US20200358085A1 - Solid electrolyte film for sulfide-based all-solid-state batteries - Google Patents
Solid electrolyte film for sulfide-based all-solid-state batteries Download PDFInfo
- Publication number
- US20200358085A1 US20200358085A1 US16/409,275 US201916409275A US2020358085A1 US 20200358085 A1 US20200358085 A1 US 20200358085A1 US 201916409275 A US201916409275 A US 201916409275A US 2020358085 A1 US2020358085 A1 US 2020358085A1
- Authority
- US
- United States
- Prior art keywords
- solid electrolyte
- solid
- sulfide
- electrolyte film
- solvent
- 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.)
- Abandoned
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 128
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- 239000002904 solvent Substances 0.000 claims abstract description 47
- 150000002500 ions Chemical class 0.000 claims abstract description 35
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- 229910052732 germanium Inorganic materials 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical group [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- 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
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
- H01M10/3954—Sodium-sulfur cells containing additives or special arrangement in the sulfur compartment
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a solid electrolyte film for sulfide-based all-solid-state batteries, and more particularly to a composite of a solid electrolyte, a binder, and a solvent used to manufacture a solid electrolyte film for sulfide-based all-solid-state batteries that is thin and has high ion conductivity.
- a lithium-ion secondary battery or a lithium secondary battery includes a positive electrode layer, a negative electrode layer, and an electrolyte containing lithium salt interposed between the positive electrode layer and the negative electrode layer.
- the electrolyte may be a non-aqueous liquid or solid electrolyte.
- a liquid electrolyte it is necessary to equip a battery with a device configured to minimize an increase in the temperature of the battery when a short circuit occurs in the battery or with a system configured to prevent the occurrence of a short circuit in the battery, since the liquid electrolyte is combustible.
- the danger posed by such a liquid electrolyte has increased due to the increased demand for high-capacity and high-density batteries and the full-scale advance of electric vehicles into markets.
- An all-solid-state battery configured such that a solid electrolyte is interposed between a positive electrode and a negative electrode, whereby the battery is completely solidified, fundamentally solves the above problem and does not need additional safety devices, whereby the all-solid-state battery is economical. For these reasons, much research has been conducted into all-solid-state batteries.
- a battery having a solid electrolyte applied thereto exhibits higher stability than a conventional liquid electrolyte system.
- the capacity and output of the battery having the solid electrolyte applied thereto are lower than those of the conventional liquid electrolyte system, since the solid electrolyte has low ion conductivity.
- the reason that ion conductivity is low in the battery having the solid electrolyte applied thereto is that the area of contact between an electrode active material and the solid electrolyte is not larger than the area of contact between the electrode active material and the liquid electrolyte in the conventional liquid electrolyte system and that the ion conductivity of the solid electrolyte itself is low.
- the sulfide-based solid electrolyte maintains the solidity thereof in spite of the high ion conductivity thereof, the area of contact of the sulfide-based solid electrolyte at the interface between the positive electrode and the negative electrode is insufficient.
- a solid electrolyte having a predetermined thickness or more is applied. This physical restriction acts as a roadblock to the improvement of the energy density of all-solid-state batteries. In the case in which the thickness of the solid electrolyte is reduced, the time during which the solid electrolyte is capable of being stably used is also reduced.
- Patent Document 1 relates to an electrode for all-solid-state lithium batteries, an all-solid-state lithium battery, and a device. There are provided an electrode for all-solid-state lithium batteries configured such that a metal layer is prevented from being corroded, eluted, and alloyed and such that the resistance of a battery is reduced and an all-solid-state lithium battery including the same.
- the all-solid-state lithium battery includes a positive metal layer, a positive-electrode conductive resin layer stacked on the positive metal layer, a positive-electrode active material layer stacked on the positive-electrode conductive resin layer, a negative metal layer, a negative-electrode conductive resin layer stacked on the negative metal layer, a negative-electrode active material layer stacked on the negative-electrode conductive resin layer, and a solid electrolyte layer interposed between the positive-electrode active material layer and the negative-electrode active material layer.
- Patent Document 1 in order to manufacture the solid electrolyte layer, Li 2 S—P 2 S 5 (mass ratio 70:30), as a solid electrolyte, an SBR resin, and toluene were mixed at a mass ratio of 49.95:0.05:50 to manufacture a solid electrolyte sheet.
- the thickness of the solid electrolyte is not considered, and a solid electrolyte that is capable of being operated for a long time even in the state of being thin is not acknowledged at all.
- Patent Document 2 relates to a solid electrolyte composition, a method of manufacturing the same, and a method of manufacturing an all-solid-state battery using the same, and in particular, it is an object thereof to provide a solid electrolyte having a passivation layer formed on the surface thereof.
- the passivation layer may include at least one of an inorganic layer including at least one of an oxide, a nitride, or a sulfide, an organic layer including a polydopamine derivative, or a self-assembled monolayer including organosilane.
- Patent Document 2 is characterized in that the solid electrolyte is protected while a wet-type process is performed by the provision of a separate passivation layer.
- the solid electrolyte is manufactured so as to have a thickness of 50 ⁇ m; however, long-term stability, which is required in the present invention, is not achieved even though the passivation layer is formed.
- Non-Patent Document 1 relates to an optimum combination of a solid electrolyte, a binder, and a solvent, whereby solid electrolyte particles are uniformly dispersed in a slurry and high adhesive force is provided.
- the thickness of the solid electrolyte is not considered, and a solid electrolyte that is capable of being used for a long time even in the state of being thin is not acknowledged at all.
- the present invention has been made in view of the above problems, and it is an object of the present invention to provide a solid electrolyte film for sulfide-based all-solid-state batteries that is flexible, thin, characterized by high electrical conductivity, and usable for a long time and a wet-type manufacturing method thereof.
- the above and other objects can be accomplished by the provision of a solid electrolyte film composition for sulfide-based all-solid-state batteries, the solid electrolyte film composition including a sulfide-based solid electrolyte, a polymer binder including C and H therein but not including O, N, and F therein, and a solvent having a dielectric constant of x (1.0 ⁇ x ⁇ 3.1).
- the solvent may be at least one of benzene, CCl 4 , hexane, cyclohexane, heptane, or xylene.
- a solid electrolyte film for sulfide-based all-solid-state batteries manufactured using the solid electrolyte film composition for sulfide-based all-solid-state batteries and a sulfide-based all-solid-state battery comprising the solid electrolyte film.
- the thickness of the solid electrolyte film for sulfide-based all-solid-state batteries may be 60 ⁇ m or less, and the operating time of the solid electrolyte film based on the evaluation of Li plating and stripping may be 1000 hours or more.
- the ion conductivity of the solid electrolyte film for sulfide-based all-solid-state batteries may be 10 ⁇ 4 S/cm or more.
- the present invention relates to a solid electrolyte film for sulfide-based all-solid-state batteries, and more particularly to a composite of a solid electrolyte, a binder, and a solvent used to manufacture a solid electrolyte film for sulfide-based all-solid-state batteries that is thin and has high ion conductivity.
- a solid electrolyte film for sulfide-based all-solid-state batteries that is flexible, thin, characterized by high electrical conductivity, and usable for a long time and a wet-type manufacturing method thereof.
- the present invention provides a solid electrolyte film composition for sulfide-based all-solid-state batteries, wherein the solid electrolyte film composition includes a solvent having a dielectric constant of x (1.5 ⁇ x ⁇ 3.0), the thickness of a solid electrolyte film for sulfide-based all-solid-state batteries manufactured using the same is 60 ⁇ m or less, and the solid electrolyte film is capable of being stably used for at least 1000 hours or more, and up to 2000 hours, based on the evaluation of Li plating and stripping.
- FIG. 1 is a view showing the results of observation of the effect of dispersion of a binder and a solvent.
- FIG. 2 is a view showing the results of XRD measurement for measuring the compatibility of a solid electrolyte and a solvent.
- FIG. 3 is a view showing the results of impedance measurement for measuring the compatibility of a solid electrolyte and a solvent.
- FIG. 4 is a view showing the results of measurement of ion conductivity based on temperature for observing the compatibility of a solid electrolyte and a solvent.
- FIG. 5 is an electron microscope photograph showing the section of an all-solid-state battery according to the present invention.
- FIG. 6 is a view showing the result of evaluation of the lifespan of the all-solid-state battery according to the present invention.
- the present invention relates to a solid electrolyte film for sulfide-based all-solid-state batteries, and more particularly to a composite of a solid electrolyte, a binder, and a solvent used to manufacture a solid electrolyte film for sulfide-based all-solid-state batteries that is thin and has high ion conductivity.
- a solid electrolyte layer is manufactured so as to be thin, it is possible to greatly increase the energy density of a sulfide-based all-solid-state battery. To this end, first of all, it is necessary to maintain the ion conductivity of a solid electrolyte in a high state, and it is preferable to form the solid electrolyte layer so as to have the shape of a flexible thin film.
- a wet-type manufacturing method of an electrode including a binder having no electro-negative functional group, a non-polar solvent, and a sulfide-based solid electrolyte is provided.
- the sulfide-based solid electrolyte may be at least one of Li 6 PS 5 (hereinafter, referred to as “LPS”), Li 6 PS 5 Cl (hereinafter, referred to as “LPSCl”), Li 3 PS 4 , Li 10 GeP 2 S 12 , Thio-LISICON (Li 3.25 Ge 0.25 P 0.75 S 4 ), Li 2 S—P 2 S 5 —LiCl, Li 2 S—SiS 2 , LiI—Li 2 S—SiS 2 , LiI—Li 2 S—P 2 S 5 , LiI—Li 2 S—P 2 O 5 , LiI—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 , Li 7 P 3 S 11 , LiI—Li 2 S—B 2 S 3 , Li 3 PO 4 —Li 2 S—Si 2 S, Li 3 PO 4 —Li 2 S—SiS 2 , LiPO 4 —Li 2 S—S—S
- Any sulfide-based materials available on the market may be used, or a material manufactured by crystallizing an amorphous sulfide-based material may also be used.
- the average particle diameter of sulfide-based solid electrolyte particles is used within a range suitable for all-solid-state batteries.
- the average particle diameter of the sulfide-based solid electrolyte particles may be 0.1 ⁇ m to 50 ⁇ m, preferably 0.5 ⁇ m to 20 ⁇ m. If the average particle diameter of the sulfide-based solid electrolyte particles is less than the above range, the particles may aggregate with each other. If the average particle diameter of the sulfide-based solid electrolyte particles is greater than the above range, on the other hand, the porosity of the manufactured solid electrolyte is high, whereby the capacity of the battery may be reduced, and therefore the characteristics of the battery may be deteriorated.
- each of the sulfide-based particles has an ion conductivity of 1 ⁇ 10 ⁇ 4 S/cm or more. More preferably, each of the sulfide-based particles has an ion conductivity of 1 ⁇ 10 ⁇ 3 S/cm or more.
- an inorganic solid electrolyte such as Li 2 O—B 2 O 3 , Li 2 O—B 2 O 3 —P 2 O 5 , Li 2 O—V 2 O 5 —SiO 2 , Li 3 PO 4 , Li 2 O—Li 2 WO 4 —B 2 O 3 , LiPON, LiBON, Li 2 O—SiO 2 , LiI, Li 3 N, Li 5 La 3 Ta 2 O 12 , Li 7 La 3 Zr 2 O 12 , Li 6 BaLa 2 Ta 2 O 12 , Li 3 PO (4-3/2w) N w (w ⁇ 1), or Li 3.6 Si 0.6 P 0.4 O 4 , may be used.
- an inorganic solid electrolyte such as Li 2 O—B 2 O 3 , Li 2 O—B 2 O 3 —P 2 O 5 , Li 2 O—V 2 O 5 —SiO 2 , Li 3 PO 4 , Li 2 O—Li 2 WO 4 —B 2 O 3 , LiPON, LiBON
- a polymer binder including C and H therein but not including 0, N, and F therein is preferably used as the binder having no electro-negative functional group.
- a preferred example of the polymer binder may be at least one of styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene-styrene (SBS), or styrene-butadiene rubber (SBR).
- a solvent having a dielectric constant of x (1.5 ⁇ x ⁇ 3.0) is used in the wet-type electrode manufacturing method according to the present invention.
- a concrete example of the solvent may be at least one of benzene, CCl 4 , hexane, cyclohexane, heptane, or xylene.
- the sulfide-based solid electrolyte is at least one of LPS, Li 6 PS 5 Cl (LPSCl), or Li 7 P 3 S 11
- the polymer binder is SEBS
- the solvent is at least one of hexane, heptane, or xylene.
- the present invention provides a solid electrolyte film for sulfide-based all-solid-state batteries manufactured using the solid electrolyte film composition for sulfide-based all-solid-state batteries and a sulfide-based all-solid-state battery including the solid electrolyte film for sulfide-based all-solid-state batteries.
- the thickness of the solid electrolyte film for sulfide-based all-solid-state batteries according to the present invention is 60 ⁇ m or less, preferably 50 ⁇ m or less, and the operating time of the solid electrolyte film based on the evaluation of Li plating and stripping is 1000 hours or more, preferably 2000 hours or more.
- an all-solid-state battery according to the present invention includes a positive electrode, a negative electrode, and the above-described sulfide-based solid electrolyte interposed between the positive electrode and the negative electrode.
- An electrode of the all-solid-state battery has a structure in which an electrode active material is formed on an electrode current collector.
- the electrode current collector may be omitted depending on the structure of the electrode.
- the electrode current collector is a positive electrode current collector.
- the electrode current collector is a negative electrode current collector.
- the all-solid-state battery is manufactured through a dry compression process, in which electrode powder and solid electrolyte powder are manufactured, introduced into a predetermined mold, and pressed, or a slurry coating process, in which a slurry composition including an active material, a solvent, and a binder is manufactured, coated, and dried.
- a dry compression process in which electrode powder and solid electrolyte powder are manufactured, introduced into a predetermined mold, and pressed, or a slurry coating process, in which a slurry composition including an active material, a solvent, and a binder is manufactured, coated, and dried.
- a slurry coating process in which a slurry composition including an active material, a solvent, and a binder is manufactured, coated, and dried.
- the solid electrolyte is disposed between the positive electrode and the negative electrode, and then the same is compressed in order to assemble a cell.
- the assembled cell is mounted in a sheathing member, and then the sheathing member is encapsulated by heating and compression.
- a laminated case made of aluminum or stainless steel, a cylindrical metal container, or a prismatic metal container may be appropriately used as the sheathing member.
- the electrode slurry may be coated on the current collector using a method of placing the electrode slurry on the current collector and uniformly dispersing the electrode slurry with a doctor blade, a die casting method, a comma coating method, or a screen printing method.
- the electrode slurry and the current collector may be formed on a separate substrate, and the electrode slurry and the current collector may be joined to each other through pressing or lamination. At this time, the concentration of a slurry solution or the number of coatings may be adjusted in order to adjust the final coating thickness.
- the drying process is a process of removing the solvent or moisture from the slurry in order to dry the slurry coated on the metal current collector.
- the drying process may vary depending on the solvent that is used.
- the drying process may be performed in a vacuum oven having a temperature of 50° C. to 200° C.
- drying may be performed using a warm-air drying method, a hot-air drying method, a low-humidity-air drying method, a vacuum drying method, a (far-)infrared drying method, or an electron-beam radiation method.
- the drying time is not particularly restricted. In general, drying is performed within a range of 30 seconds to 24 hours.
- a cooling process may be further performed.
- slow cooling to normal temperature may be performed such that the recrystallized structure of the binder is sufficiently formed.
- a rolling process in which the electrode is passed through a gap between two heated rolls such that the electrode is compressed so as to have a desired thickness, may be performed in order to increase the capacity density of the electrode and to improve adhesion between the current collector and the active material after the drying process.
- the rolling process is not particularly restricted.
- a well-known rolling process, such as pressing, may be performed.
- the electrode may pass through a gap between rotating rolls, or a flat press machine may be used to press the electrode.
- a positive electrode current collector is not particularly restricted, as long as the positive electrode current collector exhibits high conductivity while the positive electrode current collector does not induce any chemical change in a battery to which the positive electrode current collector is applied.
- the positive electrode current collector may be made of stainless steel, aluminum, nickel, titanium, or plastic carbon.
- the positive electrode current collector may be made of aluminum or stainless steel, the surface of which is treated with carbon, nickel, titanium, or silver.
- a positive electrode active material includes an excellent positive electrode active material particle for sulfide-based all-solid-state batteries, the surface of which is reformed, according to the present invention.
- an additional material may be added depending on what a lithium secondary battery is used for.
- a transition-metal-compound-based active material or a sulfide-based active material may be used.
- an oxide, sulfide, or halide of scandium, ruthenium, titanium, vanadium, molybdenum, chrome, manganese, iron, cobalt, nickel, copper, or zinc may be used as the transition metal compound. More specifically, TiS 2 , ZrS 2 , RuO 2 , Co 3 O 4 , Mo 6 S 8 , or V 2 O 5 may be used. However, the present invention is not limited thereto.
- Other well-known materials may also be included.
- a negative electrode current collector is not particularly restricted, as long as the negative electrode current collector exhibits high conductivity while the negative electrode current collector does not induce any chemical change in an all-solid-state battery.
- the negative electrode current collector may be made of copper, stainless steel, aluminum, nickel, titanium, or plastic carbon.
- the negative electrode current collector may be made of copper or stainless steel, the surface of which is treated with carbon, nickel, titanium, or silver, or an aluminum-cadmium alloy.
- the negative electrode current collector may be configured in any of various forms, such as that of a film, a sheet, a foil, a net, a porous body, a foam body, or a non-woven fabric body, on the surface of which a micro-scale uneven pattern is formed, in the same manner as in the positive electrode current collector.
- a negative electrode active material may be one selected from the group consisting of a lithium metal, a lithium alloy, a lithium-metal composite oxide, a titanium composite oxide containing lithium (LTO), and a combination thereof.
- An alloy of lithium and at least one metal selected from among Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, and Sn may be used as the lithium alloy.
- the lithium-metal composite oxide may include lithium and an oxide (MeO x ) of a metal (Me) selected from the group consisting of Si, Sn, Zn, Mg, Cd, Ce, Ni, and Fe.
- the lithium-metal composite oxide may be Li x Fe 2 O 3 (0 ⁇ x ⁇ 1) or Li x WO 2 (0 ⁇ x ⁇ 1).
- a metal composite oxide such as Sn x Me 1-x Me′ y O z (Me: Mn, Fe, Pb, Ge; Me′: Al, B, P, Si, Group 1, 2 and 3 elements of the periodic table, halogen; 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8), or an oxide, such as SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , or Bi 2 O 5 , may be used as the negative electrode active material.
- a carbon-based negative electrode active material such as crystalline carbon, amorphous carbon, or a carbon composite, may be used, either alone or in a combination of two or more materials.
- a conductive agent As needed, a conductive agent, a solid electrolyte, or a dispersant may be further added, in addition to the active material.
- Nickel powder, a cobalt oxide, a titanium oxide, or carbon may be used as the conductive agent.
- At least one selected from the group consisting of Ketjen black, acetylene black, furnace black, graphite, carbon fiber, and fullerene may be used as the carbon.
- Binders and solvents were mixed to prepare Examples according to the present invention and Comparative Examples, and the effect of dispersion of the binders was observed.
- Acetonitrile (ACN), dimethyl carbonate (DMC), toluene (TOL), and xylene (XYL) were used as the solvents.
- the following compounds were used as the binders.
- LPS Li 6 PS 5
- Li 6 PS 5 Li 6 PS 5
- a change in the structure of the solid electrolyte was measured using XRD.
- “Pristine” indicates the powdered state immediately after the composition of the solid electrolyte.
- the total amount of the solid electrolyte LPS was 10 mg.
- LPS and 3 ml of a solvent were mixed for 1 hour, and vacuum drying was performed for 12 hours. After the solvent was evaporated, powder was collected and measured using XRD. XRD measurement was performed from 5 degrees to 80 degrees, and the step size was 0.2.
- the measurement source was a Cu target.
- Example 2-1 and Example 2-2 according to the present invention were similar to pristine as to the shapes of the graphs compared to Comparative Example 2-1 and Comparative Example 2-2, indicating that the change in the structure of the solid electrolyte was slight.
- LPS was dispersed in solvents ACN, DMC, TOL, and XYL according to Examples and Comparative Examples, and the ion conductivity of LPS in a pristine state was also measured.
- SEBS was used as a binder.
- the diameter of the sample was 1 cm, and the thickness of the sample was 0.055 mm.
- Platinum or copper electrodes having high electric conductivity, as ion blocking electrodes, were formed on opposite surfaces of a flat sample through dry deposition.
- Alternating-current voltage was applied through the electrodes on the opposite surfaces of the sample.
- the amplitude of the voltage was set to 30 mV, which was an amplitude used to measure the impedance of a secondary battery using a general liquid electrolyte, and the measurement frequency range was set to a range of 0.1 Hz to 1 MHz.
- the resistance R b of the bulk electrolyte was calculated from an intersection point at which a semicircle of the measured impedance track joins an actual axis, and the ion conductivity ⁇ of LPS was calculated from the area A and the thickness t (or l) of the sample, as expressed by the following equation.
- FIG. 3 shows the impedance measurement values, wherein the X axis indicates the resistance value and the Y axis indicates a reactance value.
- the ion conductivity values ( ⁇ cm) ⁇ 1 of LPS depending on the solvent based on the measurement results are as follows. The value right next to each solvent indicates the dielectric constant of the solvent.
- the ion conductivity value was 1.11 ⁇ 10 ⁇ 5 ( ⁇ cm) ⁇ 1 when the dielectric constant was 3.1, and in the case of Example 3-1, i.e. toluene (dielectric constant 2.4), the ion conductivity value was 1.12 ⁇ 10 ⁇ 3 ( ⁇ cm) ⁇ 1 . Since the value of the ion conductivity is changed in the unit thereof as the value of the dielectric constant is reduced, it can be estimated that the value of the ion conductivity is changed approximately according to a logarithmic scale.
- the dielectric constant of the solvent suitable to achieve the object of the present invention must be less than 3.1, preferably 3.0 or less, and more preferably less than 3.0.
- the dielectric constant since the value of the ion conductivity increases as the value of the dielectric constant decreases, a solvent having a small dielectric constant is advantageous; however, the dielectric constant must be greater than 1, since the dielectric constant is a value relative to the permittivity of a vacuum.
- the dielectric constant of the solvent suitable to achieve the object of the present invention ranges from more than 1 to less than 3.1.
- the binder suitable to achieve the object of the present invention is a polymer including only C and H.
- the dielectric constant is changed depending on the temperature.
- the ion conductivity was measured using a method identical to the method used in Experimental Example 3 but while changing the temperature. Xylene, heptane, and hexane were used as ion solvents, and SEBS was used as a binder. As can be seen from the following table, the ion conductivity was higher as the dielectric constant was lower.
- FIG. 4 shows changes in ion conductivity depending on the time and solvent. It can be seen that the ion conductivity value at normal temperature was the lowest and that the ion conductivity increased as the temperature increased. This phenomenon was particularly prominent for hexane, the dielectric constant of which was low. Consequently, it can be seen that, since the temperature of a battery becomes higher than normal temperature as the battery is operated, it is more advantageous to use a solvent having a low dielectric constant.
- Li plating and stripping evaluation was performed on Example 3-2.
- Electrochemical evaluation was performed under conditions of 0.11 mA/cm 2 10 h charging, 10 h discharging, and 200 ⁇ m. About 40 mg of a solid electrolyte film was used. In addition, an Li metal was disposed on opposite surfaces of the solid electrolyte layer. The film was manufactured so as to have a diameter of 1.3 cm.
- FIG. 5 is an SEM photograph related thereto, and FIG. 6 shows the result of evaluation of (potential) stability based on long-term operation.
- FIG. 5( a ) is a general SEM photograph, which shows the thickness of the solid electrolyte film.
- FIG. 5( b ) is a P EDX image, which shows the solid electrolyte film.
- FIG. 5( c ) is an S EDX image, which shows the solid electrolyte film.
- FIG. 5( d ) is an actual photograph showing the flexible state of the solid electrolyte film.
- the all-solid-state battery according to the present invention is stable for 2000 hours or more.
- the solid electrolyte according to the present invention has excellent lifespan characteristics that ensure stability for a long time while maintaining high ion conductivity even in the state in which the solid electrolyte is thin.
Abstract
Description
- The present invention relates to a solid electrolyte film for sulfide-based all-solid-state batteries, and more particularly to a composite of a solid electrolyte, a binder, and a solvent used to manufacture a solid electrolyte film for sulfide-based all-solid-state batteries that is thin and has high ion conductivity.
- A lithium-ion secondary battery or a lithium secondary battery includes a positive electrode layer, a negative electrode layer, and an electrolyte containing lithium salt interposed between the positive electrode layer and the negative electrode layer. The electrolyte may be a non-aqueous liquid or solid electrolyte. In the case in which a liquid electrolyte is used, it is necessary to equip a battery with a device configured to minimize an increase in the temperature of the battery when a short circuit occurs in the battery or with a system configured to prevent the occurrence of a short circuit in the battery, since the liquid electrolyte is combustible. The danger posed by such a liquid electrolyte has increased due to the increased demand for high-capacity and high-density batteries and the full-scale advance of electric vehicles into markets.
- An all-solid-state battery, configured such that a solid electrolyte is interposed between a positive electrode and a negative electrode, whereby the battery is completely solidified, fundamentally solves the above problem and does not need additional safety devices, whereby the all-solid-state battery is economical. For these reasons, much research has been conducted into all-solid-state batteries.
- A battery having a solid electrolyte applied thereto exhibits higher stability than a conventional liquid electrolyte system. However, the capacity and output of the battery having the solid electrolyte applied thereto are lower than those of the conventional liquid electrolyte system, since the solid electrolyte has low ion conductivity. The reason that ion conductivity is low in the battery having the solid electrolyte applied thereto is that the area of contact between an electrode active material and the solid electrolyte is not larger than the area of contact between the electrode active material and the liquid electrolyte in the conventional liquid electrolyte system and that the ion conductivity of the solid electrolyte itself is low.
- Various attempts have been made to increase the ion conductivity of the solid electrolyte so as to approach the ion conductivity of the liquid electrolyte through the development and improvement of materials. A sulfide-based solid electrolyte has high ion conductivity, and therefore research into all-solid-state batteries to which the sulfide-based solid electrolyte is applied has been very actively conducted.
- Since the sulfide-based solid electrolyte maintains the solidity thereof in spite of the high ion conductivity thereof, the area of contact of the sulfide-based solid electrolyte at the interface between the positive electrode and the negative electrode is insufficient. In order to solve this problem, a solid electrolyte having a predetermined thickness or more is applied. This physical restriction acts as a roadblock to the improvement of the energy density of all-solid-state batteries. In the case in which the thickness of the solid electrolyte is reduced, the time during which the solid electrolyte is capable of being stably used is also reduced.
- Patent Document 1 relates to an electrode for all-solid-state lithium batteries, an all-solid-state lithium battery, and a device. There are provided an electrode for all-solid-state lithium batteries configured such that a metal layer is prevented from being corroded, eluted, and alloyed and such that the resistance of a battery is reduced and an all-solid-state lithium battery including the same. In Patent Document 1, the all-solid-state lithium battery includes a positive metal layer, a positive-electrode conductive resin layer stacked on the positive metal layer, a positive-electrode active material layer stacked on the positive-electrode conductive resin layer, a negative metal layer, a negative-electrode conductive resin layer stacked on the negative metal layer, a negative-electrode active material layer stacked on the negative-electrode conductive resin layer, and a solid electrolyte layer interposed between the positive-electrode active material layer and the negative-electrode active material layer.
- In Patent Document 1, in order to manufacture the solid electrolyte layer, Li2S—P2S5 (mass ratio 70:30), as a solid electrolyte, an SBR resin, and toluene were mixed at a mass ratio of 49.95:0.05:50 to manufacture a solid electrolyte sheet. In Patent Document 1, however, the thickness of the solid electrolyte is not considered, and a solid electrolyte that is capable of being operated for a long time even in the state of being thin is not acknowledged at all.
- Patent Document 2 relates to a solid electrolyte composition, a method of manufacturing the same, and a method of manufacturing an all-solid-state battery using the same, and in particular, it is an object thereof to provide a solid electrolyte having a passivation layer formed on the surface thereof. The passivation layer may include at least one of an inorganic layer including at least one of an oxide, a nitride, or a sulfide, an organic layer including a polydopamine derivative, or a self-assembled monolayer including organosilane. Patent Document 2 is characterized in that the solid electrolyte is protected while a wet-type process is performed by the provision of a separate passivation layer. In Patent Document 2, the solid electrolyte is manufactured so as to have a thickness of 50 μm; however, long-term stability, which is required in the present invention, is not achieved even though the passivation layer is formed.
- Non-Patent Document 1 relates to an optimum combination of a solid electrolyte, a binder, and a solvent, whereby solid electrolyte particles are uniformly dispersed in a slurry and high adhesive force is provided. In Non-Patent Document 1, however, the thickness of the solid electrolyte is not considered, and a solid electrolyte that is capable of being used for a long time even in the state of being thin is not acknowledged at all.
- In manufacturing the solid electrolyte through the wet-type process, as described above, technology capable of reducing the thickness of the solid electrolyte and at the same time enabling the solid electrolyte to be stably used for 1000 hours or more has not been suggested. Above all, it is important to provide a method of manufacturing a solid electrolyte capable of being stably used for a long time, which is the greatest restriction to the practical use of an all-solid-state battery; however, a definite solution thereto has not been proposed.
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- Japanese Patent Application Publication No. 2009-289534 (2009.12.10)
- Korean Patent Application Publication No. 2018-0043152 (2018.04.27)
- J. of The Electrochem. Soc., 164 (9) A2075-A2081 (2017) (2017.07.18)
- The present invention has been made in view of the above problems, and it is an object of the present invention to provide a solid electrolyte film for sulfide-based all-solid-state batteries that is flexible, thin, characterized by high electrical conductivity, and usable for a long time and a wet-type manufacturing method thereof.
- In accordance with a first aspect of the present invention, the above and other objects can be accomplished by the provision of a solid electrolyte film composition for sulfide-based all-solid-state batteries, the solid electrolyte film composition including a sulfide-based solid electrolyte, a polymer binder including C and H therein but not including O, N, and F therein, and a solvent having a dielectric constant of x (1.0<x<3.1).
- The solvent may be at least one of benzene, CCl4, hexane, cyclohexane, heptane, or xylene.
- In accordance with a second aspect of the present invention, there are provided a solid electrolyte film for sulfide-based all-solid-state batteries manufactured using the solid electrolyte film composition for sulfide-based all-solid-state batteries and a sulfide-based all-solid-state battery comprising the solid electrolyte film.
- The thickness of the solid electrolyte film for sulfide-based all-solid-state batteries may be 60 μm or less, and the operating time of the solid electrolyte film based on the evaluation of Li plating and stripping may be 1000 hours or more.
- In addition, the ion conductivity of the solid electrolyte film for sulfide-based all-solid-state batteries may be 10−4 S/cm or more.
- The present invention relates to a solid electrolyte film for sulfide-based all-solid-state batteries, and more particularly to a composite of a solid electrolyte, a binder, and a solvent used to manufacture a solid electrolyte film for sulfide-based all-solid-state batteries that is thin and has high ion conductivity.
- According to the present invention, it is possible to provide a solid electrolyte film for sulfide-based all-solid-state batteries that is flexible, thin, characterized by high electrical conductivity, and usable for a long time and a wet-type manufacturing method thereof.
- In particular, the present invention provides a solid electrolyte film composition for sulfide-based all-solid-state batteries, wherein the solid electrolyte film composition includes a solvent having a dielectric constant of x (1.5<x<3.0), the thickness of a solid electrolyte film for sulfide-based all-solid-state batteries manufactured using the same is 60 μm or less, and the solid electrolyte film is capable of being stably used for at least 1000 hours or more, and up to 2000 hours, based on the evaluation of Li plating and stripping.
-
FIG. 1 is a view showing the results of observation of the effect of dispersion of a binder and a solvent. -
FIG. 2 is a view showing the results of XRD measurement for measuring the compatibility of a solid electrolyte and a solvent. -
FIG. 3 is a view showing the results of impedance measurement for measuring the compatibility of a solid electrolyte and a solvent. -
FIG. 4 is a view showing the results of measurement of ion conductivity based on temperature for observing the compatibility of a solid electrolyte and a solvent. -
FIG. 5 is an electron microscope photograph showing the section of an all-solid-state battery according to the present invention. -
FIG. 6 is a view showing the result of evaluation of the lifespan of the all-solid-state battery according to the present invention. - The present invention relates to a solid electrolyte film for sulfide-based all-solid-state batteries, and more particularly to a composite of a solid electrolyte, a binder, and a solvent used to manufacture a solid electrolyte film for sulfide-based all-solid-state batteries that is thin and has high ion conductivity.
- In the case in which a solid electrolyte layer is manufactured so as to be thin, it is possible to greatly increase the energy density of a sulfide-based all-solid-state battery. To this end, first of all, it is necessary to maintain the ion conductivity of a solid electrolyte in a high state, and it is preferable to form the solid electrolyte layer so as to have the shape of a flexible thin film.
- To this end, a wet-type manufacturing method of an electrode including a binder having no electro-negative functional group, a non-polar solvent, and a sulfide-based solid electrolyte is provided.
- Specifically, the sulfide-based solid electrolyte may be at least one of Li6PS5 (hereinafter, referred to as “LPS”), Li6PS5Cl (hereinafter, referred to as “LPSCl”), Li3PS4, Li10GeP2S12, Thio-LISICON (Li3.25Ge0.25P0.75S4), Li2S—P2S5—LiCl, Li2S—SiS2, LiI—Li2S—SiS2, LiI—Li2S—P2S5, LiI—Li2S—P2O5, LiI—Li3PO4—P2S5, Li2S—P2S5, Li7P3S11, LiI—Li2S—B2S3, Li3PO4—Li2S—Si2S, Li3PO4—Li2S—SiS2, LiPO4—Li2S—SiS, Li9.54Si1.74P1.44S11.7Cl0.3, or Li7P3S11.
- Any sulfide-based materials available on the market may be used, or a material manufactured by crystallizing an amorphous sulfide-based material may also be used.
- The average particle diameter of sulfide-based solid electrolyte particles is used within a range suitable for all-solid-state batteries. For example, the average particle diameter of the sulfide-based solid electrolyte particles may be 0.1 μm to 50 μm, preferably 0.5 μm to 20 μm. If the average particle diameter of the sulfide-based solid electrolyte particles is less than the above range, the particles may aggregate with each other. If the average particle diameter of the sulfide-based solid electrolyte particles is greater than the above range, on the other hand, the porosity of the manufactured solid electrolyte is high, whereby the capacity of the battery may be reduced, and therefore the characteristics of the battery may be deteriorated.
- Preferably, each of the sulfide-based particles has an ion conductivity of 1×10−4 S/cm or more. More preferably, each of the sulfide-based particles has an ion conductivity of 1×10−3 S/cm or more.
- In addition to the above-mentioned sulfide-based solid electrolytes, other well-known solid electrolytes may also be used. In an example, an inorganic solid electrolyte, such as Li2O—B2O3, Li2O—B2O3—P2O5, Li2O—V2O5—SiO2, Li3PO4, Li2O—Li2WO4—B2O3, LiPON, LiBON, Li2O—SiO2, LiI, Li3N, Li5La3Ta2O12, Li7La3Zr2O12, Li6BaLa2Ta2O12, Li3PO(4-3/2w)Nw (w<1), or Li3.6Si0.6P0.4O4, may be used.
- Specifically, a polymer binder including C and H therein but not including 0, N, and F therein is preferably used as the binder having no electro-negative functional group. A preferred example of the polymer binder may be at least one of styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene-styrene (SBS), or styrene-butadiene rubber (SBR).
- In addition, a solvent having a dielectric constant of x (1.5<x<3.0) is used in the wet-type electrode manufacturing method according to the present invention. A concrete example of the solvent may be at least one of benzene, CCl4, hexane, cyclohexane, heptane, or xylene.
- In a preferred combination of the present invention, the sulfide-based solid electrolyte is at least one of LPS, Li6PS5Cl (LPSCl), or Li7P3S11, the polymer binder is SEBS, and the solvent is at least one of hexane, heptane, or xylene.
- In addition, the present invention provides a solid electrolyte film for sulfide-based all-solid-state batteries manufactured using the solid electrolyte film composition for sulfide-based all-solid-state batteries and a sulfide-based all-solid-state battery including the solid electrolyte film for sulfide-based all-solid-state batteries.
- The thickness of the solid electrolyte film for sulfide-based all-solid-state batteries according to the present invention is 60 μm or less, preferably 50 μm or less, and the operating time of the solid electrolyte film based on the evaluation of Li plating and stripping is 1000 hours or more, preferably 2000 hours or more.
- Manufacture of all-Solid-State Battery
- Specifically, an all-solid-state battery according to the present invention includes a positive electrode, a negative electrode, and the above-described sulfide-based solid electrolyte interposed between the positive electrode and the negative electrode.
- An electrode of the all-solid-state battery has a structure in which an electrode active material is formed on an electrode current collector. The electrode current collector may be omitted depending on the structure of the electrode. In the case in which the electrode is a positive electrode, the electrode current collector is a positive electrode current collector. In the case in which the electrode is a negative electrode, the electrode current collector is a negative electrode current collector.
- The all-solid-state battery is manufactured through a dry compression process, in which electrode powder and solid electrolyte powder are manufactured, introduced into a predetermined mold, and pressed, or a slurry coating process, in which a slurry composition including an active material, a solvent, and a binder is manufactured, coated, and dried. In the present invention, the method of manufacturing the all-solid-state battery having the above-described structure is not particularly restricted. Any well-known method may be used.
- In an example, the solid electrolyte is disposed between the positive electrode and the negative electrode, and then the same is compressed in order to assemble a cell. The assembled cell is mounted in a sheathing member, and then the sheathing member is encapsulated by heating and compression. A laminated case made of aluminum or stainless steel, a cylindrical metal container, or a prismatic metal container may be appropriately used as the sheathing member.
- The electrode slurry may be coated on the current collector using a method of placing the electrode slurry on the current collector and uniformly dispersing the electrode slurry with a doctor blade, a die casting method, a comma coating method, or a screen printing method. Alternatively, the electrode slurry and the current collector may be formed on a separate substrate, and the electrode slurry and the current collector may be joined to each other through pressing or lamination. At this time, the concentration of a slurry solution or the number of coatings may be adjusted in order to adjust the final coating thickness.
- The drying process is a process of removing the solvent or moisture from the slurry in order to dry the slurry coated on the metal current collector. The drying process may vary depending on the solvent that is used. In an example, the drying process may be performed in a vacuum oven having a temperature of 50° C. to 200° C. For example, drying may be performed using a warm-air drying method, a hot-air drying method, a low-humidity-air drying method, a vacuum drying method, a (far-)infrared drying method, or an electron-beam radiation method. The drying time is not particularly restricted. In general, drying is performed within a range of 30 seconds to 24 hours.
- After the drying process, a cooling process may be further performed. In the cooling process, slow cooling to normal temperature may be performed such that the recrystallized structure of the binder is sufficiently formed.
- In addition, if necessary, a rolling process, in which the electrode is passed through a gap between two heated rolls such that the electrode is compressed so as to have a desired thickness, may be performed in order to increase the capacity density of the electrode and to improve adhesion between the current collector and the active material after the drying process. In the present invention, the rolling process is not particularly restricted. A well-known rolling process, such as pressing, may be performed. In an example, the electrode may pass through a gap between rotating rolls, or a flat press machine may be used to press the electrode.
- Positive Electrode
- A positive electrode current collector is not particularly restricted, as long as the positive electrode current collector exhibits high conductivity while the positive electrode current collector does not induce any chemical change in a battery to which the positive electrode current collector is applied. For example, the positive electrode current collector may be made of stainless steel, aluminum, nickel, titanium, or plastic carbon. Alternatively, the positive electrode current collector may be made of aluminum or stainless steel, the surface of which is treated with carbon, nickel, titanium, or silver.
- A positive electrode active material includes an excellent positive electrode active material particle for sulfide-based all-solid-state batteries, the surface of which is reformed, according to the present invention. In addition, an additional material may be added depending on what a lithium secondary battery is used for. For example, a transition-metal-compound-based active material or a sulfide-based active material may be used.
- A concrete example of the positive electrode active material particle, before the surface thereof is treated, includes a material for the active material selected from the group consisting of one or more of a layered compound, such as a lithium manganese composite oxide (LiMn2O4 or LiMnO2), a lithium cobalt oxide (LiCoO2), or a lithium nickel oxide (LiNiO2), or a compound substituted with one or more transition metals; a lithium manganese oxide represented by the chemical formula Li1+xMn2-xO4 (where x=0 to 0.33) or a lithium manganese oxide, such as LiMnO3, LiMn2O3, or LiMnO2; a lithium copper oxide (Li2CuO2); a vanadium oxide, such as LiV3O8, LiFe3O4, V2O5, or Cu2V2O7; an Ni-sited lithium nickel oxide represented by the chemical formula LiNi1-xMxO2 (where M=Co, Mn, Al, Cu, Fe, Mg, B, or Ga, and x=0.01 to 0.3); a lithium manganese composite oxide represented by the chemical formula LiMn2-xMxO2 (where M=Co, Ni, Fe, Cr, Zn, or Ta, and x=0.01 to 0.1) or the chemical formula Li2Mn3MO8 (where M=Fe, Co, Ni, Cu, or Zn); LiMn2O4 in which a portion of Li in the chemical formula is replaced by alkaline earth metal ions; a disulfide compound; and Fe2(MoO4)3, and a derivative thereof.
- For example, an oxide, sulfide, or halide of scandium, ruthenium, titanium, vanadium, molybdenum, chrome, manganese, iron, cobalt, nickel, copper, or zinc may be used as the transition metal compound. More specifically, TiS2, ZrS2, RuO2, Co3O4, Mo6S8, or V2O5 may be used. However, the present invention is not limited thereto.
- A sulfur element, a disulfide compound, an organosulfur compound, or a carbon-sulfur polymer ((C2Sx)n, where x=2.5 to 50, n≥2) may be used as the sulfide-based active material. Other well-known materials may also be included.
- Negative Electrode
- A negative electrode current collector is not particularly restricted, as long as the negative electrode current collector exhibits high conductivity while the negative electrode current collector does not induce any chemical change in an all-solid-state battery. For example, the negative electrode current collector may be made of copper, stainless steel, aluminum, nickel, titanium, or plastic carbon. Alternatively, the negative electrode current collector may be made of copper or stainless steel, the surface of which is treated with carbon, nickel, titanium, or silver, or an aluminum-cadmium alloy. In addition, the negative electrode current collector may be configured in any of various forms, such as that of a film, a sheet, a foil, a net, a porous body, a foam body, or a non-woven fabric body, on the surface of which a micro-scale uneven pattern is formed, in the same manner as in the positive electrode current collector.
- A negative electrode active material may be one selected from the group consisting of a lithium metal, a lithium alloy, a lithium-metal composite oxide, a titanium composite oxide containing lithium (LTO), and a combination thereof. An alloy of lithium and at least one metal selected from among Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, and Sn may be used as the lithium alloy. In addition, the lithium-metal composite oxide may include lithium and an oxide (MeOx) of a metal (Me) selected from the group consisting of Si, Sn, Zn, Mg, Cd, Ce, Ni, and Fe. In an example, the lithium-metal composite oxide may be LixFe2O3 (0<x≤1) or LixWO2 (0<x≤1).
- In addition, a metal composite oxide, such as SnxMe1-xMe′yOz (Me: Mn, Fe, Pb, Ge; Me′: Al, B, P, Si, Group 1, 2 and 3 elements of the periodic table, halogen; 0<x≤1; 1≤y≤3; 1≤z≤8), or an oxide, such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, or Bi2O5, may be used as the negative electrode active material. Furthermore, a carbon-based negative electrode active material, such as crystalline carbon, amorphous carbon, or a carbon composite, may be used, either alone or in a combination of two or more materials.
- Conductive Agent and Dispersant
- As needed, a conductive agent, a solid electrolyte, or a dispersant may be further added, in addition to the active material.
- Nickel powder, a cobalt oxide, a titanium oxide, or carbon may be used as the conductive agent. At least one selected from the group consisting of Ketjen black, acetylene black, furnace black, graphite, carbon fiber, and fullerene may be used as the carbon.
- Hereinafter, the present invention will be described with reference to preferred manufacturing examples and examples. However, the following manufacturing examples and examples are provided only for illustration of the present invention and should not be construed as limiting the scope of the present invention.
- Binders and solvents were mixed to prepare Examples according to the present invention and Comparative Examples, and the effect of dispersion of the binders was observed. Acetonitrile (ACN), dimethyl carbonate (DMC), toluene (TOL), and xylene (XYL) were used as the solvents. The following compounds were used as the binders.
- The result of dispersion of 1 g of each binder in 3 ml of each solvent when the binder and the solvent were mixed with each other is shown in
FIG. 1 . SEBS, which included only C and H, exhibited the most dispersibility. -
TABLE 1 PEO PVDF-HFP MBR SEBS ACN Comparative Comparative Comparative Comparative Example 1-1 Example 1-2 Example 1-3 Example 1-4 DMC Comparative Comparative Comparative Comparative Example 1-5 Example 1-6 Example 1-7 Example 1-8 TOL Comparative Comparative Example 1-1 Example 1-2 Example 1-9 Example 1-10 XYL Comparative Comparative Example 1-3 Example 1-4 Example 1-11 Example 1-12 - In order to measure the compatibility of a solid electrolyte and a solvent, LPS (Li6PS5), as a sulfide-based solid electrolyte, was dispersed in solvents ACN, DMC, TOL, and XYL according to Examples and Comparative Examples, and a change in the structure of the solid electrolyte was measured using XRD. “Pristine” indicates the powdered state immediately after the composition of the solid electrolyte.
- Example 2-1: TOL+LPS
- Example 2-2: XYL+LPS
- Comparative Example 2-1: ACN+LPS
- Comparative Example 2-2: DMC+LPS
- Comparative Example 2-3: Pristine+LPS
- At the time of measurement using XRD, the total amount of the solid electrolyte LPS was 10 mg. LPS and 3 ml of a solvent were mixed for 1 hour, and vacuum drying was performed for 12 hours. After the solvent was evaporated, powder was collected and measured using XRD. XRD measurement was performed from 5 degrees to 80 degrees, and the step size was 0.2. The measurement source was a Cu target.
- The results are shown in
FIG. 2 . It can be seen fromFIG. 2 that the structure of the solid electrolyte in a solvent having a low dielectric constant was only slightly changed. InFIG. 2 , the solvents were ACN, DMC, TOL, XYL, and pristine from top to bottom. That is, it can be seen that Example 2-1 and Example 2-2 according to the present invention were similar to pristine as to the shapes of the graphs compared to Comparative Example 2-1 and Comparative Example 2-2, indicating that the change in the structure of the solid electrolyte was slight. - In order to observe a change in the ion conductivity of LPS depending on a solvent, LPS was dispersed in solvents ACN, DMC, TOL, and XYL according to Examples and Comparative Examples, and the ion conductivity of LPS in a pristine state was also measured. At this time, SEBS was used as a binder.
- Example 3-1: TOL+LPS+SEBS
- Example 3-2: XYL+LPS+SEBS
- Comparative Example 3-1: ACN+LPS+SEBS
- Comparative Example 3-2: DMC+LPS+SEBS
- Comparative Example 3-3: Pristine+LPS+SEBS
- In order to measure impedance, a solid electrolyte sample having a predetermined area A and a thickness t, like a cylindrical shape, was prepared. The diameter of the sample was 1 cm, and the thickness of the sample was 0.055 mm. A film including about 7 mg of LPS was introduced, and then measurement was performed.
- Platinum or copper electrodes having high electric conductivity, as ion blocking electrodes, were formed on opposite surfaces of a flat sample through dry deposition.
- Alternating-current voltage was applied through the electrodes on the opposite surfaces of the sample. At this time, as application conditions, the amplitude of the voltage was set to 30 mV, which was an amplitude used to measure the impedance of a secondary battery using a general liquid electrolyte, and the measurement frequency range was set to a range of 0.1 Hz to 1 MHz.
- The resistance Rb of the bulk electrolyte was calculated from an intersection point at which a semicircle of the measured impedance track joins an actual axis, and the ion conductivity σ of LPS was calculated from the area A and the thickness t (or l) of the sample, as expressed by the following equation.
-
- The impedance measurement results related thereto are shown in
FIG. 3 .FIG. 3 shows the impedance measurement values, wherein the X axis indicates the resistance value and the Y axis indicates a reactance value. The ion conductivity values (Ωcm)−1 of LPS depending on the solvent based on the measurement results are as follows. The value right next to each solvent indicates the dielectric constant of the solvent. - Comparative Example 3-3 Pristine: 1.20×10−3(Ωcm)−1
- Example 3-2 XYL (2.3): 1.19×10−3 (Ωcm)−1
- Example 3-1 TOL (2.4): 1.12×10−3 (Ωcm)−1
- Comparative Example 3-2 DMC(3.1): 1.11×10−5(Ωcm)−1
- Comparative Example 3-1 ACN(35.7): 7.4×10-?(Ωcm)−1
- It can be seen that, in the case of Comparative Example 3-2, the ion conductivity value was 1.11×10−5(Ωcm)−1 when the dielectric constant was 3.1, and in the case of Example 3-1, i.e. toluene (dielectric constant 2.4), the ion conductivity value was 1.12×10−3(Ωcm)−1. Since the value of the ion conductivity is changed in the unit thereof as the value of the dielectric constant is reduced, it can be estimated that the value of the ion conductivity is changed approximately according to a logarithmic scale. Consequently, it can be seen from the comparison results that the dielectric constant of the solvent suitable to achieve the object of the present invention must be less than 3.1, preferably 3.0 or less, and more preferably less than 3.0. Meanwhile, since the value of the ion conductivity increases as the value of the dielectric constant decreases, a solvent having a small dielectric constant is advantageous; however, the dielectric constant must be greater than 1, since the dielectric constant is a value relative to the permittivity of a vacuum. Preferably, therefore, the dielectric constant of the solvent suitable to achieve the object of the present invention ranges from more than 1 to less than 3.1. It can be seen from the comparison experiment that the binder suitable to achieve the object of the present invention is a polymer including only C and H.
- Meanwhile, the dielectric constant is changed depending on the temperature. In order to evaluate the effects related thereto, therefore, the ion conductivity was measured using a method identical to the method used in Experimental Example 3 but while changing the temperature. Xylene, heptane, and hexane were used as ion solvents, and SEBS was used as a binder. As can be seen from the following table, the ion conductivity was higher as the dielectric constant was lower.
-
TABLE 2 Dielectric SSE Solvent Polymer σ @ RT/S cm−1 constant Example Li7P3S11 Xylene SEBS 0.6 × 10−3 2.2 3-2 Example Li6PS5Cl Heptane SEBS 0.8 × 10−3 1.9 3-3 Example Li6PS5Cl Hexane SEBS 1.2 × 10−3 1.89 3-4 -
FIG. 4 shows changes in ion conductivity depending on the time and solvent. It can be seen that the ion conductivity value at normal temperature was the lowest and that the ion conductivity increased as the temperature increased. This phenomenon was particularly prominent for hexane, the dielectric constant of which was low. Consequently, it can be seen that, since the temperature of a battery becomes higher than normal temperature as the battery is operated, it is more advantageous to use a solvent having a low dielectric constant. - In order to evaluate the stability of the solid electrolyte layer according to the present invention, Li plating and stripping evaluation was performed on Example 3-2.
- Electrochemical evaluation was performed under conditions of 0.11 mA/cm2 10 h charging, 10 h discharging, and 200 μm. About 40 mg of a solid electrolyte film was used. In addition, an Li metal was disposed on opposite surfaces of the solid electrolyte layer. The film was manufactured so as to have a diameter of 1.3 cm.
FIG. 5 is an SEM photograph related thereto, andFIG. 6 shows the result of evaluation of (potential) stability based on long-term operation. -
FIG. 5(a) is a general SEM photograph, which shows the thickness of the solid electrolyte film. -
FIG. 5(b) is a P EDX image, which shows the solid electrolyte film. -
FIG. 5(c) is an S EDX image, which shows the solid electrolyte film. -
FIG. 5(d) is an actual photograph showing the flexible state of the solid electrolyte film. - It can be seen from
FIG. 6 that the all-solid-state battery according to the present invention is stable for 2000 hours or more. - As is apparent from the above description, the solid electrolyte according to the present invention has excellent lifespan characteristics that ensure stability for a long time while maintaining high ion conductivity even in the state in which the solid electrolyte is thin.
Claims (10)
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