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WO2022145645A1 - Matériau actif revêtu d'électrolyte solide, électrode, et batterie tout à l'état solide utilisant ceux-ci - Google Patents

Matériau actif revêtu d'électrolyte solide, électrode, et batterie tout à l'état solide utilisant ceux-ci Download PDF

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Publication number
WO2022145645A1
WO2022145645A1 PCT/KR2021/013791 KR2021013791W WO2022145645A1 WO 2022145645 A1 WO2022145645 A1 WO 2022145645A1 KR 2021013791 W KR2021013791 W KR 2021013791W WO 2022145645 A1 WO2022145645 A1 WO 2022145645A1
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WO
WIPO (PCT)
Prior art keywords
active material
solid electrolyte
solid
state battery
chloride
Prior art date
Application number
PCT/KR2021/013791
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English (en)
Korean (ko)
Inventor
박건호
조우석
김경수
유지상
Original Assignee
한국전자기술연구원
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Publication of WO2022145645A1 publication Critical patent/WO2022145645A1/fr

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Definitions

  • the present invention relates to an all-solid-state battery, and more particularly, to an active material coated with a solid electrolyte that can improve the performance of an all-solid-state battery by expanding the ionic contact area between the active material and the solid electrolyte, an electrode, and an all-solid-state battery using the same it's about
  • Lithium secondary batteries have been widely commercialized because of their excellent energy density and output characteristics among various secondary batteries.
  • a lithium secondary battery (hereinafter referred to as a 'liquid-type secondary battery') including a liquid-type electrolyte containing an organic solvent is mainly used.
  • liquid type secondary battery the liquid electrolyte is decomposed by the electrode reaction, causing the battery to expand, and the risk of ignition due to leakage of the liquid electrolyte is pointed out.
  • a lithium secondary battery hereinafter referred to as an 'all-solid-state battery' to which a solid electrolyte having excellent stability is applied is attracting attention.
  • Sulfide-based solid electrolytes have a high ionic conductivity similar to that of conventional organic liquid electrolytes, and have excellent mechanical ductility, which is why they are attracting attention as solid electrolytes for bulk-type all-solid-state batteries.
  • an active material coated with a solid electrolyte In order to construct an all-solid-state battery having such excellent performance, it is preferable to use an active material coated with a solid electrolyte uniformly.
  • the sulfide-based solid electrolyte is easily oxidized on the surface of the active material, making it unsuitable for use as a coating layer.
  • An object of the present invention is to provide an active material coated with a solid electrolyte, an electrode, and an all-solid-state battery using the same, which can improve the performance of an all-solid-state battery by increasing the ionic contact area between the active material and the solid electrolyte.
  • the present invention provides a raw material active material; and a coating layer formed by coating the surface of the raw material with a chloride-based solid electrolyte.
  • the chloride-based solid electrolyte is Li 2-2x M 2 1+x X 4 (0 ⁇ x ⁇ 0.5, M 2 is at least among Be, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu and Zn one, and X may be at least one of F, Cl, and Br).
  • the chloride-based solid electrolyte is Li 3-x M 3 1-x M 4 x X 6 (0 ⁇ x ⁇ 1, M 3 is one of Sc, Y, Er, Yb, Cr, Fe and Co, M 4 is One of Ti, Zr, and Hf, and X may be at least one of F, Cl, and Br).
  • the coating layer may be formed by physically mixing the raw material active material and the chloride-based solid electrolyte.
  • the present invention also provides a raw material active material, an active material having a coating layer formed by coating the surface of the raw material active material with a chloride-based solid electrolyte; and a sulfide-based solid electrolyte; provides an electrode for an all-solid-state battery comprising.
  • the present invention provides an all-solid-state battery including the electrode.
  • the coating layer with the chloride-based solid electrolyte on the surface of the raw material active material as described above, the ionic contact area between the raw material active material and the solid electrolyte can be enlarged, thereby improving the performance of the all-solid-state battery.
  • an all-solid-state battery having an active material coated with a chloride-based solid electrolyte can provide improved atmospheric stability and high voltage stability.
  • FIG. 1 is a view showing an electrode for an all-solid-state battery including an active material coated with a chloride-based solid electrolyte on the surface of a raw active material according to the present invention.
  • FIG. 2 is a view showing an electrode for an all-solid-state battery in which a raw material active material and a solid electrolyte are mixed according to Comparative Example 1.
  • FIG. 3 is a graph showing the results of X-ray diffraction analysis of active materials according to Examples and Comparative Examples.
  • FIG. 1 is a view showing an electrode for an all-solid-state battery including an active material coated with a chloride-based solid electrolyte on the surface of a raw active material according to the present invention.
  • the electrode 100 for an all-solid-state battery according to the present invention includes an active material 40 .
  • the active material 40 includes a raw active material 10 and a coating layer 30 coated with a chloride-based solid electrolyte on the surface of the raw active material 10 . That is, the active material 40 according to the present invention has a structure in which the chloride-based solid electrolyte 30 is coated on the surface of the raw active material 10 .
  • a mechanical (physical) coating method using a mechanical (physical) mixer such as a corotatory mixer may be used as a method of forming the coating layer 30 on the raw material 10 .
  • the active material 40 on which the coating layer 30 is formed can be obtained by mixing the raw material 10 and the chloride-based solid electrolyte into a corotatory mixer.
  • the active material 40 for an all-solid-state battery according to the present invention will be described in detail as follows.
  • the raw material active material 10 an oxide-based active material having excellent mechanical strength may be used. And the chloride-based solid electrolyte has excellent mechanical ductility.
  • the coating layer 30 may be formed by coating the surface of the raw material active material 10 with the chloride-based solid electrolyte. That is, since the chloride-based solid electrolyte has higher electrochemical and oxidation stability than the sulfide-based solid electrolyte, it is suitable as the coating layer 30 for expanding the ionic contact area. And since the chloride-based solid electrolyte has excellent mechanical ductility as described above compared to the oxide-based or sulfide-based solid electrolyte, it is easy to apply the coating layer 30 on the surface of the raw material 10 even with a simple mechanical coating process. can be formed
  • Li 2-2x M 2 1+x X 4 (0 ⁇ x ⁇ 0.5, M 2 is at least among Be, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu and Zn) one, and X may be at least one of F, Cl, and Br).
  • Li 3-x M 3 1-x M 4 x X 6 (0 ⁇ x ⁇ 1, M 3 is one of Sc, Y, Er, Yb, Cr, Fe and Co, M 4 is one of Ti, Zr, and Hf, and X is at least one of F, Cl, and Br) may be used.
  • the electrode 100 may include the active material 40 according to the present invention and a sulfide-based solid electrolyte.
  • a sulfide-based solid electrolyte Li 10 GeP 2 S 12 , Li 3 PS 4 or Li 6 PS 5 Cl may be used, but is not limited thereto.
  • the electrode 100 may be manufactured so that the mass ratio of the raw material 10, the chloride-based solid electrolyte, and the sulfide-based solid electrolyte is 75: 3 to 20: 5 to 22.
  • the electrode 100 may further include a binder and a conductive material. Since the binder and the conductive material may be materials generally used for manufacturing the electrode 100 , a description thereof will be omitted.
  • the active material according to the present invention forms a coating layer with a chloride-based solid electrolyte on the surface of the raw material active material, thereby increasing the ionic contact area between the raw material active material and the solid electrolyte, thereby improving the performance of the all-solid-state battery.
  • an all-solid-state battery having an active material coated with a chloride-based solid electrolyte can provide improved atmospheric stability and high voltage stability.
  • active materials according to Examples and Comparative Examples were prepared.
  • the room temperature ionic conductivity of the Li 3 YCl 6 solid electrolyte synthesized through the AC-impedance method was confirmed to be 0.45 mS/cm.
  • An electrode according to Comparative Example 1 was prepared by mixing a raw material active material not coated with a chloride-based solid electrolyte and a Li 6 PS 5 Cl solid electrolyte in a mass ratio of 75 to 25.
  • the electrode 200 according to Comparative Example 1 may be displayed as shown in FIG. 2 .
  • 2 is a view showing an electrode 200 for an all-solid-state battery in which the raw material active material 10 and the solid electrolyte 20 according to Comparative Example 1 are mixed. That is, the electrode 200 according to Comparative Example 1 has a structure in which the solid electrolyte 20 particles are disposed between the raw material active material 10 particles.
  • an all-solid-state battery was manufactured by sequentially stacking a positive electrode, a solid electrolyte layer, and a negative electrode.
  • an all-solid-state battery was manufactured by sequentially stacking a positive electrode, a solid electrolyte layer, and a negative electrode.
  • An electrode was prepared by coating a chloride-based solid electrolyte and a raw material active material in a mass ratio of 75 to 8.33, and mixing it with a 16.67% Li 6 PS 5 Cl solid electrolyte.
  • the electrode was prepared by mixing with 11.76% Li 6 PS 5 Cl solid electrolyte.
  • an all-solid-state battery was manufactured by sequentially stacking a positive electrode, a solid electrolyte layer, and a negative electrode.
  • the chloride-based solid electrolyte and the raw material were coated in a mass ratio of 75 to 18.75, and then mixed with 6.25% Li 6 PS 5 Cl solid electrolyte to prepare an electrode.
  • an all-solid-state battery was manufactured by sequentially stacking a positive electrode, a solid electrolyte layer, and a negative electrode.
  • Table 1 summarizes the performance evaluation results of the all-solid-state batteries according to Comparative Example 1 and Examples 1-4.
  • the all-solid-state battery according to Examples 1 to 4 has an improved discharge capacity compared to the all-solid-state battery according to Comparative Example 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un matériau actif revêtu d'un électrolyte solide, une électrode, et une batterie tout à l'état solide utilisant ceux-ci, et le but de la présente invention est d'améliorer les performances de la batterie tout à l'état solide en agrandissant la surface de contact ionique entre le matériau actif et l'électrolyte solide. Le matériau actif pour batterie tout à l'état solide selon la présente invention comprend un matériau actif source et une couche de revêtement formée par revêtement d'un électrolyte solide à base de chlorure sur la surface du matériau actif source.
PCT/KR2021/013791 2020-12-30 2021-10-07 Matériau actif revêtu d'électrolyte solide, électrode, et batterie tout à l'état solide utilisant ceux-ci WO2022145645A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2020-0186937 2020-12-30
KR1020200186937A KR20220097560A (ko) 2020-12-30 2020-12-30 고체전해질이 코팅된 활물질, 전극 및 그를 이용한 전고체전지

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WO2022145645A1 true WO2022145645A1 (fr) 2022-07-07

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160128670A (ko) * 2015-04-29 2016-11-08 현대자동차주식회사 고체 전해질 및 이를 포함하는 전고체 전지
WO2019135323A1 (fr) * 2018-01-05 2019-07-11 パナソニックＩｐマネジメント株式会社 Batterie
WO2019146236A1 (fr) * 2018-01-26 2019-08-01 パナソニックＩｐマネジメント株式会社 Matériau d'électrode positive et batterie
KR20200021731A (ko) * 2018-08-21 2020-03-02 전자부품연구원 전고체 이차전지용 양극 나노복합체 및 이의 제조 방법
JP2020109047A (ja) * 2018-12-28 2020-07-16 パナソニックＩｐマネジメント株式会社 固体電解質材料、およびそれを用いた電池

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102452005B1 (ko) 2017-12-27 2022-10-06 현대자동차주식회사 질소가 첨가된 전고체 전지용 황화물계 고체전해질

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160128670A (ko) * 2015-04-29 2016-11-08 현대자동차주식회사 고체 전해질 및 이를 포함하는 전고체 전지
WO2019135323A1 (fr) * 2018-01-05 2019-07-11 パナソニックＩｐマネジメント株式会社 Batterie
WO2019146236A1 (fr) * 2018-01-26 2019-08-01 パナソニックＩｐマネジメント株式会社 Matériau d'électrode positive et batterie
KR20200021731A (ko) * 2018-08-21 2020-03-02 전자부품연구원 전고체 이차전지용 양극 나노복합체 및 이의 제조 방법
JP2020109047A (ja) * 2018-12-28 2020-07-16 パナソニックＩｐマネジメント株式会社 固体電解質材料、およびそれを用いた電池

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