Sb-doped solid electrolyte and preparation method and application thereof

Abstract

The invention discloses a Sb-doped solid electrolyte, the chemical formula of the Sb-doped solid electrolyte is Li < 10 + 2x > P < 3-x > Sb < x > S < 12 > I, and x is more than or equal to 0.05 and less than or equal to 0.20. According to the invention, Sb with a specific content is doped to the P site of Li10P3S12I, and the Li content is increased, so that lattice distortion can be stabilized, the structural stability can be improved, and the lithium dendrite inhibition capability can be enhanced; a [SbS3] pyramid unit is formed, and a lithium ion transmission channel is widened, so that the solid electrolyte has good lithium ion migration capability; meanwhile, Sb ions and S < 2-> form strong covalent bonds, H2O erosion is inhibited, and air stability is enhanced. Therefore, the solid electrolyte disclosed by the invention has high ionic conductivity, interface stability, air stability and good inhibition capability on lithium dendrites. The solid electrolyte disclosed by the invention realizes a breakthrough in comprehensive performance, and is more suitable for industrialization requirements of solid-state batteries.

Description

Technical Field

[0001] The present invention relates to the technical field of solid-state batteries, and in particular to an Sb-doped solid-state electrolyte and a preparation method and application thereof. Background Art

[0002] In recent years, all-solid-state lithium batteries have become a research hotspot due to their high energy density and excellent safety. Solid-state electrolytes, as their core components, directly affect the performance of batteries.

[0003] Traditional liquid electrolytes have safety hazards such as flammability and leakage. Compared with liquid electrolytes, solid electrolytes are safer. Among them, oxide solid electrolytes (such as LLZO) have low ionic conductivity and high interface impedance; sulfide electrolytes (such as Li 10 P3S 12 I) has high lithium ion conductivity and good mechanical processing properties, but its chemical / electrochemical stability is insufficient and it easily reacts with the lithium negative electrode to form interfacial byproducts, leading to degradation of battery cycle performance, which restricts its practical application.

[0004] To address this problem, the prior art provides several improvements. One such improvement involves protecting metallic lithium through a surface coating, such as lithium nitride coated on lithium or used as an interlayer, which modifies the effect of Li+ and induces a uniform stripping / plating process due to the strong lithium affinity and high ionic conductivity of lithium nitride. However, this process is a two-step process and an expensive method for preventing the formation of lithium dendrites. Another improvement involves modifying the solid electrolyte by substituting the metal or halide in the sulfide solid electrolyte.

[0005] In order to reduce the side reaction between the solid electrolyte and the lithium negative electrode, the reaction of H2O to S 2 -corrosion, improve air stability significantly, the related technology discloses a germanium-doped lithium phosphosulfide solid electrolyte and its preparation method, the specific preparation process is as follows: Li2S, P2S5, LiI and GeS2 are weighed according to the stoichiometric ratio, mixed in an argon glove box, and ball milled for 6 hours using a planetary ball mill with a ball milling speed of 400 rpm and a ball-to-material ratio of 20:1. In a vacuum-sealed quartz tube, the temperature is raised to 500°C at 3°C / min and kept warm for 12 hours to obtain Li 10-x Ge x P3S 12 I (0.05≤x≤0.3) solid electrolyte. Related technology discloses a chlorine-doped sulfide solid electrolyte and its preparation method, which is obtained by ball milling Li2S and P2S5. 10 P3S 12 I glass ceramics, Li 10 P3S 12I glass ceramic and LiCl powder were placed at both ends of a sealed quartz tube and heated in a vacuum environment: first, kept at 350℃ for 5 hours, then annealed at 500℃ for 2 hours to obtain Li 7-x P3S 11-x Cl x (0.1≤x≤0.5).

[0006] The above patents have the following problems with the modification of solid electrolytes: 1. It is impossible to achieve both ionic conductivity and stability; 2. The process threshold is high: complex preparation or expensive raw materials; 3. Poor long-term reliability: interface / air sensitivity and other issues.

[0007] Therefore, providing a sulfide solid electrolyte that can balance high ionic conductivity, good lithium interface stability and air stability is a technical problem that needs to be solved urgently. Summary of the Invention

[0008] In view of the above technical problems existing in the prior art, the purpose of the present invention is to provide a Sb-doped solid electrolyte and its preparation method and application.

[0009] To achieve the above object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a Sb-doped solid electrolyte, wherein the chemical formula of the Sb-doped solid electrolyte is Li 10+2x P 3-x Sb x S 12 I, where 0.05≤x≤0.20.

[0011] In the Sb-doped solid electrolyte of the present invention, 0.05≤x≤0.20, for example, x can be 0.05, 0.06, 0.08, 0.10, 0.12, 0.14, 0.15, 0.17, 0.18 or 0.20.

[0012] The present invention dopes a specific amount of Sb into Li 10 P3S 12 The P position of I and the increase of Li content can stabilize the lattice distortion, improve the structural stability and enhance the ability to inhibit lithium dendrites; and form a [SbS3] triangular pyramid unit, which broadens the lithium ion transmission channel, so that the solid electrolyte has good lithium ion migration ability; at the same time, Sb ions and S 2- The solid electrolyte of the present invention forms a strong covalent bond, inhibits H2O corrosion, and enhances air stability. Therefore, it has high ionic conductivity, interfacial stability, air stability, and good inhibition of lithium dendrites. The solid electrolyte of the present invention achieves a breakthrough in comprehensive performance and is more suitable for the industrialization needs of solid-state batteries.

[0013] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.

[0014] In a second aspect, the present invention provides a method for preparing the Sb-doped solid electrolyte as described in the first aspect, the preparation method comprising the following steps:

[0015] (1) Synthesize the precursor Li by chemical vapor deposition 10 P3S 12 I;

[0016] (2) Using the precursor and Sb source as raw materials, the Sb-doped solid electrolyte is prepared by chemical vapor deposition at a temperature of less than or equal to 300°C.

[0017] The present invention uses Sb as the precursor Li 10 P3S 12 The method of the present invention is simple, uses readily available raw materials, and has a low process threshold.

[0018] In summary, the method of the present invention breaks through the bottleneck of the existing technology and is expected to give priority to the layout of power batteries (such as electric vehicle batteries) and aerospace fields, and promote the large-scale commercial use of all-solid-state batteries.

[0019] In the method of the present invention, by regulating Li 10 P3S 12 The preparation parameters of step I and the preparation parameters of step (2) can regulate the performance of the prepared Sb-doped solid electrolyte.

[0020] As a preferred technical solution of the preparation method of the present invention, the chemical vapor deposition method in step (1) includes: 10 P3S 12 I, the lithium source, sulfur source, phosphorus source, sulfur source and iodine source are first ball-milled, and then subjected to a first heat treatment under sealed conditions to obtain Li 10 P3S 12 I.

[0021] The rotation speed of the first ball mill is 300 r / min to 500 r / min, for example, it can be 300 r / min, 325 r / min, 350 r / min, 375 r / min, 400 r / min, 425 r / min, 450 r / min, 460 r / min, 480 r / min or 500 r / min.

[0022] Preferably, the first ball milling time is 20 min to 40 min, for example, 20 min, 22 min, 25 min, 27 min, 30 min, 35 min or 40 min.

[0023] Preferably, the temperature of the first heat treatment is 200°C to 300°C, for example, 200°C, 220°C, 240°C, 260°C, 285°C or 300°C.

[0024] Preferably, the first heat treatment time is 1.5 h to 4 h, for example, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h or 4 h.

[0025] Preferably, the first heat treatment is performed under the protection of a protective gas.

[0026] Preferably, during the first heat treatment, the pressure of the sealing condition is 170 mtorr to 230 mtorr, for example, 170 mtorr, 180 mtorr, 190 mtorr, 200 mtorr, 210 mtorr, 220 mtorr or 230 mtorr.

[0027] As a preferred technical solution of the preparation method of the present invention, the chemical vapor deposition method in step (2) includes: 10+2x P 3-x Sb x S 12 I formula amount, the Li 10 P3S 12 After the I and Sb sources are subjected to a second ball milling, a second heat treatment is performed under sealed conditions to obtain the Sb-doped solid electrolyte. In this method, no other heat treatment steps are performed after or before the second heat treatment, or other heat treatment steps are performed after and / or before the second heat treatment, and the heat treatment temperature is lower than the second heat treatment temperature.

[0028] Preferably, the rotation speed of the second ball mill is 300 r / min to 500 r / min, for example, it can be 300 r / min, 325 r / min, 350 r / min, 375 r / min, 400 r / min, 425 r / min, 450 r / min, 460 r / min, 480 r / min or 500 r / min.

[0029] Preferably, the second ball milling time is 20 min to 40 min, for example, 20 min, 22 min, 25 min, 27 min, 30 min, 35 min or 40 min.

[0030] Preferably, the temperature of the second heat treatment is 200°C to 300°C, for example, 200°C, 220°C, 240°C, 260°C, 285°C or 300°C.

[0031] Preferably, the second heat treatment time is 1.5 h to 4 h, for example, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h or 4 h.

[0032] Preferably, the second heat treatment is performed under the protection of a protective gas.

[0033] Preferably, during the second heat treatment, the sealing pressure is between 170 mtorr and 230 mtorr, for example, 170 mtorr, 180 mtorr, 190 mtorr, 200 mtorr, 210 mtorr, 220 mtorr, or 230 mtorr. If the pressure is too low, vapor phase transport will dominate, leading to insufficient precursor dissociation. The Sb source will not be fully vaporized, resulting in uneven doping. Excessive pressure shortens the molecular mean free path and increases the collision probability. While this helps with reactant mixing, it also increases the probability of side reactions. In particular, sulfide systems are prone to producing insulating byproducts such as Li2Sx under high pressure.

[0034] In a third aspect, the present invention provides a solid-state battery comprising an anode, a cathode and a solid electrolyte layer, wherein the solid electrolyte layer is located between the anode and the cathode, and the solid electrolyte in the solid electrolyte layer comprises the Sb-doped solid electrolyte described in the first aspect.

[0035] Preferably, the cathode layer includes a cathode active material, a halide solid electrolyte and a conductive agent.

[0036] Preferably, the mass ratio of the cathode active material, the halide solid electrolyte and the conductive agent is (65-75): (21-32): (0.5-3), wherein the selection range of the cathode active material is "65-75", for example, it can be 65, 66, 68, 70, 72, 73 or 75, etc.; the selection range of the halide solid electrolyte is "21-32", for example, it can be 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 or 32, etc.; the selection range of the conductive agent is "0.5-3", for example, it can be 0.5, 1, 1.5, 2, 2.5 or 3, etc.

[0037] Preferably, the halide solid electrolyte includes Li6PS5Cl, and the preparation method of Li6PS5Cl includes the following steps: according to the formula amount of Li6PS5Cl, a lithium source, a phosphorus source, a sulfur source and a chlorine source are ball-milled to obtain a precursor, and the precursor is annealed to obtain Li6PS5Cl.

[0038] Preferably, in the preparation method of Li6PS5Cl, the ball milling speed is 400r / min to 600r / min, for example, it can be 400r / min, 425r / min, 450r / min, 460r / min, 480r / min, 500r / min, 525r / min, 550r / min, 570r / min, 585r / min or 600r / min, etc.; the ball milling time is 10h to 18h, for example, it can be 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h or 18h, etc.

[0039] Preferably, the annealing temperature is 400°C to 500°C, for example, it can be 400°C, 425°C, 450°C, 460°C, 480°C or 500°C; the annealing time is 6h to 10h, for example, it can be 6h, 7h, 7.5h, 8h, 8.5h, 9h or 10h.

[0040] Preferably, the annealing is performed under the protection of a protective gas.

[0041] The numerical range described in the present invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] The present invention dopes a specific amount of Sb into Li 10 P3S 12The P position of I and the increase of Li content can stabilize the lattice distortion, improve the structural stability and enhance the ability to inhibit lithium dendrites; and form a [SbS3] triangular pyramid unit, which broadens the lithium ion transmission channel, so that the solid electrolyte has good lithium ion migration ability; at the same time, Sb ions and S 2- The solid electrolyte of the present invention forms a strong covalent bond, inhibits H2O corrosion, and enhances air stability. Therefore, it has high ionic conductivity, interfacial stability, air stability, and good inhibition of lithium dendrites. The solid electrolyte of the present invention achieves a breakthrough in comprehensive performance and is more suitable for the industrialization needs of solid-state batteries. DETAILED DESCRIPTION

[0044] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0045] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. It should be noted that, unless there is a conflict, the embodiments and features in the embodiments of the present application can be combined with each other in any way.

[0046] Example 1

[0047] This embodiment provides a Sb-doped solid electrolyte, the chemical formula of which is Li 10.1 P 2.95 Sb 0.05 S 12 I.

[0048] The above-mentioned Sb-doped solid electrolyte was prepared according to the following method:

[0049] (1) According to Li 10 P3S 12 I, Li2S, P2S5, S, LiI stored in nitrogen were weighed at a molar ratio of Li:P:S:I of 10:3:12:1, the weighed materials were placed in a ball mill, and ball milled at a speed of 400r / min for 30min, and then the ball-milled powder was subjected to chemical vapor deposition. The chemical vapor deposition method is as follows: the ball-milled powder was placed in a boron nitride crucible, sealed in a quartz tube (pressure of 200mtorr), passed nitrogen, and heat treated at 220°C for 2 hours. After the heat treatment, the quartz tube was brought into an argon glove box, and Li was recovered from the crucible. 10 P3S 12 I precursor, stored under nitrogen until use.

[0050] (2) According to Li 10.1 P 2.95 Sb 0.05 S12 The formula amount of I, for Li stored in nitrogen 10 P3S 12 The I precursor and Sb2S3 were weighed, the weighed materials were placed in a ball mill, and ball-milled at a speed of 400 r / min for 30 minutes. The ball-milled powder was then subjected to chemical vapor deposition. The chemical vapor deposition method was as follows: the ball-milled powder was loaded into a boron nitride crucible, sealed in a quartz tube (pressure of 200 mtorr), passed through nitrogen, and heat treated at 220°C for 2 hours. After the heat treatment was completed, the quartz tube was brought into an argon glove box, and the Sb-doped solid electrolyte was recovered from the crucible.

[0051] Example 2

[0052] The difference between this embodiment and embodiment 1 is that by changing the amount of Sb2S3 in step (2), the chemical formula of the prepared Sb-doped solid electrolyte is Li 10.2 P 2.9 Sb 0.1 S 12 I.

[0053] Example 3

[0054] The difference between this embodiment and embodiment 1 is that by changing the amount of Sb2S3 in step (2), the chemical formula of the prepared Sb-doped solid electrolyte is Li 10.3 P 2.85 Sb 0.15 S 12 I.

[0055] Example 4

[0056] The difference between this embodiment and embodiment 1 is that by changing the amount of Sb2S3 in step (2), the chemical formula of the prepared Sb-doped solid electrolyte is Li 10.4 P 2.8 Sb 0.2 S 12 I.

[0057] Example 5

[0058] This embodiment provides a Sb-doped solid electrolyte, the chemical formula of which is Li 10.1 P 2.95 Sb 0.05 S 12 I.

[0059] The above-mentioned Sb-doped solid electrolyte was prepared according to the following method:

[0060] (1) According to Li 10 P3S12 I, Li2S, P2S5, S, LiI stored in nitrogen were weighed at a molar ratio of Li:P:S:I of 10:3:12:1, the weighed materials were placed in a ball mill, and ball milled at a speed of 300r / min for 40min, and then the ball-milled powder was subjected to chemical vapor deposition. The chemical vapor deposition method is as follows: the ball-milled powder is placed in a boron nitride crucible, sealed in a quartz tube (pressure of 180mtorr), nitrogen is passed through, and heat treated at 250°C for 1.5 hours. After the heat treatment is completed, the quartz tube is brought into an argon glove box, and Li is recovered from the crucible. 10 P3S 12 I precursor, stored under nitrogen until use.

[0061] (2) According to Li 10.1 P 2.95 Sb 0.05 S 12 The formula amount of I, for Li stored in nitrogen 10 P3S 12 The I precursor and Sb2S3 were weighed, the weighed materials were placed in a ball mill, and ball-milled at a speed of 300 r / min for 40 minutes. The ball-milled powder was then subjected to chemical vapor deposition. The chemical vapor deposition method was as follows: the ball-milled powder was loaded into a boron nitride crucible, sealed in a quartz tube (pressure of 180 mtorr), passed through nitrogen, and heat treated at 250°C for 1.5 hours. After the heat treatment was completed, the quartz tube was brought into an argon glove box, and the Sb-doped solid electrolyte was recovered from the crucible.

[0062] Example 6

[0063] This embodiment provides a Sb-doped solid electrolyte, the chemical formula of which is Li 10.1 P 2.95 Sb 0.05 S 12 I.

[0064] The above-mentioned Sb-doped solid electrolyte was prepared according to the following method:

[0065] (1) According to Li 10 P3S 12I, Li2S, P2S5, S, LiI stored in nitrogen were weighed at a molar ratio of Li:P:S:I of 10:3:12:1, the weighed materials were placed in a ball mill, ball milled at a speed of 350r / min for 25min, and then the ball-milled powder was subjected to chemical vapor deposition. The chemical vapor deposition method is as follows: the ball-milled powder was placed in a boron nitride crucible, sealed in a quartz tube (pressure of 220mtorr), nitrogen was passed through, and heat treated at 270°C for 3 hours. After the heat treatment was completed, the quartz tube was brought into an argon glove box, and Li was recovered from the crucible. 10 P3S 12 I precursor, stored under nitrogen until use.

[0066] (2) According to Li 10.1 P 2.95 Sb 0.05 S 12 The formula amount of I, for Li stored in nitrogen 10 P3S 12 The I precursor and Sb2S3 were weighed, the weighed materials were placed in a ball mill, and ball-milled at a speed of 320 r / min for 35 minutes. The ball-milled powder was then subjected to chemical vapor deposition. The chemical vapor deposition method was as follows: the ball-milled powder was loaded into a boron nitride crucible, sealed in a quartz tube (pressure of 200 mtorr), passed through nitrogen, and heat treated at 235°C for 4 hours. After the heat treatment was completed, the quartz tube was brought into an argon glove box, and the Sb-doped solid electrolyte was recovered from the crucible.

[0067] Example 7

[0068] The difference between this embodiment and embodiment 1 is that in step (2) of the preparation method, the pressure of the quartz tube is 150 mtorr.

[0069] Example 8

[0070] The difference between this embodiment and embodiment 1 is that in step (2) of the preparation method, the pressure of the quartz tube is 250 mtorr.

[0071] Comparative Example 1

[0072] The difference between the preparation method of this comparative example and that of Example 1 is that step (2) is not performed.

[0073] The solid electrolyte of this comparative example is not doped with Sb.

[0074] Comparative Example 2

[0075] The difference between this comparative example and Example 1 is that by changing the amount of Sb2S3 in step (2), the chemical formula of the prepared Sb-doped solid electrolyte is Li10.06 P 2.97 Sb 0.03 S 12 I.

[0076] Comparative Example 3

[0077] The difference between this comparative example and Example 1 is that by changing the amount of Sb2S3 in step (2), the chemical formula of the prepared Sb-doped solid electrolyte is Li 10.6 P 2.7 Sb 0.3 S 12 I.

[0078] Comparative Example 4

[0079] The difference between the preparation method of this comparative example and that of Example 1 is that the sintering temperature in step (2) is 500°C.

[0080] Application Examples

[0081] A solid-state battery is provided, wherein a preparation method thereof comprises:

[0082] (1) Preparation of cathode

[0083] According to the formula of Li6PS5Cl, a lithium source, a phosphorus source, a sulfur source, and a chlorine source were ball-milled at a speed of 500 r / min for 14 h. The grinding balls used in the ball milling were 10 mm in diameter zirconium dioxide balls, and the number of grinding balls was 50. After ball milling, a precursor was obtained. The precursor was sealed in a quartz bottle and annealed under inert conditions at a temperature of 450° C. for 8 h to obtain Li6PS5Cl.

[0084] LiNi 0.8 Co 0.1 Mn 0.1 O2, Li6PS5Cl, and carbon black were mixed in a mass ratio of 69:30:1 and pressed into a cathode. Graphite was used as the anode active material to prepare an anode, and the solid electrolyte layer was prepared using the solid electrolytes of various examples and comparative examples. In a glove box filled with Ar and under a pressure of 6.8 MPa, the solid electrolyte layer was placed between the cathode and anode to prepare a solid-state battery. The electrochemical performance of the solid-state battery was tested at a temperature of 25°C.

[0085] Table 1

[0086]

[0087]

[0088] In summary, Sb doping P site and forming [SbS3] triangular pyramidal unit helps to improve ionic conductivity and broaden the Li+ The transmission channel enhances structural stability, inhibits lattice distortion, improves interface compatibility, reduces side reactions with the lithium negative electrode, and improves the electrochemical performance of the battery. Comparative Example 1 is not doped with Sb, the ionic conductivity of the solid electrolyte is low, and the electrochemical performance of the battery is poor.

[0089] By comparing Example 1 with Examples 7-8, it can be seen that during the doping process, the pressure of the quartz tube has an optimal range. If the pressure is too low (Example 7), the gas phase transmission will dominate and the precursor dissociation will be insufficient. The Sb source will not be completely vaporized, resulting in uneven doping. If the pressure is too high (Example 8), the molecular mean free path will be shortened and the collision probability will increase. Although it helps the mixing of reactants, the probability of side reactions will also increase. In particular, the sulfide system is prone to produce Li2S under high pressure. x Therefore, compared with Example 1, the ionic conductivity of the solid electrolyte and the electrochemical performance of the battery in Examples 7 and 8 are both reduced.

[0090] By comparing Example 1 with Comparative Examples 2-3, it can be seen that the Sb doping amount is too small (Comparative Example 2), Sb 3+ Replace P 5+ The generated -2 ​​charge defects cannot be fully compensated, resulting in negatively charged vacancies in the lattice. These vacancies will become traps for lithium ion migration, significantly reducing conductivity; or the Sb doping amount is too much (Comparative Example 3), and excessive P sites are occupied by Sb. Although the SbS3 triangular pyramid can widen the channel, excessive substitution will destroy the original continuous [PS4] tetrahedral network. When the substitution rate is >20%, the distance between adjacent SbS3 units is too small, and its larger ionic radius produces repulsion, resulting in lattice expansion and microcracks. Therefore, the performance of Comparative Examples 2 and 3 is poor.

[0091] By comparing Example 1 with Comparative Example 4, it can be seen that the high-temperature process triggers side reactions, including decomposition of LiI (iodine volatilization), oxidation of Sb2S3 to Sb2O3, and breakage and recombination of PS bonds. These side reactions cause the chemical formula to deviate from the design, changes in the Sb valence state and coordination structure, and the generation of impurity phases. These three factors together cause overall performance degradation.

[0092] The applicant states that the present invention is intended to illustrate the detailed methods of the present invention through the above-described embodiments, but the present invention is not limited to the above-described detailed methods, that is, it does not mean that the present invention must rely on the above-described detailed methods in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for various raw materials in the products of the present invention, addition of auxiliary ingredients, and selection of specific methods, etc., are all within the scope of protection and disclosure of the present invention.

Claims

1. A Sb-doped solid electrolyte, characterized in that: The chemical formula of the Sb-doped solid electrolyte is Li 10+ 2x P 3-x Sb x S 12 I, where 0.05≤x≤0.

20.

2. A method for preparing the Sb-doped solid electrolyte according to claim 1, characterized in that: The preparation method comprises the following steps: (1) Synthesize the precursor Li by chemical vapor deposition 10 P3S 12 I; (2) Using the precursor and Sb source as raw materials, the Sb-doped solid electrolyte is prepared by chemical vapor deposition at a temperature of less than or equal to 300°C.

3. The preparation method according to claim 2, characterized in that The chemical vapor deposition method in step (1) comprises: 10 P3S 12 I, the lithium source, sulfur source, phosphorus source, sulfur source and iodine source are first ball-milled, and then subjected to a first heat treatment under sealed conditions to obtain Li 10 P3S 12 I.

4. The preparation method according to claim 3, characterized in that The rotation speed of the first ball mill is 300 r / min to 500 r / min; Preferably, the first ball milling time is 20 min to 40 min; Preferably, the temperature of the first heat treatment is 200°C to 300°C; Preferably, the first heat treatment time is 1.5h to 4h; Preferably, the first heat treatment is performed under the protection of a protective gas; Preferably, during the first heat treatment, the pressure of the sealing condition is 170 mtorr to 230 mtorr.

5. The preparation method according to any one of claims 2 to 4, characterized in that The chemical vapor deposition method in step (2) includes: 10+2x P 3-x Sb x S 12 I formula amount, the Li 10 P3S 12 After the I and Sb sources are subjected to a second ball milling, a second heat treatment is performed under a sealed condition to obtain the Sb-doped solid electrolyte.

6. The preparation method according to claim 5, characterized in that The rotation speed of the second ball mill is 300 r / min to 500 r / min; Preferably, the second ball milling time is 20 min to 40 min; Preferably, the temperature of the second heat treatment is 200°C to 300°C; Preferably, the second heat treatment time is 1.5h to 4h; Preferably, the second heat treatment is performed under the protection of a protective gas; Preferably, during the second heat treatment, the pressure of the sealing condition is 170 mtorr to 230 mtorr.

7. A solid-state battery comprising an anode, a cathode and a solid electrolyte layer, wherein the solid electrolyte layer is located between the anode and the cathode, characterized in that: The solid electrolyte in the solid electrolyte layer includes the Sb-doped solid electrolyte according to claim 1 .

8. The solid-state battery according to claim 7, characterized in that The cathode layer includes a cathode active material, a halide solid electrolyte and a conductive agent; Preferably, the mass ratio of the cathode active material, the halide solid electrolyte and the conductive agent is (65-75):(21-32):(0.5-3).

9. The solid-state battery according to claim 8, characterized in that The halide solid electrolyte includes Li6PS5Cl, and the preparation method of Li6PS5Cl includes the following steps: ball-milling and mixing a lithium source, a phosphorus source, a sulfur source, and a chlorine source according to the formula of Li6PS5Cl to obtain a precursor, and annealing the precursor to obtain Li6PS5Cl.

10. The solid-state battery according to claim 9, characterized in that In the preparation method of Li6PS5Cl, the ball milling speed is 400r / min to 600r / min, and the ball milling time is 10h to 18h; Preferably, the annealing temperature is 400° C. to 500° C., and the annealing time is 6 h to 10 h; Preferably, the annealing is performed under the protection of a protective gas.

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