WO2015111801A1 - Nanopâte de polyaniline et son procédé de préparation - Google Patents

Nanopâte de polyaniline et son procédé de préparation Download PDF

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WO2015111801A1
WO2015111801A1 PCT/KR2014/003702 KR2014003702W WO2015111801A1 WO 2015111801 A1 WO2015111801 A1 WO 2015111801A1 KR 2014003702 W KR2014003702 W KR 2014003702W WO 2015111801 A1 WO2015111801 A1 WO 2015111801A1
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polyaniline
conductive composition
particles
flexible
present
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PCT/KR2014/003702
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Korean (ko)
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류광선
오지우
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울산대학교 산학협력단
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2375/00—Polyureas; Polyurethanes

Definitions

  • the present invention relates to a conductive composition comprising polyaniline particles having excellent crystallinity and capable of solution processing, a method for preparing the same, a flexible electrode manufactured using the same, and a flexible lithium secondary battery including the flexible electrode.
  • polyaniline in the conjugated polymer is polymerized relatively simply by chemical oxidation, and is stable in air even in a state of high conductivity.
  • polyaniline has a different chemical structure in the oxidation-reduction, doping-dedoping state, and this structural change is reversible and thus has stable and various electrochemical properties. Accordingly, various studies related to the structure, synthesis, and application for using polyaniline for lithium secondary batteries and the like have been conducted.
  • Japanese Patent Laid-Open No. 06-200019 discloses a method for producing soluble polyaniline using iron sulfate as a catalyst
  • Korean Patent Laid-Open Nos. 2005-0110911 and 2013-0017336 disclose additives in phenolic solvents. Mixing and dispersing polyaniline to disclose an electrode material capable of a solution process.
  • Patent Document 1 the polyaniline produced is only soluble in N-methylpyrrolidone (NMP, Nmethylpyrrolidone) and N, N-dimethylformamide (DMP, N, N-Dimethyl Formamide) Toluene, which is mainly used as a resin coating agent, has a problem that the solubility is remarkably inferior.
  • Patent Documents 2 and 3 have to use excessive carcinogenic organic solvent in order to manufacture polyaniline, the risk of work is high, the structural modification of polyaniline due to the heat treatment (150-200 °C) process to remove the high boiling point solvent And there is a problem that the performance is caused by this.
  • An object of the present invention is to provide a polyaniline nano paste excellent in crystallinity and possible solution process.
  • Another object of the present invention to provide a method for producing the polyaniline nano paste.
  • Another object of the present invention to provide a flexible electrode prepared using the polyaniline nano paste.
  • Still another object of the present invention is to provide a flexible lithium secondary battery including the flexible electrode.
  • the present invention in one embodiment, the polyaniline particles; And
  • P 1 is the diffraction peak intensity of 22 to 23 ° represented by 2 ⁇ ,
  • P 2 is the diffraction peak intensity of 26 to 27 ° is represented by ⁇ 2.
  • the present invention in one embodiment, the method comprising the steps of preparing a polyaniline (ES) doped with a first dopant;
  • It provides a method for producing a conductive composition comprising the step of doping the polyaniline by mixing the undoped polyaniline solution and the second dopant.
  • the present invention in one embodiment, a flexible substrate; Negative electrode current collector; And it provides a flexible electrode comprising a polyaniline nano paste layer comprising the conductive composition.
  • the flexible electrode
  • a flexible lithium secondary battery including a counter electrode.
  • the conductive composition including the polyaniline particles according to the present invention includes polyaniline particles with improved crystallinity and doping level in high density, so that a large amount of flexible electrode can be prepared in a solution process, thereby making it easy to work and economically advantageous.
  • the flexible electrode manufactured using the same has excellent electrical conductivity, and the flexible lithium secondary battery including the flexible electrode and the solid polymer electrolyte has an advantage of improving stability against leakage of electrolyte.
  • 1 is an image showing the FT-IR spectrum of polyaniline included in polyaniline nanopaste in one embodiment
  • FIG. 2 is an image showing the UV spectrum of polyaniline in one embodiment: wherein (a) is the spectrum of de-doped polyaniline, (b) is the spectrum of doped polyaniline, and (c) is polyaniline The spectrum of the nanopaste is shown;
  • FIG. 3 is an image showing the X-ray diffraction spectrum of doped polyaniline in one embodiment, wherein (a) is the spectrum of doped polyaniline and (b) is the spectrum of polyaniline nanopaste;
  • SEM scanning electron microscope
  • FIG. 5 is an image taken of painting test results of doped polyaniline in one embodiment: (a) is an image using a doped polyaniline solution, and (b) is an image using polyaniline nanopaste; FIG.
  • FIG. 6 is an image photographing a coating result using a screen printing technique of polyaniline nanopaste in one embodiment
  • FIG. 9 is an image photographing generated voltage results of the manufactured flexible lithium secondary battery according to one embodiment.
  • 10 is an image showing the structure of a flexible lithium secondary battery according to the present invention: where 100 is a flexible lithium secondary battery, 101: counter electrode, 102: solid-state polymer electrolyte, 103: flexible electrode, 104: positive electrode active material, 105 : Positive electrode current collector, 106: polyaniline nano paste layer, 107: negative electrode current collector, 108: flexible substrate;
  • FIG. 11 is a graph showing charge and discharge curves for each flexible lithium secondary battery prepared using a doped polyaniline solution and a doped polyaniline nanopaste in one embodiment: wherein (a) is a doped polyaniline nano A flexible lithium secondary battery made of a paste, and (b) is a flexible lithium secondary battery made of a doped polyaniline solution;
  • FIG. 12 is a graph showing charge and discharge cycles for each flexible lithium secondary battery prepared using a doped polyaniline solution and a doped polyaniline nanopaste, in one embodiment: wherein (a) is a doped polyaniline nano A flexible lithium secondary battery made of a paste, and (b) is a flexible lithium secondary battery made of a doped polyaniline solution.
  • the terms "comprises” or “having” are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.
  • low boiling point solvent means an organic solvent having a boiling point in the range of 0 to 100 ° C.
  • low boiling point solvent for example, diethylether, acetone, actone, methylethylketone, chloroform, chloroform, dichloromethane, methanol, ethanol, n-hexane, tetrahydrofuran, etc. are mentioned.
  • the present invention provides a conductive composition comprising polyaniline particles, a method for preparing the same, a flexible electrode prepared using the same, and an all-solid-state flexible lithium secondary battery including the flexible electrode.
  • the present invention proposes a conductive composition including polyaniline particles, a method for preparing the same, a flexible electrode manufactured using the same, and an all-solid-state flexible lithium secondary battery including the flexible electrode.
  • the conductive composition including the polyaniline particles according to the present invention includes polyaniline particles with improved crystallinity and doping level in high density, so that a large amount of flexible electrode can be prepared in a solution process, thereby making it easy to work and economically advantageous.
  • the flexible electrode manufactured using the same has excellent electrical conductivity, and the flexible lithium secondary battery including the flexible electrode and the all-solid electrolyte has an advantage in that stability against electrolyte leakage is improved.
  • the present invention in one embodiment, the polyaniline particles; And
  • P 1 is the diffraction peak intensity of 22 to 23 ° represented by 2 ⁇ ,
  • P 2 is the diffraction peak intensity of 26 to 27 ° is represented by ⁇ 2.
  • the polyaniline particles included in the conductive composition according to the present invention have diffraction peaks of 22 to 23 ° and 26 to 27 ° represented by 2 ⁇ when measured by X-ray diffraction.
  • 22 to 23 ° peak (P 1) represented by the 2 ⁇ is a peak plane index of [100], the relevant period and of the vertical surface
  • 26 to 27 ° peak (P 2) is a surface index [110] of the peak As a peak reflecting the local crystallinity of the polyaniline itself.
  • the conductive composition according to the present invention includes polyaniline particles having excellent crystallinity and doping level.
  • 16.7 °, 22.4 °, 26.5 ° expressed by ⁇ 2 can have a 27.5 ° and 30.2 ° a diffraction peak value.
  • FIG. 3 is a graph depicting an X-ray diffraction pattern for (a) doped polyaniline and (b) doped polyaniline nanopaste, the conductive composition according to the present invention, in one embodiment.
  • the X-ray diffraction measurement of the conductive composition comprising the polyaniline particles and the organic solvent according to the present invention the diffraction peak represented by 2 ⁇ is 16.7 °, 22.4 °, 26.5 °, At 27.5 ° and 30.2 °, the interference between the peaks was relatively less visible and clear. In this case, the less interference and sharpness of each peak means that the area having amorphous is reduced.
  • the conductive composition according to the present invention includes polyaniline particles having excellent crystallinity and doping level, and the electrical conductivity is also improved due to the improved crystallinity and doping level.
  • Particles having an average particle diameter of 40 to 60 nm are at least 70% of the total particles
  • Particles having an average particle diameter of 30 to 80 nm may include polyaniline particles that are at least 95% of the total particles.
  • the polyaniline particles are not particularly limited in form, but specifically, the maximum angle inside the hexahedron may be a hexahedron having 90 to 120 °.
  • FIG. 4 is a scanning electron microscope image of (a) doped polyaniline and (b) doped polyaniline nanopaste, the conductive composition according to the present invention, in one embodiment.
  • the polyaniline nano paste of the conductive composition according to the present invention includes particles having an average particle diameter of 40 to 60 nm polyaniline particles of 70% or more of the total particles. It can also be seen that the particles having an average particle diameter of 30 to 80 nm include polyaniline particles which are 95% of the total particles. Furthermore, it can be seen that the conductive composition is a mixture of polyaniline particles in the form of a cube or a cube. This means that the polyaniline particles have a uniform size of 100 nm or less, and their shape is also constant as a cuboid or a cube.
  • the conductive composition including the uniform polyaniline particles not only has excellent crystallinity but also excellent electrical conductivity due to improved crystallinity.
  • the conductive composition according to the present invention may be in the form of a paste, wherein the density (D) of the polyaniline particles included in the conductive composition may satisfy the following Equation 2:
  • the conductive composition may include polyaniline particles having excellent crystallinity in a minimum density in a high organic solvent, and thus may be applied to a solution process when manufacturing a large area electrode, thereby having an economical advantage.
  • the polyaniline particles are specifically 40 mg / mL to 20 mg / mL; 40 mg / mL to 150 mg / mL; 40 mg / mL to 100 mg / mL; 50 mg / mL to 180 mg / mL; 50 mg / mL to 100 mg / mL; 50 mg / mL to 80 mg / mL; It may have a density of 100 mg / mL to 200 mg / mL or 100 mg / mL to 150 mg / mL.
  • FIG. 5 is an image photographing a painting test result of the polyaniline solution and the polyaniline nanopaste in one embodiment.
  • the coating of the conductive composition (b) doped polyaniline nanopaste showed that polyaniline was uniformly applied to the substrate.
  • the conventionally prepared (a) doped polyaniline solution not only the area where polyaniline is applied to the substrate is markedly small, but also the polyaniline to be applied is not uniform.
  • the conductive composition according to the present invention has excellent solution processability.
  • the organic solvent of the conductive composition according to the present invention is not particularly limited as long as it is a solvent in which polyaniline is dissolved. More specifically, for example, N-methylpyrrolidone (NMP, N-methylpyrrolidone), chloroform (cnloroform), N, N- dimethylformamide (DMF, N, N-dimethylformamide), m-cresol (m -cresol) can be used.
  • NMP N-methylpyrrolidone
  • chloroform chloroform
  • N, N- dimethylformamide DMF, N, N-dimethylformamide
  • m-cresol m-cresol
  • an organic solvent having a low boiling point such as chloroform
  • the organic solvent of the conductive composition has an effect of preventing structural deformation of polyaniline generated by high temperature heat treatment to remove the organic solvent having a high boiling point when manufacturing a flexible electrode. have.
  • the conductive composition according to the present invention may further include any one or more additives of a binder and a conductive agent.
  • the binder may be used to adhere the conductive composition to the flexible substrate in the manufacture of the flexible electrode.
  • the binder applicable to the present invention for example, polyvinylidene fluoride (PVdF, polyvinylidene fluoride), polytetrafluoroethylene (PTFE, polytetrafluoroethylene), carboxymethyl cellulose / styrene-butadiene rubber (CMC- SBR, carboxymethyl cellulose / styrene-butadiene rubber), polyolefins, polyimides, polyurethanes, polyesters or mixtures thereof, but is not limited thereto.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • CMC- SBR carboxymethyl cellulose / styrene-butadiene rubber
  • polyolefins polyimides
  • polyurethanes polyesters or mixtures thereof, but is not limited thereto.
  • the conductive agent may be used to improve the flow of current in the flexible electrode manufactured using the conductive composition according to the present invention.
  • the conductive agent applicable to the present invention for example, super-p, carbon black, acetylene flag, acetylene black, denka black, ketjen black Or a carbon-based conductive agent including vapor grown carbon fiber (VGCF); Silver (Ag); Aluminum (Al); Copper (Cu); Zinc (Zn) or mixtures thereof, but is not limited thereto.
  • a method of making a conductive composition comprising mixing a undoped polyaniline solution and a second dopant to dope polyaniline in a solution.
  • the first dopant dissolved in water and aniline monomers are mixed and stirred, and then an initiator is added to polymerize the aniline monomers, and the reaction mixture is filtered.
  • Polyaniline can be prepared.
  • the polyaniline prepared may be an emeraldine salt (ES) in a doped state.
  • ES emeraldine salt
  • the first dopant applicable to the present invention may be, for example, hydrofluoric acid (HF), hydrochloric acid (HCl), perchloric acid (HClO 4 ), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), or fluorosulfonic acid ( FSO 3 H), sulfonic acid (CH 3 SO 3 H), camphorsulfonic acid (camphorsulfonic acid), polystyrenesulfonate (PSS, polystyrenesulfonate), p-toluenesulfonic acid (p-TSA, p-toluenesulfonic acid), dodecyl benzene sulfonic acid (DBSA dodecyl benzene sulfonic acid) or mixtures thereof, but is not limited thereto.
  • HF hydrofluoric acid
  • HCl hydrochloric acid
  • HSO 4 nitric acid
  • sulfuric acid H 2 SO 4
  • the polymerization may be carried out by stirring at room temperature for 5 minutes to 1 hour, and when preparing a polyaniline having a weight average molecular weight (M w ) of about 50,000, it may be performed by stirring at 0 ° C. for 24 hours.
  • M w weight average molecular weight
  • a undoped polyaniline that is, emeralide base (EB)
  • EB emeralide base
  • a reducing agent applicable to the present invention for example, ammonium hydroxide (NH 4 OH), sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) 2 ) or a mixture thereof may be mentioned. However, it is not limited thereto.
  • the de-doped polyaniline solution may be prepared by dissolving the de-doped polyaniline in the organic solvent included in the conductive composition.
  • the size and shape of the doped polyaniline particles can be controlled according to the amount of the undoped polyaniline powder in the organic solvent, that is, the concentration of the dissolved solution.
  • the organic solvent according to the present invention is not particularly limited as long as it is a solvent in which polyaniline is dissolved. More specifically, for example, N-methylpyrrolidone (NMP, N-methylpyrrolidone), chloroform (cnloroform), N, N- dimethylformamide (DMF, N, N-dimethylformamide), m-cresol (m -cresol) can be used.
  • NMP N-methylpyrrolidone
  • chloroform chloroform
  • N, N- dimethylformamide DMF, N, N-dimethylformamide
  • m-cresol m-cresol
  • the doped polyaniline solution may be prepared by mixing the undoped polyaniline solution prepared in the step and the second dopant and performing a reaction in a reactor in which mechanical external force is applied.
  • the mechanical external force used in this step serves to maintain the uniform size and shape of the particles of polyaniline.
  • the size and shape of the doped polyaniline particles can be adjusted according to the concentration of the second dopant mixed in the undoped polyaniline solution.
  • Examples of the second dopant applicable to the present invention include hydrofluoric acid (HF), hydrochloric acid (HCl), perchloric acid (HClO 4 ), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), and fluorosulfonic acid (FSO).
  • HF hydrofluoric acid
  • HCl hydrochloric acid
  • HNO 3 perchloric acid
  • FSO fluorosulfonic acid
  • the reactor to which the mechanical external force acts is not particularly limited as long as it is a device capable of pulverizing the reactant at the same time. Specifically, a ball mill etc. are mentioned, for example.
  • Centrifugation may further comprise any one or more of the steps of removing excess solvent.
  • the step of pulverizing the undoped polyaniline according to the present invention serves to homogenize the particles of polyaniline by pulverizing the polyaniline with an external force before dissolving the polyaniline in the organic solvent included in the conductive composition.
  • Polyaniline particles homogenized by this step can be improved in electrical conductivity with better crystallinity.
  • the step of mixing an additive in the doped polyaniline solution according to the present invention is to improve the adhesion of the polyaniline solution to the flexible substrate by mixing a binder or a conductive agent with the doped polyaniline solution, or using a polyaniline solution It is possible to improve the current flow of the flexible electrode to be manufactured.
  • the step of removing the excess solvent by centrifugation can increase the polyaniline density of the polyaniline solution.
  • the density of the polyaniline solution is low, it is not easy to manufacture a large-area flexible electrode.
  • the supernatant which is a surplus solvent, is removed to increase the density of polyaniline in the polyaniline solution to 40 mg / mL. To 200 mg / mL.
  • the flexible electrode is manufactured by using the polyaniline nanopaste according to the present invention, and has an advantage in that electrical conductivity is superior to that of a flexible electrode prepared using a conventional general polyaniline solution.
  • the flexible substrate according to the present invention is a substrate on which the flexible electrode is based, and when the external force is applied from the outside, the flexible substrate should have a characteristic that the flexibility works.
  • the flexible substrate applicable to the present invention is not particularly limited as long as it is a flexible substrate.
  • a flexible substrate for example, polyethylene terephthalate (PET, poly (ethyleneterephthalate)), polyethylene naphthalate (PEN, poly (ethylene naphthalate))
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PES polyether sulfone
  • the negative electrode current collector according to the present invention generally has a thickness of 3 to 500 ⁇ m, and is not particularly limited as long as it has high conductivity without causing chemical change in the battery, for example, copper or stainless steel.
  • Steel, aluminum, nickel, titanium, calcined carbon, or aluminum, stainless steel, etc. to which carbon, nickel, titanium, silver, etc. were surface-treated can be used. More specifically, nickel can be used.
  • the negative electrode current collector may form fine irregularities on its surface to increase the adhesion of the negative electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the polyaniline nanopaste layer according to the present invention is a layer comprising a conductive composition containing the polyaniline particles according to the present invention, by using the conductive composition, when manufacturing a large area of the flexible electrode, a solution process is possible It is easy to work with and has an economic advantage.
  • the polyaniline particles included in the conductive composition have improved crystallinity and doping level, the electrical conductivity is excellent.
  • the flexible electrode according to the present invention can be manufactured by the following manufacturing method:
  • coating the conductive composition may be performed by a solution process.
  • a dip coating method, a spin coating method, a meniscus coating method, a printing method, a spray coating method, etc. are mentioned, for example. More specifically, the printing method can be used.
  • the solution process can be simple, low installation cost and manufacturing cost, by depositing the material in the desired pattern position, there is no material loss in principle, there is no waste of raw materials, and the environmental load can be low.
  • a process such as development and etching is not required like photolithography, there is an advantage that the characteristics of the substrate and the material are not degraded by chemical influence.
  • the step of drying by heat treatment may be performed for 5 to 48 hours at a temperature of 50 to 100 °C.
  • the flexible electrode according to the present invention may be manufactured by the manufacturing method as described above, but is not limited thereto, and may be manufactured by various manufacturing methods conventionally used in the art.
  • the flexible electrode
  • a flexible lithium secondary battery including a counter electrode.
  • the flexible lithium secondary battery includes the flexible electrode according to the present invention
  • the flexible lithium secondary battery has not only excellent electrical conductivity as compared to an electrode including a general polyaniline, but also includes a solid polymer electrolyte, thereby improving safety of leakage of electrolyte. have.
  • the flexible lithium secondary battery according to the present invention has a discharge capacity of about 1.5 times as compared to a flexible lithium secondary battery prepared from a polyaniline solution which is generally manufactured during charging and discharging of a battery. In addition to being excellent, it can be seen that it has an excellent charge and discharge cycle of 100 or more times.
  • the flexible lithium secondary battery 100 has a structure in which the flexible electrode 103, the solid polymer electrolyte 102, and the counter electrode 101 are sequentially stacked.
  • the counter electrode 101 refers to a lithium electrode, and is supported on a positive electrode current collector 105 and one or both surfaces of the positive electrode current collector 105, and includes a positive electrode active material 104. It includes.
  • the cathode active material 104 uses a lithium metal sheet, or LiCoO 2 , LiClO 4 , LiNiO 2 , LiCF 3 SO 3 , LiBF 4 , LiPF 6 , LiAsF 6 , Li (CF 3 SO 2 ) 2 N
  • a porous conductive substrate or a nonporous conductive substrate may be used.
  • these conductive substrates copper, stainless steel, aluminum, nickel, titanium, calcined carbon, aluminum, stainless steel, etc. which processed carbon, nickel, titanium, silver, etc. on the surface are mentioned, for example.
  • the counter electrode 101 may include a binder for bonding the positive electrode active material 104 and the positive electrode current collector 105 or connecting the positive electrode active material 104; And it may further include any one of a conductive agent for improving the current flow of the counter electrode (101).
  • solid polymer electrolyte 102 for example, polyethylene-based resin, polyethylene oxide-based resin, polypropylene oxide-based resin, phosphate ester polymer, poly-edgetion lysine, polyester liquor
  • a fused resin a polyvinyl alcohol resin, a polyvinylidene fluoride resin, a resin including an ionic dissociating group, and the like may be used, but is not limited thereto.
  • the flexible lithium secondary battery 100 according to the present invention may improve the safety against leakage of the lithium secondary battery 100 generated by using an electrolyte solution by using the solid polymer electrolyte 102.
  • the flexible electrode 103 according to the present invention is an electrode that serves as a cathode, the flexible substrate 108; The negative electrode current collector 107; And a polyaniline nanopaste layer 106 including the conductive composition.
  • the electrode according to the present invention has the advantage of excellent electrical conductivity compared to the electrode produced using a polyaniline solution by using a polyaniline nano paste containing uniform polyaniline particles.
  • the flexible lithium secondary battery according to the present invention may be manufactured by the following manufacturing method:
  • Impregnating a solid polymer electrolyte before solidification into a material such as polyethylene, polypropylene, nonwoven fabric, or the like;
  • the impregnation of the solid polymer electrolyte before solidification may be performed by impregnation of the solid polymer electrolyte before solidification into a material such as polyethylene, polypropylene, and nonwoven fabric.
  • the solidifying the solid polymer electrolyte before solidification may be performed by solidifying the impregnated solid polymer electrolyte before the solidification in an oven at 80 to 100 ° C.
  • the flexible lithium secondary battery according to the present invention may be manufactured by the manufacturing method as described above, but is not limited thereto, and may be manufactured by various manufacturing methods conventionally used in the art.
  • the emeraldine salt (ES) was added to 300 mL of a 1 M NH 4 OH aqueous solution, stirred for 1 hour, dedoped, and the precipitate was filtered using a filter paper and an aspirator.
  • the filtered filtrate was washed with 500 mL of 1 M NH 4 OH, dried in a vacuum oven at 60 ° C. for 48 hours, and then the filtrate was uniformly ground with a mortar to prepare an emeraldine base (EB) powder. It was.
  • Emeraldine base (10.330 g) was added dropwise and dissolved in N-methyl-2-pyrrolidone (500 mL, NMP) stirred at room temperature over 2 hours to give 2% by weight of emeraldine base (EB). ) Solution was prepared. The solution (60 mL) was injected into a zirconia vessel, 1 M HCl (1 mL) was added, followed by mixing with eight zirconia balls to form the emeraldine base (EB) in the emeraldine salt. doped with (emeraldine salt, ES).
  • the doped emeraldine salt solution was centrifuged at 5,000 rpm for 30 minutes, the excess supernatant was removed, the precipitate was again injected into a container of zirconia, mixed with eight zirconia balls at 300 rpm and doped polyaniline nano Paste was prepared.
  • the polyaniline according to the present invention has peaks at 1588, 1492, 1302, 1142, 832 and 677 cm ⁇ 1 .
  • the peak by the benzonoid ring appears stronger than the peak by the quinoid ring, meaning that the synthesized polyaniline is doped with emeraldine.
  • the sheet was cut to a size of 5 cm and 5 cm, and coated by printing using silver (Ag) paste.
  • the masking tape was then removed from the silver (Ag) paste coated substrate and dried in a 150 ° C. oven for 15 minutes.
  • N-methyl-2-pyrrolidone (0.3 mL, NMP) and polyvinylidene fluoride (0.01 g, PVdF) were added to the vessel and then mixed with eight zirconia balls at 120 rpm for 20 minutes.
  • the conductive agent super-P (0.02 g, super-p) was added and mixed for 30 minutes, and the doped polyaniline nano paste (1.5 mL, solid content) prepared in Example 1 having a solid density of about 50 mg / mL.
  • a weight of 0.07 g) was injected into the container, followed by mixing at 320 rpm for 2 hours to prepare a polyaniline nanopaste including a binder and a conductive agent.
  • the mixing ratio of the doped polyaniline, the polyvinylidene fluoride (PVdF) as a binder and the super-p as the conductive agent is 70:10:10 (wt./wt.).
  • the remaining portion was masked with a tape so that the silver paste portion area was exposed to 3 cm and 3 cm, and the exposed portion was coated with polyaniline nanopaste using screen printing technique.
  • the masking tape was then removed and dried in an oven at 60 ° C. for 24 hours to produce a 60 ⁇ m thick flexible electrode.
  • the coated substrate coated with the screen printing technique and the flexible electrode produced are shown in FIGS. 6 and 7.
  • the nonwoven fabric was impregnated with the liquid-phase solidified polymer electrolyte, which was laminated on the flexible electrode prepared in Example 2.
  • the nonwoven fabric has a size of 3.8 cm wide, 3.8 cm long and 14 ⁇ m high.
  • a lithium sheet of 3.2 cm in width and 3.2 cm in length was laminated on the nickel mesh, which is a negative electrode current collector, to compress the lithium sheet and the nickel mesh to a thickness of 0.2 mm.
  • the pressed lithium sheet and nickel mesh were laminated on the nonwoven fabric and then heat treated in an 80 ° C. oven for 30 minutes.
  • the heat-treated laminate was fixed with a flexible electrode and a counter electrode with polyimide tape, coated with a polyvinyl acetate resin, except for a tab, and dried for 24 hours to prepare a flexible lithium secondary battery. .
  • the flexible lithium secondary battery thus prepared is shown in FIG. 8.
  • the open circuit voltage of the flexible lithium secondary battery according to the present invention is about 3.1V.
  • the emeraldine salt (ES) was added to 300 mL of a 1 M NH 4 OH aqueous solution, stirred for 1 hour, dedoped, and the precipitate was filtered using a filter paper and an aspirator. The filtered filtrate was washed with 500 mL of 1 M NH 4 OH, dried in a vacuum oven at 60 ° C. for 48 hours, and then dissolved in N-methyl-2-pyrrolidone (500 mL, NMP) to form an emeraldine base solution. (EB) was prepared.
  • EB emeraldine base N-methyl Emeraldine base solution
  • UV-Vis for (a) didoped polyaniline solution, (b) doped polyaniline solution and (c) doped polyaniline nanopaste prepared in Comparative Examples 1, 2 and 1, respectively.
  • the spectrum was measured using a UV-Vis analyzer (Optizen analyzer, Mecasys co.) At 25 °C, 200-1000 nm range, the results are shown in FIG.
  • the polyaniline particles of the (c) polyaniline nano paste of the conductive composition according to the present invention has an excellent doping level.
  • peaks around 327 nm were observed in all polyanilines. This peak is the peak attributable to the ⁇ ⁇ ⁇ * transition of polyaniline.
  • Polyaniline has a property of being easily oxidized because the band gap is high at 4.0 eV and the ionization energy is small at 5.1 eV. That is, when polyaniline is doped with a dopant, a part of the valence band is missing. As a result, electrons may be transferred to the generated conduction band to impart conductivity, and thus, ⁇ ⁇ ⁇ * of (b) the doped polyaniline solution of Comparative Example 2 and (c) the doped polyaniline nanopaste of Example 1 at the same wavelength. The transition occurs more actively, showing a higher peak than the (a) didoped polyaniline solution of Comparative Example 1.
  • the peak of the (c) doped polyaniline nanopaste is higher than the (b) doped polyaniline solution and shifted toward the longer wavelength. This indicates that (c) the ⁇ ⁇ ⁇ * transition of the doped polyaniline nanopaste is more active and more easily generated, from which the (c) doped polyaniline nanopaste has the highest doping effect and the highest conductivity. have.
  • the doped polyaniline solution and (c) the doped polyaniline nanopaste have a near infrared absorption peak over 500 nm to 1000 nm.
  • the peak is due to the delocalization of the charge carrier, which is common in materials with high electrical conductivity, and indicates that (c) the charge carrier of the doped polyaniline nanopaste is more delocalized.
  • the conductive composition according to the present invention includes polyaniline particles having an excellent doping level, as compared with the conventionally prepared didoped polyaniline solution and doped polyaniline solution.
  • X-ray diffraction spectra of (a) the doped polyaniline solution and (b) the doped polyaniline nanopaste prepared in Comparative Example 2 and Example 1 were measured.
  • the polyaniline sample was used to make each of (a) the doped polyaniline solution and (b) each of the doped polyaniline nano pastes completely dried in an oven at 60 ° C. for 48 hours and then finely ground in a mortar to form a powder.
  • Each of the samples was measured to be evenly distributed on the sample holder, and the amount used was such that the sample distributed on the holder was evenly filled with a diameter of about 1 cm.
  • Rigaku ultra-X (Cu Ka radiation, 40kV, 120mA) was used as a measuring instrument, and the wavelength was 1.5406 kHz, and the X-ray diffraction pattern was obtained at a scanning speed of 0.02 ° / sec in the 10-80 ° range at 2 ⁇ . The results are shown in FIG. The results are shown in FIG.
  • the polyaniline particles of the polyaniline nanopaste which is a conductive composition according to the present invention, not only have excellent crystallinity and doping level, but also have excellent electrical conductivity.
  • the doping degree of the polyaniline is the ratio of the dopant and nitrogen atoms, that is, [Cl] / [N] ratio This means less than 0.5.
  • the doped polyaniline nanopaste it can be seen that the relative ratio of 26.5 ° peak is greater than 22.4 ° peak, from which the [Cl] / [N] ratio has reached a level of about 0.5. Able to know.
  • the 27.5 ° peak with the surface index [1 1 1] and the 30.2 ° peak with the [0 2 0] surface index are also peaks indicating a high doping level.
  • the conductive composition according to the present invention has excellent crystallinity and doping level.
  • the pattern of the polyaniline nanopaste (b) with less interference and clearness between peaks as a whole means that the portion having an amorphous phase was reduced, it can be seen that the conductive composition has better electrical conductivity compared to a general polyaniline solution.
  • the polyaniline nanopaste which is a conductive composition according to the present invention, includes polyaniline particles having excellent crystallinity.
  • the doped polyaniline nano paste of Example 1 is a particle having an average particle diameter of 40 to 60 nm is 70% or more of the total particles, the average particle diameter of 30 to 80 nm It can be seen that the particles having a uniform size are generally at least 95% of the total particles.
  • polyaniline particles have been shown to have the form of a cube or a cube.
  • the (a) doped polyaniline solution of Comparative Example 2 was confirmed that the primary particles of 20 to 50 nm size, such as skeins agglomerated with each other to produce secondary particles of 10 to 100 ⁇ m size.
  • the shape has a spherical granular structure, but the granularity was found to be remarkably inferior.
  • the conductive composition according to the present invention is excellent in solution processability.
  • the conductive composition according to the present invention is excellent in solution processability by including polyaniline particles having excellent crystallinity with a high density in a minimum organic solvent.
  • the conductive composition according to the present invention has improved electrical conductivity.
  • the substrate using the doped polyaniline nanopaste of Example 1 (b), which is a conductive composition according to the present invention was found to have an electrical conductivity of 1.70 ⁇ 10 ⁇ 1 S / cm.
  • the substrate using the doped polyaniline solution of Comparative Example 2 (a), which is generally prepared was found to have an electrical conductivity of 1.09 ⁇ 10 ⁇ 1 S / cm.
  • the conductive composition according to the present invention includes polyaniline particles having excellent crystallinity and doping level, and thus has about 1.6 times better electrical conductivity compared to the conventionally prepared doped polyaniline solution.
  • the charge and discharge curves of the (a) flexible lithium secondary battery prepared in Example 3 were measured.
  • the measurement was performed at a room temperature of 25 °C, a voltage range of 2.5 V to 4.1 V, the current density was fixed at 5 ⁇ A / cm 2 .
  • the measured results are shown in FIGS. 11 and 12.
  • the flexible lithium secondary battery according to the present invention has excellent charge and discharge capacity.
  • the charge and discharge curves of the (a) flexible lithium secondary battery prepared in Example 3 represent charge and discharge characteristics of typical polyaniline, and the discharge capacity was found to be about 112 mAh / g.
  • the shape of the charge / discharge curve shows the charge / discharge characteristics of typical polyaniline, but the discharge capacity is about 75 mAh / g. Appeared.
  • the flexible lithium secondary battery according to the present invention has an excellent discharge capacity of about 1.5 times as compared to the flexible lithium secondary battery prepared with a polyaniline solution, which is generally manufactured in general, and also has a superior charge / discharge cycle.

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Abstract

La présente invention concerne une composition conductrice comprenant des particules de polyaniline, son procédé de préparation, une électrode souple préparée en l'utilisant, et une batterie rechargeable au lithium souple tout solide comprenant l'électrode souple. La composition conductrice comprenant des particules de polyaniline, selon la présente invention, comprend une haute densité de particules de polyaniline ayant un degré de cristallinité amélioré et un niveau de dopage amélioré, ce qui permet un traitement en solution et facilite le travail durant la fabrication d'électrodes souples de grande superficie, entraînant donc un avantage économique. De plus, l'électrode souple fabriquée en utilisant cette composition possède une excellente conductivité électrique, et la batterie rechargeable au lithium souple comprenant l'électrode souple et un électrolyte polymère en phase solide offre l'avantage d'améliorer la stabilité concernant la fuite de l'électrolyte.
PCT/KR2014/003702 2014-01-23 2014-04-28 Nanopâte de polyaniline et son procédé de préparation WO2015111801A1 (fr)

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