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WO2025211609A1 - Feuille d'électrolyte solide et batterie à électrolyte solide la comprenant - Google Patents

Feuille d'électrolyte solide et batterie à électrolyte solide la comprenant

Info

Publication number
WO2025211609A1
WO2025211609A1 PCT/KR2025/003433 KR2025003433W WO2025211609A1 WO 2025211609 A1 WO2025211609 A1 WO 2025211609A1 KR 2025003433 W KR2025003433 W KR 2025003433W WO 2025211609 A1 WO2025211609 A1 WO 2025211609A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
sheet
electrolyte sheet
average particle
paragraph
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/KR2025/003433
Other languages
English (en)
Korean (ko)
Inventor
오광석
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 WO2025211609A1 publication Critical patent/WO2025211609A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • 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
    • H01M2300/008—Halides
    • 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 present invention relates to a solid electrolyte sheet and an all-solid-state battery including the same.
  • Inorganic solid electrolytes are generally used as the solid electrolytes used in the above-mentioned all-solid-state batteries, and various studies are being conducted on sulfide-based solid electrolytes having a composition such as Li 6 PS 5 Cl, which has an argyrodite structure among the above-mentioned all-solid-state batteries.
  • all-solid-state batteries require the production of large-area batteries. This necessitates the sheet-forming of the cathode, separator, and anode, as in conventional lithium-ion batteries.
  • the separator in all-solid-state batteries consists of a solid electrolyte and a binder, and its properties (ionic conductivity, electrochemical stability, and chemical stability) vary depending on the manufacturing method and the selected solid electrolyte material.
  • the solid electrolyte layer used as a separator in all-solid-state batteries must prevent short-circuiting of the cell by suppressing lithium dendrites during charge and discharge.
  • one object of the present invention is to provide a solid electrolyte sheet that has improved ionic conductivity by reducing internal voids, can suppress internal short circuits when applied to an all-solid-state battery, and can improve rate characteristics.
  • Another object of the present invention is to provide an all-solid-state battery comprising the solid electrolyte sheet.
  • a solid electrolyte sheet is provided, wherein the average particle diameter (D50) of the first solid electrolyte is larger than the average particle diameter (D50) of the second solid electrolyte, the content of the second solid electrolyte is 17 to 43 wt% based on the total weight of the first solid electrolyte and the second solid electrolyte, and the average particle diameter (D50) of the second solid electrolyte is 0.5 to 3.5 ⁇ m.
  • the solid electrolyte sheet according to the present invention can be manufactured according to the following manufacturing method, which will be described below.
  • the binder may be, but is not limited to, for example, nitrile butadiene rubber (NBR), hydrogenated nitrile butadiene rubber (HNBR), PTFE, styrene-butadiene-styrene copolymer, acrylic resin, styrene-butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, vinylidene fluoride/hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, or a combination thereof.
  • NBR nitrile butadiene rubber
  • HNBR hydrogenated nitrile butadiene rubber
  • PTFE nitrile butadiene rubber
  • SBR styrene-butadiene-styrene copolymer
  • acrylic resin styrene-butadiene rubber
  • SBR styrene-butadiene rubber
  • the solvent may be, for example, xylene, toluene, isobutyl isobutyrate, or a combination thereof, but is not necessarily limited thereto, and any solvent used in the art may be used.
  • the above solid electrolyte composition may further include a dispersant that can improve the dispersibility of the solid content in the solid electrolyte composition, and may further include other additives as needed.
  • the solid electrolyte composition is applied onto a substrate or porous support.
  • the above substrate is not particularly limited as long as it is chemically stable with respect to the solid electrolyte composition.
  • the substrate may be, but is not necessarily limited to, PET (polyethylene terephthalate), PEN (polyethylenenaphthalate), PES (polyethersulfone), PC (polycarbonate), PP (polypropylene), or a combination thereof.
  • the porous support may include, but is not necessarily limited to, a polymer resin made of, for example, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyvinylidene fluoride (PVDF), Teflon (PTFE), or a combination thereof.
  • PET polyethylene terephthalate
  • PP polypropylene
  • PE polyethylene
  • PC polycarbonate
  • PVDF polyvinylidene fluoride
  • PTFE Teflon
  • the above application is not particularly limited as long as it is commonly used in the relevant technical field, but may be performed by, for example, a slurry casting method.
  • the above positive electrode layer may include a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector.
  • 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 coating layer formation method is selected within a range that does not adversely affect the properties of the cathode active material. Examples of coating methods include spray coating and immersion. Since specific coating methods are readily understood by those working in the field, a detailed description will be omitted.
  • the positive electrode 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 relevant technical field may be used.
  • the positive electrode active material layer may further include, for example, additives such as fillers, coating agents, dispersants, and ion conductive aids in addition to the above-described positive electrode active material, solid electrolyte, binder, and conductive agent.
  • additives such as fillers, coating agents, dispersants, and ion conductive aids in addition to the above-described positive electrode active material, solid electrolyte, binder, and conductive agent.
  • the positive electrode active material layer may include, 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 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 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.
  • a solid electrolyte was manufactured in the same manner as in Manufacturing Example 1, except that the synthesized solid electrolyte was pulverized through ball milling to obtain an average particle size (D50) of 7 ⁇ m.
  • the solid electrolyte manufactured according to Manufacturing Example 2 was used as a first solid electrolyte, and the solid electrolyte manufactured according to Manufacturing Example 1 was used as a second solid electrolyte.
  • the first solid electrolyte:second solid electrolyte were mixed so that the mixing weight ratio was 80:20, and xylene solvent containing 3 wt% of NBR binder dissolved therein was additionally mixed to form a solid electrolyte composition (slurry).
  • the solid electrolyte composition (slurry) was applied onto a PET (polyethylene terephthalate) substrate using a blade coating method.
  • the applied solid electrolyte composition (slurry) was dried at 50°C and then detached from the PET substrate to produce a solid electrolyte sheet.
  • the above-mentioned solid electrolyte sheet was stamped into an area of 0.785 cm 2 and placed in a pressure cell, and then a composite electrode was loaded thereon.
  • the composite electrode was manufactured by loading 20.0 mg of a cathode slurry containing a cathode active material (NCM 811): solid electrolyte (Li 5.7 PS 4.7 Cl 1.3 ): conductive material (denka black) in a weight ratio of 70:29:1 into an area of 0.785 cm 2 and densifying it to 300 MPa. Thereafter, the Li counter electrode was bonded as the cathode at 20 MPa, and the cell was clamped at the same pressure.
  • NCM 811 cathode active material
  • conductive material denka black
  • Table 1 is a table that summarizes the solid electrolyte particle size and mixing weight ratio in the solid electrolyte sheets of examples and comparative examples.
  • Tables 2 and 3 below are tables that summarize the results of evaluating the ionic conductivity and porosity of a solid electrolyte sheet according to Experimental Example 2 described below, and the results of evaluating the rate characteristics of an all-solid-state battery according to Experimental Example 3 described below, respectively.
  • the solid electrolyte sheet manufactured according to the examples and comparative examples was used as a working electrode and the cell was fastened at a pressure of 70 MPa using SUS, and then the impedance was measured by applying a voltage of 10 mV at 30°C.
  • Porosity% ⁇ 1 - (V true / V bulk ) ⁇ ⁇ 100
  • the all-solid-state battery After manufacturing the all-solid-state battery, it was aged at room temperature for 2 hours and then subjected to initial cycling. Capacity evaluation was performed with 180 mAh/g as the reference capacity, and the charge/discharge conditions were CC/CV 2.5 ⁇ 4.20 V, 1/20 C cut-off. One cycle was performed under 0.1 C charge/0.1 C discharge conditions. At this time, the rate characteristic was evaluated by calculating the discharge capacity at 1.5 C current in the second cycle as a percentage of the discharge capacity in the first cycle.
  • the solid electrolyte sheet includes a first solid electrolyte having a large particle size and a second solid electrolyte having a small particle size, and the content of the second solid electrolyte, etc., is appropriately controlled, it was confirmed that the membrane porosity of the solid electrolyte sheet was generally small, the ionic conductivity was excellent, and the rate characteristics of the all-solid-state battery were excellent.

Landscapes

  • 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)

Abstract

La présente invention concerne une feuille d'électrolyte solide comprenant un premier électrolyte solide et un second électrolyte solide, le diamètre de particule moyen D50 du premier électrolyte solide étant supérieur au diamètre de particule moyen D50 du second électrolyte solide, la teneur du second électrolyte solide étant de 20 à 40 % en poids sur la base du poids total du premier électrolyte solide et du second électrolyte solide, le diamètre de particule moyen D50 du second électrolyte solide étant de 0,5 à 3,5 µm.
PCT/KR2025/003433 2024-04-03 2025-03-17 Feuille d'électrolyte solide et batterie à électrolyte solide la comprenant Pending WO2025211609A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020240045342A KR20250147129A (ko) 2024-04-03 2024-04-03 고체 전해질 시트 및 이를 포함하는 전고체 전지
KR10-2024-0045342 2024-04-03

Publications (1)

Publication Number Publication Date
WO2025211609A1 true WO2025211609A1 (fr) 2025-10-09

Family

ID=97267681

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2025/003433 Pending WO2025211609A1 (fr) 2024-04-03 2025-03-17 Feuille d'électrolyte solide et batterie à électrolyte solide la comprenant

Country Status (2)

Country Link
KR (1) KR20250147129A (fr)
WO (1) WO2025211609A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150060584A (ko) * 2013-11-26 2015-06-03 주식회사 엘지화학 고체 전해질층을 포함하는 이차전지
JP2018101467A (ja) * 2016-12-19 2018-06-28 Fdk株式会社 全固体電池の製造方法および全固体電池
JP2018120709A (ja) * 2017-01-24 2018-08-02 日立造船株式会社 全固体電池およびその製造方法
KR20190079132A (ko) * 2017-12-27 2019-07-05 현대자동차주식회사 전고체 전지
KR20210047886A (ko) * 2018-09-11 2021-04-30 맥셀 홀딩스 가부시키가이샤 고체 전해질 시트 및 전고체 리튬 이차전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150060584A (ko) * 2013-11-26 2015-06-03 주식회사 엘지화학 고체 전해질층을 포함하는 이차전지
JP2018101467A (ja) * 2016-12-19 2018-06-28 Fdk株式会社 全固体電池の製造方法および全固体電池
JP2018120709A (ja) * 2017-01-24 2018-08-02 日立造船株式会社 全固体電池およびその製造方法
KR20190079132A (ko) * 2017-12-27 2019-07-05 현대자동차주식회사 전고체 전지
KR20210047886A (ko) * 2018-09-11 2021-04-30 맥셀 홀딩스 가부시키가이샤 고체 전해질 시트 및 전고체 리튬 이차전지

Also Published As

Publication number Publication date
KR20250147129A (ko) 2025-10-13

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