WO2018169336A1 - Électrode et batterie secondaire au lithium la comprenant - Google Patents

Électrode et batterie secondaire au lithium la comprenant Download PDF

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Publication number
WO2018169336A1
WO2018169336A1 PCT/KR2018/003074 KR2018003074W WO2018169336A1 WO 2018169336 A1 WO2018169336 A1 WO 2018169336A1 KR 2018003074 W KR2018003074 W KR 2018003074W WO 2018169336 A1 WO2018169336 A1 WO 2018169336A1
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WO
WIPO (PCT)
Prior art keywords
tube
metal
electrode
electrode active
lithium
Prior art date
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PCT/KR2018/003074
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English (en)
Korean (ko)
Inventor
손병국
최장욱
김병곤
장민철
박은경
최정훈
강동현
Original Assignee
주식회사 엘지화학
한국과학기술원
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Priority claimed from KR1020180030476A external-priority patent/KR102081772B1/ko
Application filed by 주식회사 엘지화학, 한국과학기술원 filed Critical 주식회사 엘지화학
Priority to CN201880004358.8A priority Critical patent/CN109964344B/zh
Priority to EP18768524.3A priority patent/EP3514861A4/fr
Priority to JP2019537736A priority patent/JP7062152B2/ja
Publication of WO2018169336A1 publication Critical patent/WO2018169336A1/fr
Priority to US16/368,149 priority patent/US11380888B2/en

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/76—Containers for holding the active material, e.g. tubes, capsules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrode that can be used as a positive electrode or a negative electrode of a lithium secondary battery, and a lithium secondary battery comprising the same.
  • Lithium metal is an ideal material as a cathode of a high energy density lithium secondary battery, having a high theoretical capacity of 3,862 mAh / g and a low standard electrode potential (-3.04 vs SHE).
  • a negative electrode material of a lithium battery due to safety problems due to internal short circuit of the battery due to lithium dendrite growth, it has not been commercialized as a negative electrode material of a lithium battery.
  • lithium metal may adversely react with the active material or the electrolyte, which may greatly affect the short circuit and the life of the battery. Therefore, stabilization of lithium metal electrodes and reduction of battery capacity through the suppression of dendrite and improvement of battery safety technology are core technologies that must be preceded for the development of next-generation lithium secondary batteries.
  • a negative electrode active material in which Au is deposited on an inner surface of a hollow capsule and lithium metal is filled in the hollow capsule using Au as a seed has been developed (Yan, et al. , Nature Energy 1). , Article number: 16010 (2016), "Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth").
  • the hollow capsule-type negative electrode active material can secure stability in the electrolyte due to the sealed shape, but it is not easy to control the volume of the lithium metal filled in the hollow capsule, the electrode configuration due to the spherical shape There is a problem that the electrical conductivity may be reduced.
  • a technology for a lithium electrode of a type in which a lithium metal or a lithium alloy is filled in pores after fabricating a three-dimensional porous structure has been disclosed (Korean Patent No. 1417268).
  • the lithium electrode may react not only on the surface of the lithium electrode but also in pores of the porous structure, thereby improving charge and discharge cycle characteristics of the lithium metal battery and improving output characteristics.
  • Patent Document 1 Republic of Korea Patent No. 1417268, "Lithium electrode for lithium metal battery and its manufacturing method”
  • Patent Document 2 Republic of Korea Patent No. 0447792, "Li-electrode using porous three-dimensional current collector, its manufacturing method and lithium battery”
  • Non-Patent Document 1 Yan, et al., Nature Energy 1, Article number: 16010 (2016), “Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth”
  • an electrode manufactured by including a structure capable of supporting an electrode active material in a dispersed state in an electrode active layer an electrode active material supported in the structure
  • an electrode active material supported in the structure By controlling the capacity of, it was confirmed that the charge and discharge performance of the battery can be improved, and due to the morphological characteristics of the structure on which the electrode active material is supported, dendrite growth at the electrode can be prevented to improve the safety of the battery.
  • an object of the present invention to provide an electrode capable of improving safety as well as functional aspects such as battery capacity and charge / discharge performance.
  • Another object of the present invention is to provide a lithium secondary battery including such an electrode.
  • the present invention to achieve the above object, the current collector; And an electrode active layer including an electrode active material supporting structure formed on the electrical contact.
  • the present invention also provides a lithium secondary battery comprising the electrode.
  • a structure for supporting an electrode active material is dispersed in an electrode active layer, and the structure serves as an electrode active material both in a state in which an electrode active material is not supported therein or in a state in which the electrode active material is supported.
  • the charge and discharge performance can be improved by the morphological features of the tube-shaped structure.
  • the electrode active material is supported in the structure, it is possible to prevent the growth of the dendrite and the reaction of the electrode active material and the electrolyte in the electrode can improve the safety of the electrode.
  • the metal formed on the inner surface of the structure included in the electrode active layer it is possible to prevent the electrode active material is formed around the metal to grow in the dendrite shape, and also to prevent the reaction with the electrolyte to prevent It can improve safety.
  • the structure may be used as a negative electrode active material by itself or as a negative electrode active material in a state in which lithium metal is supported therein.
  • the structure is a tube-shaped structure having an aspect ratio of more than 1, the structure itself may be a path of electrical conduction due to the morphological characteristics of the tube shape.
  • FIG. 1A and 1B are schematic views of an electrode according to an embodiment of the present invention.
  • FIG. 1A before supporting lithium metal as a structure
  • FIG. 1B after supporting lithium metal as a structure
  • 3A and 3B are schematic views showing longitudinal and transverse cross sections of a tube in a structure according to one embodiment of the invention, respectively.
  • FIG. 4 is a schematic diagram of a dual-nozzle system as an electrospinning apparatus used to manufacture a structure according to an embodiment of the present invention.
  • 5a to 5c are graphs showing the results of charge and discharge experiments for a lithium half battery manufactured using the negative electrodes of Examples and Comparative Examples of the present invention.
  • FIG. 6 is a TEM (Transmission electron microscopy) photograph of morphological changes before and after the charge and discharge of a lithium half battery manufactured using the negative electrode of Example 1 (Pristine: before charge and discharge, 20 th D: after the 20th discharge, 20 th C: After 20th charge) ..
  • SEM 7 is a scanning electron microscope (SEM) photograph observing a growth pattern of lithium metal during charging of a lithium half battery manufactured by using negative electrodes of Examples and Comparative Examples.
  • the present invention relates to an electrode that can be used as a positive electrode or a negative electrode of a lithium secondary battery.
  • the active layer of the electrode includes an electrode active material supported in a structure, thereby improving charge and discharge performance of the lithium secondary battery.
  • the functional aspects of the battery may be strengthened, and the growth of the dendrite in the electrode may be prevented, and the reaction between the electrode active material and the electrolyte may be prevented to improve the safety of the lithium secondary battery.
  • FIG. 1A and 1B are schematic diagrams of an electrode 100 according to an embodiment of the present invention.
  • the electrode 100 may include an electrode active layer 1 including an electrode active material supporting structure 10, and the electrode active layer 1 may be formed on the current collector 2.
  • the electrode active layer 1 may have a form including a plurality of pores, and thus the charge and discharge performance may be improved.
  • the lithium anode is in the form of a flat foil, the charge and discharge characteristics are not good, and there is a problem in that a short circuit occurs due to the formation of lithium dendrites. This can be prevented.
  • the lithium metal electrode since the lithium metal electrode has pores, the specific surface area of the lithium metal electrode may be increased as compared with the foil form, thereby improving the C-rate characteristics of the battery.
  • the structure 10 carrying the electrode active material may be dispersed in the electrode active layer 1.
  • the shape in which the electrode active material is supported on the entire structure 10 is illustrated, but the electrode active material may be supported on a portion of the structure 10.
  • the number of cycles of the battery may be adjusted according to the extent of supporting the electrode active material in the structure 10, and the volume ratio of the supported electrode active material may be defined as described below.
  • the structure 10 can function as an electrode active material even when the electrode active material is not supported.
  • the structure when the structure is included in the negative electrode of the lithium metal battery, even if lithium metal as an electrode active material is not supported inside the structure, lithium ions generated at the positive electrode may move to the negative electrode while the lithium metal battery starts to operate. .
  • lithium ions transferred to the cathode are reduced, lithium metal is formed in the structure, and the number of charge and discharge cycles may be determined by the capacity of the lithium metal formed in the structure.
  • the current collector 2 serves to collect electrons generated by the electrochemical reaction of the electrode active material or to supply electrons required for the electrochemical reaction, and is made of copper, stainless steel, aluminum, nickel, titanium, and calcined carbon. It may be at least one selected from, the stainless steel may be surface treated with carbon, nickel, titanium or silver.
  • the electrode active layer 1 may include the structure 10, a binder (not shown), and a conductive material (not shown), and specifically, 80 to 99.5 wt% of the structure 10, 0.3 to 19.8 wt% of the binder, and conductive material Ash from 0.2 to 19.7 weight percent.
  • the content of the structure 10 refers to a weight not including or including an electrode active material included therein.
  • the structure 10 when the structure 10 is loaded with lithium metal as an electrode active material, the structure 10 and the lithium supported thereon are included.
  • the sum of the weights of the metals may be the content of the structure 10, and when the electrode active material is not contained in the structure 10, the weight of the structure 10 itself may be the content of the structure 10.
  • the content of the structure 10 is less than 80% by weight, the charge and discharge characteristics of the battery may be lowered. If the content of the structure 10 is greater than 99.5% by weight, the content of the structure 10 in the slurry for forming the electrode active layer 1 is a binder or The electrode active layer 1 may be difficult to form because the slurry coating property is lowered on the current collector 2 due to relatively higher than the conductive material.
  • the structure may have a core-shell shape, and specifically, the core-shell structure may be spherical or tubular.
  • the tubular structure may be a tubular structure in which one side is open or a tubular structure in which both sides are open.
  • FIGS. 2A and 2B are schematic views of a structure according to an embodiment of the present invention.
  • the structure 10 includes a tube 11 having both sides open; And a metal 13 formed on the inner surface of the tube 11.
  • the tube 11 illustrates a form in which both sides are open, but one side may be in an open form.
  • 3A and 3B are schematic views showing longitudinal and transverse cross sections of a tube in a structure according to one embodiment of the invention, respectively.
  • the aspect ratio a of the longitudinal cross section of the tube 11 may be greater than one.
  • the aspect ratio of the tube 11 longitudinal section may be calculated by the following equation (1).
  • L is the length of the tube 11 and D ex is the outer diameter of the tube 11.
  • the length L of the tube 11 may be 2 ⁇ m to 25 ⁇ m, preferably 3 ⁇ m to 15 ⁇ m, more preferably 4 ⁇ m to 10 ⁇ m. If it is less than the above range it may be difficult to implement a tube having an aspect ratio of 1 or more by Equation 1, if the above range is low packing density (packing density) is a problem that the gap of the electrode even after rolling, the energy density per cell volume lowers There can be.
  • the outer diameter D ex of the tube 11 may be 0.2 ⁇ m to 2 ⁇ m, preferably 0.3 ⁇ m to 1.2 ⁇ m, more preferably 0.5 ⁇ m to 1 ⁇ m. If it is less than the above range, the lithium metal 14 contained in the structure 10 is reduced in volume, thereby reducing lithium dendrite suppression and battery cycle life, lowering the specific capacity of the active material and the energy density per weight of the battery. If it is exceeded, it is difficult to maintain the tube shape during the manufacturing process, and the tube shape collapses during the electrode manufacturing and rolling processes, thereby lowering the lithium dendrite suppressing effect.
  • the actual size of the tube 11, such as length L, outer diameter D ex and inner diameter D in, can be measured with a scanning electron microscope (SEM) or transmission electron microscope (TEM).
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the structure 10 has the shape of a tube 11 having an aspect ratio greater than 1 (a> 1) as described above, and the tube 11 includes a carbon-based polymer, so that the structure 10 itself is an electrically conductive path.
  • the tube 11 has a cylindrical shape with both sides open, and may itself be an electric conduction path and improve ion conductivity by electrolyte wetting.
  • the structure is a sphere-shaped hollow capsule, due to the closed shape is difficult to impregnate the electrolyte compared to the open tube form, it is difficult to transfer lithium ions to the inside of the structure and to control the volume of the lithium metal filled inside Not easy to do, due to the spherical shape there is a problem that the electrical conductivity can be reduced when configuring the electrode.
  • the shell of the tube 11 may exhibit electrical conductivity and may also exhibit lithium ion conductivity.
  • the shell of the tube 11 may include carbon, and the carbon may be amorphous carbon.
  • the tube 11, specifically, the shell of the tube 11 may be porous, in this case, when the outer diameter of the tube is large, the thickness of the shell must be thickened to increase the strength, in which case the shell has pores In this case, the electrolyte can penetrate to the inside of the shell, thereby reducing the battery resistance.
  • the pore size may have a size of 2 nm to 200 nm and the porosity is preferably maintained at a value of 0% to 50% to maintain the strength of the tube.
  • the metal 13 may be included in the form formed on the inner surface of the tube 11, the metal 13 based on the total weight of the structure 10, that is, the tube 11 and the metal 13 is 0.1 To 25% by weight, preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight.
  • the site to which the electrode active material may bind may not be sufficient. If the weight of the metal 13 is greater than the above range, the amount of the metal 13 may be excessive so that the amount of the electrode active material may be filled. As a result, the specific capacity of the electrode active material may be reduced.
  • the metal 13 may be formed on the inner surface of the tube 11 in the form of particles, the particle diameter of the metal 13 is 1 to 50 nm, preferably 5 to 40 nm, more preferably 10 to 30 nm Can be. If the area is less than the above range, the electrode active material may not be bonded enough to induce smooth growth of the electrode active material. If the area is more than the above range, the area of the metal 13 may be increased, thereby reducing the specific amount of the electrode active material.
  • the tube 11 may be for supporting the electrode active material.
  • the electrode active material may be a positive electrode active material or a negative electrode active material that is commonly used.
  • the cathode active material may be an oxide consisting of lithium and a transition metal having a structure capable of intercalating lithium, and for example, may be represented by the following Chemical Formula 1.
  • a 1, 0.1 ⁇ x ⁇ 0.3, 0.15 ⁇ y ⁇ 0.25, 0 ⁇ b ⁇ 0.05
  • M is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, Zn and It may be any one selected from a transition metal or a lanthanide element selected from the group consisting of a combination thereof.
  • Examples of the negative electrode active material include amorphous carbon such as graphite carbon, non-graphitized carbon, crystalline carbon, and the like.
  • amorphous carbon such as graphite carbon, non-graphitized carbon, crystalline carbon, and the like.
  • the electrode active material is lithium metal
  • a metal having a low overvoltage compared to Cu (current collector) when forming a lithium metal has a low interfacial energy when reacting with lithium metal or a diffusion energy barrier of Li ions on the metal surface.
  • the metal may be at least one selected from the group consisting of Au, Zn, Mg, Ag, Al, Pt, In, Co, Ni, Mn, and Si, and may be multiphase with the lithium metal.
  • the metal having) may be Ca as a metal having a plurality of sites capable of reacting with lithium metal.
  • the present invention provides a tube 11 having one side or both sides open; Metal 13 contained in the inner surface of the tube 11; And a lithium metal 14 formed on the metal 13.
  • An alloy of the metal 13 and the lithium metal 14 may be formed between the metal 13 and the lithium metal 14, and the alloy may be Li x Au, where x is 0 ⁇ x ⁇ 3.75. It may be a mistake.
  • the hollow 12 inside the tube 11 on which the metal 13 is formed as described above may be filled with the lithium metal 14.
  • the lithium metal 14 may fill the inside of the hollow 12 while growing by bonding to the metal 13, and the volume of the lithium metal 14 filled in the inside of the hollow 12 may be defined as a free volume of the tube 11.
  • ⁇ the volume ratio of the lithium metal to the free volume, it can be calculated by the following Equation 2, where 0 ⁇ ⁇ ⁇ 1.
  • V F is the free volume of the tube
  • V Li is the volume of the lithium metal
  • V F is calculated by the following equation 3:
  • V F ⁇ (D in / 2) 2 L
  • Equation 3 D in is the inner diameter of the tube, L is the length of the tube.
  • the volume of the lithium metal included in the structure 10 increases, so that the cycle life of the battery may be improved.
  • the structure 10 may be mixed with a conductive material and a binder to be formed of a slurry, and then lithium metal may be formed by electroplating or the like in a state of being applied to a current collector.
  • the length L of the tube 11 may be 2 ⁇ m to 25 ⁇ m, preferably 3 ⁇ m to 15 ⁇ m, more preferably 4 ⁇ m to 10 ⁇ m. If it is less than the above range it may be difficult to implement a tube having an aspect ratio of 1 or more by Equation 1, if the above range is low packing density (packing density) is a problem that the gap of the electrode even after rolling, the energy density per cell volume lowers There can be.
  • the inner diameter D in of the tube 11 may be 0.1 ⁇ m to 1.8 ⁇ m, preferably 0.2 ⁇ m to 1.1 ⁇ m, more preferably 0.4 ⁇ m to 0.9 ⁇ m. If it is less than the above range, the lithium metal 14 contained in the structure 10 is reduced in volume, thereby reducing lithium dendrite suppression and battery cycle life, lowering the specific capacity of the active material and the energy density per weight of the battery. If it is exceeded, it is difficult to maintain the tube shape during the manufacturing process and the tube shape collapses during the electrode manufacturing and rolling process, thereby reducing the lithium dendrite suppressing effect.
  • the binder serves to improve adhesion between the electrode active material particles and the adhesion between the electrode active material and the current collector, and any binder may be used without particular limitation as long as it is an aqueous binder used in the composition for forming an electrode active layer.
  • the aqueous binder may be at least one selected from the group consisting of acrylate rubber and styrene rubber, and specifically, styrene-butadiene rubber (SBR) and acrylate-styrene butadiene copolymer rubber ( styrene rubbers such as acrylate-co-SBR) and acrylonitrile-styrene-butadiene copolymer rubber; Or acrylates such as methyl methacrylate-lithium methacrylate (MMA-co-LiMA)) or alkyl acrylate-acrylonitrile-acrylic acid copolymers; Compound and the like, and one kind or a mixture of two or more kinds thereof can be used.
  • SBR styrene-butadiene rubber
  • styrene rubbers such as acrylate-co-SBR
  • acrylates such as methyl me
  • the aqueous binder may be styrene butadiene-based rubber.
  • the styrene butadiene-based rubber may improve the dispersibility of the electrode active material and the conductive material in the composition, and may have a strong adhesive force to reduce the content of the binder.
  • the styrene butadiene-based rubber can improve the structural stability of the electrode to improve the overall characteristics of the battery.
  • the styrene butadiene-based rubber may be an SBR (styrenebutadiene rubber) having an average particle diameter (D50) of 90 to 150 nm and a tensile strength of 90 to 160 kgf. Styrene butadiene-based rubber that satisfies the above average particle diameter and physical properties can exhibit more excellent adhesion.
  • the average particle diameter (D50) of the styrene butadiene-based rubber can be defined as the particle size at 50% of the particle size distribution, the average particle diameter (D50) using a laser diffraction method commonly used in the art. It can be measured.
  • the content of the binder is less than 0.3% by weight, it may be difficult to exhibit sufficient adhesion in the electrode, and when the content of the binder is greater than 19.8% by weight, there may be a risk of deterioration in capacity characteristics of the battery. 0.3 to 19.8 weight percent.
  • the conductive material is used to impart conductivity to the electrode, and may be used without particular limitation as long as it has conductivity without causing chemical change.
  • the conductive material is graphite; Carbon-based materials; Metal powder or metal fiber; Conductive whiskers; Conductive metal oxides; And conductive polymers; may be one or more selected from the group consisting of, specific examples of graphite such as natural graphite or artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Needle or branched conductive whisker such as zinc oxide whisker, calcium carbonate whisker, titanium dioxide whisker, silicon oxide whisker, silicon carbide whisker, aluminum borate whisker, magnesium borate whisker, potassium titanate whisker, silicon nitride whisker, silicon carbide whisker, alumina whisker Whisker; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, and the like, or a mixture of two or more kinds thereof may be used.
  • graphite such as natural graphit
  • the conductive material may be a carbon-based material, and more specifically, carbon black, acetylene black, ketjen black, channel It may be a carbon-based material comprising any one or a mixture of two or more selected from the group consisting of black, furnace black, lamp black, summer black and carbon fiber.
  • the conductive material may have an average particle diameter (D50) of several hundred nanometers. Specifically, the average particle diameter (D50) of the conductive material may be 20nm to 1 ⁇ m. When the average particle diameter (D50) of the conductive material exceeds 1 ⁇ m, the dispersibility in the composition for forming an electrode is low, and as a result, the conductive path formation of the conductive material in the electrode active layer is not easy, which may lower the conductivity, and the bulky structure Due to the characteristics, the energy density of the electrode may be lowered. More specifically, the average particle diameter (D50) of the conductive material may be 0.4 to 0.9 ⁇ m.
  • the average particle diameter (D50) of the conductive material may be defined as the particle size at 50% of the particle size distribution, the average particle diameter (D50) to be measured using a laser diffraction method commonly used in the art. Can be.
  • the content of the conductive material is less than 0.2% by weight, the effect of improving the conductivity and the cycle characteristics according to the use of the conductive material is insignificant. If the content of the conductive material is greater than 19.7% by weight, the reaction between the conductive material and the electrolyte increases due to the increase in the specific surface area of the conductive material. Therefore, the cycle characteristics may be lowered, so that the content of the conductive material included in the electrode active layer 1 may be 0.2 to 19.7 wt%.
  • the electrode is a negative electrode
  • the active material that can be supported in the tubular structure may be lithium metal as a negative electrode active material
  • the present invention also relates to an electrode manufacturing method, the electrode manufacturing method comprising the steps of (A) mixing a structure, a binder, a conductive material and a solvent to form a slurry for forming an electrode active layer; (B) applying the slurry on an electrode current collector to form a coating film; And (C) drying the coating film.
  • the method may further include, after step (B), supporting (P) an electrode active material in the structure.
  • the amount of the structure, the binder, and the conductive material, which are raw materials for forming the slurry for forming the electrode active layer in step (A), and the specific types of the binder and the conductive material are the same as described above.
  • the structure may be prepared by a method for manufacturing a structure including the following steps (S1) to (S4).
  • the solvent may be at least one selected from the group consisting of dimethyl sulfoxide (DMSO), alcohol, N-methylpyrrolidone (NMP), acetone and water, and is removed in the drying process.
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • step (B) the slurry formed in step (A) may be applied to the electrode current collector to form an electrode active layer coating film.
  • the electrode current collector that can be used is as described above.
  • the method of applying the slurry may include bar coating, spin coating, roll coating, slot die coating, or spray coating, and any one or two or more of these methods may be mixed.
  • the slurry when the slurry is coated, the slurry may be coated to an appropriate thickness in consideration of the loading amount and thickness of the electrode active material in the electrode active layer to be finally manufactured to form a coating film.
  • step (C) by drying the coating film formed on the electrode current collector, it is possible to remove the moisture contained in the electrode as much as possible with evaporation of the solvent contained in the coating film, and at the same time increase the binding strength of the binder.
  • the drying process may be performed at a temperature below the boiling point of the solvent or below the melting point of the binder by a method such as heating or hot air injection. Preferably, it may be carried out for 1 to 50 hours at a pressure of 100 to 150 °C, more preferably 100 to 120 °C and 10 torr or less.
  • the electrode may be manufactured after the rolling process is further performed according to a conventional method.
  • step (P) of supporting the inside of the structure included in the coating film formed in step (B) with an electrode active material may be further included.
  • the electrode active material may be the positive electrode active material or the negative electrode active material as described above.
  • the method of supporting the electrode active material in the structure may be electroplating, but the method of forming the electrode active material is not limited thereto.
  • the electrode active material is lithium metal
  • the lithium metal may start to form by binding to the metal on the inner surface of the tube and may be filled inside the tube. Accordingly, the phenomenon in which lithium metal is grown in the dendrite shape can be prevented, and since lithium metal is filled in the tube without growing in the dendrite shape, the interfacial stability can be enhanced to prevent the reaction with the electrolyte solution.
  • the lithium source for forming the lithium metal may be one or more selected from the group consisting of lithium salts, lithium ingots and lithium metal oxides, but is not limited thereto as long as the compound can provide lithium ions.
  • the lithium salt may be LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN ( C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
  • an electrode including an electrode active layer having a lithium metal-supported structure dispersed therein may be particularly suitable as a negative electrode of a lithium metal battery, and the formation of lithium metal dendrite, which is a problem of the conventional lithium metal battery, and the The interface instability problem can be solved.
  • the structure included in the electrode active layer may be widely applied to various types of batteries by supporting the positive electrode active material or the negative electrode active material as described above.
  • the present invention also comprises the steps of electrospinning (S1) the metal precursor solution and the carbon-based polymer solution to form a tube precursor; (S2) first heat treating the tube precursor; (S3) second heat treating the first heat-treated tube precursor; And (S4) forming a lithium metal in the inside of the tube obtained in the step (S3).
  • the first heat treatment temperature and the second heat treatment temperature are different, and the second heat treatment temperature may be relatively higher than the first heat treatment temperature.
  • the tube precursor may be formed by electrospinning the metal precursor solution and the carbon-based polymer solution.
  • Electrospinning can be performed by electrospinning using double nozzles including inner and outer nozzles, using a high pressure electrospinner, using SUS (steel use stainless) as a collector, and a voltage range of 10 to 20 kV It may be performed in a tip to collector distance (TCD) range of 5 to 20 cm.
  • TCD tip to collector distance
  • the electrospinning may use an electrospinning method that may be commonly used in the art.
  • a dual-nozzle system As shown in FIG. 4 may be used.
  • the metal precursor solution and the carbon-based polymer solution may be injected into the inner and outer nozzles, respectively, and electrospun to form a core-shell-shaped tube precursor.
  • the metal precursor solution may be prepared by dissolving the metal precursor and the polymer in a solvent.
  • the metal precursor solution may include 0.1 to 5% by weight of the metal precursor, 1 to 20% by weight of the polymer and 75 to 95% by weight of the solvent.
  • the metal precursor may be at least one selected from the group consisting of alkoxides, acetylacetates, nitrates, oxalates, halides and cyanides containing metals, specifically, the metals are Au, Zn, Mg, Ag, Al , Pt, In, Co, Ni, Mn, Si and Ca may be one or more selected from the group consisting of.
  • precursors of Au in the group consisting of HAuCl 4 , HAuCl 4 ⁇ 3H 2 O, HAuCl 4 ⁇ 4H 2 O, AuCl 3 and AuCl It may be one or more selected.
  • the metal precursor When the metal precursor is less than 0.1% by weight, the metal that serves as a seed metal for growth of lithium metal cannot be sufficiently formed inside the structure, so that lithium metal cannot be filled inside the tube as much as desired, and when the metal precursor is more than 5% by weight, the total weight of the structure Since the amount of the metal to be formed increases, the amount of the lithium metal formed in the structure may be relatively reduced, thereby deteriorating the cycle life characteristics of the battery.
  • the polymer is polymethyl methacrylate (PMMA), polyvinylpyrrolidone (PVP), polyvinylacetate (PVAc), polyvinyl alcohol (PVA), polystyrene (PS) and polyvinylidene fluoride (PVDF)
  • PMMA polymethyl methacrylate
  • PVP polyvinylpyrrolidone
  • PVAc polyvinylacetate
  • PVA polyvinyl alcohol
  • PS polystyrene
  • PVDF polyvinylidene fluoride
  • the polymer When the polymer is less than 1% by weight, it may be difficult to form a tube precursor by electrospinning, and when the polymer is more than 20% by weight, the polymer may not remain sufficiently removed during the first heat treatment to reduce battery performance.
  • the solvent may be at least one selected from the group consisting of methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and mixtures thereof.
  • NMP methylpyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethyl sulfoxide
  • THF tetrahydrofuran
  • the solvent When the solvent is less than 75% by weight, it may be difficult to prepare a metal precursor solution, and when the solvent is more than 95% by weight, the amount of the metal precursor and the polymer may be relatively reduced to form as much metal as desired within the structure.
  • the carbon-based polymer solution may be prepared by dissolving the carbon-based polymer in a solvent.
  • the carbon-based polymer is polyacrylonitrile (PAN), polyaniline (Polyaniline: PANI), polypyrrole (PPY), polyimide (PI), polybenzimidazole (Polybenzimidazole: PBI), polypyrrolidone ( Polypyrrolidone (Ppy), Polyamide (PA), Polyamide-imide (PAI), Polyaramide, Melamine, Melamine-formaldehyde and Fluorine mica It may be at least one selected from the group consisting of. Meanwhile, the carbon density of the carbon included in the tube may be 2.0 to 2.5 g / cm 3.
  • the solvent may be at least one selected from the group consisting of methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and mixtures thereof.
  • NMP methylpyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethyl sulfoxide
  • THF tetrahydrofuran
  • the carbon-based polymer solution may be prepared by dissolving 1 to 20% by weight of the carbon-based polymer in 80 to 99% by weight of the solvent.
  • the carbon-based polymer is less than 1% by weight, the weight of the carbon-based polymer may not be sufficient to form a tube, and thus, the tube may not be formed after electrospinning. Because of this, electrospinning may not proceed smoothly.
  • the concentration of the carbon-based polymer solution is excessively high, so that the electrospinning may not proceed smoothly, and when the solvent is more than 99% by weight, the tube form may not be formed after the electrospinning.
  • the solvent used in the preparation of the metal precursor solution and the carbon-based polymer solution may be the same or different.
  • step (S2) by heating the tube precursor to the first heat treatment, it is possible to remove the polymer contained in the core of the tube precursor.
  • the heating temperature at the time of the first heat treatment may be 200 °C to 700 °C, may be to heat treatment while raising the temperature.
  • the polymer included in the core of the tube precursor may be removed and the metal precursor may be reduced to form a metal.
  • the first heat treatment temperature is less than 200 ° C
  • the polymer contained in the core of the tube precursor may not be removed and the metal precursor may not be reduced.
  • the temperature of the first heat treatment is greater than 700 ° C
  • the metal may be formed on the outer surface of the tube as well as the inner surface of the tube. There is a problem that is formed.
  • the metal is formed on the inner surface of the tube through the reduction reaction through the heat treatment, the metal is in the form of particles, the size of the particles may be a nano size of 1 to 50 nm.
  • the first heat treatment may be performed under an inert atmosphere.
  • the inert atmosphere may be formed by at least one inert gas selected from the group consisting of Ar, N 2 , He, Ne, and Ne.
  • step S3 the first heat-treated tube precursor is heated to a second heat treatment to carbonize the shell of the tube precursor to form a tube structure including carbon.
  • the heating temperature at the time of the second heat treatment may be more than 700 °C and less than 1000 °C, if the second heat treatment temperature is 700 °C or less may not be completely carbonized, if the tube is formed by high temperature heat treatment if more than 1000 °C The physical properties of the structure may be degraded.
  • a pore size controlled in the tube shell at a heating temperature around 800 °C.
  • the pores become small, and the lower the heating temperature below 800 ° C, the pores become larger, thereby controlling the temperature within the heating temperature range.
  • the pore size can be controlled.
  • step S4 lithium metal may be formed in the tube structure.
  • the method of forming the lithium metal in the tube structure may be one method selected from the group consisting of electroplating, non-plating, and evaporation, but is not limited thereto, and forms lithium metal in the tube structure. It is possible to use a wide range of filling methods.
  • the lithium source for forming the lithium metal may be one or more selected from the group consisting of lithium salts, lithium ingots, and lithium metal oxides, but is not limited thereto as long as the compound can provide lithium ions.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F9SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
  • the lithium metal-supported structure manufactured by the above method is applied as a negative electrode active material of a lithium metal battery, thereby solving the problem of the formation of lithium metal dendrite and the interface instability, which is a problem of the conventional lithium metal battery.
  • the present invention also relates to a lithium secondary battery comprising the electrode as described above.
  • the electrode may be a negative electrode or a positive electrode, it is possible to obtain a negative electrode or a positive electrode of the battery to be applied according to the type of the electrode active material supported on the structure, the type and amount of the positive electrode active material or negative electrode active material as the electrode active material is Same as described.
  • the structure may be dispersed in a negative electrode active layer in an empty state or in a state in which lithium metal is supported to form a negative electrode for a lithium metal battery, wherein the lithium metal battery is a form of a structure that is a negative electrode active material dispersed in a negative electrode active layer Due to the characteristics and optimized loading of lithium metal, the charge and discharge performance may be improved and safety may be improved.
  • a carbon-based polymer solution was prepared by dissolving 13% by weight of PAN, a carbon-based polymer, in 87% by weight of dimethylformamide (DMF), a solvent.
  • DMF dimethylformamide
  • the metal precursor solution and the carbon-based polymer solution were introduced into the internal nozzle and the external nozzle of the dual-nozzle system (Adv. Mater., 2010, 22, 496) including the internal nozzle and the external nozzle, respectively, and electrospun to form a tube precursor. Was formed.
  • Electrospinning power 14.5 kV
  • the tube precursor was first heat-treated in a furnace at 280 ° C. to remove PMMA contained in the core of the tube precursor and to raise the temperature to reduce HAuCl 4 to form Au particles on the inner surface of the tube precursor shell.
  • the PAN of the tube precursor was carbonized at 850 ° C. to prepare a structure.
  • Production Example 2 fabrication of a structure in which a lithium metal is formed
  • Au of Preparation Example 1 formed lithium metal through electroplating in the tubular structure formed on the inner surface. At this time, LiClO 4 which is a lithium salt was used as a lithium source.
  • the electroplating was carried out by flowing a current at a current density of 1 mA / cm2 to a lithium half battery manufactured by the following method.
  • LiTFSI lithiumbis-trifluoromethanesulfonimide
  • DME 1,2-dimethoxyethane
  • DOL 1,3-dioxolane
  • separator a polyethylene separator was used.
  • a lithium half cell was manufactured using the prepared negative electrode, polyethylene separator, and electrolyte solution.
  • a tubular structure containing no metal (Au) was prepared in the same manner as in Preparation Example 1.
  • the slurry prepared in 1-1 was applied to the Cu foil, which is a negative electrode current collector, with a loading amount of 2.6 mAh / cm 2 by spin coating to form a coating film for forming a negative electrode active layer.
  • the coating film formed in 1-2 was heated at 110 ° C. for 2 hours, dried, and rolled to prepare a negative electrode.
  • Example 2 lithium metal Supported Cathode Manufacturing Including Structure
  • Example 2 In the same manner as in Example 1, a negative electrode was prepared using a tubular structure in which the lithium metal prepared in Preparation Example 2 was supported.
  • a negative electrode was prepared in the same manner as in Example 1, except that the negative electrode was manufactured using a tubular structure containing no metal (Au) prepared in Comparative Preparation Example 1 instead of Preparation Example 1.
  • a negative electrode having a lithium foil formed on a Bare Cu foil was prepared.
  • Example 1 The negative electrodes prepared in Example 1 and Comparative Examples 1 and 2, respectively, were prepared.
  • LiTFSI lithiumbis-trifluoromethanesulfonimide
  • a mixed solvent volume ratio 1: 1 of DME (1,2-dimethoxyethane) and DOL (1,3-dioxolane) as an electrolyte and 1% LiNO 3
  • the electrolyte solution was mixed and used.
  • separator a polyethylene separator was used.
  • a lithium half cell was prepared using the prepared negative electrode, polyethylene separator, and electrolyte solution, respectively.
  • Preparation Example 3 charging and discharging were performed on the lithium half battery manufactured using the negative electrodes of Example 1 and Comparative Examples 1 and 2, respectively.
  • the charge / discharge test was performed under the conditions of 1 mA / cm 2 current density, 1 mAh / cm 2 discharge capacity, and 1 V cut-off conditions.
  • 5a to 5c are graphs showing the results of charge and discharge experiments for a lithium half battery manufactured using the negative electrodes of Examples and Comparative Examples of the present invention.
  • the lithium half battery manufactured by using the negative electrode prepared in Example 1 includes the tubular structure of Preparation Example 1, and it can be seen that the capacity decrease does not appear until 300 cycles.
  • FIG. 6 is a TEM (Transmission electron microscopy) photograph of before and after charging and discharging of a lithium half battery manufactured using the negative electrode of Example 1 ((a): before charging and discharging; (b) 20th discharge (C) after the 20th charge).
  • FIG. 7 is a scanning electron microscope (SEM) photograph of the growth pattern of lithium metal during charging of a lithium half battery manufactured using the negative electrodes of Example 1 and Comparative Examples 1 and 2.
  • SEM scanning electron microscope

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Abstract

La présente invention concerne une électrode et une batterie secondaire au lithium la comprenant et, plus spécifiquement, une électrode, comprenant une couche active d'électrode formée à l'aide d'une structure permettant à la couche active d'électrode d'être supportée à l'intérieur de celle-ci, est fabriquée, ce qui permet d'améliorer la sécurité et la caractéristique de charge/décharge de la batterie en raison d'une caractéristique morphologique pour laquelle un matériau actif d'électrode est supporté à l'intérieur de la structure.
PCT/KR2018/003074 2017-03-16 2018-03-16 Électrode et batterie secondaire au lithium la comprenant WO2018169336A1 (fr)

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CN201880004358.8A CN109964344B (zh) 2017-03-16 2018-03-16 电极和包含所述电极的锂二次电池
EP18768524.3A EP3514861A4 (fr) 2017-03-16 2018-03-16 Électrode et batterie secondaire au lithium la comprenant
JP2019537736A JP7062152B2 (ja) 2017-03-16 2018-03-16 電極及びこれを含むリチウム二次電池
US16/368,149 US11380888B2 (en) 2017-03-16 2019-03-28 Electrode and lithium secondary battery comprising same

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KR10-2017-0033415 2017-03-16
KR10-2018-0030476 2018-03-15
KR1020180030476A KR102081772B1 (ko) 2017-03-16 2018-03-15 전극 및 이를 포함하는 리튬 이차전지

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Cited By (1)

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EP3550058A4 (fr) * 2017-07-13 2020-02-05 LG Chem, Ltd. Procédé de fabrication d'une structure

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JPH10321218A (ja) * 1998-04-21 1998-12-04 Mitsubishi Chem Corp 二次電池用電極
KR20130106238A (ko) * 2012-03-19 2013-09-27 한국생산기술연구원 터널 형태 나노구조체를 포함하는 전기화학 에너지 저장용 구조물 및 이의 제조방법
KR20140001905A (ko) * 2010-10-22 2014-01-07 암프리우스, 인코포레이티드 껍질에 제한된 고용량 활물질을 함유하는 복합 구조물
KR20140026193A (ko) * 2012-08-24 2014-03-05 삼성에스디아이 주식회사 음극 및 이를 포함하는 리튬 전지
KR20160032807A (ko) * 2014-09-17 2016-03-25 (주)오렌지파워 음극 및 이를 포함하는 이차전지

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JPH10321218A (ja) * 1998-04-21 1998-12-04 Mitsubishi Chem Corp 二次電池用電極
KR20140001905A (ko) * 2010-10-22 2014-01-07 암프리우스, 인코포레이티드 껍질에 제한된 고용량 활물질을 함유하는 복합 구조물
KR20130106238A (ko) * 2012-03-19 2013-09-27 한국생산기술연구원 터널 형태 나노구조체를 포함하는 전기화학 에너지 저장용 구조물 및 이의 제조방법
KR20140026193A (ko) * 2012-08-24 2014-03-05 삼성에스디아이 주식회사 음극 및 이를 포함하는 리튬 전지
KR20160032807A (ko) * 2014-09-17 2016-03-25 (주)오렌지파워 음극 및 이를 포함하는 이차전지

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3550058A4 (fr) * 2017-07-13 2020-02-05 LG Chem, Ltd. Procédé de fabrication d'une structure

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