WO2023153715A1 - 리튬 이차 전지용 음극의 전리튬화 방법, 음극 중간체 및 음극을 포함하는 리튬 이차 전지 - Google Patents
리튬 이차 전지용 음극의 전리튬화 방법, 음극 중간체 및 음극을 포함하는 리튬 이차 전지 Download PDFInfo
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- WO2023153715A1 WO2023153715A1 PCT/KR2023/001515 KR2023001515W WO2023153715A1 WO 2023153715 A1 WO2023153715 A1 WO 2023153715A1 KR 2023001515 W KR2023001515 W KR 2023001515W WO 2023153715 A1 WO2023153715 A1 WO 2023153715A1
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- WIPO (PCT)
- Prior art keywords
- negative electrode
- active material
- layer
- lithium metal
- secondary battery
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present application relates to a lithium secondary battery including a prelithiation method of a negative electrode for a lithium secondary battery, an anode intermediate, and a negative electrode.
- a secondary battery is a representative example of an electrochemical device using such electrochemical energy, and its use area is gradually expanding.
- lithium secondary batteries having high energy density and voltage, long cycle life, and low self-discharge rate have been commercialized and widely used.
- an electrode for such a high-capacity lithium secondary battery research is being actively conducted on a method for manufacturing a high-density electrode having a higher energy density per unit volume.
- a secondary battery is composed of an anode, a cathode, an electrolyte, and a separator.
- the negative electrode includes a negative electrode active material for intercalating and deintercalating lithium ions from the positive electrode, and silicon-based particles having a high discharge capacity may be used as the negative electrode active material.
- a carbon material such as graphite is used as an anode of a lithium secondary battery, but the theoretical capacity density of carbon is 372 mAh/g (833 mAh/cm 3 ). Therefore, in order to improve the energy density of the negative electrode, silicon (Si), tin (Sn) alloyed with lithium, oxides and alloys thereof, and the like are reviewed as negative electrode materials. Among them, silicon-based materials have attracted attention due to their low price and high capacity (4200 mAh/g).
- a method of prelithiation of a silicon anode including a silicon-based anode active material is known.
- a prelithiation method a method of manufacturing an electrode after lithiation by physical/chemical methods such as electrolytic plating, lithium metal transfer, and lithium metal deposition, and a method of electrochemically prelithiation of a negative electrode are known.
- a transfer method of lithium metal during the pre-lithiation process is being considered, and research on a method of safely and easily transferring lithium metal is in progress.
- the transfer process of the lithium metal is carried out according to the R2R lamination process, and when the mass production process of the negative electrode is applied, the negative electrode is manufactured in a wide width and is cut and used according to the purpose.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2009-080971
- the present application is intended to provide a lithium secondary battery including a pre-lithiation method of a negative electrode for a lithium secondary battery, a negative electrode intermediate, and a negative electrode.
- An exemplary embodiment of the present specification includes forming a negative electrode current collector layer and a negative electrode active material layer on one or both surfaces of the negative electrode current collector layer; And transferring lithium metal on the negative electrode active material layer; in the pre-lithiation method of a negative electrode for a lithium secondary battery comprising the step of transferring the lithium metal, the step of pre-treating one surface of the substrate layer in the form of a pattern; forming a transfer laminate by sequentially stacking a release layer and lithium metal on the pretreated one surface of the substrate layer; laminating the transfer laminate on the negative electrode active material layer so that the opposite surface of the surface of the lithium metal in contact with the release layer is in contact with the opposite surface of the negative electrode active material layer in contact with the negative electrode current collector layer; and removing the base layer, wherein the lithium metal and the negative electrode active material layer satisfy Equation 1 below.
- X means the width of the lithium metal
- X1 means the width of the negative electrode active material layer.
- a negative electrode current collector layer comprising an anode active material layer formed on one or both surfaces of the anode current collector layer;
- a negative electrode intermediate comprising a; transfer laminate formed on the opposite surface of the negative electrode active material layer in contact with the negative electrode current collector layer, wherein the transfer laminate has a structure in which a substrate layer, a release layer, and lithium metal are sequentially stacked.
- One side of the substrate layer in contact with the release layer includes a pattern-shaped pretreatment, and the lithium metal and the negative electrode active material layer satisfy Formula 1 above to provide an anode intermediate.
- a cathode for a lithium secondary battery A negative electrode for a lithium secondary battery pre-lithiated according to the method of the present application; a separator provided between the anode and the cathode; And an electrolyte; to provide a lithium secondary battery comprising a.
- the surface of the substrate layer in contact with the release layer is pretreated in the form of a pattern (corona or plasma treatment), so that the transfer power of the substrate layer can be controlled, thereby forming a pattern.
- a pattern corona or plasma treatment
- the adhesive strength between the pretreated surface and the release layer is increased, and when the substrate layer is removed, the release layer and lithium metal are removed together, so lithium in a desired capacity and size. It has the characteristic of being able to transfer metal to the upper part of the negative electrode active material layer.
- the pre-lithiation method of a negative electrode for a lithium secondary battery uses a lithium metal transfer process, specifically satisfies the range of Equation 1, and the width of the transferred lithium metal is transferred together. It is smaller than the width of the release layer, so that the substrate layer of the transfer laminate can be easily removed during lithium metal transfer. That is, problems related to transfer power, such as reverse transfer, in the conventional lithium metal transfer process have been solved through physical width control as described above.
- the width of the transferred lithium metal is smaller than the width of the release layer transferred together, and the release layer is transferred to the negative electrode together, so that highly reactive lithium metal is not exposed to the atmosphere, so that it can block the atmosphere and function as a protective layer. have possible characteristics.
- FIG. 1 is a diagram illustrating a process of transferring lithium metal to a negative electrode for a lithium secondary battery according to an exemplary embodiment of the present application.
- FIG. 2 is a diagram showing an anode intermediate according to an exemplary embodiment of the present application.
- FIG. 3 is a diagram showing a laminated structure of a lithium secondary battery according to an exemplary embodiment of the present application.
- Example 4 is a diagram showing a transfer laminate according to Example 1 of the present application.
- FIG. 6 is a diagram showing the result of transferring lithium metal to the top of the negative electrode according to Comparative Example 3 of the present application.
- Example 7 is a diagram showing the result of transferring lithium metal to the top of the negative electrode according to Example 1 of the present application.
- 'p to q' means a range of 'p or more and q or less'.
- specific surface area is measured by the BET method, and is specifically calculated from the nitrogen gas adsorption amount under liquid nitrogen temperature (77K) using BELSORP-mino II of BEL Japan. That is, in the present application, the BET specific surface area may mean the specific surface area measured by the above measuring method.
- Dn means a particle size distribution, and means a particle size at the n% point of the cumulative distribution of the number of particles according to the particle size. That is, D50 is the particle diameter (average particle diameter, central particle diameter) at the 50% point of the cumulative distribution of the number of particles according to the particle size, D90 is the particle size at the 90% point of the cumulative distribution of the number of particles according to the particle size, and D10 is the particle size according to the particle size It is the particle diameter at the 10% point of the particle number cumulative distribution. Meanwhile, the particle size distribution can be measured using a laser diffraction method.
- a commercially available laser diffraction particle size measuring device e.g. Microtrac S3500
- a commercially available laser diffraction particle size measuring device e.g. Microtrac S3500
- a polymer includes a certain monomer as a monomer unit means that the monomer participates in a polymerization reaction and is included as a repeating unit in the polymer.
- this is interpreted as the same as that the polymer includes a monomer as a monomer unit.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured using a commercially available monodisperse polystyrene polymer (standard sample) of various degrees of polymerization for molecular weight measurement as a standard material, and gel permeation chromatography (Gel Permeation It is the molecular weight in terms of polystyrene measured by chromatography; GPC).
- molecular weight means a weight average molecular weight unless otherwise specified.
- An exemplary embodiment of the present specification includes forming a negative electrode current collector layer and a negative electrode active material layer on one or both surfaces of the negative electrode current collector layer; And transferring lithium metal on the negative electrode active material layer; in the pre-lithiation method of a negative electrode for a lithium secondary battery comprising the step of transferring the lithium metal, the step of pre-treating one surface of the substrate layer in the form of a pattern; forming a transfer laminate by sequentially stacking a release layer and lithium metal on the pretreated one surface of the substrate layer; laminating the transfer laminate on the negative electrode active material layer so that the opposite surface of the surface of the lithium metal in contact with the release layer is in contact with the opposite surface of the negative electrode active material layer in contact with the negative electrode current collector layer; and removing the base layer, wherein the lithium metal and the negative electrode active material layer satisfy Equation 1 below.
- X means the width of the lithium metal
- X1 means the width of the negative electrode active material layer.
- FIG. 1 is a diagram illustrating a process of transferring lithium metal to a negative electrode for a lithium secondary battery according to an exemplary embodiment of the present application. Specifically, transfer lamination in which the substrate layer 10, the release layer 35, and the lithium metal 20 are sequentially stacked on the anode 200 for a lithium secondary battery formed of the anode current collector layer 40 and the anode active material layer 30 After laminating the body 100, the process of removing the base layer 10 of the transfer laminate 100 can be confirmed.
- the release layer 35 and the lithium metal 20 are formed, and accordingly, the release force of the surface of the substrate layer subjected to corona or plasma treatment in the form of a pattern is lowered, thereby reducing the lithium metal It has a feature that can be patterned and transferred into a desired shape.
- the pre-lithiation method of the negative electrode for a lithium secondary battery according to the present application satisfies the range of Equation 1, and has excellent characteristics in terms of stability of the lithium metal transfer process. That is, when outside the range of Equation 1, after lithium metal transfer, lithium metal in a region larger than the negative active material layer comes off together and adheres to the negative active material layer, and lithium residue is separated in the form of particles in the assembly process, which is a post-process. From a safety point of view, it is very dangerous.
- the pre-lithiation method of a negative electrode for a lithium secondary battery may include forming an anode current collector layer and an anode active material layer on one or both surfaces of the anode current collector layer.
- the negative current collector layer generally has a thickness of 1 ⁇ m to 100 ⁇ m.
- Such an anode current collector layer is not particularly limited as long as it does not cause chemical change in the battery and has high conductivity.
- a surface treated with carbon, nickel, titanium, silver, or the like, an aluminum-cadmium alloy, or the like may be used.
- fine irregularities may be formed on the surface to enhance the bonding strength of the negative active material, and may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and nonwoven fabrics.
- the width of the negative electrode current collector layer may be greater than or equal to the width of the negative electrode active material layer.
- the negative electrode current collector layer may have a thickness of 1 ⁇ m or more and 100 ⁇ m or less, and the negative electrode active material layer may have a thickness of 20 ⁇ m or more and 500 ⁇ m or less.
- the thickness may be variously modified depending on the type and purpose of the negative electrode used, but is not limited thereto.
- a method of manufacturing a negative electrode for a lithium secondary battery according to an exemplary embodiment of the present application includes forming a negative electrode for a lithium secondary battery by forming a negative electrode current collector layer and a negative electrode active material layer on one or both surfaces of the negative electrode current collector layer.
- the step of forming the negative electrode current collector layer and the negative electrode active material layer on one side or both sides of the negative electrode current collector layer is to apply the negative electrode slurry including the negative electrode active material layer composition to one side or both sides of the negative electrode current collector layer. and coating both surfaces, wherein the negative electrode active material layer composition includes a silicon-based active material; cathode conductive material; And a negative electrode binder; provides a method for pre-lithiation of a negative electrode for a lithium secondary battery comprising at least one selected from the group consisting of.
- the negative electrode slurry is a negative electrode active material layer composition
- a slurry solvent may include.
- the solid content of the negative electrode slurry may satisfy 5% or more and 40% or less.
- the solid content of the negative electrode slurry may satisfy a range of 5% or more and 40% or less, preferably 7% or more and 35% or less, and more preferably 10% or more and 30% or less.
- the solids content of the negative electrode slurry may refer to the content of the negative active material layer composition included in the negative electrode slurry, and may refer to the content of the negative active material composition based on 100 parts by weight of the negative electrode slurry.
- the negative active material layer When the solids content of the negative electrode slurry satisfies the above range, the negative active material layer has an appropriate viscosity during formation of the negative active material layer, thereby minimizing particle aggregation of the negative active material layer composition, thereby enabling efficient formation of the negative active material layer.
- the slurry solvent is not limited thereto as long as it can dissolve the negative electrode active material layer composition, but specifically includes acetone; Distilled water; Alternatively, NMP may be used.
- a negative electrode according to an exemplary embodiment of the present application may be formed by coating and drying the negative electrode slurry on a negative electrode current collector layer.
- the slurry solvent in the negative electrode slurry may be dried, and then an electrode rolling step may be further included.
- the negative active material layer composition may include a silicon-based active material; cathode conductive material; And negative electrode binder; may include one or more selected from the group consisting of.
- the silicon-based active material may use pure silicon (Si) as the silicon-based active material.
- lithium released from the positive electrode is inserted into the negative electrode during charging, and is desorbed from the negative electrode during discharge and returns to the positive electrode.
- volume change and surface side reactions are severe, A large amount of lithium inserted into the negative electrode does not return to the positive electrode, and thus the initial irreversible capacity increases. When the initial irreversible capacity increases, the battery capacity and cycle rapidly decrease.
- the negative electrode of the lithium secondary battery is prelithiated to solve the initial irreversible capacity problem.
- the prelithiation process when the lithium transfer process is performed, lithium metal It relates to a process in which lithium is easily transferred from a transfer laminate and uniformly prelithiated in a negative electrode active material layer.
- a binder in order to solve the problem of maintaining a conductive path according to volume expansion and maintaining the combination of a conductive material, a binder, and an active material while using only a silicon-based active material as an anode active material to improve capacity performance, a binder under specific conditions and Existing problems have been solved by using a conductive material composite bonded to a binder.
- the average particle diameter (D50) of the silicon-based active material of the present invention may be 5 ⁇ m to 10 ⁇ m, specifically 5.5 ⁇ m to 8 ⁇ m, and more specifically 6 ⁇ m to 7 ⁇ m.
- the average particle diameter is within the above range, the viscosity of the negative electrode slurry is formed within an appropriate range, including the specific surface area of the particles within a suitable range. Accordingly, the dispersion of the particles constituting the negative electrode slurry becomes smooth.
- the contact area between the silicon particles and the conductive material is excellent due to the composite made of the conductive material and the binder in the negative electrode slurry, so that the possibility of continuing the conductive network increases, thereby increasing the capacity retention rate is increased.
- the average particle diameter satisfies the above range, excessively large silicon particles are excluded to form a smooth surface of the negative electrode, thereby preventing current density non-uniformity during charging and discharging.
- the silicon-based active material generally has a characteristic BET surface area.
- the BET surface area of the silicon-based active material is preferably 0.01 m 2 /g to 150.0 m 2 /g, more preferably 0.1 m 2 /g to 100.0 m 2 /g, particularly preferably 0.2 m 2 /g to 80.0 m 2 /g, most preferably from 0.2 m 2 /g to 18.0 m 2 /g.
- the BET surface area is measured according to DIN 66131 (using nitrogen).
- the silicon-based active material may exist, for example, in a crystalline or amorphous form, and is preferably not porous.
- the silicon particles are preferably spherical or fragment-shaped particles. Alternatively but less preferably, the silicon particles may also have a fibrous structure or be present in the form of a silicon-comprising film or coating.
- the silicon-based active material may be 60 parts by weight or more based on 100 parts by weight of the negative electrode active material layer composition.
- the silicon-based active material may include 60 parts by weight or more, preferably 65 parts by weight or more, more preferably 70 parts by weight or more based on 100 parts by weight of the negative electrode active material layer composition, and 95 parts by weight part or less, preferably 90 parts by weight or less, more preferably 80 parts by weight or less.
- the negative electrode composition according to the present application uses a specific conductive material and a binder capable of controlling the volume expansion rate during charging and discharging even when a silicon-based active material having a significantly high capacity is used in the above range, and the performance of the negative electrode even includes the above range It does not degrade and has excellent output characteristics in charging and discharging.
- the silicon-based active material may have a non-spherical shape and its sphericity is, for example, 0.9 or less, for example, 0.7 to 0.9, for example 0.8 to 0.9, for example 0.85 to 0.9 am.
- the circularity (circularity) is determined by the following formula A-1, A is an area, P is a boundary line.
- the negative electrode conductive material is a dotted conductive material; linear conductive material; And it may include one or more selected from the group consisting of planar conductive material.
- the dotted conductive material may be used to improve the conductivity of the negative electrode, and refers to a conductive material having conductivity without causing chemical change.
- the point-shaped conductive material is natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, channel black, farnes black, lamp black, thermal black, conductive fiber, fluorocarbon, aluminum powder, nickel powder, zinc oxide, It may be at least one selected from the group consisting of potassium titanate, titanium oxide, and polyphenylene derivatives, and may preferably include carbon black in terms of high conductivity and excellent dispersibility.
- the point-shaped conductive material may have a BET specific surface area of 40 m 2 /g or more and 70 m 2 /g or less, preferably 45 m 2 /g or more and 65 m 2 /g or less, more preferably 50 m 2 /g or less . /g or more and 60 m 2 /g or less.
- the particle diameter of the dotted conductive material may be 10 nm to 100 nm, preferably 20 nm to 90 nm, and more preferably 40 nm to 60 nm.
- the negative electrode conductive material may include a planar conductive material.
- the planar conductive material may improve conductivity by increasing surface contact between silicon particles in the negative electrode, and at the same time suppress the disconnection of the conductive path due to volume expansion, and may serve as a bulk conductive material or a plate-shaped conductive material. used as an inclusive concept.
- the planar conductive material may include at least one selected from the group consisting of plate-like graphite, graphene, graphene oxide, and graphite flakes, and preferably may be plate-like graphite.
- the average particle diameter (D50) of the planar conductive material may be 2 ⁇ m to 7 ⁇ m, specifically 3 ⁇ m to 6 ⁇ m, and more specifically 4 ⁇ m to 5 ⁇ m. .
- D50 average particle diameter
- the planar conductive material provides a negative active material layer composition in which D10 is 0.5 ⁇ m or more and 1.5 ⁇ m or less, D50 is 2.5 ⁇ m or more and 3.5 ⁇ m or less, and D90 is 7.0 ⁇ m or more and 15.0 ⁇ m or less. .
- the planar conductive material is a high specific surface area planar conductive material having a high BET specific surface area; Alternatively, a planar conductive material having a low specific surface area may be used.
- the planar conductive material includes a high specific surface area planar conductive material;
- a planar conductive material with a low specific surface area can be used without limitation, but in particular, the planar conductive material according to the present application can be affected to some extent in the electrode performance by the dispersion effect, so that a planar conductive material with a low specific surface area that does not cause a problem in dispersion is used. may be particularly desirable.
- the planar conductive material may have a BET specific surface area of 5 m 2 /g or more.
- the planar conductive material may have a BET specific surface area of 5 m 2 /g or more and 500 m 2 /g or less, preferably 5 m 2 /g or more and 300 m 2 /g or less, more preferably 5 m 2 /g or more. g or more and 300 m 2 /g or less.
- the planar conductive material is a high specific surface area planar conductive material, and the BET specific surface area is 50 m 2 /g or more and 500 m 2 /g or less, preferably 80 m 2 /g or more and 300 m 2 /g or less, more preferably Preferably, a range of 100 m 2 /g or more and 300 m 2 /g or less may be satisfied.
- the planar conductive material is a planar conductive material with a low specific surface area, and the BET specific surface area is 5 m 2 /g or more and 40 m 2 /g or less, preferably 5 m 2 /g or more and 30 m 2 /g or less, more preferably Preferably, a range of 5 m 2 /g or more and 25 m 2 /g or less may be satisfied.
- Other negative electrode conductive materials may include linear conductive materials such as carbon nanotubes.
- the carbon nanotubes may be bundled carbon nanotubes.
- the bundled carbon nanotubes may include a plurality of carbon nanotube units.
- the term 'bundle type' herein means, unless otherwise specified, a bundle in which a plurality of carbon nanotube units are arranged side by side or entangled in substantially the same orientation with axes in the longitudinal direction of the carbon nanotube units. It refers to a secondary shape in the form of a bundle or rope.
- the carbon nanotube unit has a graphite sheet having a cylindrical shape with a nano-sized diameter and an sp2 bonding structure.
- the characteristics of a conductor or a semiconductor may be exhibited according to the angle and structure of the graphite surface being rolled.
- the bundled carbon nanotubes can be uniformly dispersed during manufacturing of the negative electrode, and the conductivity of the negative electrode can be improved by smoothly forming a conductive network in the negative electrode.
- the negative electrode conductive material may be 10 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the negative electrode active material layer composition.
- the negative electrode conductive material is 10 parts by weight or more and 40 parts by weight or less, preferably 10 parts by weight or more and 30 parts by weight or less, more preferably 15 parts by weight or more based on 100 parts by weight of the negative electrode active material layer composition. 25 parts by weight or less.
- the negative electrode conductive material according to the present application has a completely different configuration from the conductive material applied to the positive electrode. That is, in the case of the anode conductive material according to the present application, it serves to hold the contact between silicon-based active materials whose volume expansion of the electrode is very large due to charging and discharging. As a role of imparting, its composition and role are completely different from those of the negative electrode conductive material of the present invention.
- the negative electrode conductive material according to the present application is applied to a silicon-based active material, and has a completely different configuration from that of a conductive material applied to a graphite-based active material. That is, since the conductive material used in the electrode having the graphite-based active material simply has smaller particles than the active material, it has characteristics of improving output characteristics and imparting some conductivity, unlike the negative electrode conductive material applied together with the silicon-based active material as in the present invention. Their composition and role are completely different.
- the planar conductive material used as the negative electrode conductive material described above has a different structure and role from the carbon-based active material generally used as the negative electrode active material.
- the carbon-based active material used as the negative electrode active material may be artificial graphite or natural graphite, and refers to a material processed into a spherical or dotted shape to facilitate storage and release of lithium ions.
- the planar conductive material used as the negative electrode conductive material is a material having a planar or plate-shaped shape, and may be expressed as plate-shaped graphite. That is, as a material included to maintain a conductive path in the negative active material layer, it means a material used to secure a conductive path in a planar shape inside the negative active material layer, rather than playing a role in storing and releasing lithium.
- plate-like graphite is used as a conductive material means that it is processed into a planar or plate-like shape and used as a material that secures a conductive path rather than a role of storing or releasing lithium.
- the negative active material included together has high capacity characteristics for storing and releasing lithium, and serves to store and release all lithium ions transferred from the positive electrode.
- a carbon-based active material as an active material means that it is processed into a point shape or sphere and used as a material that stores or releases lithium.
- artificial graphite or natural graphite which is a carbon-based active material, may satisfy a BET specific surface area of 0.1 m 2 /g or more and 4.5 m 2 /g or less.
- the plate-like graphite which is a planar conductive material, may have a planar BET specific surface area of 5 m 2 /g or more.
- the negative electrode binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride, polyacrylonitrile, Polymethylmethacrylate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene -Selected from the group consisting of propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, and materials in which hydrogen is substituted with Li, Na or Ca, etc. It may include at least one that is, and may also include various copolymers thereof.
- PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
- the binder according to an exemplary embodiment of the present application serves to hold the negative electrode active material and the negative electrode conductive material in order to prevent distortion and structural deformation of the negative electrode structure in volume expansion and relaxation of the silicon-based active material.
- All general anode binders may be applied, specifically, a water-based binder may be used, and more specifically, a PAM-based binder may be used.
- the negative electrode binder may include 30 parts by weight or less, preferably 25 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the negative electrode active material layer composition, and 5 parts by weight part or more, and may include 10 parts by weight or more.
- the step of transferring lithium metal on the negative electrode active material layer may include a pre-lithiation method of a negative electrode for a lithium secondary battery comprising a.
- the prelithiation process is to chemically or physically prelithiate lithium metal on the negative electrode, and specifically, it may be carried out by a lithium metal transfer process, a lithium metal powder deposition, an electrochemical/chemical process, or a lithium metal deposition process,
- the prelithiation process according to the present application may include a lithium metal transfer process.
- the lithium metal transfer process highly reactive lithium metal can be more stably transferred to the upper portion of the negative electrode active material layer.
- a process for easily transferring lithium metal from the transfer laminate to the upper portion of the negative electrode active material layer is required, and the prelithiation method according to the present application is characterized in that a release layer is formed to improve the transfer power. .
- the step of transferring the lithium metal includes pre-treating one surface of the substrate layer in a pattern form; forming a transfer laminate by sequentially stacking a release layer and lithium metal on the pretreated one surface of the substrate layer; laminating the transfer laminate on the negative electrode active material layer so that the opposite surface of the surface of the lithium metal in contact with the release layer is in contact with the opposite surface of the negative electrode active material layer in contact with the negative electrode current collector layer; and removing the base layer.
- the step of transferring the lithium metal includes pre-treating one surface of the substrate layer in a pattern form.
- the shape of the pattern is not limited and can be used without limitation depending on the desired size of lithium metal, and a mesh pattern, a honeycomb pattern, and the like can be used without limitation.
- the pre-lithiation method is characterized in that the substrate layer can be patterned and transferred by increasing the release force through corona or plasma treatment in the form of a pattern in advance.
- the pretreatment step includes a step of corona or plasma treatment, and the adhesive force of the pretreated surface with respect to the surface in contact with the base layer and the release layer is at least 4B of the cross-cut evaluation criterion, and the untreated Provided is a method for prelithiation of an anode for a lithium secondary battery having a surface adhesion of 1B or less, a cross-cut evaluation criterion.
- the cross-cut test can be measured by preparing a transfer laminate in which a substrate layer, a release layer, and a lithium metal layer are sequentially stacked, and conducting a cross-cut test according to ASTM3359. Specifically, 5B (0% peeling ), 4B (less than 5% peeling), 3B (5% to 15% peeling), 2B (15% to 35% peeling), 1B (35% to 65% peeling), 0B (65% or more peeling) can be measured
- the plasma treatment may generate plasma with a combination of nitrogen (N 2 ), air, argon (Ar), and oxygen gas (O 2 ), specifically, a gas containing oxygen Plasma, which is an ionized gas, can be generated by injecting into the facility and applying power. For example, if a voltage of 300 kW is applied while injecting N 2 300 LPM (liter per minute) and Air 10 LPM together, plasma is generated in the plasma facility, and the base layer is passed through this part to pattern the base layer to form plasma. can handle
- the adhesive strength of the pretreated surface with respect to the surface where the base layer and the release layer come into contact may be 200 gf/inch or more, preferably 250 gf/inch or more.
- the adhesive force of the non-pretreated surface with respect to the surface in contact with the base layer and the release layer may be 100 gf / inch or less, preferably 80 gf / inch or less.
- the lithium metal can be patterned and transferred to the upper portion of the negative electrode active material layer through the pretreatment process of the substrate layer as described above, in the process of cutting the negative electrode for a desired use. Problems such as fire do not occur, and it has the characteristics of obtaining a pre-lithiated negative electrode to a desired degree.
- the deposition method for depositing the lithium metal on the substrate layer includes evaporation deposition, chemical vapor deposition, chemical vapor deposition (CVD), and It may be selected from physical vapor deposition, but is not limited thereto, and various deposition methods used in the art may be used.
- a lamination process may be performed through roll pressing by applying a load of 5 kgf/cm to 500 kgf/cm to the lithium secondary battery electrode on which the transfer laminate is stacked. Thereafter, a process of removing the substrate layer is included, and during removal, the release layer and lithium metal stacked on the pretreated substrate layer may be removed together.
- the release layer is transferred to the negative electrode together, so that highly reactive lithium metal is not exposed to the air, so that it can block the atmosphere and function as a protective layer.
- the base layer can withstand process conditions such as high temperature in the step of depositing lithium metal, and during a winding process for transferring the deposited lithium metal, lithium metal is deposited on the base layer. It can be used without limitation as long as it has characteristics that can prevent the problem of reverse peeling transferred to.
- the base layer is polyethylene terephthalate (PET), polyimide (polyimide, PI), poly(methylmethacrylate), PMMA), polypropylene ( Polypropylene), polyethylene (Polyethylene) and polycarbonate (Polycarbonate) may be at least one selected from the group consisting of.
- the thickness of the base layer may be 1 ⁇ m or more and 300 ⁇ m or less, and may satisfy a range of 5 ⁇ m or more and 200 ⁇ m or less, 10 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the lithium metal may be 1 ⁇ m or more and 10 ⁇ m or less, preferably 3 ⁇ m or more and 10 ⁇ m or less.
- the transfer of the lithium metal to the negative electrode active material layer can occur efficiently and reverse transfer can be prevented.
- the base layer and lithium of the transfer laminate Provided is a method for prelithiation of a negative electrode for a lithium secondary battery, further comprising a release layer on a surface in contact with a metal.
- the base layer may have a release layer formed on at least one side, and may have a release layer formed on both sides. Due to the release layer, it is possible to prevent a reverse peeling problem in which the lithium metal is transferred onto the substrate layer during the winding process for transferring the deposited lithium metal to the negative electrode, and also, after the lithium metal is transferred onto the negative electrode active material layer, the substrate The layers can be easily separated.
- the release layer includes at least one selected from the group consisting of silicon-modified polyester in which a silicon chain is graft-bonded to a polyester main chain, an acrylic resin, Si, melamine, and fluorine All lithium of a negative electrode for a lithium secondary battery provides a way to
- the release layer may be formed by a coating method, for example, the coating method includes dip coating, spray coating, spin coating, and die coating. It may be a method selected from the group consisting of die coating, gravure coating, micro-gravure coating, comma coating, and roll coating, but is limited thereto It is not, and various coating methods that can be used to form a coating layer in the art can be used.
- the coating method includes dip coating, spray coating, spin coating, and die coating. It may be a method selected from the group consisting of die coating, gravure coating, micro-gravure coating, comma coating, and roll coating, but is limited thereto It is not, and various coating methods that can be used to form a coating layer in the art can be used.
- a prelithiation process may proceed from the step of depositing and transferring the lithium metal on the negative electrode active material layer, which will be referred to as a prelithiation reaction due to the high reactivity of the lithium metal before the activation process.
- activating the transferred lithium metal may be included.
- the step of activating the lithium metal provides a method of prelithiation of a negative electrode for a lithium secondary battery in which an activation reaction occurs within 30 minutes to 3 hours under conditions of 25 ° C. and 1 atm.
- the activation step is a step of setting a condition for diffusing lithium metal into the negative electrode active material layer, and whether or not pre-lithiation is completed can be determined by whether or not lithium on top of the metal layer has completely disappeared.
- the activation reaction time may be 30 minutes to 3 hours, preferably 1 hour to 2 hours.
- a method for prelithiation of a negative electrode for a lithium secondary battery in which the width of the release layer satisfies Equation 2 below.
- Equation 2 X means the width of the lithium metal, and Y means the width of the negative current collector layer.
- the pre-lithiation method of the negative electrode according to the present application may be characterized in that it can transfer the patterned lithium metal as described above and additionally satisfies Equation 2 above.
- a method for pre-lithiation of a negative electrode for a lithium secondary battery uses a lithium metal transfer process.
- the width of the transferred lithium metal is smaller than the width of the release layer to be transferred together, It has a feature that the substrate layer of the transfer laminate can be easily removed. That is, problems related to transfer power, such as reverse transfer, in the conventional lithium metal transfer process have been solved through physical width control as described above.
- the width of the transferred lithium metal is smaller than the width of the release layer transferred together, and the release layer is transferred to the negative electrode together, so that highly reactive lithium metal is not exposed to the atmosphere, so that it can block the atmosphere and function as a protective layer. have possible characteristics.
- the width of the above-described release layer, the width of the lithium metal, the width of the negative electrode active material layer, and the width of the negative electrode current collector layer are each in a direction perpendicular to the direction (MD, Machine Direction) of the R2R process. It may mean the width of (TD, Transverse direction). Specifically, it may mean a width in a direction perpendicular to the direction in which the R2R process proceeds.
- the range of Equation 2 can be confirmed, and it can be seen that the width of the release layer 35 is formed larger than the width of the lithium metal 20, and accordingly, during lithium metal transfer, the transfer laminate It has a feature that the base layer can be easily removed. That is, problems related to transfer power, such as reverse transfer in the existing lithium metal transfer process, can be solved by adjusting the physical width as described above.
- the negative current collector layer an anode active material layer formed on one or both surfaces of the anode current collector layer;
- a negative electrode intermediate comprising a; transfer laminate formed on the opposite surface of the negative electrode active material layer in contact with the negative electrode current collector layer, wherein the transfer laminate has a structure in which a substrate layer, a release layer, and lithium metal are sequentially stacked.
- One side of the substrate layer in contact with the release layer includes a pattern-shaped pretreatment, and the lithium metal and the negative electrode active material layer satisfy the following formula 1.
- X means the width of the lithium metal
- X1 means the width of the negative electrode active material layer.
- a positive electrode for a lithium secondary battery A negative electrode for a lithium secondary battery pre-lithiated according to the method of the present application; a separator provided between the anode and the cathode; And electrolyte solution; it provides a lithium secondary battery comprising a.
- FIG. 3 is a diagram showing a laminated structure of a lithium secondary battery according to an exemplary embodiment of the present application.
- the negative electrode 200 for a lithium secondary battery including the negative electrode active material layer 30 on one surface of the negative electrode current collector layer 40 can be confirmed.
- the width of the negative electrode current collector layer 40 may be larger than the width of the negative electrode active material layer 30, but this is not shown in FIG. 3.
- the cathode 300 for a lithium secondary battery including the cathode active material layer 70 on one side of the cathode current collector layer 60 can be confirmed, and the anode 200 for a lithium secondary battery and the cathode 100 for a lithium secondary battery are a separator film. It indicates that it is formed in a laminated structure with (50) interposed therebetween.
- the release layer 35 used during pre-lithiation may be completely removed depending on the electrolyte solution used, and accordingly, it does not remain on the upper portion of the cathode, thereby preventing an unnecessary increase in resistance. That is, the release layer improves transfer power, can also be used to protect lithium metal before pre-lithiation, and can be removed after injection of the electrolyte.
- the electrolyte may include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte that can be used in manufacturing a lithium secondary battery, It is not limited to these.
- the electrolyte solution may include a non-aqueous organic solvent and a metal salt.
- non-aqueous organic solvent for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyllolactone, 1,2-dimethine Toxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxorane, formamide, dimethylformamide, dioxorane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid Triester, trimethoxy methane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, propionic acid
- An aprotic organic solvent such as ethyl may be used.
- ethylene carbonate and propylene carbonate which are cyclic carbonates
- an electrolyte having high electrical conductivity can be made and can be used more preferably.
- the metal salt may be a lithium salt, and the lithium salt is a material that is easily soluble in the non-aqueous electrolyte.
- the anion of the lithium salt is F - , Cl - , 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 - , CF3CF2(CF3)2CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3 C -
- the electrolyte solution includes, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides for the purpose of improving battery life characteristics, suppressing battery capacity decrease, and improving battery discharge capacity.
- haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides
- Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imida
- One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be further included.
- One embodiment of the present invention provides a battery module including the lithium secondary battery as a unit cell and a battery pack including the same. Since the battery module and the battery pack include the secondary battery having high capacity, high rate and cycle characteristics, a medium or large-sized device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system can be used as a power source for
- a polyethylene terephthalate base layer was prepared. Thereafter, a voltage of 15Kv was applied to the plasma generating unit for the base layer, N 2 (800 slm) and CDA (5 slm) were flowed to generate plasma, and the base layer was passed through at a rate of 5 lpm to clean the surface of the base layer. Patterned and plasma treated.
- a laminate I One Film Co. coated with an acrylic resin at a level of 1 ⁇ m as a release layer was laminated on top of the base layer.
- a transfer laminate was prepared by depositing lithium metal on the release layer of the laminate by thermal evaporation to form a lithium metal layer having a thickness of 6 ⁇ m.
- the deposition device was ULVAC's EWK-050, and the deposition process was performed by setting the speed to 2.5 m/min, the temperature of the lithium supply unit to 500 °C, and the temperature of the main roll to -25 °C.
- Si average particle diameter (D50): 3.5 ⁇ m
- denka black as a conductive material
- SBR as a binder
- CMC as a thickener
- the conductive material, binder, thickener, and water were dispersed at 2500 rpm for 30 min using a homo mixer, and then an active material was added and then dispersed at 2500 rpm for 30 min to prepare a slurry.
- both sides of a copper current collector were coated with the negative electrode slurry at a loading amount of 85 mg/25 cm 2 , rolled, and dried in a vacuum oven at 130° C. for 10 hours to obtain a negative electrode
- An active material layer (thickness: 33 ⁇ m) was formed and used as a negative electrode (thickness of negative electrode: 41 ⁇ m, porosity of negative electrode 40.0%).
- the lithium metal of the transfer laminate was placed on the negative active material layer, and then roll pressing was performed while applying a load of 200 kgf/cm.
- the temperature was set at 80° C., and the PET layer of the transfer laminate was removed immediately after lamination, and the negative electrode was pre-lithiated.
- the negative electrode was cut along the patterned line to obtain a target negative electrode.
- the width (X) of the lithium metal was 20 mm
- the width (X1) of the negative electrode active material layer was 20 mm
- the width of the release layer was 30 mm
- the width (Y) of the negative electrode current collector layer was 40 mm.
- Example 4 is a diagram showing a transfer laminate according to Example 1 of the present application. Specifically, after the transfer process, it was confirmed that the lithium metal and the release layer on the non-plasma treated surface were transferred onto the negative electrode active material layer, and it was confirmed that the lithium metal on the plasma-treated surface remained intact.
- Example 7 is a diagram showing the result of transferring lithium metal to the top of the negative electrode according to Example 1 of the present application. As can be seen in FIG. 7, it was confirmed that the range of Equation 1 of the present application was satisfied, and lithium in the edge portion was not desorbed together, so that it was excellent in terms of safety in the subsequent process.
- the width (X) of the lithium metal is 20 mm
- the width (X1) of the negative electrode active material layer is 25 mm
- the width of the release layer is 30 mm
- the width (Y) of the negative electrode current collector layer is It was prepared in the same manner as in Example 1 except that 40 mm was manufactured satisfactorily.
- Example 1 In the preparation of Example 1, the width (X) of the lithium metal is 20 mm, the width (X1) of the negative electrode active material layer is 20 mm, the width of the release layer is 20 mm, and the width (Y) of the negative electrode current collector layer is It was prepared in the same manner as in Example 1 except that 20 mm was manufactured satisfactorily.
- the surface of the substrate layer in contact with the release layer is pretreated in the form of a pattern (corona or plasma treatment), It was confirmed that the transfer force of the substrate layer can be adjusted, and the release force of the surface treated with corona or plasma in a pattern form is lowered to have a feature that can be patterned and transferred to lithium metal in a desired form.
- the stability of the process was improved by satisfying the range of Equation 1.
- the adhesive strength between the pretreated surface and the release layer is increased, and when the base layer is removed, the release layer and lithium metal are removed together, so that lithium metal is prepared in a desired capacity and size. It can be transferred to the upper part of the negative electrode active material layer, so it was confirmed that a negative electrode having a desired use and capacity can be manufactured by cutting a portion where lithium metal is not transferred later.
- the pre-lithiation method of a negative electrode for a lithium secondary battery uses a lithium metal transfer process, specifically, the width of the transferred lithium metal is smaller than the width of the release layer transferred together, and the lithium metal During transfer, the substrate layer of the transfer laminate could be easily removed, and the width of the transferred lithium metal was smaller than the width of the release layer transferred together, and the release layer was transferred to the negative electrode together to form highly reactive lithium metal. It was confirmed by comparing Example 1 and Example 3 that it had the characteristic of being able to function as an air barrier and a protective layer without being exposed to the atmosphere.
- a polyethylene terephthalate base layer was prepared. Thereafter, a voltage of 15 kV is applied to the substrate layer to the plasma generating unit, N 2 (800 slm) and CDA (5 slm) are flowed to generate plasma, and the substrate layer is passed through at a rate of 5 lpm to the entire surface of the substrate layer. was plasma treated.
- a laminate I One Film Co. coated with an acrylic resin at a level of 1 ⁇ m as a release layer was laminated on top of the base layer.
- a transfer laminate was prepared by depositing lithium metal on the release layer of the laminate by thermal evaporation to form a lithium metal layer having a thickness of 6 ⁇ m.
- the deposition device was ULVAC's EWK-050, and the deposition process was performed by setting the speed to 2.5 m/min, the temperature of the lithium supply unit to 500 °C, and the temperature of the main roll to -25 °C.
- Si average particle diameter (D50): 3.5 ⁇ m
- denka black as a conductive material
- SBR as a binder
- CMC as a thickener
- the conductive material, binder, thickener, and water were dispersed at 2500 rpm for 30 min using a homo mixer, and then an active material was added and then dispersed at 2500 rpm for 30 min to prepare a slurry.
- both sides of a copper current collector were coated with the negative electrode slurry at a loading amount of 85 mg/25 cm 2 , rolled, and dried in a vacuum oven at 130° C. for 10 hours to obtain a negative electrode
- An active material layer (thickness: 33 ⁇ m) was formed and used as a negative electrode (thickness of negative electrode: 41 ⁇ m, porosity of negative electrode 40.0%).
- the lithium metal of the transfer laminate was placed on the negative active material layer, and then roll pressing was performed while applying a load of 200 kgf/cm.
- the temperature was set to 80 ° C., and the PET layer of the transfer laminate was removed immediately after lamination, but the adhesion between the release layer and the substrate layer was strong, so that lithium metal was not transferred to the negative electrode active material layer, so prelithiation did not proceed smoothly.
- FIG. 5 is a diagram showing a transfer laminate according to Comparative Example 1 of the present application. Specifically, it was confirmed that the entire surface of the substrate layer was treated with plasma so that the lithium metal remained and thus the lithium metal was not transferred to the upper portion of the negative electrode active material layer.
- a laminate (I One Film Co.) coated with an acrylic resin at a level of 1 ⁇ m as a release layer on a polyethylene terephthalate base layer was prepared.
- a transfer laminate was prepared by depositing a lithium metal layer on the release layer of the laminate by thermal evaporation to form a lithium metal layer having a thickness of 6 ⁇ m.
- the deposition device was ULVAC's EWK-050, and the deposition process was performed by setting the speed to 2.5 m/min, the temperature of the lithium supply unit to 500 °C, and the temperature of the main roll to -25 °C.
- Si average particle diameter (D50): 3.5 ⁇ m
- denka black as a conductive material
- SBR as a binder
- CMC as a thickener
- the conductive material, binder, thickener, and water were dispersed at 2500 rpm for 30 min using a homo mixer, and then an active material was added and then dispersed at 2500 rpm for 30 min to prepare a slurry.
- both sides of a copper current collector were coated with the negative electrode slurry at a loading amount of 85 mg/25 cm 2 , rolled, and dried in a vacuum oven at 130° C. for 10 hours to obtain a negative electrode
- An active material layer (thickness: 33 ⁇ m) was formed and used as a negative electrode (thickness of negative electrode: 41 ⁇ m, porosity of negative electrode 40.0%).
- the lithium metal of the transfer laminate was placed on the negative active material layer, and then roll pressing was performed while applying a load of 200 kgf/cm.
- the temperature was set at 80° C., and the PET layer of the transfer laminate was removed immediately after lamination, and the negative electrode was pre-lithiated.
- the negative electrode was pre-lithiated according to Comparative Example 2, the entire surface of the wide negative electrode was pre-lithiated with lithium metal, so the cutting process could not be performed with a negative electrode having a target size.
- Example 1 the width (X) of the lithium metal is 25 mm, the width (X1) of the negative electrode active material layer is 20 mm, the width of the release layer is 25 mm, and the width (Y) of the negative electrode current collector layer is 20 mm. It was prepared in the same manner as in Example 1 except that it was prepared satisfactorily.
- the width (X) of the lithium metal is greater than the width (X1) of the negative electrode active material layer, and corresponds to a case where the range of Equation 1 according to the present application is not satisfied.
- the width (X) of the lithium metal is greater than the width (X1) of the negative electrode active material layer, and corresponds to a case where the range of Equation 1 according to the present application is not satisfied.
- FIG. 6 is a diagram showing the result of transferring lithium metal to the top of the negative electrode according to Comparative Example 3 of the present application. As can be seen in FIG. 6, it can be confirmed that the lithium at the edge is desorbed together and the residue is separated, and accordingly, it can be confirmed that there is a risk in terms of safety in the subsequent process.
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Abstract
Description
Claims (10)
- 음극 집전체층 및 상기 음극 집전체층의 일면 또는 양면에 음극 활물질층을 형성하는 단계; 및상기 음극 활물질층 상에 리튬 금속을 전사하는 단계;를 포함하는 것인 리튬 이차 전지용 음극의 전리튬화 방법으로,상기 리튬 금속을 전사하는 단계는 기재층의 일면을 패턴 형태로 전처리하는 단계; 상기 기재층의 전처리된 일면의 상부에 이형층 및 리튬 금속을 순차적으로 적층하여 전사 적층체를 형성하는 단계; 상기 리튬 금속의 상기 이형층과 접하는 면의 반대면을 상기 음극 활물질층의 상기 음극 집전체층과 접하는 면의 반대면에 접하도록 상기 전사 적층체를 상기 음극 활물질층 상에 적층하는 단계; 및 상기 기재층을 제거하는 단계;를 포함하며,상기 리튬 금속 및 음극 활물질층은 하기 식 1을 만족하는 것인 리튬 이차 전지용 음극의 전리튬화 방법:[식 1]X ≤ X1상기 식 1에 있어서,X는 상기 리튬 금속의 폭을 의미하고,X1은 음극 활물질층의 폭을 의미한다.
- 청구항 1에 있어서,상기 이형층의 폭은 하기 식 2를 만족하는 것인 리튬 이차 전지용 음극의 전리튬화 방법:[식 2]X < 이형층의 폭 < Y상기 식 2에 있어서, X는 상기 리튬 금속의 폭을 의미하고, Y는 상기 음극 집전체층의 폭을 의미한다.
- 청구항 1에 있어서,상기 전처리 단계는 코로나 또는 플라즈마 처리 하는 단계를 포함하며,상기 기재층과 상기 이형층이 접하는 면에 대하여, 상기 전처리된 면의 접착력이 Cross-cut 평가 기준 4B 이상이고, 상기 전처리되지 않은 면의 접착력이 Cross-cut 평가 기준 1B 이하인 리튬 이차 전지용 음극의 전리튬화 방법.
- 청구항 1에 있어서,음극 집전체층 및 상기 음극 집전체층의 일면 또는 양면에 음극 활물질층을 형성하는 단계는 음극 활물질층 조성물을 포함하는 음극 슬러리를 상기 음극 집전체층의 일면 또는 양면에 코팅하는 단계를 포함하며,상기 음극 활물질층 조성물은 실리콘계 활물질; 음극 도전재; 및 음극 바인더;로 이루어진 군에서 선택되는 1 이상을 포함하는 것인 리튬 이차 전지용 음극의 전리튬화 방법.
- 청구항 4에 있어서,상기 실리콘계 활물질은 SiOx (x=0), SiOx (0<x<2), SiC, 및 Si 합금으로 이루어진 군에서 선택되는 1 이상을 포함하는 리튬 이차 전지용 음극의 전리튬화 방법.
- 청구항 4에 있어서, 상기 실리콘계 활물질은 SiOx (x=0) 및 SiOx (0<x<2)로 이루어진 군에서 선택되는 1 이상을 포함하며, 상기 실리콘계 활물질 100 중량부 기준 상기 SiOx (x=0)를 70 중량부 이상 포함하는 리튬 이차 전지용 음극의 전리튬화 방법.
- 청구항 1에 있어서,상기 리튬 금속의 두께는 1μm 이상 10μm 이하인 것인 리튬 이차 전지용 음극의 전리튬화 방법.
- 청구항 1에 있어서,상기 이형층은, 폴리에스터 주사슬에 실리콘 사슬이 그라프트 결합된 실리콘 변성 폴리에스터, 아크릴계 수지, Si, 멜라민 및 불소로 이루어진 군에서 선택된 1종 이상을 포함하는 것인 리튬 이차 전지용 음극의 전리튬화 방법.
- 음극 집전체층;상기 음극 집전체층의 일면 또는 양면에 형성된 음극 활물질층;상기 음극 활물질층의 상기 음극 집전체층과 접하는 면의 반대면에 형성된 전사 적층체;를 포함하는 음극 중간체로,상기 전사 적층체는 기재층, 이형층, 및 리튬 금속이 순차적으로 적층된 구조이며,상기 기재층의 이형층과 접하는 일면은 패턴 형태의 전처리부를 포함하고,상기 리튬 금속 및 음극 활물질층은 하기 식 1을 만족하는 것인 음극 중간체:[식 1]X ≤ X1상기 식 1에 있어서,X는 상기 리튬 금속의 폭을 의미하고,X1은 음극 활물질층의 폭을 의미한다.
- 리튬 이차 전지용 양극;청구항 1 내지 청구항 8 중 어느 한 항의 방법에 따라 전리튬화된 리튬 이차 전지용 음극;상기 양극과 상기 음극 사이에 구비된 분리막; 및전해액;을 포함하는 리튬 이차 전지.
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KR20220016612A (ko) | 2020-08-03 | 2022-02-10 | 이도일 | 브러쉬 결합 팩 용기 |
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JP2013020974A (ja) * | 2006-03-09 | 2013-01-31 | Panasonic Corp | 転写用フィルムの製造方法、および電気化学素子用の極板の製造方法 |
JP2009080971A (ja) | 2007-09-25 | 2009-04-16 | Tokyo Univ Of Science | リチウムイオン電池用負極 |
KR101625602B1 (ko) * | 2015-10-28 | 2016-05-30 | 주식회사 케이엠지 | 전사코팅법을 이용한 연속 이차전지 제조방법 |
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