76 results about "Argyrodite" patented technology

A method of manufacturing a free-standing, sheet-type solid-state electrolyte is provided. The method includes: mixing a sulfide ion conductor-containing material and a non-polar or low-polar binder in a solvent to obtain a slurry composition; disposing the slurry composition onto a planar substrate; spreading the slurry composition on the substrate to obtain a film; calendering the film to densify the film; and subsequently drying the film under vacuum. The binder may be polyisobutylene and may be present in the slurry composition in an amount of up to 10 wt. %, optionally between 1 and 5 wt. %. The sulfide ion conductor-containing material may be a lithium argyrodite having the chemical formula Li6PS5X in which X is Cl, Br, or I. The solvent may be toluene or xylene. The film may have a thickness of between 10 and 200 μm.

The invention discloses a modified composite sulfide solid electrolyte as well as a preparation method and application thereof. The chemical composition of the modified composite sulfide solid electrolyte is xLi < 7-a > PS < 6-a > X . YLi < 7-b-c + dPbM < 1-b > S < 6-c-dOcId, X is at least one of Br, Cl or F, a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 0 and less than 1, c is more than or equal to 0 and less than or equal to 2, d is more than or equal to 1 and less than or equal to 2, x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, and x + y is equal to 1. The sulfide solid electrolyte is subjected to doping modification through a halogen-rich strategy and a soft acid and hard alkali theory, F / Cl / Br-rich and Sn-O-rich double doping is performed on the argyrodite type sulfide electrolyte, the argyrodite type sulfide electrolyte with the same structure is obtained, and the argyrodite type sulfide electrolyte has high ionic conductivity and low activation energy. The sulfide solid electrolyte disclosed by the invention is applied to a solid-state battery and has relatively high initial coulombic efficiency, capacity and cycle performance.

Provided herein are methods for synthesizing a sulfide-based solid state electrolyte, including a sulfide-based solid state electrolyte having an argyrodite phase. The methods generally include mixing an electrolyte precursor in a blend of solvents, the blend of solvents including a catalytic solvent and a spectator solvent.

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.

Provided herein are solid materials that are ionically conductive and electrochemically stable. Embodiments of the solid materials are argyrodite-type compositions that have high ionic conductivity. The compositions include small amounts of thiophilic metals, whose binary sulfides do not react with water to hydrogen sulfide (H2S). As such, H2S release is minimized or eliminated. Also provided are methods of fabricating the materials and batteries and battery components containing the materials.

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 an argyrodite-type sulfide solid electrolyte represented by chemical formula 1, and a solid electrolyte membrane and an all-solid-state secondary battery, comprising same. [Chemical formula 1] (LiaM1 xM2 w)P(S(y-α-β)OαNβ)M3 z In chemical formula 1, M1 is at least one element selected from groups 2 and 11 of the periodic table, M2 is at least one element other than Li selected from group 1 of the periodic table, M3 is at least one element selected from group 17 of the periodic table, 4≤a≤8, 0<x<0.5, 0≤w<0.5, 3≤y≤7, 0<α / y≤0.2, 0<β / y≤0.04, and 0≤z≤2.

Prepare a compound A containing Li, S, and M elements (M is phosphorus, etc.) and containing a crystal phase having an argyrodite-type crystal structure, and mix the compound A with a conductive material to obtain a composite material formed by compounding the two. In the XRD pattern of the compound A, the intensity of peak A observed at 2θ = 29.7° ± 1.00° is set as I0, and in the XRD pattern of the composite material, the intensity of peak B observed at 2θ = 29.7° ± 1.00° is set as I t When, the degree of amorphization N obtained by 100×(I0 - I t ) / I0 is mixed in such a way that it becomes 97% or more. It is suitable that the atomic ratio of the halogen (X) element contained in the compound A to the phosphorus (P) element is less than 1.0.

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 active material of the present invention comprises a conductive material and a compound containing lithium (Li), sulfur (S), and M, and comprising a crystalline phase having an argyrodite-type crystal structure, wherein the conductive material is dispersed on the surface and within the particles of the compound. The M element represents phosphorus (P), etc. The active material of the present invention is a composite material of the aforementioned compound and the aforementioned conductive material. The aforementioned conductive material is preferably a carbon material or a metal material. The content of the aforementioned lithium element in the aforementioned active material is also preferably not less than 10% by mass and not more than 25% by mass.

Disclosed is a solid argyrodite electrolyte doped with fluorine (F). In some embodiments, the argyrodite electrolyte has a formula (I), Li7-nPS6-nHan-xFx (I), wherein Ha is a halogen element other than fluorine (F), 0.02 ≤ x < 0.1, and 1.0 < n < 2.0. In some embodiments, 1.2 ≤ n ≤ 1.6. In some embodiments, 0.02 ≤ x ≤ 0.08. In some embodiments, the ASSB comprising the solid argyrodite electrolyte exhibits an increased CCD and an improved electrochemical performance.

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.

A negative electrode mixture constituting a negative electrode layer, the negative electrode mixture containing particles of a solid electrolyte and particles of a conductive material disposed on the surfaces of the particles of the solid electrolyte. It is preferable that the solid electrolyte contains a crystal phase having an argyrodite-type crystal structure. Preferably, the conductive material is a carbon material or a metal material. It is also preferable that the viscosity of a slurry containing the negative electrode mixture, the binder, and the solvent is 0.05-3 Pa.s (inclusive) at 25 DEG C at a shear rate of 10 (1 / s).

The present invention relates to a solid electrolyte, an all-solid-state battery comprising same, and a method for manufacturing same and more specifically comprises: an argyrodite-type compound; and impurities in an amount of more than 0 ppm and at most 500 ppm, wherein the lightness (L*) value is 90 or more.

A sulfide solid electrolyte is provided having: diffraction peak A observed within a range of 2θ=20.0° to 24.0°; and diffraction peak B observed within a range of 2θ=24.4° to 26.4°, diffraction peak A and diffraction peak B being observed by performing X-ray diffraction measurement using CuKα1 radiation, and the ratio of IA to IB, IA / IB, being 2.0 or less, wherein IA is an intensity of diffraction peak A and IB is an intensity of diffraction peak B. Preferably, the sulfide solid electrolyte contains elemental lithium, elemental phosphorus, elemental sulfur, and an elemental halogen. It is also preferable that the sulfide solid electrolyte has an argyrodite-type crystal structure. It is also preferable that the sulfide solid electrolyte contains a lithium halide hydrate.

A method of production of a solid electrolyte having an Argyrodite-type crystal structure, including steps of mixing raw materials such that lithium (Li), phosphorus (P), sulfur (S), oxygen (O), and halogen (X) satisfy the following formulas (11) to (14) to obtain a mixture; and heating the mixture:4.8≤Li / P≤5.3  (11)3.8≤S / P≤4.4  (12)0<O / P≤0.8  (13)1.0<X / P≤2.0  (14)wherein the formula (11) represents a molar ratio of Li to P, the formula (12) represents a molar ratio of S to P, the formula (13) represents a molar ratio of O to P, and the formula (14) represents a molar ratio of halogen (X) to P.

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 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.

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 solid-state electrolyte material includes doped lithium argyrodite of formula of Li6-2a-bMaTCh5-a-bOaX1+b; where 0<a≤0.5; 0<b≤0.5, M is Zn, Mg, Ca, Sr, Be or a combination of any two or more thereof; T is P, As, Sb, or a combination of any two or more thereof; Ch is S, Se, or a combination thereof; and X is F, Cl, Br, I, or a combination of any two or more 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 invention discloses an argyrodite type solid electrolyte, a modification method and application, and the method is as follows: in the argyrodite type solid electrolyte, metal element cations with larger ionic radius than P element are introduced to partially replace the P element, and / or Br element anions are introduced to partially replace S element and Cl element in the argyrodite type solid electrolyte. The argyrodite type sulfide solid electrolyte has the advantages that positive ions and negative ions are synchronously doped in the argyrodite type sulfide solid electrolyte, the defect of single ion doping is overcome, and the ionic conductivity of the electrolyte is greatly improved through cooperation of the positive ions and the negative ions; (2) the doping of Ta < 5 + > plasma improves the capability of inhibiting the growth of lithium dendrites, enhances the interface compatibility with a lithium metal negative electrode, and is beneficial to the realization of a high-energy-density all-solid-state lithium metal battery; and (3) on the positive electrode side, an interface decomposition product between the electrolyte / active substance and the electrolyte / conductive carbon can achieve a good passivation effect, and the continuous occurrence of side reactions in subsequent circulation is prevented.

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.

The present invention refers to a solid electrolyte having an Argyrodite-type crystal structure, and having a composition represented by the following formula (A), and having diffraction peaks at 2θ = 25.2±0.5 deg and 29.7±0.5 deg in powder X-ray diffraction measurement using a CuKα line:         LiaPbScOdXe ...     (A) wherein the formula, X is halogen, and a to e indicate the composition ratios of respective elements, and satisfy 4.8≦a≦5.3, b=1, 3.8≦c≦4.4, 0<d≦0.8, and 1<e≦2.0, respectively.

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