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WO2025135760A1 - Électrolyte solide et batterie tout solide le comprenant - Google Patents

Électrolyte solide et batterie tout solide le comprenant Download PDF

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Publication number
WO2025135760A1
WO2025135760A1 PCT/KR2024/020551 KR2024020551W WO2025135760A1 WO 2025135760 A1 WO2025135760 A1 WO 2025135760A1 KR 2024020551 W KR2024020551 W KR 2024020551W WO 2025135760 A1 WO2025135760 A1 WO 2025135760A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
compound
sulfide
molar ratio
based solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/KR2024/020551
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English (en)
Korean (ko)
Inventor
오광석
남상철
권오민
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Posco Holdings Inc
Original Assignee
Posco Holdings Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Posco Holdings Inc filed Critical Posco Holdings Inc
Publication of WO2025135760A1 publication Critical patent/WO2025135760A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the argyrodite crystal structure is fully maintained, so that the effect of improving the ion conductivity of the solid electrolyte can be more preferably implemented.
  • the above positive electrode layer may more specifically include a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector.
  • the above-described positive electrode active material layer may further include, for example, a positive electrode active material and optionally a solid electrolyte as needed.
  • the solid electrolyte included in the positive electrode active material layer may be the same as or different from the solid electrolyte according to one embodiment of the present invention, and may be the same as or different from the solid electrolyte included in the solid electrolyte layer.
  • A is Ni, Co, Mn, or a combination thereof
  • B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof
  • D is O, F, S, P, or a combination thereof
  • E is Co, Mn, or a combination thereof
  • F is F, S, P, or a combination thereof
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof
  • Q is Ti, Mo, Mn, or a combination thereof
  • I is Cr, V, Fe, Sc, Y, or a combination thereof
  • J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
  • the coating layer added to the surface of such a compound includes, for example, a coating element compound of an oxide, a hydroxide, an oxyhydroxide of the coating element, an oxycarbonate of the coating element, or a hydroxycarbonate of the coating element of the coating element.
  • the compound forming the coating layer is amorphous or crystalline.
  • the coating element included in the coating layer is Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof.
  • the method of forming the coating layer is selected within a range that does not adversely affect the properties of the positive electrode active material.
  • the coating method includes, for example, spray coating, dipping, etc. Since the specific coating method is well understood by those working in the relevant field, a detailed description will be omitted.
  • the positive electrode active material layer may include, for example, a binder.
  • the binder may include, but is not limited to, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, and the like, and any binder used in the art may be used.
  • SBR styrene butadiene rubber
  • the cathode active material layer may include, for example, a conductive material.
  • the conductive material may include, but is not limited to, graphite, carbon black, acetylene black, Ketjen black, carbon fiber, metal powder, etc., and any conductive material used in the art may be used.
  • the cathode active material layer may further include, for example, additives such as fillers, coating agents, dispersants, and ion conductive assistants in addition to the cathode active material, solid electrolyte, binder, and conductive agent described above.
  • additives such as fillers, coating agents, dispersants, and ion conductive assistants in addition to the cathode active material, solid electrolyte, binder, and conductive agent described above.
  • coating agents As fillers, coating agents, dispersants, ion conductive assistants, etc. that can be included in the cathode active material layer, known materials generally used in electrodes of all-solid-state secondary batteries can be used.
  • the positive electrode collector may be, for example, a plate or foil made of indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.
  • the thickness of the positive electrode collector may be, for example, 1 um to 100 um, 1 um to 50 um, 5 um to 25 um, or 10 um to 20 um.
  • the above negative electrode layer may more specifically include a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
  • the above negative electrode active material layer may include, for example, a negative electrode active material and a binder, and may optionally further include a solid electrolyte as needed.
  • the above negative electrode active material may include, for example, a carbon-based negative electrode active material, a metal/metalloid negative electrode active material, or a combination thereof.
  • the above carbon-based negative electrode active material may be amorphous carbon, crystalline carbon, or a mixture or composite thereof.
  • the amorphous carbon may be, for example, carbon black (CB), acetylene black (AB), furnace black (FB), ketjen black (KB), graphene, or the like, but is not necessarily limited thereto, and any material classified as amorphous carbon in the relevant technical field may be used.
  • Amorphous carbon is carbon that has no crystallinity or very low crystallinity, and is distinguished from crystalline carbon or graphite-based carbon.
  • the crystalline carbon may be, for example, natural graphite, artificial graphite, or a combination thereof.
  • the metal/metalloid negative electrode active material includes at least one selected from the group consisting of lithium (Li), gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn), but is not necessarily limited thereto, and any metal negative electrode active material or metalloid negative electrode active material that forms an alloy or compound with lithium in the relevant technical field may be used.
  • the binder included in the negative electrode active material layer is, for example, styrene-butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, vinylidene fluoride/hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, etc., but is not necessarily limited thereto and any binder used in the relevant technical field may be used.
  • the binder may be composed of a single binder or a plurality of different binders.
  • the negative active material layer includes a binder, the negative active material layer is stabilized on the negative current collector. In addition, cracking of the negative active material layer is suppressed despite changes in the volume and/or relative positions of the negative active material layer during the charge and discharge process.
  • the negative active material layer may further include additives used in conventional all-solid-state batteries, such as fillers, coating agents, dispersants, and ion conductive assistants.
  • the all-solid-state battery may further include a second negative electrode active material layer disposed between the negative electrode current collector and the negative electrode active material layer by charging.
  • the second negative electrode active material layer may be deposited between the negative electrode current collector and the negative electrode current collector during the charging process, or may be further disposed on the negative electrode active material layer during electrode assembly.
  • the second negative electrode active material layer may be a metal layer including lithium or a lithium alloy.
  • the lithium alloy may include, but is not limited to, a Li-Al alloy, a Li-Sn alloy, a Li-In alloy, a Li-Ag alloy, a Li-Au alloy, a Li-Zn alloy, a Li-Ge alloy, a Li-Si alloy, and the like, and any lithium alloy used in the art may be used.
  • the second negative electrode active material layer may be made of one of these alloys and/or lithium, or may be made of multiple types of alloys and/or lithium.
  • the negative electrode current collector may be composed of, for example, a material that does not react with lithium, i.e., does not form an alloy or a compound.
  • the negative electrode current collector may include, but is not necessarily limited to, copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel (Ni), and any material that is used as an electrode current collector in the relevant technical field may be used.
  • the negative electrode current collector may be composed of one of the above-described metals, or may be composed of an alloy or a coating material of two or more metals.
  • the negative electrode current collector may be, for example, in the form of a plate or a foil.
  • the solid electrolyte included in the negative electrode active material layer may be the same as or different from the solid electrolyte according to one embodiment of the present invention, and may be the same as or different from the solid electrolyte included in the solid electrolyte layer.
  • the above solid electrolyte layer can be manufactured by mixing and drying the above-described solid electrolyte and binder, or by rolling the above-described solid electrolyte powder into a certain shape under a pressure of 1 ton to 10 tons.
  • the solid electrolyte may be in the form of a powder or a molded article.
  • the solid electrolyte in the form of a molded article may be in the form of, for example, pellets, sheets, thin films, etc., but is not necessarily limited thereto and may have various forms depending on the intended use.
  • the above solid electrolyte layer may, if necessary, further include a solid electrolyte, such as a conventional sulfide-based solid electrolyte and/or an oxide-based solid electrolyte, in addition to the above-described solid electrolyte.
  • a solid electrolyte such as a conventional sulfide-based solid electrolyte and/or an oxide-based solid electrolyte, in addition to the above-described solid electrolyte.
  • the above binder may be, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polyvinyl alcohol, etc., but is not limited thereto, and any binder used in the relevant technical field may be used.
  • SBR styrene butadiene rubber
  • the binder of the solid electrolyte layer may be the same as or different from the binders of the positive and negative electrode layers.
  • pellets were heat-treated at 550°C for about 4 hours in an argon (Ar) atmosphere to produce a Li 5.58 Al 0.02 Sn 0.05 P 0.93 S 4.65 Cl 1.19 solid electrolyte.
  • the reactants Li 2 S, P 2 S 5 and LiCl were mixed using a planetary mill at 300 rpm for about 8 hours to form a mixture.
  • the pellets were heat-treated at 550°C in an argon (Ar) atmosphere to produce a Li 6 PS 5 Cl solid electrolyte.
  • Tables 1 and 2 below are tables summarizing the experimental results according to Experimental Examples 2 and 3 described below for the solid electrolytes of Examples and Comparative Examples.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention se rapporte à un électrolyte solide à base de sulfure qui contient du lithium (Li), du phosphore (P), du soufre (S) et un élément halogène (D) et comprend un composé ayant une structure cristalline à base d'argyrodite, au moins une partie de la structure cristalline étant dopée avec de l'indium (In) et de l'étain (Sn), et la conductivité ionique à 30 °C étant d'au moins 3,21 mS/cm.
PCT/KR2024/020551 2023-12-18 2024-12-17 Électrolyte solide et batterie tout solide le comprenant Pending WO2025135760A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020230185168A KR20250094411A (ko) 2023-12-18 2023-12-18 고체 전해질 및 이를 포함하는 전고체 전지
KR10-2023-0185168 2023-12-18

Publications (1)

Publication Number Publication Date
WO2025135760A1 true WO2025135760A1 (fr) 2025-06-26

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PCT/KR2024/020551 Pending WO2025135760A1 (fr) 2023-12-18 2024-12-17 Électrolyte solide et batterie tout solide le comprenant

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KR (1) KR20250094411A (fr)
WO (1) WO2025135760A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230022158A (ko) * 2020-06-10 2023-02-14 미쓰이금속광업주식회사 고체 전해질, 전극 합제 및 전지

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230022158A (ko) * 2020-06-10 2023-02-14 미쓰이금속광업주식회사 고체 전해질, 전극 합제 및 전지

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEN TING; ZENG DEWU; ZHANG LONG; YANG MENG; SONG DAWEI; YAN XINLIN; YU CHUANG: "Sn-O dual-doped Li-argyrodite electrolytes with enhanced electrochemical performance", JOURNAL OF ENERGY CHEMISTRY, vol. 59, 11 December 2020 (2020-12-11), AMSTERDAM, NL , pages 530 - 537, XP086547423, ISSN: 2095-4956, DOI: 10.1016/j.jechem.2020.11.031 *
CHOI YEONG JUN, KIM SUN-I, SON MINGYU, LEE JUNG WOO, LEE DUCK HYUN: "Cl- and Al-Doped Argyrodite Solid Electrolyte Li6PS5Cl for All-Solid-State Lithium Batteries with Improved Ionic Conductivity", NANOMATERIALS, vol. 12, no. 24, 1 January 2022 (2022-01-01), pages 1 - 11, XP093202626, ISSN: 2079-4991, DOI: 10.3390/nano12244355 *
JANG GEUM-JI, RAJAGOPAL RAJESH, KANG SUNG, RYU KWANG-SUN: "Preparation of argyrodite Li6–2xZnxPS5−xOxCl with improved electrochemical performance and air stability for all-solid-state batteries", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 957, 25 September 2023 (2023-09-25), CH , pages 1 - 10, XP093325103, ISSN: 0925-8388, DOI: 10.1016/j.jallcom.2023.170273 *
KANG SEUL-GI, KIM DAE-HYUN, KIM BO-JOONG, YOON CHANG-BUN: "Sn-Substituted Argyrodite Li6PS5Cl Solid Electrolyte for Improving Interfacial and Atmospheric Stability", MATERIALS, vol. 16, no. 7, 1 January 2023 (2023-01-01), pages 1 - 9, XP093325099, ISSN: 1996-1944, DOI: 10.3390/ma16072751 *

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KR20250094411A (ko) 2025-06-25

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