38 results about "Argyrodite" patented technology

The invention belongs to the technical field of all-solid-state battery materials, and discloses argyrodite type sulfide solid electrolyte as well as a preparation method and application thereof. A lithium source 1, a lithium source 2, a sulfur source, a phosphorus source and LiX (X is Cl, Br or I) which are low in cost are used as raw materials, a Li2S raw material which is high in cost is replaced, and the argyrodite type sulfide solid electrolyte is prepared through vacuum ball milling, sintering and grinding. The argyrodite-type sulfide solid electrolyte has the advantages of low raw material cost, strong reaction activity and simple preparation process, and the prepared argyrodite-type sulfide solid electrolyte has excellent ionic conductivity, strong air stability and high (electro-chemical) stability, has excellent electrochemical performance when being applied to all-solid-state lithium batteries, and can be widely applied to all-solid-state lithium batteries. And large-scale application of the all-solid-state lithium battery is promoted.

The invention discloses a SbBr co-doped argyrodite type solid electrolyte and a preparation method thereof.The preparation method comprises the steps that Li2S, LiCl, P2S5 and SbBr3 are weighed according to the stoichiometric ratio and then subjected to ball milling treatment, and mixed powder is obtained; the mixed powder obtained in the step S1 is subjected to compression molding and placed in a muffle furnace to be heated and calcined, and a solid-phase reaction is conducted; and after the reaction is finished, naturally cooling to room temperature, and grinding to obtain the SbBr co-doped argyrodite type solid electrolyte. According to the preparation process of the argyrodite type solid electrolyte, a traditional solid-phase sintering process is adopted, the synthesis process is simple, and the repeatability is high. The ionic conductivity of the argyrodite type solid electrolyte prepared by the process can reach 10.4 mScm <-1 > at room temperature. The argyrodite type solid electrolyte prepared by the invention has high ionic conductivity and excellent air stability, and meets the requirements of industrial large-scale production. When the solid-state electrolyte provided by the invention is assembled into an all-solid-state battery, the cycle life of the all-solid-state battery can be remarkably prolonged due to good compatibility with lithium metal.

The present invention relates to a sulfide-based solid electrolyte, a method for preparing same, and an all-solid-state battery comprising same. The sulfide-based solid electrolyte includes a compound containing lithium (Li), phosphorus (P), sulfur (S), and chlorine (Cl) and having an argyrodite-based crystal structure, wherein at least a portion of the crystal structure is doped with aluminum (Al), a Group 14 element (α), and oxygen (O), and the ion conductivity retention rate after exposure to moisture at a dew point of -40°C for 8 hours is 50.0% or more.

The present invention relates to a sulfide-based solid electrolyte comprising lithium (Li), phosphorus (P), oxygen (O), sulfur (S), and two or more halogen elements, wherein the sulfide-based solid electrolyte has an argyrodite-based crystal structure, and a 31P-NMR spectrum of the sulfide-based solid electrolyte satisfies formula 1: [Formula 1] C / A≥3.5 In formula 1, A is the area of a peak appearing at 85 to 87 ppm, and C is the area of a peak appearing at 82 to 83 ppm.

The present invention relates to a sulfide-based solid electrolyte comprising lithium (Li), phosphorus (P), sulfur (S), oxygen (O), and a plurality of halogen elements, wherein the sulfide-based solid electrolyte has an argyrodite-based crystal structure, and exhibits a single phase in the region of 400 to 450 cm-1 in Raman analysis of the sulfide-based solid electrolyte.

The invention provides a sulfide electrolyte, a preparation method thereof and a solid-state battery, and the preparation method comprises the following steps: a) providing a raw material containing Li, S, M and X, the D50 particle size of the raw material being 1-10 [mu] m, and the surface adsorbed water content of the raw material being less than or equal to 100 ppm; and b) sintering the raw material containing Li, S, M and X, and crushing to obtain the Argyrolite type sulfide electrolyte. The raw materials containing Li, S, M and X with the D50 particle size being 1-10 microns and the surface adsorbed water content being smaller than or equal to 100 ppm are adopted for sintering to prepare the Argyrolite type sulfide electrolyte, the contact area between the raw materials can be increased, the reaction activation energy can be reduced, the solid-solid reaction rate can be increased, meanwhile, side reactions are prevented, the pure-phase Argyrolite type sulfide electrolyte is obtained, and the ionic conductivity of the electrolyte is improved.

The invention provides a sulfide solid electrolyte, a preparation method thereof and an all-solid-state battery. The sulfide solid electrolyte provided by the invention comprises an inner core and a shell layer coating the surface of the inner core, the material of the inner core is argyrodite type electrolyte Li6PS5Cl, and the material of the shell layer is Li10SnP2S12. The sulfide solid electrolyte provided by the invention adopts argyrodite type electrolyte Li6PS5Cl as a core material and adopts Li10SnP2S12 as a shell material, so that the lithium ion conductivity is remarkably improved, and in a dew point environment of-10 DEG C, the H2S gas release amount is remarkably reduced, and the hydrolysis reaction starting time is remarkably delayed. Meanwhile, excellent cycling stability and interface stability are shown, and good performance can be kept even under the ultralow external pressure (0.5 MPa).

The present invention relates to a sulfide solid electrolyte powder having a crystal phase having an argyrodite-type crystal structure, the value represented by ((strain value-0.001) / specific surface area (m2 / g)) * 100 being 0.010-0.070.

The present invention relates to a sulfide-based solid electrolyte including a compound containing lithium (Li), phosphorus (P), sulfur (S), and a halogen element (D), and having an argyrodite-based crystal structure, at least a portion of the crystal structure being doped with oxygen (O) and a transition metal element (M) consisting of Nb, Ta, V, or a combination thereof.

A sulfide solid electrolyte to be use in a lithium-ion secondary battery includes an argyrodite crystal structure represented by LiaPSbHac (where 5≤a≤7, 4≤b≤6, and 0<c≤2, and Ha represents a halogen element), in which in an X-ray diffraction spectrum using a Cu-Kα ray, the argyrodite crystal structure has a peak A and a peak B, each having a full width at half maximum of 0.07° or more, within a range of 2θ=30.3°±0.5°, and a difference between diffraction angles (2θ) of the peak A and the peak B is 0.05° or more.

Provided is a sulfide-based solid electrolyte having improved atmospheric stability. A solid electrolyte comprises lithium (Li), phosphorus (P), sulfur (S), and a halogen element and has an argyrodite-based crystal structure, wherein at least a portion of the crystal structure is doped with oxygen and at least one element selected from Group 13 elements, with a ratio of a peak area at 191.4 (±0.1) eV to a peak area at 189.38 (±0.1) eV in X-ray photoelectron spectroscopy (XPS) being 0.2 to 0.22.

The present invention concerns a positive electrode active material powder comprising iron disulfide, a sulfur source, a carbon source and a lithium based argyrodite compound and having a ratio A / B, wherein 0.05 < A / B < 0.40, with A representing the crystallite size of the lithium based argyrodite compound and B representing the crystallite size of iron disulfide.

To provide a solid material having ion conductivity and an electrochemically stable composition, a manufacturing method of the material, and a battery and a battery component including the material.SOLUTION: The solid material is an argyrodite-type composition (Li6PS5Cl) that has high ionic conductivity and is easy to process, and contains small amounts of thiophilic metals (compositions selected from Mn, Fe, Co, Ni, Cu, Zn, Hg, Mo and combinations thereof), but whose binary sulfides do not react with water to form hydrogen sulfide (H2S). As such, the release of H2S is minimized or eliminated.SELECTED DRAWING: Figure 1

Described herein are methods for the generation of argyrodite solid electrodes utilizing a dry microwave process, removing the necessity of additional mechanical processing, solvent removal and high temperature annealing. The described methods reduce both time and cost for generating argyrodite materials, while maintaining phase purity and electrochemical properties that make argyrodites desirable as electrolytes. The provided methods and materials are versatile and can be used with a variety of argyrodite compositions, including Li7−yPS6−yXy (X═Cl, Br, I).

The present invention relates to a sulfide-based solid electrolyte which contains an argyrodite-based compound that contains a lithium element, a phosphorus element, a sulfur element, a halogen element and a boron-based element and has an argyrodite crystal structure, in which a part of the crystal structure is substituted by the boron-based element, and in which a part of the crystal structure is substituted by the boron-based element, the sulfide-based solid electrolyte contains an argyrodite-based compound that contains a lithium element, a phosphorus element, a sulfur element, a halogen element and a boron-based element and has an argyrodite crystal structure. Therefore, the electrochemical stability and the atmospheric stability can be improved.

An argyrodite companion compound having high ionic conductivity and low material hardness, a solid electrolyte composite including the argyrodite companion compound, and a solid state battery device including the argyrodite companion compound and / or the composite. The argyrodite companion compound is a sulfide solid electrolyte compound with a distinctive crystal structure defined by an XRD pattern featuring peaks at 2θ=20.9°±0.5°, 31°±0.5°, and 33°±0.5°. The argyrodite companion compound comprises at least lithium (Li), phosphorus (P), and sulfur (S).

The invention discloses a solid-state battery based on argyrodite type sulfide and PEO-LiTFSI composite electrolyte and a preparation method of the solid-state battery, and relates to the technical field of solid-state batteries, the solid-state battery comprises argyrodite type electrolyte Li < 6-a > PS < 5-a > X < 1 + a-b > Y , wherein X and Y are halogen, 0 < = a < = 0.8, and 0 < = b < = 0.7. Through co-doping of halogen such as Cl, Br and the like, the purposes of solving the compatibility problem of a positive electrode and an electrolyte interface and safely and stably improving the conductivity are achieved, and the effect of balancing the ionic conductivity and the air stability is achieved.

The invention relates to an anion high-entropy argyrodite phase solid electrolyte with high ionic conductivity and lattice relaxation effect and preparation thereof, and belongs to the technical field of solid electrolytes. The chemical formula of the electrolyte is Li < 5.5-a > PS < 4.5-a-b > Se Cl < 1.5 + a-c-d > Br < c > X < d >, the configuration entropy of the electrolyte is 2R-2.8 R, R is a gas constant, and Se in the electrolyte is doped at a 4a / 4d site and a 16e site of an argyrodite structure; meanwhile, S < 2-> (16e) in [PS4] < 3-> is replaced by Se < 2-> due to the high doping concentration of Se < 2->, a plurality of tetrahedral units with different S / Se coordination numbers are formed, S < 2-> / Se < 2-> anion disorder is formed at the 16e site, and the anion high-entropy argyrodite phase solid electrolyte with the lattice relaxation effect is obtained.

Disclosed is a solid argyrodite electrolyte doped with nitrogen (N). In some embodiments, the solid argyrodite electrolyte has a formula (I), Li7-n+xPS6-n-xNxHan (I), wherein Ha is a halogen element, 0.01 ≤ x ≤ 0.1, and 1.0 < n < 2.0. In some embodiments, 1.2 ≤ n ≤ 1.8. In some embodiments, 1.2 ≤ n ≤ 1.6. In some embodiments, the ASSB comprising the solid electrolyte exhibits an increased CCD and an improved electrochemical performance.

The invention provides a low-cost synthesis method of a chlorine-rich argyrodite electrolyte. Raw materials Li2O, P2S5 and LiCl are placed in a high-speed ball mill according to a certain proportion to be evenly mixed, the ball milling time is 2-48 h, after ball milling is completed, an electrolyte powder precursor is pressed into blocks under a certain pressure (10-1000 Mpa), then the blocks are sealed in a vacuum quartz tube to be subjected to follow-up annealing treatment, and the electrolyte powder is obtained. And grinding the blocky electrolyte subjected to annealing treatment in a mortar to obtain the final electrolyte marked as Li < 6-x > PS2 < 2.5 > O < 2.5-x > Cl < 1 + x >. The invention provides a low-cost chlorine-rich argyrodite electrolyte and application thereof in a solid-state lithium battery. The method is simple in process, low in cost, good in reproducibility and excellent in performance.

This invention belongs to the technical field of solid electrolytes and discloses a method for preparing a liquid-phase doped silver-germanium sulfide solid electrolyte with high ionic conductivity. The method includes: 1) dispersing lithium sulfide and phosphorus pentasulfide in an organic solvent, heating and stirring to obtain a precursor solution containing Li3PS4; 2) mixing lithium iodide, sulfur powder, and additives with the precursor solution, heating and stirring to remove the organic solvent, and obtaining a powder; 3) sintering the powder under a protective atmosphere to obtain a silver-germanium sulfide solid electrolyte; the additives are one or more of SiS2, GeS2, SnS2, As2S3, and Sb2S3. This invention is simple, and the prepared silver-germanium sulfide electrolyte undergoes elemental doping during thermal crystallization, improving the electrolyte's ionic conductivity and air stability. This method is suitable for industrial production.

Particular embodiments may provide interfacial materials for a solid-state electrolyte interface. In some embodiments, the solid-state electrolyte is argyrodite-based. In some embodiments, the interfacial material may comprise a binary halide, a ternary halide, a binary sulfide, a ternary sulfide, or a combination thereof. In some embodiments, the interfacial material may be disposed at the interface of the anode and the solid-state electrolyte and / or the interface of the cathode and the solid-state electrolyte.

The invention relates to an isovalently substituted argyrodite type solid electrolyte. These solid electrolytes exhibit increased ionic conductivity.

The present invention relates to a sulfide-based solid electrolyte, a preparation method therefor, and an all-solid-state battery comprising same, the sulfide-based solid electrolyte comprising a compound which contains lithium (Li), phosphorus (P), sulfur (S), and chlorine (Cl), and which has an argyrodite-based crystal structure, wherein at least a portion of the crystal structure is doped with boron (B), a group 14 element (α), and oxygen (O), and the molar ratio of boron (B) and the group 14 element (α) to oxygen (O) (([B]+[α]) / [O]) in the doped material is 0.7 to 1.6.

This invention relates to an iodine-based silver-sulfur germanium mineral-phase solid electrolyte and its preparation method, possessing both high ionic conductivity and interfacial stability, belonging to the field of solid electrolyte technology. The electrolyte is an iodine-based silver-sulfur germanium mineral-phase solid electrolyte Li6PS5I doped with M, Sb, and O elements. The chemical formula of the electrolyte is Li. 6+ a M a Sb b P 1‑a‑b S 5‑c O c I and M are one or more of Si, Ge, and Sn, with 0.1≤a≤0.3, 0.5≤b≤0.65, and 0.1≤c≤0.2. M and Sb elements occupy the P sites of the iodine-based silver-germanium sulfide solid electrolyte Li6PS5I, while oxygen occupies the S sites. The electrolyte is obtained through wet ball milling, pressing, sintering, and quenching. This process improves the ionic conductivity of the iodine-based silver-germanium sulfide solid electrolyte, while also enhancing its interfacial compatibility and cycle stability with lithium metal.

Embodiments of the present application provide a composite sulfide electrolyte, a preparation method and a solid-state battery. The composite sulfide electrolyte comprises a argyrodite sulfide electrolyte core and a halide electrolyte coating layer coated on the surface of the argyrodite sulfide electrolyte core. The chemical formula of the argyrodite sulfide electrolyte core is Li 7‑x PS 6‑x M x The chemical formula of the halide electrolyte coating layer is Li3Ta3O4Cl 10‑y Q y M is at least one of Cl, Br, I and F, Q is at least one of Cl, Br and F, the value range of x is 0.1≤x≤5.9, and the value range of y is 1≤y≤5. The composite sulfide electrolyte can improve the environmental stability and electrochemical stability of the traditional sulfide electrolyte.

This invention relates to a sulfide-based solid electrolyte comprising lithium (Li), phosphorus (P), sulfur (S) and halogen (D), having an Argyrodite-like crystal structure, wherein at least a portion of the crystal structure is doped with at least one element selected from boron (B) and aluminum (Al), and has a water stability of 75% or more.

The present invention relates to a sulfide-based solid electrolyte containing lithium (Li), phosphorus (P), sulfur (S), and a halogen element, having an argyrodite-based crystal structure, at least a part of which is doped with aluminum (Al) and tin (Sn), and having an ionic conductivity of 3.2 mS / cm or more at 30 DEG C.

The present invention relates to a sulfide-based solid electrolyte that includes a compound containing lithium (Li), phosphorus (P), sulfur (S), and chlorine (Cl) and having an argyrodite-based crystal structure, wherein at least a portion of the crystal structure is doped with a Group 13 element, a Group 14 element, and oxygen (O), and the compound is represented by chemical formula 1. [Chemical formula 1] Li6(1-x-y)A2xByP(1-x-y)S5.0(1-x-y)O3xCl(1-x-y)+4y In chemical formula 1, 0.01 ≤ x ≤ 0.08, 0.03 ≤ y ≤ 0.45, element A is the Group 13 element, and element B is the Group 14 element.