[go: up one dir, main page]

WO2018169337A1 - Structure - Google Patents

Structure Download PDF

Info

Publication number
WO2018169337A1
WO2018169337A1 PCT/KR2018/003077 KR2018003077W WO2018169337A1 WO 2018169337 A1 WO2018169337 A1 WO 2018169337A1 KR 2018003077 W KR2018003077 W KR 2018003077W WO 2018169337 A1 WO2018169337 A1 WO 2018169337A1
Authority
WO
WIPO (PCT)
Prior art keywords
tube
metal
lithium
active material
lithium metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/003077
Other languages
English (en)
Korean (ko)
Inventor
박은경
최장욱
김병곤
장민철
손병국
최정훈
강동현
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Korea Advanced Institute of Science and Technology KAIST
Original Assignee
LG Chem Ltd
Korea Advanced Institute of Science and Technology KAIST
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180030410A external-priority patent/KR102115601B1/ko
Application filed by LG Chem Ltd, Korea Advanced Institute of Science and Technology KAIST filed Critical LG Chem Ltd
Priority to CN201880003657.XA priority Critical patent/CN109792057B/zh
Priority to ES18767599T priority patent/ES2940317T3/es
Priority to PL18767599.6T priority patent/PL3486982T3/pl
Priority to EP18767599.6A priority patent/EP3486982B1/fr
Priority to JP2019528013A priority patent/JP6765699B2/ja
Publication of WO2018169337A1 publication Critical patent/WO2018169337A1/fr
Priority to US16/268,925 priority patent/US11251438B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements 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
    • 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 a structure that can be used for supporting an electrode active material.
  • Lithium metal is an ideal material for cathodes of high energy density lithium secondary batteries with a high theoretical capacity of 3862 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 and dendrite suppression technology of lithium metal electrode is a core technology that must be preceded for the development of the next-generation lithium secondary battery.
  • Au is deposited on the inner surface of the hollow capsule, and a cathode active material in which lithium metal is filled in the hollow capsule has been developed using the Au as a seed (Yan, et al ., Nature Energy 1 , Article number: 16010 (2016), "Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth").
  • the hollow active material of the hollow capsule form can secure stability in the electrolyte due to the sealed shape, but it is not easy to control the volume of the lithium metal to be filled in the hollow capsule, the electrode configuration due to the spherical shape There is a problem that the electrical conductivity may be reduced.
  • Patent Document 1 Republic of Korea Patent No. 1155909, "Negative active material for lithium secondary battery, a manufacturing method thereof and a lithium secondary battery comprising the same"
  • Non-Patent Document 1 Yan, et al ., Nature Energy 1, Article number: 16010 (2016), "Selectve deposition and stable encapsulation of lithium through heterogeneous seeded growth"
  • the present invention forms a tube having one or both sides with an open shape, and the electrode active material is formed on the inner surface of the tube.
  • a structure was formed to form a highly reactive metal.
  • Such a structure can prevent a phenomenon in which an electrode active material supported therein grows in a dendrite shape, and prevents a reaction between the electrode active material and an electrolyte solution to improve battery stability. It was confirmed that it could be improved.
  • the present invention to achieve the above object, one side or both sides open the tube; And a metal included in the inner surface of the tube.
  • the aspect ratio (a) of the tube longitudinal section included in the structure is calculated by the following Equation 1, it may be greater than one.
  • Equation 1 L is the length of the tube, D ex is the outer diameter of the tube.
  • the invention also provides a tube that is open on one side or both sides; A metal contained in the inner surface of the tube; And a lithium metal formed on the metal.
  • the structure according to the present invention due to the metal on the inner surface of the tube included in the structure, it is possible to prevent the electrode active material is formed around the metal to grow in the form of dendrites, and also to prevent the reaction with the electrolyte solution The safety of the battery can be improved.
  • the structure may be used as a negative electrode active material in which lithium metal is supported.
  • the tube-shaped structure is one side or both sides open form, there is a more advantageous effect in that it is possible to secure the electrically conductive path.
  • the structure is a tube-shaped structure having an aspect ratio of more than 1, the tube shape itself having an aspect ratio of more than 1 may be a path of electrical conduction.
  • FIG. 1A and 1B are schematic views of a structure according to an embodiment of the present invention (FIG. 1A: before supporting lithium metal as a structure, and FIG. 1B: after supporting lithium metal as a structure).
  • FIGS. 2A and 2B are schematic views showing longitudinal and transverse cross sections of a tube in a structure according to one embodiment of the invention, respectively.
  • FIG 3 is a schematic view of a dual-nozzle system as an electrospinning apparatus used for manufacturing a structure according to an embodiment of the present invention.
  • 4A to 4C are graphs showing the results of charge and discharge experiments on lithium half cells manufactured using the structures of Examples and Comparative Examples of the present invention.
  • TEM 5 is a transmission electron microscopy (TEM) photograph of the lithium half battery manufactured using the structure of Example 1 before and after charging and discharging (Pristine: before charge and discharge, 20 th D: after the 20th discharge, 20 th C: after 20th charge).
  • FIG. 6 is a scanning electron microscope (SEM) photograph of a growth pattern of lithium metal when charging a lithium half battery manufactured using the structures of Examples and Comparative Examples.
  • SEM scanning electron microscope
  • the present invention relates to a structure capable of supporting an electrode active material.
  • the structure supports lithium metal as a negative electrode active material
  • the growth of lithium metal in a dendrite form in a negative electrode of a lithium metal battery is disclosed.
  • the present invention relates to a structure capable of preventing the lithium metal and the electrolyte from directly reacting at the same time.
  • FIG. 1A and 1B 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.
  • FIGS. 2A and 2B 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 tube 11 longitudinal section 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 positive electrode active material may be an oxide composed 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 tube 11 may include a semiconductor element and an oxide of the semiconductor element.
  • the oxide of the semiconducting element may include an oxide of the Group 14 semiconducting element of the periodic table excluding carbon.
  • the oxide of the semiconducting element may include an oxide of Si, Ge, or Sn element.
  • Oxides of the semiconducting element SiOx (here 0.3 ⁇ x ⁇ 1.2), GeOy (here 0.2 ⁇ y ⁇ 1.1), SnOz (here 0.3 ⁇ z ⁇ 1.2), or a combination thereof, and examples thereof.
  • the oxide of the semiconducting element may be SiOx (0.3 ⁇ x ⁇ 1.2) or GeOy (0.2 ⁇ y ⁇ 1.1).
  • the present invention also relates to a structure capable of supporting an electrode active material to improve battery safety.
  • the structure supports lithium metal as a negative electrode active material
  • lithium metal is dendrites at a negative electrode of a lithium metal battery. It is possible to prevent the lithium metal and the electrolyte from directly reacting with each other while preventing growth in the form of (dendrite).
  • the present invention is one side or both sides of the tube 11 is open; Metal 13 contained in the inner surface of the tube 11; And a lithium metal 14 formed on the metal 13; FIG. 1B.
  • 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 including the metal 13 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.
  • ⁇ volume ratio of the lithium metal to the free volume
  • 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 14 included in the structure 10 increases, so that the cycle life of the battery may be improved.
  • 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 processes, thereby reducing the lithium dendrite suppressing effect.
  • the present invention comprises the steps of electrospinning (S1) the metal precursor solution and the carbon-based polymer solution to form a tube precursor;
  • (S3) a second heat treatment of the first heat-treated tube precursor; relates to a method of manufacturing a structure comprising, (S4) forming a lithium metal in the interior of the tube obtained in the step (S3); It may further include.
  • both the first heat treatment 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. 3 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), and tetrahydrofuran (THF).
  • 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 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 at the same time, the metal precursor may not be reduced. 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 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 .
  • 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 metal precursor HAuCl 4 and 11% by weight of the polymer PMMA were dissolved in 88.5% by weight of the solvent to prepare a metal precursor solution.
  • the solvent used was a mixed solvent in which dimethylformamide (DMF) and acetone were mixed in a weight ratio of 85:15.
  • 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 heat-treated in a furnace at 280 ° C. to remove PMMA contained in the core of the tube precursor, and elevated 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.
  • Example 2 manufacture of a structure in which a lithium metal is formed
  • Au of Example 1 formed lithium metal through electroplating inside the tube 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.
  • Example 1 The structure prepared in Example 1, Super-P carbon as a conductive material and PVdF as a binder were mixed in a weight ratio of 95: 2.5: 2.5, and then coated and dried on a Cu current collector to prepare a negative electrode.
  • 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.
  • Example 2 In the same manner as in Example 1, a tubular structure containing no metal on the inner surface of the tube was prepared.
  • Example 1 The structure prepared in Example 1 and Comparative Example 2, Super-P carbon as a conductive material and PVdF as a binder were mixed in a weight ratio of 95: 2.5: 2.5, and then coated and dried on a Cu current collector to prepare a negative electrode.
  • 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.
  • 4A to 4C are graphs showing the results of charge and discharge experiments on lithium half cells manufactured using the structures of Examples and Comparative Examples of the present invention.
  • the lithium half battery manufactured using the structure prepared in Example 1 does not exhibit a capacity reduction until 300 cycles.
  • FIG. 5 is a transmission electron microscopy (TEM) photograph of the lithium half battery manufactured using the structure of Example 1 before and after charging and discharging (Pristine: before charge and discharge, 20 th D: after the 20th discharge , 20 th C: after 20th charge).
  • TEM transmission electron microscopy
  • FIG. 6 is a scanning electron microscope (SEM) photograph of a growth pattern of lithium metal when charging a lithium half battery manufactured using the structures of Examples and Comparative Examples.
  • SEM scanning electron microscope

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une structure. Plus particulièrement, une structure en forme de tube, dont une surface latérale est ouverte, ou dont les deux surfaces latérales sont ouvertes, est fabriquée, et un matériau d'électrode actif, tel qu'un métal de lithium, est ensuite formé autour d'un métal inclus dans la surface intérieure du tube, ce qui permet d'empêcher la formation de dendrites de métal de lithium et la réaction entre le métal de lithium et l'électrolyte.
PCT/KR2018/003077 2017-03-16 2018-03-16 Structure Ceased WO2018169337A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201880003657.XA CN109792057B (zh) 2017-03-16 2018-03-16 结构体
ES18767599T ES2940317T3 (es) 2017-03-16 2018-03-16 Estructura
PL18767599.6T PL3486982T3 (pl) 2017-03-16 2018-03-16 Struktura
EP18767599.6A EP3486982B1 (fr) 2017-03-16 2018-03-16 Structure
JP2019528013A JP6765699B2 (ja) 2017-03-16 2018-03-16 構造体
US16/268,925 US11251438B2 (en) 2017-03-16 2019-02-06 Tube structure having metal on inner surface thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170033414 2017-03-16
KR10-2017-0033414 2017-03-16
KR10-2018-0030410 2018-03-15
KR1020180030410A KR102115601B1 (ko) 2017-03-16 2018-03-15 구조체

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/268,925 Continuation US11251438B2 (en) 2017-03-16 2019-02-06 Tube structure having metal on inner surface thereof

Publications (1)

Publication Number Publication Date
WO2018169337A1 true WO2018169337A1 (fr) 2018-09-20

Family

ID=63522525

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/003077 Ceased WO2018169337A1 (fr) 2017-03-16 2018-03-16 Structure

Country Status (1)

Country Link
WO (1) WO2018169337A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005174755A (ja) * 2003-12-11 2005-06-30 Nissan Motor Co Ltd 電極触媒、該触媒を用いた触媒担持電極およびｍｅａ
KR20140138806A (ko) * 2012-03-02 2014-12-04 코넬 유니버시티 나노섬유들을 포함하는 리튬 이온 배터리들
KR20150092980A (ko) * 2014-02-06 2015-08-17 한국교통대학교산학협력단 다공성 중공구조의 나노섬유 형태를 갖는 리튬이차전지용 양극활물질의 제조방법 및 그 제조방법에 의해 제조된 양극활물질 및 그 양극활물질을 포함한 리튬이차전지
JP5919138B2 (ja) * 2012-08-22 2016-05-18 株式会社ノリタケカンパニーリミテド Ｐｔ担持マイクロチューブとその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005174755A (ja) * 2003-12-11 2005-06-30 Nissan Motor Co Ltd 電極触媒、該触媒を用いた触媒担持電極およびｍｅａ
KR20140138806A (ko) * 2012-03-02 2014-12-04 코넬 유니버시티 나노섬유들을 포함하는 리튬 이온 배터리들
JP5919138B2 (ja) * 2012-08-22 2016-05-18 株式会社ノリタケカンパニーリミテド Ｐｔ担持マイクロチューブとその製造方法
KR20150092980A (ko) * 2014-02-06 2015-08-17 한국교통대학교산학협력단 다공성 중공구조의 나노섬유 형태를 갖는 리튬이차전지용 양극활물질의 제조방법 및 그 제조방법에 의해 제조된 양극활물질 및 그 양극활물질을 포함한 리튬이차전지

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIN, DINGCHANG ET AL.: "Reviving the Lithium Metal Anode for High-energy Batteries", NATURE NANOTECHNOLOGY, vol. 12, 7 March 2017 (2017-03-07), pages 194 - 206, XP055567835 *
See also references of EP3486982A4 *

Similar Documents

Publication Publication Date Title
WO2020040586A1 (fr) Composite à base de silicium, anode le comprenant, et batterie secondaire au lithium
WO2017052281A1 (fr) Matériau actif d'anode pour pile rechargeable au lithium et procédé de production correspondant
WO2021025349A1 (fr) Anode, son procédé de fabrication et batterie secondaire la comprenant
WO2017052278A1 (fr) Matériau actif d'anode pour pile rechargeable au lithium et son procédé de fabrication
WO2020080831A1 (fr) Électrode à structure tridimensionnelle et élément électrochimique la comprenant
WO2021010753A1 (fr) Anode lithium-métal et batterie lithium-métal la comprenant
WO2021040386A1 (fr) Batterie rechargeable au lithium et son procédé de fabrication
WO2021251663A1 (fr) Anode et batterie secondaire la comprenant
WO2022154309A1 (fr) Procédé pour charger et décharger une batterie secondaire
WO2021066580A1 (fr) Matériau actif d'anode, procédé de préparation de matériau actif d'anode, anode le comprenant et pile secondaire au lithium
WO2020067830A1 (fr) Matériau actif pour électrode positive destiné à une batterie secondaire, son procédé de production et batterie secondaire au lithium le comprenant
WO2020180125A1 (fr) Batterie secondaire au lithium
WO2023059151A1 (fr) Composition d'électrode négative, électrode négative pour batterie secondaire au lithium comprenant celle-ci, batterie secondaire au lithium comprenant une électrode négative et procédé de préparation de la composition d'électrode négative
WO2020235909A1 (fr) Matériau actif de cathode pour batterie secondaire au sodium dopé au calcium, et batterie secondaire au sodium le comprenant
WO2024117675A1 (fr) Batterie à l'état solide
WO2017074109A1 (fr) Cathode pour pile rechargeable, son procédé de préparation, et pile rechargeable au lithium la comprenant
WO2023214711A1 (fr) Électrode négative pour batterie secondaire au lithium, procédé de fabrication d'électrode négative pour batterie secondaire au lithium, et batterie secondaire au lithium comprenant une électrode négative
WO2019013467A2 (fr) Procédé de fabrication d'une structure
WO2022010225A1 (fr) Anode, et batterie rechargeable comprenant cette anode
WO2024253469A1 (fr) Dispositif électrochimique à haute densité d'énergie contenant du phosphate de fer et de lithium
WO2024205084A1 (fr) Batterie lithium-métal et son procédé de fabrication
WO2024147645A1 (fr) Matériau actif d'électrode positive, suspension de matériau actif d'électrode positive, électrode positive, batterie secondaire au lithium-ion et procédé de préparation d'un matériau actif d'électrode positive
WO2023075573A1 (fr) Électrode négative à nanotubes de carbone simple paroi et batterie secondaire la comprenant
WO2018169337A1 (fr) Structure
WO2022255630A1 (fr) Électrode négative de batterie secondaire au lithium et batterie secondaire au lithium la comprenant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18767599

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019528013

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018767599

Country of ref document: EP

Effective date: 20190213

NENP Non-entry into the national phase

Ref country code: DE