WO2023136502A1 - 전고체 전지용 전극의 제조방법 및 이에 의해 제조된 전극 - Google Patents
전고체 전지용 전극의 제조방법 및 이에 의해 제조된 전극 Download PDFInfo
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- WO2023136502A1 WO2023136502A1 PCT/KR2022/021074 KR2022021074W WO2023136502A1 WO 2023136502 A1 WO2023136502 A1 WO 2023136502A1 KR 2022021074 W KR2022021074 W KR 2022021074W WO 2023136502 A1 WO2023136502 A1 WO 2023136502A1
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- granules
- solid
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- solid electrolyte
- state battery
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- 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
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- 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
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- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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Definitions
- the present invention relates to a method for manufacturing an electrode for an all-solid-state battery and an electrode manufactured thereby. Specifically, the present invention relates to a method for manufacturing an electrode for an all-solid-state battery using secondary granules formed from primary granules by a mechanofusion method and an electrode manufactured thereby.
- a metal-air battery with a very large theoretical capacity in terms of capacity compared to lithium secondary batteries, an all-solid-state battery with no risk of explosion in terms of safety, and a super capacitor in terms of output (supercapacitor), NaS battery or RFB (redox flow battery) in terms of large size, thin film battery (thin film battery) in terms of miniaturization, etc. are continuously being researched in academia and industry.
- the all-solid-state battery refers to a battery in which the liquid electrolyte used in conventional lithium secondary batteries is replaced with a solid one, and since no flammable solvent is used in the battery, ignition or explosion due to the decomposition reaction of the conventional electrolyte does not occur at all. Safety can be greatly improved.
- Li metal or Li alloy can be used as a negative electrode material, there is an advantage in that the energy density for the mass and volume of the battery can be dramatically improved.
- inorganic solid electrolytes can be classified into sulfide-based and oxide-based solid electrolytes.
- the most developed solid electrolyte is a sulfide-based solid electrolyte, and the ion conductivity of this solid electrolyte has been developed even to a material having an ion conductivity close to that of organic electrolyte.
- the all-solid-state battery uses a solid electrolyte unlike conventional lithium secondary batteries that use a liquid electrolyte, problems such as physical contact may occur because the solid electrolyte cannot easily penetrate into the pores of the electrode.
- a method of preparing granules containing an active material to secure pores outside the granules and then injecting a liquid solid electrolyte into the pores and then solidifying them has been studied.
- additional problems such as the formation of a non-uniform surface layer due to the decrease in fluidity of the granules when rolling at a high temperature to form an electrode layer occurred.
- the present inventors completed the present invention after researching a method for solving the physical contact problem between the solid electrolyte and the granules containing the active material in the manufacture of an electrode for an all-solid-state battery.
- Patent Document 1 Republic of Korea Patent Publication No. 10-2016-0146737
- an electrode for an all-solid-state battery In order to improve the performance of an electrode for an all-solid-state battery, it is intended to provide a method for manufacturing an electrode for an all-solid-state battery using secondary granules formed from primary granules by a mechanofusion method and an electrode manufactured thereby.
- a method for manufacturing an electrode for an all-solid-state battery comprising the step of preparing an electrode by applying secondary granules on a current collector is provided.
- the primary granules have an average particle diameter (D 50 ) of 50 ⁇ m to 110 ⁇ m.
- the secondary granules have an average particle diameter (D 50 ) of 10 ⁇ m to 30 ⁇ m.
- the primary granule has a porosity of 55% to 75%.
- the active material is a cathode active material
- the solid electrolyte is a sulfide-based solid electrolyte
- the sulfide-based solid electrolyte is Li 2 SP 2 S 5 , Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 OP 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-LiCl-P 2 S 5 , Li 2 S-Li 2 OP 2 S 5 , Li 2 S-Li 3 PO 4 -P 2 S 5 , Li 2 SP 2 S 5 -P 2 O 5 , Li 2 SP 2 S 5 -SiS 2 , Li 2 SP 2 S 5 -SnS, Li 2 SP 2 S 5 -Al 2 S 3 , Li 2 S- GeS 2 , Li 2 S-GeS 2 -ZnS, and combinations thereof.
- the primary granules include 85% to 99.8% by weight of an active material, 0.1% to 10% by weight of a binder, and 0.1% to 10% by weight based on the total weight of the primary granules. It includes a first conductive material of.
- the secondary granules include 5% by weight to 25% by weight of the solid electrolyte based on the total weight of the secondary granules.
- the secondary granules have a porosity of 5% to 25%.
- the secondary granules are applied to a thickness of 100 ⁇ m to 300 ⁇ m on the current collector.
- An electrode for an all-solid-state battery including a current collector and a granular layer formed on the current collector is provided.
- the granular layer is composed of a plurality of granules, and the granules include an active material, a conductive material, and a binder, and are coated with a solid electrolyte.
- the granules have an average particle diameter (D 50 ) of 10 ⁇ m to 30 ⁇ m.
- the solid electrolyte is included in the granules in an amount of 5% to 25% by weight based on the total weight of the granules.
- primary particles having a large average particle size are prepared, and then a solid electrolyte is mixed with the prepared primary particles to form 1 through a mechanofusion method.
- the solid electrolyte can be more densely and uniformly coated on the secondary particles to be actually applied on the current collector.
- FIG. 1 is a view schematically showing a process in which secondary granules are formed from primary granules according to one embodiment of the present invention.
- One aspect of the present invention is to provide a method for manufacturing an electrode for an all-solid-state battery by applying granules containing an active material on a current collector.
- a method for manufacturing an electrode for an all-solid-state battery includes the steps of preparing primary granules containing an active material, a conductive material and a binder, mixing the prepared primary granules with a solid electrolyte in a mechanofusion method. preparing secondary granules coated with a solid electrolyte, and preparing an electrode by applying the prepared secondary granules on a current collector.
- the primary granules and the secondary granules may be classified according to the stage in which they are produced, but may also be classified according to physical characteristics such as particle size, and specific physical characteristics will be described later.
- Primary granules are prepared by aggregating the active material, the conductive material, and the binder.
- the primary granule may be prepared by a method commonly used in the art, and is not particularly limited.
- the primary granules may be prepared by spray drying after preparing a slurry.
- the active material which is a fine particle in a powder state, is injected into a binder solution together with a conductive material to grow the size of the granule to a specific level.
- the primary granule is a spherical particle containing an active material, a conductive material and a binder.
- a spherical shape does not mean a perfect sphere in a strict sense, and is generally used as a comprehensive concept including round particles.
- the primary granules have an average particle diameter (D 50 ) of 50 ⁇ m to 110 ⁇ m.
- the average diameter (D 50 ) is the particle diameter (median diameter) at 50% cumulative volume based particle size distribution, and the cumulative value is 50% in the cumulative curve where the particle size distribution is obtained on a volume basis and the total volume is 100%. Means the particle diameter of a point.
- the average diameter (D 50 ) may be measured by a laser diffraction method.
- the average diameter (D 50 ) of the primary granules is 50 ⁇ m or more, 55 ⁇ m or more, 60 ⁇ m or more, 65 ⁇ m or more, 70 ⁇ m or more, and 110 ⁇ m or less, 105 ⁇ m or less, 100 ⁇ m or less, or 95 ⁇ m. Or less, 90 ⁇ m or less, and may be 50 ⁇ m to 110 ⁇ m, 60 ⁇ m to 100 ⁇ m, and 70 ⁇ m to 90 ⁇ m.
- the average diameter (D 50 ) of these primary granules is adjusted in consideration of the particle size of the secondary granules prepared by mixing the primary granules and the solid electrolyte and then treating them with a mechanofusion method.
- the primary granule has a porosity of 55% to 75%.
- the porosity of the granules means the volume ratio of voids in the granules, and the porosity can be measured, for example, by a BET (Brunauer-Emmett-Teller) measurement method or a mercury permeation method (Hg porosimeter), but is not limited thereto. .
- the porosity can be calculated using other parameters such as size, thickness and density. In an all-solid-state battery, it is important that the granules containing the active material form an electrical network with the solid electrolyte.
- the porosity of the primary granule is not the final shape to be applied on the current collector, the porosity has a significant effect on the shape of the secondary granule.
- the porosity of the primary granule is 55% or more, 56% or more, 57% or more, 58% or more, 59% or more, 60% or more, 75% or less, 74% or less, 73% or less, 72% or less , 71% or less, 70% or less, and may be 55% to 75%, 57% to 72%, or 60% to 70%.
- the primary granules are easy to form secondary granules of an appropriate shape by the mechanofusion method.
- An electrode for an all-solid-state battery may be any one of a negative electrode and a positive electrode, and more specifically, the electrode for an all-solid-state battery may be a positive electrode.
- the electrode active material included in the primary granules is not particularly limited as long as it can be used as an anode active material for a lithium ion secondary battery.
- the negative electrode active material carbon such as non-graphitizable carbon and graphite-based carbon; Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me' y O z (Me:Mn,Fe,Pb,Ge; Me' : Metal composite oxides such as Al, B, P, Si, elements of groups 1, 2, and 3 of the periodic table, halogens, 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3;1 ⁇ z ⁇ 8); lithium metal; lithium alloy; silicon-based alloys; tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4
- the electrode active material included in the primary granule is not particularly limited as long as it can be used as a positive electrode active material for a lithium ion secondary battery.
- a lithium transition metal oxide containing at least one transition metal may be used as the cathode active material.
- the conductive material included in the primary granules is not particularly limited as long as it is located in the granules and can impart conductivity between the active material and the electrolyte.
- nickel powder, cobalt oxide, titanium oxide, carbon, etc. may be used as the conductive material, and as the carbon, any one selected from the group consisting of ketjen black, acetylene black, furnace black, graphite, carbon fiber, and fullerene One or more than one of these can be mentioned.
- the binder included in the primary granules is mixed with the active material and the conductive material, which are fine particles in a powder state, and binds each component to help the growth of the particles.
- the binder is an organic binder.
- the organic binder refers to a binder that is dissolved or dispersed in an organic solvent, particularly N-methylpyrrolidone (NMP), and is distinguished from an aqueous binder that uses water as a solvent or dispersion medium.
- the organic binder is polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, starch, hydroxypropyl cellulose, regenerated cellulose It may be selected from the group consisting of woods, polyvinylpyrrolidone, polyimide, polyamideimide, polyethylene, polypropylene, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butyrene rubber and fluoro rubber, It is not limited to this.
- the active material in the primary granule is 85% to 99.8% by weight, specifically 88% to 99.5% by weight, more specifically 90% to 99.3% by weight
- the binder is 0.1% by weight % to 10% by weight, specifically 0.2% to 8% by weight, more specifically 0.3% to 7% by weight
- the conductive material is 0.1% to 10% by weight, specifically 0.2% to 8% by weight, more specifically 0.3% to 7% by weight.
- the prepared primary granules are mixed with a solid electrolyte to prepare secondary granules coated with a solid electrolyte by a mechanofusion method.
- 1 schematically shows a process in which secondary granules are formed from primary granules.
- the solid electrolyte 20 is coated on the collapsed primary granule 10 to form the secondary granule 2.
- the solid electrolyte may be coated on at least a part or all of the surface of the collapsed primary granules.
- the solid electrolyte may use at least one species selected from a polymer-based solid electrolyte, a sulfide-based solid electrolyte, and an oxide-based solid electrolyte.
- the polymer-based solid electrolyte is a polymer solid electrolyte formed by adding a polymer resin to a solvated lithium salt, or a polymer gel containing an organic electrolyte solution containing an organic solvent and a lithium salt, an ionic liquid, a monomer or an oligomer, and the like in a polymer resin. may be an electrolyte.
- the lithium salt is an ionizable lithium salt and can be expressed as Li + X - .
- the anion of the lithium salt is not particularly limited, but F - , Cl - , Br - , I - , NO 3 - , N(CN) 2 - , BF 4 - , ClO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3
- the solid electrolyte is a sulfide-based solid electrolyte.
- the sulfide-based solid electrolyte contains sulfur (S) and has ionic conductivity of a metal belonging to group 1 or group 2 of the periodic table, and may include Li-PS-based glass or Li-PS-based glass ceramic.
- Non-limiting examples of such sulfide-based solid electrolytes are Li 2 SP 2 S 5 , Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 OP 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-LiCl-P 2 S 5 , Li 2 S-Li 2 OP 2 S 5 , Li 2 S-Li 3 PO 4 -P 2 S 5 , Li 2 SP 2 S 5 -P 2 O 5 , Li 2 SP 2 S 5 -SiS 2 , Li 2 SP 2 S 5 -SnS, Li 2 SP 2 S 5 -Al 2 S 3 , Li 2 S-GeS 2 , Li 2 S-GeS 2 -ZnS, etc. and may include one or more of them.
- a method of coating the solid electrolyte on the granules containing the active material various methods commonly used in the art may be used, but mechanochemical bonding may be formed to increase the bonding strength between the solid electrolyte coating layer and the granules. Any coating method can be used.
- a mechanofusion method capable of applying high shear force during coating is used as a method of coating the solid electrolyte on the granules.
- the mechanofusion method basically applies a high shear force to the granules, and depending on the physical properties of the granules, the shape of the granules may be deformed or collapsed.
- the primary granules according to one embodiment of the present invention have a larger particle size than the secondary granules coated on the actual current collector and have larger pores, so that the structure can be more easily collapsed by the mechanofusion method.
- the mechanofusion method may be performed for 5 minutes to 20 minutes at a rotation speed of 1000 rpm to 5000 rpm.
- the rotation speed may be 1000 rpm to 5000 rpm, 1500 rpm to 4500 rpm, 2000 rpm to 4000 rpm, or 2500 rpm to 3500 rpm
- the running time may be 5 minutes to 20 minutes, 8 minutes to 17 minutes, or 10 minutes to 15 minutes.
- the secondary granules have an average particle diameter (D 50 ) of 10 ⁇ m to 30 ⁇ m.
- the average diameter (D 50 ) of the secondary granules is measured in the same way as for the primary granules.
- the average diameter (D 50 ) of the secondary granules is 10 ⁇ m or more, 11 ⁇ m or more, 12 ⁇ m or more, 13 ⁇ m or more, 14 ⁇ m or more, 15 ⁇ m or more, 16 ⁇ m or more, 30 ⁇ m or less, 29 ⁇ m or more Or less, 28 ⁇ m or less, 27 ⁇ m or less, 26 ⁇ m or less, 25 ⁇ m or less, 24 ⁇ m or less, and may be 10 ⁇ m to 30 ⁇ m, 13 ⁇ m to 27 ⁇ m, or 16 ⁇ m to 24 ⁇ m.
- the secondary granules have a porosity of 5% to 25%.
- the porosity of the secondary granules is measured in the same way as for the primary granules. Specifically, the porosity of the secondary granule is 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 25% or less, 24% or less, 23% or less, 22% or less , 21% or less, 20% or less, and may be 5% to 25%, 7% to 22%, or 10% to 20%.
- the secondary granules are formed by collapsing the primary granules and coated with a solid electrolyte, they have a lower porosity than the primary granules. Within the porosity range, the secondary granules may form an appropriate level of electrical network between the solid electrolyte and the active material.
- the secondary granules include 5% by weight to 25% by weight of the solid electrolyte based on the total weight of the secondary granules.
- the content of the solid electrolyte is 5% by weight or more, 6% by weight or more, 7% by weight or more, 8% by weight or more, 9% by weight or more, 10% by weight or more, 25% by weight or less, 24% by weight or less, 23 wt% or less, 22 wt% or less, 21 wt% or less, 20 wt% or less, and may be 5 wt% to 25 wt%, 7 wt% to 22 wt%, or 10 wt% to 20 wt%.
- the content of the solid electrolyte may be increased in that the solid electrolyte can be sufficiently supplied between the pores of the granules, but evenly throughout the surface of the granules. In that the solid electrolyte can be coated, the content of the solid electrolyte can be reduced.
- An electrode for an all-solid-state battery is prepared by loading the prepared secondary granules on a current collector to form a granular layer in the form of a sheet.
- the current collector exhibits electrical conductivity such as a metal plate, and an electrode known in the art may be appropriately used according to the polarity of the battery.
- the secondary granules constituting the granular layer are individually coated with a solid electrolyte, a sufficient electrical network can be formed between the granules constituting the granular layer.
- the above-described electrical network may be supplemented by impregnating a solid electrolyte into the voids between the granular layers and drying them. Using the same kind of solid electrolyte as the coating layer may contribute to improving battery performance by reducing resistance in the battery and the like as the additionally supplemented solid electrolyte.
- the secondary granules are applied to a thickness of 100 ⁇ m to 300 ⁇ m on the current collector.
- the electrode active material layer has a thickness of 100 ⁇ m to 300 ⁇ m.
- the electrode active material layer means a layer in the form of a sheet applied on the current collector excluding the current collector when the current collector is used in the manufacture of the electrode, and the electrode active material layer is formed between the granules as necessary along with the above-described granules.
- the thickness of the electrode active material layer is 100 ⁇ m or more, 110 ⁇ m or more, 120 ⁇ m or more, 130 ⁇ m or more, 140 ⁇ m or more, 150 ⁇ m or more, and 300 ⁇ m or less, 290 ⁇ m or less, 280 ⁇ m or less, or 270 ⁇ m or less.
- 260 ⁇ m or less, 250 ⁇ m or less and may be 100 ⁇ m to 300 ⁇ m, 120 ⁇ m to 270 ⁇ m, or 150 ⁇ m to 250 ⁇ m.
- the thickness of the electrode active material layer is less than the above range, the loading amount of the active material is reduced, so that battery performance may not be improved significantly. may not be evident.
- the porosity of the granular layer formed by applying the secondary granules on the current collector is 30% to 60%.
- the granular layer means a region formed by granules applied on the current collector, and means the same layer as the electrode active material layer in which no additional solid electrolyte is introduced in addition to the secondary granules.
- the porosity of the granular layer is measured in the same way as for the primary or secondary granules.
- the porosity of the granular layer is 30% or more, 31% or more, 32% or more, 33% or more, 34% or more, 35% or more, 60% or less, 59% or less, 58% or less, 57% or less, 56 % or less, 55% or less, and may be 30% to 60%, 32% to 57%, or 35% to 55%. If necessary, an additional solid electrolyte may be introduced into the pores of the granular layer.
- an all-solid-state battery including the above-described all-solid-state battery electrode as a positive electrode and/or a negative electrode is provided.
- a separate solid electrolyte layer may be introduced between the positive electrode and the negative electrode in addition to the solid electrolyte included in the electrode, and this solid electrolyte layer plays the same role as a separator in a general lithium secondary battery. can do.
- the above-described electrode may be used as a semi-solid battery by being used together with a liquid electrolyte in some cases. In this case, a separate polymer separator may be further required.
- the polymer separator is interposed between the negative electrode and the positive electrode, and serves to electrically insulate the negative electrode and the positive electrode while allowing lithium ions to pass through.
- the polymer separator may be used as long as it is used as a polymer separator membrane used in a general all-solid-state battery field, and is not particularly limited.
- a battery module including the all-solid-state battery as a unit cell, a battery pack including the battery module, and a device including the battery pack as a power source are provided.
- the device include a power tool powered by an electric motor and moving; electric vehicles, including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooters); electric golf carts; A power storage system and the like may be mentioned, but is not limited thereto.
- electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like
- electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooters)
- electric golf carts A power storage system and the like may be mentioned, but is not limited thereto.
- active material After preparing a slurry by mixing in a weight ratio of conductive material: binder), primary granules (porosity: about 65%) having an average diameter of about 80 ⁇ m (D 50 ) were prepared by spray drying.
- Mechanofusion device manufactured: Hosokawa Micron, product: Nobilta NOB-130
- Mechanofusion device was driven at 3,000 rpm for 10 minutes with the primary granules prepared with Li 2 SP 2 S 5 as a sulfide-based solid electrolyte
- Secondary granules having an average diameter of about 20 ⁇ m (D 50 ) coated with about 15% by weight of the solid electrolyte were prepared.
- the average diameter (D 50 ) was measured using a particle analyzer (manufacturer: Malvern, product name: Mastersizer), and the porosity was measured using a mercury porosity analyzer (manufacturer: Micromeritics, product name: Autopore).
- the prepared secondary granules on an aluminum current collector of about 100 ⁇ m, it was rolled with a roll to prepare a cathode having a thickness of about 300 ⁇ m.
- the granular layer has a porosity of about 45%.
- a slurry was prepared by mixing Li 2 S-LiCl-P 2 S 5 with a polyvinylidene fluoride (PVDF) solution (a solution in which PVDF and toluene were mixed in a weight ratio of 8:92), and then dried to obtain a thickness of about 50 ⁇ m.
- PVDF polyvinylidene fluoride
- a thick solid electrolyte membrane was prepared.
- a lithium foil (Li foil) having a thickness of about 100 ⁇ m was used as the negative electrode.
- An electrode assembly was prepared by laminating and compressing the positive electrode, the solid electrolyte membrane, and the negative electrode, and then placed inside a battery case to prepare an all-solid-state battery.
- An all-solid-state battery was manufactured in the same manner as in Example 1, except that primary granules having an average diameter (D 50 ) of about 150 ⁇ m were prepared and used.
- An all-solid-state battery was manufactured in the same manner as in Example 1, except that primary granules having an average diameter (D 50 ) of about 20 ⁇ m were prepared and used when preparing the positive electrode.
- an all-solid-state battery was prepared in the same manner as in Example 1, except that a simple mechanical mixing device (manufacturer: Red Devil, product: Classic Shaker 1400, condition: 60Hz, 60 minutes) was used instead of the mechanofusion device. manufactured.
- the average diameters (D 50 ) of the primary and secondary granules prepared in Example 1 and Comparative Examples 1 to 3 are shown in Table 1 below.
- Example 2 in the case of Example 1, the primary particles are broken into secondary particles of an appropriate size by strong shear force according to the mechanofusion method, and the solid electrolyte is thinly and uniformly coated on the surface of the broken secondary particles. It became. Accordingly, the all-solid-state battery of Example 1 exhibited high discharge capacity and high coulombic efficiency.
- Comparative Example 2 the size of the primary particles including the active material, the conductive material, and the binder is too small, and when a strong shear force is applied according to the mechanofusion method, the conductive material and the binder are separated and coated with a solid electrolyte. did Since this may act as resistance in utilizing the active material, the all-solid-state battery of Comparative Example 2 did not exhibit a discharge capacity and coulombic efficiency as high as that of Example 1.
- Comparative Example 3 even though the mechanical mixing method is used, it is possible to form secondary particles of an appropriate size similarly to Example 1, but a detailed analysis of the particle surface shows that the surface of the secondary particle is not coated with a thin and uniform solid electrolyte. and was coated in an island form with uneven aggregation. Accordingly, the all-solid-state battery of Comparative Example 3 did not exhibit a discharge capacity and coulombic efficiency as high as that of Example 1 because the active material and the solid electrolyte did not electrically contact properly.
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Abstract
Description
1차 입자의 평균 직경 (D50, ㎛) |
2차 입자의 평균 직경 (D50, ㎛) |
|
실시예 1 | 80 | 20 |
비교예 1 | 150 | 70 |
비교예 2 | 20 | 10 |
비교예 3 | 80 | 25 |
방전 용량(mAh/g) | 쿨롱 효율(%) | |
실시예 1 | 180.1 | 91.2 |
비교예 1 | 82.5 | 72.5 |
비교예 2 | 111.4 | 65.0 |
비교예 3 | 124.8 | 73.8 |
Claims (11)
- (1) 활물질, 도전재 및 바인더를 포함하는 1차 과립을 제조하는 단계;(2) 제조된 1차 과립을 고체 전해질과 혼합하여 메카노퓨전법에 의해 고체 전해질이 코팅된 2차 과립을 제조하는 단계; 및(3) 제조된 2차 과립을 집전체 상에 도포하여 전극을 제조하는 단계;를 포함하는 전고체 전지용 전극의 제조방법.
- 청구항 1에 있어서,상기 1차 과립은 입자의 평균 직경(D50)이 50㎛ 내지 110㎛인 것을 특징으로 하는 전고체 전지용 전극의 제조방법.
- 청구항 1에 있어서,상기 2차 과립은 입자의 평균 직경(D50)이 10㎛ 내지 30㎛인 것을 특징으로 하는 전고체 전지용 전극의 제조방법.
- 청구항 1에 있어서,상기 1차 과립은 55% 내지 75%의 공극률을 가지는 것을 특징으로 하는 전고체 전지용 전극의 제조방법.
- 청구항 1에 있어서,상기 활물질은 양극 활물질이며,상기 양극 활물질은 LiCoO2, LiNiO2, LiMnO2, Li2MnO3, LiMn2O4, Li(NiaCobMnc)O2(0<a<1, 0<b<1, 0<c<1, a+b+c=1), LiNi1-yCoyO2(O<y<1), LiCo1-yMnyO2, LiNi1-yMnyO2(O<y<1), Li(NiaCobMnc)O4(0<a<2, 0<b<2, 0<c<2, a+b+c=2), LiMn2-zNizO4(0<z<2), LiMn2-zCozO4(0<z<2) 및 이의 조합으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 전고체 전지용 전극의 제조방법.
- 청구항 1에 있어서,상기 고체 전해질은 황화물계 고체 전해질이며,상기 황화물계 고체 전해질은 Li2S-P2S5, Li2S-LiI-P2S5, Li2S-LiI-Li2O-P2S5, Li2S-LiBr-P2S5, Li2S-LiCl-P2S5, Li2S-Li2O-P2S5, Li2S-Li3PO4-P2S5, Li2S-P2S5-P2O5, Li2S-P2S5-SiS2, Li2S-P2S5-SnS, Li2S-P2S5-Al2S3, Li2S-GeS2, Li2S-GeS2-ZnS 및 이의 조합으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 전고체 전지용 전극의 제조방법.
- 청구항 1에 있어서,상기 1차 과립은 1차 과립의 총 중량을 기준으로 85 중량% 내지 99.8 중량%의 활물질, 0.1 중량% 내지 10 중량%의 바인더 및 0.1 중량% 내지 10 중량%의 제1 도전재를 포함하는 것을 특징으로 하는 전고체 전지용 전극의 제조방법.
- 청구항 1에 있어서,상기 2차 과립은 2차 과립의 총 중량을 기준으로 5 중량% 내지 25 중량%의 고체 전해질을 포함하는 것을 특징으로 하는 전고체 전지용 전극의 제조방법.
- 청구항 1에 있어서,상기 2차 과립은 5% 내지 25%의 공극률을 가지는 것을 특징으로 하는 전고체 전지용 전극의 제조방법.
- 청구항 1에 있어서,상기 2차 과립은 집전체 상에 100㎛ 내지 300㎛의 두께로 도포되는 것을 특징으로 하는 전고체 전지용 전극의 제조방법.
- 집전체, 및 상기 집전체 상에 형성된 과립층을 포함하는 전고체 전지용 전극으로서,상기 과립층은 복수의 과립에 의해 구성되며,상기 과립은 활물질, 도전재 및 바인더를 포함하고, 고체 전해질로 코팅된 형태이며,상기 과립은 입자의 평균 직경(D50)이 10㎛ 내지 30㎛이고,상기 고체 전해질은 과립의 총 중량을 기준으로 5 중량% 내지 25 중량%가 과립에 포함되는 전고체 전지용 전극.
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US18/282,494 US20240154083A1 (en) | 2022-01-12 | 2022-12-22 | Method for manufacturing electrode for all-solid-state battery, and electrode manufactured thereby |
JP2023567210A JP2024516028A (ja) | 2022-01-12 | 2022-12-22 | 全固体電池用電極の製造方法及びこれによって製造された電極 |
CN202280021981.0A CN117063303A (zh) | 2022-01-12 | 2022-12-22 | 全固态电池用电极的制造方法及由其制造的电极 |
EP22920830.1A EP4293738A1 (en) | 2022-01-12 | 2022-12-22 | Method for manufacturing electrode for all-solid-state battery, and electrode manufactured thereby |
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KR1020220004645A KR20230108922A (ko) | 2022-01-12 | 2022-01-12 | 전고체 전지용 전극의 제조방법 및 이에 의해 제조된 전극 |
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JP2005026191A (ja) * | 2003-07-03 | 2005-01-27 | Tdk Corp | 電極及び電気化学素子並びに電極の製造方法及び電気化学素子の製造方法 |
KR20130107352A (ko) * | 2011-01-26 | 2013-10-01 | 도요타 지도샤(주) | 고체 전지용 전극 |
JP2016024916A (ja) * | 2014-07-17 | 2016-02-08 | トヨタ自動車株式会社 | 全固体電池用電極及びその製造方法 |
KR20160146737A (ko) | 2014-04-28 | 2016-12-21 | 니폰 제온 가부시키가이샤 | 전기 화학 소자 전극용 복합 입자의 제조 방법 |
KR20190134537A (ko) * | 2018-05-25 | 2019-12-04 | 주식회사 엘지화학 | 음극 활물질용 복합 입자 및 이를 포함하는 전고체 전지용 음극 |
KR20200060370A (ko) * | 2017-09-29 | 2020-05-29 | 니폰 제온 가부시키가이샤 | 전고체 이차 전지 전극용 복합 입자 및 그 제조 방법, 전고체 이차 전지용 전극, 그리고, 전고체 이차 전지 |
KR20220004645A (ko) | 2019-03-27 | 2022-01-11 | 주노 다이어그노스틱스, 인크. | 최적화된 초저 부피 액체 생검 방법, 시스템 및 장치 |
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2022
- 2022-01-12 KR KR1020220004645A patent/KR20230108922A/ko active Search and Examination
- 2022-12-22 CN CN202280021981.0A patent/CN117063303A/zh active Pending
- 2022-12-22 JP JP2023567210A patent/JP2024516028A/ja active Pending
- 2022-12-22 WO PCT/KR2022/021074 patent/WO2023136502A1/ko active Application Filing
- 2022-12-22 US US18/282,494 patent/US20240154083A1/en active Pending
- 2022-12-22 EP EP22920830.1A patent/EP4293738A1/en active Pending
Patent Citations (7)
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JP2005026191A (ja) * | 2003-07-03 | 2005-01-27 | Tdk Corp | 電極及び電気化学素子並びに電極の製造方法及び電気化学素子の製造方法 |
KR20130107352A (ko) * | 2011-01-26 | 2013-10-01 | 도요타 지도샤(주) | 고체 전지용 전극 |
KR20160146737A (ko) | 2014-04-28 | 2016-12-21 | 니폰 제온 가부시키가이샤 | 전기 화학 소자 전극용 복합 입자의 제조 방법 |
JP2016024916A (ja) * | 2014-07-17 | 2016-02-08 | トヨタ自動車株式会社 | 全固体電池用電極及びその製造方法 |
KR20200060370A (ko) * | 2017-09-29 | 2020-05-29 | 니폰 제온 가부시키가이샤 | 전고체 이차 전지 전극용 복합 입자 및 그 제조 방법, 전고체 이차 전지용 전극, 그리고, 전고체 이차 전지 |
KR20190134537A (ko) * | 2018-05-25 | 2019-12-04 | 주식회사 엘지화학 | 음극 활물질용 복합 입자 및 이를 포함하는 전고체 전지용 음극 |
KR20220004645A (ko) | 2019-03-27 | 2022-01-11 | 주노 다이어그노스틱스, 인크. | 최적화된 초저 부피 액체 생검 방법, 시스템 및 장치 |
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EP4293738A1 (en) | 2023-12-20 |
JP2024516028A (ja) | 2024-04-11 |
US20240154083A1 (en) | 2024-05-09 |
KR20230108922A (ko) | 2023-07-19 |
CN117063303A (zh) | 2023-11-14 |
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