

[0003] However, this type of electrolyte exhibits severe interfacial instability with the lithium metal anode. Its crystal structure is primarily composed of PS4 tetrahedra. Due to the low strength of PS and SS bonds, it readily reacts with the lithium anode to form Li2S, causing crystal reaction and structural fragmentation. This leads to a continuous increase in interfacial impedance and lithium dendrite growth, severely limiting the battery's long cycle life and high-rate performance. Therefore, there is an urgent need in this field to develop a novel sulfide solid electrolyte that can form a stable interface with the lithium metal anode while maintaining high ionic conductivity.

[0004] It should be noted that the information disclosed in the background section above is only for understanding the background of this application, and therefore may include information that does not constitute prior art known to those skilled in the art. Summary of the Invention

[0005] This invention provides a modified silver-germanium sulfide solid electrolyte with high interfacial stability and good cycle performance with lithium metal anode, and its preparation method.

[0006] The present invention adopts the following technical solution: In a first aspect, a method for preparing a modified silver-germanium sulfide solid electrolyte is provided, comprising the following steps: (a) Provide raw materials: Li2S, P2S5, LiCl and Ag2O; (b) Weigh the raw materials according to the predetermined molar ratio of Li:Ag:P:S:O:Cl; (c) The raw materials are ball-milled and mixed under an inert atmosphere to obtain a mixed powder; (d) The mixed powder is sintered at 550-650°C for 5-12 hours under an inert atmosphere to obtain the modified silver-germanium sulfide solid electrolyte with Ag-O anion and cation doping, the chemical formula of which is Li. 6-y Ag y PS 5-x O x Cl, where 0.1 ≤ x ≤ 0.5, y = 2x.

[0007] Secondly, a modified silver-germanium sulfide solid electrolyte with the chemical formula Li is provided. 6- y Ag y PS 5-x O x Cl, where 0.1 ≤ x ≤ 0.5, y = 2x, the modified silver-germanium sulfide solid electrolyte has a cubic phase crystal structure with space group F-43m, Ag + Partially replaces Li + Site, O 2- Partially replaces S 2- Site.

[0008] Thirdly, an all-solid-state lithium battery is provided, comprising a positive electrode, a negative electrode, and a solid electrolyte layer, characterized in that the solid electrolyte layer comprises the modified silver-germanium sulfide solid electrolyte described in the second aspect.

[0009] The present invention has the following beneficial effects: The present invention introduces Ag into a sulfide solid electrolyte of silver-germanium sulfide type by means of an Ag-O dual doping strategy of cation and anion. + and O 2- Through ball milling and sintering, uniform doping of Ag and O elements was ensured, forming a stable crystal structure. Ag doping improved the lithium-ion pathway, while O doping stabilized the PS4 tetrahedral structure. The electrolyte prepared by this invention exhibits higher ionic conductivity, higher critical current density, and longer cycle life, effectively solving the problems of unstable interface and poor cycle performance between existing silver-germanium sulfide solid electrolytes and lithium metal anodes. Attached Figure Description

[0010] Figure 1 The X-ray diffraction (XRD) patterns of the samples from Example 1 and Comparative Example 1 of this invention are shown.

[0011] Figure 2 The XRD pattern of sample LPSC-0.1 in Example 1 of this invention is shown.

[0012] Figure 3 This is a schematic diagram of the crystal structure of sample LPSC-0.1 in Example 1 of the present invention.

[0013] Figure 4 The images are scanning electron microscope (SEM) images of the LPSC sample of Comparative Example 1 of this invention at different magnifications.

[0014] Figure 5 These are scanning electron microscope (SEM) images of sample LPSC-0.1 from Example 1 of the present invention at different magnifications.

[0015] Figure 6 This is an elemental distribution (EDS-Mapping) diagram of sample LPSC-0.1 in Example 1 of the present invention.

[0016] Figure 7 The above are electrochemical impedance spectroscopy (EIS) spectra of solid electrolyte sheets prepared from the samples in Example 1 and Comparative Example 1 of this invention.

[0017] Figure 8 The image shows the electronic conductivity (IV) curve of the solid electrolyte sheet made from sample LPSC-0.1 of Example 1 of this invention.

[0018] Figure 9 The critical current density (CCD) test results are shown for the lithium-lithium symmetric batteries assembled using the samples from Example 1 and Comparative Example 1 of this invention.

[0019] Figure 10 The graph shows the long-cycle performance test results of the lithium-lithium symmetric batteries assembled using Example 1 and Comparative Example 1 of the present invention.

[0020] Figure 11 The image shows the long cycle life test results of the all-solid-state battery assembled using Example 1 and Comparative Example 1 of the present invention.

[0021] Figure 12 The graph shows the rate performance test results of the all-solid-state batteries assembled using Example 1 and Comparative Example 1 of this invention. Detailed Implementation

[0022] The embodiments of the present invention will be described in detail below. It should be emphasized that the following description is merely exemplary and not intended to limit the scope of the present invention or its application. Unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other.

[0023] This invention provides a method for preparing a modified silver-germanium sulfide solid electrolyte, comprising the following steps: (a) Provide raw materials: Li2S, P2S5, LiCl and Ag2O; (b) Weigh the raw materials according to the predetermined molar ratio of Li:Ag:P:S:O:Cl; (c) The raw materials are ball-milled and mixed under an inert atmosphere to obtain a mixed powder; (d) The mixed powder is sintered at 550-650°C for 5-12 hours under an inert atmosphere to obtain the modified silver-germanium sulfide solid electrolyte with Ag-O anion and cation doping, the chemical formula of which is Li. 6-y Ag y PS 5-x O x Cl, where 0.1 ≤ x ≤ 0.5, y = 2x.

[0024] This invention utilizes Ag₂O as a co-dopermeable in a sulfide solid electrolyte (Li₆P₀) of silver-germanium sulfide. S Ag is introduced simultaneously into 5Cl) + and O 2- By ball milling and solvent-free mixing of various raw materials followed by sintering, synergistic cation and anion doping of sulfide-type solid electrolytes (SSEs) was achieved. Specifically, Ag doping improved the lithium-ion pathway, and O doping stabilized the PS4 tetrahedral structure. + Partially replaces Li + The presence of a site can cause lattice expansion and increase lithium-ion migration gaps, thus widening the lithium-ion transport channels; O 2- Partially replaces S 2- The S sites occupy the S sites in the PS4 tetrahedron, generating stronger PO and SO bonds. Through the above-mentioned synergistic doping of anions and cations, the interfacial stability with the lithium metal anode is greatly improved (critical current density > 4.42 mA cm⁻¹). -2 The ternary cathode exhibits exceptionally long cycle stability (1300 stable cycles with capacity retention ≥99%), overcoming the core defect of poor cycle stability caused by the severe reaction between existing sulfide solid electrolytes and lithium metal anodes.

[0025] In some embodiments, the molar ratio of Li:Ag:P:S:O:Cl in step (b) is 5.8:0.2:1:4.9:0.1:1, and correspondingly, the chemical formula of the modified silver-germanium sulfide solid electrolyte obtained in step (d) is Li 5.8 Ag 0.2 PS 4.9 O 0.1 Cl.

[0026] In some embodiments, the ball milling speed in step (c) is 450-600 r / min, the ball-to-material ratio is 50:1 to 30:1, and the ball milling time is 4-6 hours.

[0027] In some embodiments, the ball milling speed in step (c) is 500 r / min, the ball-to-material ratio is 30:1, and the ball milling time is 5 hours.

[0028] In some embodiments, the sintering temperature in step (d) is 550°C and the sintering time is 12 hours.

[0029] The present invention also provides a modified silver-germanium sulfide solid electrolyte with the chemical formula Li. 6-y Ag y PS 5-x O x Cl, where 0.1 ≤ x ≤ 0.5, y = 2x, the modified silver-germanium sulfide solid electrolyte has a cubic phase crystal structure with space group F-43m, Ag + Partially replaces Li + Site, O 2- Partially replaces S 2- Site.

[0030] In some embodiments, the general chemical formula is Li 5.8 Ag 0.2 PS 4.9 O 0.1 Cl.

[0031] A specific embodiment of the present invention also provides an all-solid-state lithium battery, including a positive electrode, a negative electrode and a solid electrolyte layer, wherein the solid electrolyte layer contains the modified silver-germanium sulfide solid electrolyte.

[0032] In some embodiments, the positive electrode is a high-nickel ternary cathode material, and the negative electrode is lithium metal or a lithium alloy.

[0033] In some embodiments, the high-nickel ternary cathode material is NCM811 material coated with lithium niobate, and the anode is lithium metal.

[0034] The following describes specific embodiments of the present invention.

[0035] Example 1 A method for preparing a modified silver-germanium sulfide solid electrolyte includes the following steps: (1) Provide raw materials: Li2S, P2S5, LiCl and Ag2O; (2) Weigh the raw materials according to the molar ratio of Li:Ag:P:S:O:Cl=5.8:0.2:4.9:0.1:1; (3) After the raw materials are uniformly mixed, they are poured into a zirconia ball mill jar and ball milled for 5 h at a ball-to-material ratio of 30:1 under an argon atmosphere to obtain mixed powder. (4) The mixed powder was transferred to a graphite crucible, sealed, and then heated in a muffle furnace at 550°C under an argon atmosphere for 12 h, followed by annealing. It was then ground in a mortar for 30 min to obtain an Ag-O anion-cation dual-doped modified silver-germanium sulfide solid electrolyte with the chemical formula Li 5.8 Ag 0.2 PS 4.9 O 0.1 Cl (abbreviated as LPSC-0.1).

[0036] Comparative Example 1 (1) Raw materials provided: Li2S, P2S5 and LiCl; (2) Weigh the raw materials according to the molar ratio of Li:P:S:Cl=5:1:2; (3) After the raw materials are uniformly mixed, they are poured into a zirconia ball mill jar and ball milled for 5 h at a ball-to-material ratio of 30:1 under an argon atmosphere to obtain mixed powder. (4) The mixed powder was transferred to a graphite crucible and sealed. It was then kept at 550°C for 12 h in a muffle furnace and annealed. Finally, it was ground in a mortar for 30 min to obtain a sulfide solid electrolyte of silver-germanium sulfide type, with the chemical formula Li6PS5Cl (abbreviated as LPSC).

[0037] Solid electrolyte sheets were prepared and batteries were assembled using the electrolytes prepared in Example 1 and Comparative Example 1, respectively, including the following steps: 1. Preparation of solid electrolyte sheets Weigh 100 mg of LPSC-0.1 prepared in Example 1 and place it in the ceramic inner liner of a CL-01 mold battery (with an inner liner pore size of 10 mm), ensuring that the powder is uniform, flat, and free of obvious lumps. Use two steel columns as pressure heads and cold press for 5 minutes under a pressure of 3 tons to form a dense, uniformly thick (approximately 600 μm) solid electrolyte sheet. Remove this pressed solid electrolyte sheet from the mold for later use.

[0038] 2. Assembly of lithium-ion symmetric batteries The solid electrolyte sheet prepared in step 1 was placed into the CL-01 mold battery. A 6 mm diameter lithium metal sheet was placed as an electrode on each side of the solid electrolyte sheet, and copper foil was used as a current collector. The upper and lower steel pillars were covered, and an external pressure of 1 ton was applied to encapsulate the lithium-lithium symmetric battery (Li | LPSC-0.1 | Li) for testing.

[0039] 3. Assembly of all-solid-state batteries Cathode slurry preparation: The lithium niobate-coated ternary cathode material (LNO@NCM811), the solid electrolyte material (LPSC-0.1) prepared in Example 1, and conductive carbon black were ground and mixed uniformly in a mortar for 30 min at a mass ratio of 70:25:5.

[0040] Positive electrode preparation: The above positive electrode slurry is placed in a mold and pressed into shape under appropriate pressure.

[0041] Battery assembly: The lithium metal negative electrode, the solid electrolyte sheet prepared in step 1, and the positive electrode sheet prepared above are sequentially placed into the battery mold for assembly. Appropriate pressure is applied, and the battery is encapsulated to obtain an all-solid-state battery (NCM811 | LPSC-0.1 | Li).

[0042] Using the same method, solid electrolyte sheets, lithium-lithium symmetric batteries (Li|LPSC|Li) and all-solid-state batteries (NCM811|LPSC|Li) were assembled using the LPSC electrolyte of Comparative Example 1.

[0043] The following tests were performed on the above embodiments and comparative examples: The samples from Example 1 and Comparative Example 1 were characterized by X-ray diffraction (XRD) using a Bruker D8 Advance diffractometer with Cu Kα rays (λ = 0.15406 nm) as the radiation source. The operating conditions were a tube voltage of 45 kV and a tube current of 40 mA. The tests were performed at a scan rate of 10° / min within the 2θ range of 10°–90°. The XRD patterns of the two samples are shown below. Figure 1 As shown, the results indicate that the samples of Example 1 and Comparative Example 1 both retained the cubic phase structure of silver-germanium sulfide (space group F-43m), and no heterogeneous phases were found.

[0044] The crystal structure information of the sample obtained in Example 1 was obtained by refining using GSAS II software, such as... Figure 2 As shown, and its structural diagram is obtained from Vesta, as follows. Figure 3 As shown, the refined reliability factors Rwp = 2.18% and Rp = 1.35% (both below 10%), the difference curve (red line) has small fluctuations and is close to the baseline, indicating high fitting accuracy, reliable model, and excellent material phase purity. The incorporation of Ag atoms partially replaces the Li 48h sites. Due to the larger Ag atoms occupying Li sites, lattice expansion leads to the generation of voids; O atoms replace the S 4a sites, causing the [PS4] structure to transform into [PS... 4-z O z The tetrahedral structure forms stronger covalent bonds between PO and SO, which helps to enhance the stability of the crystal structure and thus improve electrochemical performance.

[0045] The morphology of the samples was characterized by field emission scanning electron microscopy (HITACHI S-4800, SU 8010) and equipped with an energy dispersive spectroscopy (EDS, IXRF SYSTEM, 550i), such as... Figure 4 and Figure 5 As shown, Figure 4 These are SEM images of the LPSC sample from Comparative Example 1 at different magnifications. Figure 5 These are SEM images of sample LPSC-0.1 from Example 1 at different magnifications. The scanning electron micrographs show that the synthesized sample material exhibits irregular granular shapes, which is due to the softness of the sulfide material, causing deformation during the grinding process. Figure 6 As shown in the EDS elemental distribution diagram of sample LPSC-0.1 in Example 1, the Li, P, S, Cl, Ag and O elements are uniformly distributed in LPSC-0.1 particles, indicating that the doping elements were successfully introduced and well dispersed.

[0046] Electrochemical impedance spectroscopy (EIS) measurements were performed on a multichannel electrochemical workstation (VMP3, Biologic), with a frequency range of 7 MHz to 100 mHz. Figure 7 As shown, the total impedance of the solid electrolyte sheet fabricated by LPSC is approximately 48 Ω, corresponding to an ionic conductivity of 2.02 mS·cm at room temperature. -1 The total impedance of the solid electrolyte sheet made of LPSC-0.1 is 42 Ω, corresponding to an ionic conductivity of 2.89 mS / cm at room temperature. -1 The increase in ionic conductivity is attributed to an appropriate amount of Ag. + Replace Li + The lattice expansion and increased porosity caused by the site widening broaden the Li + The transmission channel was improved, and the migration barrier was lowered. For example... Figure 8 As shown, the electronic conductivity of the solid electrolyte sheet made of LPSC-0.1, calculated by constant voltage polarization testing (IV curve), is 1.58 × 10⁻⁶. -8 mS·cm -1 This indicates that LPSC-0.1 has excellent electronic insulation properties and can effectively suppress the risk of electronic leakage and self-discharge.

[0047] The electrochemical performance of the symmetric cells was tested using a multi-channel cell testing system (LAND CT 2001 A, China), and stepwise increasing constant current deposition / stripping tests were performed to determine the critical current density (CCD). Each increment of current density corresponds to an areal capacity of 0.05 mAh·cm³. -2 (Step rate 0.177 mA·cm) -2Continue depositing / stripping until the overpotential rises sharply above the cutoff voltage (5 V) or a short circuit occurs. For example... Figure 9 As shown, the CCD of the lithium-lithium symmetric battery assembled using the sample LPSC of Comparative Example 1 is only 1.06 mA·cm⁻¹. -2 (Corresponding surface deposition capacity is 1.06 mAh·cm⁻¹) -2 Exceeding this value, the overpotential increases rapidly and a short circuit occurs, reflecting severe side reactions between the electrolyte and the lithium anode. The CCD of the lithium-lithium symmetric battery assembled using the sample LPSC-0.1 from Example 1 is significantly improved (4.42 mA·cm⁻¹). -2 Corresponding surface deposition capacity: 4.42 mAh·cm⁻¹ -2 The overpotential remains stable (<100 mV) throughout the test range. As the current continues to increase, the overpotential rises sharply above 100 mV due to poor mechanical contact, terminating the test. Figure 10 As shown, at 2 mA·cm -2 The current density and 2 mAh·cm -2 The long-cycle performance of lithium-ion symmetric batteries was tested under the deposition amount. The lithium-ion symmetric battery assembled by LPSC in Comparative Example 1 showed a sharp rise in potential and rapid short-circuit failure in less than 30 h under the conditions. The lithium-ion symmetric battery assembled by LPSC-0.1 in Example 1 still cycled stably for 1500 h under the conditions, with the overpotential remaining at a relatively low level (<500mV) and no signs of short circuit or open circuit.

[0048] The electrochemical performance of the all-solid-state battery was evaluated using a multi-channel battery testing system, with a voltage range of 2.7–4.3 V (relative to Li). + / Li). For example Figure 11 As shown ( Figure 11 In the middle, the areal capacity of the positive electrode active material is 8.91 mg·cm³. -2 The all-solid-state battery assembled using the LPSC sample from Comparative Example 1 exhibited continuous capacity decay during cycling, with the discharge specific capacity dropping to approximately 70 mAh g after 1400 cycles. -1 The capacity was only 63.3% of the initial capacity. In contrast, the all-solid-state battery assembled using the LPSC-0.1 sample from Example 1 retained nearly 100% of its capacity after 1400 cycles under the same conditions, with almost no significant capacity decay. This indicates that LPSC-0.1 can still undergo stable long-term cycling at higher rates and exhibits excellent cycle stability. Figure 12As shown, the rate performance test graphs of all-solid-state batteries assembled using sample LPSC-0.1 of Example 1 and sample LPSC of Comparative Example 1 are shown. It can be seen that the all-solid-state battery assembled using sample LPSC-0.1 of Example 1 exhibits excellent rate performance under different rate (C-rate) conditions, further verifying its good interface stability and matching with lithium metal anode.

[0049] From the comparison of the above embodiments and comparative examples, it can be seen that the LPSC-0.1 solid electrolyte has the following properties: (1) The room temperature ionic conductivity of LPSC-0.1 is 2.89 mS·cm -1 It is higher than 2.02 mS·cm for LPSC. -1 (2) The critical current density of the lithium-lithium symmetric battery assembled with LPSC-0.1 reached 4.42 mA·cm. -2 This is higher than the 1.06 mA·cm⁻¹ of LPSC-assembled lithium-lithium symmetric cells. -2 (3) At 2 mA·cm -2 and 2 mAh·cm -2 Under the conditions, the lithium-lithium symmetric battery assembled with LPSC-0.1 can operate stably for 1500 h without any signs of short circuit or open circuit; (4) When matched with LNO@NCM811 high-nickel ternary cathode, the all-solid-state battery using LPSC-0.1 has a capacity retention rate close to 100% after 1400 cycles under 1C conditions; the all-solid-state battery using LPSC has a capacity retention rate of about 63.3% under the same conditions. In summary, thanks to the synergistic enhancement mechanism of "structure optimization + interface stability", the LPSC-0.1 obtained by adopting the Ag-O anion and cation dual doping strategy for the sulfide solid electrolyte of silver-germanium sulfide in this invention has significantly better performance than the comparative LPSC material.

[0050] The above description provides a further detailed explanation of the present invention in conjunction with specific / preferred embodiments, and it should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various substitutions or modifications can be made to these described embodiments without departing from the concept of the present invention, and all such substitutions or modifications should be considered within the scope of protection of the present invention. In the description of this specification, the reference to terms such as "an embodiment," "some embodiments," "preferred embodiment," "example," "specific example," or "some examples," etc., indicates that the specific features, structures, materials, or characteristics described in connection with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in any suitable manner in one or more embodiments or examples. Without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification and the features of different embodiments or examples. Although the embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions, and modifications can be made herein without departing from the scope of protection of the patent application.

Claims

1. A method for preparing a modified silver-germanium sulfide solid electrolyte, characterized in that, Includes the following steps: (a) Provide raw materials: Li2S, P2S5, LiCl and Ag2O; (b) Weigh the raw materials according to the predetermined molar ratio of Li:Ag:P:S:O:Cl; (c) The raw materials are ball-milled and mixed under an inert atmosphere to obtain a mixed powder; (d) The mixed powder is sintered at 550-650°C for 5-12 hours under an inert atmosphere to obtain the modified silver-germanium sulfide solid electrolyte with Ag-O anion and cation doping, the chemical formula of which is Li 6-y Ag y PS 5-x O x Cl, where 0.1 ≤ x ≤ 0.5, y = 2x.

2. The preparation method according to claim 1, characterized in that, In step (b), the molar ratio of Li:Ag:P:S:O:Cl is 5.8:0.2:1:4.9:0.1:

1. Correspondingly, the chemical formula of the modified silver-germanium sulfide solid electrolyte obtained in step (d) is Li 5.8 Ag 0.2 PS 4.9 O 0.1 Cl.

3. The preparation method according to claim 1 or 2, characterized in that, The ball milling speed in step (c) is 450-600 r / min, the ball-to-material ratio is 50:1-30:1, and the ball milling time is 4-6 hours.

4. The preparation method according to claim 1 or 2, characterized in that, The ball milling speed in step (c) is 500 r / min, the ball-to-material ratio is 30:1, and the ball milling time is 5 hours.

5. The preparation method according to claim 1 or 2, characterized in that, The sintering temperature in step (d) is 550°C and the sintering time is 12 hours.

6. A modified sulfide solid electrolyte of the sulfide type, characterized in that, Its general chemical formula is Li 6-y Ag y PS 5- x O x Cl, where 0.1 ≤ x ≤ 0.5, y = 2x, the modified silver-germanium sulfide solid electrolyte has a cubic phase crystal structure with space group F-43m, Ag + Partially replaces Li + Site, O 2- Partially replaces S 2- Site.

7. The modified sulfide solid electrolyte of the silver-germanium sulfide type according to claim 6, characterized in that, The general chemical formula is Li 5.8 Ag 0.2 PS 4.9 O 0.1 Cl.

8. An all-solid-state lithium battery, comprising a positive electrode, a negative electrode, and a solid electrolyte layer, characterized in that, The solid electrolyte layer comprises the modified sulfide solid electrolyte of any one of claims 6-7.

9. The all-solid-state lithium battery according to claim 8, characterized in that, The positive electrode is a high-nickel ternary cathode material, and the negative electrode is lithium metal or lithium alloy.

10. The all-solid-state lithium battery according to claim 8, characterized in that, The high-nickel ternary cathode material is NCM811 material coated with lithium niobate, and the anode is lithium metal.

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