WO2015156446A1 - Composite de nanoparticule de graphène et de métal, composite contenant un composite de nanofibre de carbone, et batterie secondaire contenant un composite de nanoparticule de carbone - Google Patents

Composite de nanoparticule de graphène et de métal, composite contenant un composite de nanofibre de carbone, et batterie secondaire contenant un composite de nanoparticule de carbone Download PDF

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WO2015156446A1
WO2015156446A1 PCT/KR2014/005507 KR2014005507W WO2015156446A1 WO 2015156446 A1 WO2015156446 A1 WO 2015156446A1 KR 2014005507 W KR2014005507 W KR 2014005507W WO 2015156446 A1 WO2015156446 A1 WO 2015156446A1
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composite
graphene
carbon nanofiber
carbon
metal
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Korean (ko)
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양갑승
김보혜
김소연
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전남대학교산학협력단
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 carbon nanofiber composite, and more particularly, to a graphene-metal nanoparticle composite, a carbon nanofiber composite including the composite, and a secondary battery including the carbon nanoparticle composite.
  • lithium metal is used as a negative electrode active material of a lithium secondary battery.
  • carbon-based negative electrode active materials are used instead of lithium metal.
  • graphite graphite
  • the carbon-based negative electrode active material such as graphite has a limited upper limit of about 372 mAh / g. Insufficient negative electrode materials are available.
  • the development of electric vehicles is urgently required due to the depletion of fossil fuels.However, when the existing lithium secondary battery is applied, it is difficult to operate a long distance of more than 200km by a single charge. It is also not suitable for long-term energy storage systems for storing power generated by sources.
  • metal-based anode materials especially silicon (Si) -based anode materials
  • Si silicon
  • the silicon anode material has a problem that a large volume change of more than 300% occurs by causing a change in crystal structure when absorbing and storing lithium.
  • Graphite which is currently used as a cathode material, has a volume expansion rate of about 1.2 times due to lithium charging, whereas, in case of silicon, when lithium is absorbed and stored in the maximum amount, it is converted to Li 4.4 Si and is about 4.12 times larger than the volume of silicon before volume expansion. Because of the expansion, the volume of the electrode collapses due to the volume expansion, and thus the coulombic efficiency becomes low, making it difficult to continue using.
  • the lithium ion battery can be improved during the intercalation / desorption process of lithium.
  • the negative electrode active material for a silicon-based lithium secondary battery hybridized with carbon nanofibers prepared by vapor-growing carbon-coated silicon nanoparticles or carbon nanofibers is pyrolysis method, chemical / thermal vapor deposition (CVD / TVD) method, and chemicals using gel. Synthesis and hydrothermal carbonization methods are used, and these methods require high temperature reaction conditions, require expensive precursors, and have difficulty in commercialization because they are difficult to mass produce.
  • nanostructured electrodes are expected to significantly improve the energy density and velocity characteristics, and the relaxation and speed of volume change due to the insertion / extraction of lithium ions. If the anode or cathode materials have high specific surface area, the solid-state diffusion path is reduced and the interface between anode-membrane-cathode is greatly increased. Therefore, the three-dimensional structure of the nanostructured material will enable high-rate discharge characteristics and high-output lithium-ion batteries. do.
  • nanostructured materials as electrode material by electrospinning not only provides excellent electron conductivity and reduces the diffusion path in the electrode, but also a lot of Li + It is possible to alleviate the stress generated in the lithium secondary battery with high output and high energy density is expected.
  • electrospinning is the only method that can produce hundreds of nanometers to tens of nanofibers using a polymer solution.
  • Carbon nanofibers manufactured using these electrospinning techniques have high electrical conductivity, high specific surface area, metal, Since carbon nanofibers containing metal oxides, porous materials, carbon nanotubes, and the like are easily manufactured, very high electrochemical activity can be expected when manufacturing secondary battery electrode materials.
  • Carbon nanofiber composites and activated carbon nanofiber composites prepared from the composite components of the present invention are excellent in specific surface area and electrical conductivity relative to volume, and constituent fibers form a network. It can be used as an electrode material for electric double layer supercapacitor, electromagnetic wave shielding material, high conductivity material, catalyst support and composite material reinforcement material.
  • the metal nanoparticles are prevented from growing too large or aggregated to prevent them from becoming large particles, and the metal nanoparticles are uniformly dispersed in the carbon nanofibers, and the volume change is alleviated, thereby improving the electrical contactability.
  • a negative electrode active material capable of securing cycle characteristics.
  • the present inventors have completed the present invention by focusing on the fact that a large number of studies have been made to surround the metal nanoparticles with a graphene sheet to prevent the metal nanoparticles from agglomerating into large particles.
  • Another object of the present invention is to provide a carbon nanofiber composite having a graphene-metal nanoparticle composite (G / M composite) evenly dispersed in a carbon nanofiber matrix and a method of manufacturing the same.
  • Another object of the present invention is to include a carbon nanofiber composite containing a G / M composite as an electrode active material, so that the metal nanoparticles are not exposed to the outside of the carbon nanofibers to buffer the volume change of the metal nanoparticles due to charging and discharging
  • an electrode capable of inducing an effective electrochemical reaction by reducing the specific resistance of the electrode surface by preventing the aggregation of metal nanoparticles.
  • Still another object of the present invention is to provide a secondary battery having excellent charge and discharge characteristics, high capacity, and excellent volume stability by applying an electrode including a carbon nanofiber composite having a G / M composite evenly dispersed therein as an electrode active material.
  • the object of the present invention is not limited to the above-mentioned object, and even if not explicitly stated, the object of the invention that can be recognized by those skilled in the art can be naturally included from the description of the detailed description below. .
  • the present invention is a metal nanoparticle; It provides a graphene-metal nanoparticle composite comprising a; and a graphene sheet formed by surrounding the metal nanoparticles.
  • the metal nanoparticles are selected from the group consisting of Si, Sn, Ge, Al, Pb, Zn, Co, Cu, Ti, Ni, Li, Ag, Au.
  • the metal nanoparticles are modified to have a -NH 2 group.
  • the metal nanoparticles and the graphene sheet are coupled by electrostatic attraction.
  • the graphene-metal nanoparticle composite has a size of 50nm or less.
  • the present invention carbon nanofibers; It provides a carbon nanofiber composite comprising a; and graphene-metal nanoparticle composite constituting a portion of the carbon nanofiber.
  • the graphene-metal nanoparticle composite is a metal nanoparticle; And a graphene sheet formed by wrapping the metal nanoparticles.
  • the metal nanoparticles are selected from the group consisting of Si, Sn, Ge, Al, Pb, Zn, Co, Cu, Ti, Ni, Li, Ag, Au.
  • the metal nanoparticles are modified to have a -NH 2 group.
  • the metal nanoparticles and the graphene sheet are coupled by electrostatic attraction.
  • the carbon nanofiber composite has a diameter of 100 to 300 nm, a specific surface area of 300 m 2 / g or less, and an average pore diameter of 1 to 2 nm.
  • the graphene-metal nanoparticle composite is located uniformly dispersed in the carbon nanofibers.
  • the graphene-metal nanoparticle composite can be pulverized to form a powder in a state maintained.
  • the graphene-metal nanoparticle composite has a size of 50nm or less.
  • the present invention comprises the steps of preparing a spinning solution comprising any one of the above-described graphene-metal nanoparticle composite and carbon fiber precursor; Electrospinning the spinning solution to obtain precursor spinning fibers; Oxidatively stabilizing the precursor spun fiber to obtain a flame resistant fiber; And carbonizing the flame resistant fiber to obtain a carbon nanofiber composite.
  • the spinning solution is contained within 30 parts by weight of the graphene-metal nanoparticle composite per 100 parts by weight of the carbon nanofiber precursor and the graphene-metal nanoparticle composite.
  • the carbon nanofiber precursor and graphene-metal nanoparticle composite are included in a weight ratio of 4: 1 to 20: 1.
  • the concentration of the graphene-metal nanoparticle composite contained in the spinning solution to control one or more of the size and distribution of the graphene-metal nanoparticle composite contained in the carbon nanofiber composite.
  • the present invention provides an electrode comprising any one of the carbon nanofiber composites described above as an electrode active material.
  • the carbon nanofiber composite is in powder form.
  • the present invention provides a secondary battery comprising the electrode described above.
  • the secondary battery does not separate the electrode active material contained in the electrode even after 100 cycles of charge and discharge.
  • the secondary battery maintains a discharge capacity of 600 mAh / g even after 100 cycles of charge and discharge.
  • the present invention has the following excellent effects.
  • the graphene-metal nanoparticle composite of the present invention it is possible to prevent the metal nanoparticles from growing too large or aggregated to become large particles.
  • the electrode of the present invention includes a carbon nanofiber composite containing a G / M composite as an electrode active material, so that the metal nanoparticles are not exposed to the outside of the carbon nanofibers to buffer the volume change of the metal nanoparticles due to charging and discharging.
  • the specific resistance of the electrode surface can be reduced to induce an effective electrochemical reaction.
  • the secondary battery of the present invention can secure excellent charge and discharge characteristics, high capacity, excellent volume stability and the like by applying an electrode including a carbon nanofiber composite evenly dispersed G / M complex as an electrode active material.
  • FIG. 1 is a manufacturing process diagram showing an embodiment of manufacturing graphene oxide (GO) using the Hammers method (Hummers method) to produce a G / M complex according to an embodiment of the present invention.
  • FIG. 2 is a manufacturing process diagram showing an embodiment of manufacturing Amino-functionalized silicon nanoparticles to prepare a G / M complex according to an embodiment of the present invention.
  • Figure 3 is a schematic diagram of manufacturing a silicon composite (G / Si) surrounded by graphene (G) of one embodiment of the G / M complex according to an embodiment of the present invention.
  • FIG. 4 is a manufacturing process diagram of the G / Si composite shown in FIG.
  • FIG 5 (a) is a scanning microscope picture of the graphene oxide (GO) prepared according to Figure 1
  • (b) is a transmission microscope picture of graphene oxide (GO).
  • FIG 6 (a) is a scanning microscope picture of the G / Si composite prepared according to Figure 4, (b) is a high magnification scanning microscope picture of the G / Si complex, d is a transmission microscope picture of the G / Si complex, (d) is a high magnification transmission micrograph of a G / Si composite.
  • FIG. 7 is a schematic view and web pictures of carbon nanofiber composite (GSP) manufacturing process including graphene-silicon nanoparticles according to another embodiment of the present invention ((a) precursor radiation fiber, (b) flame-resistant fiber, (c) ) Carbonized fiber].
  • GSP carbon nanofiber composite
  • GSP carbon nanofiber composite
  • FIG. 8 is a scanning micrograph according to graphene-silicon nanoparticle composite content in a carbon nanofiber composite (GSP) including graphene-silicon nanoparticles according to another embodiment of the present invention [(a) 5 wt% G / Si containing, (b) containing 10 wt% G / Si, (c) containing 20 wt% G / Si, (d) containing 20 wt% Si].
  • (A) to (c) is a transmission micrograph according to the graphene-silicon nanoparticle composite content in the carbon nanofiber composite (GSP) including the graphene-silicon nanoparticles according to another embodiment of the present invention [(a) 10-GSP, (b) 20-GSP, (c) 20-SP], and (d) are 10-GSP Limited Field Electron Diffraction (SAED).
  • GSP carbon nanofiber composite
  • SAED 10-GSP Limited Field Electron Diffraction
  • (a) is an X-ray diffraction pattern (XRD) graph of GSP, G / Si, and GO
  • (b) is a Raman spectrum graph of GSP, G / Si, and GO.
  • (a) is a charge and discharge result graph of CNF
  • (b) is a charge and discharge result graph of 5-GSP
  • (c) is a charge and discharge result graph of 10-GSP
  • (d) is a 20-GSP. The charge and discharge results of the graph.
  • FIG. 12 shows a differential capacity curve of 20-GSP, and (b) shows a Nyquist plot of GSP and CNF.
  • (a) is a 50 cycle characteristic result graph of 20-GSP, 10-GSP, 5-GSP, and CNF
  • (b) is a 50 cycle characteristic result graph of 20-SP.
  • FIG 16 (a) is a top-view scanning micrograph before charge and discharge of grinded 20-GSP according to another embodiment of the present invention, (b) is a top-view scanning microscope picture after 100 cycles of charge and discharge, ( c) is a top-view scanning micrograph before charge and discharge of silicon nanoparticles, and (d) is a top-view scan micrograph of silicon nanoparticles after 100 cycles of charge and discharge.
  • the metal nanoparticles are not exposed to the outside of the carbon nanofibers, thereby buffering the volume change of the metal nanoparticles due to charging and discharging as well as the metal.
  • This is because it is possible to provide an electrode and a secondary battery having excellent charge / discharge characteristics, high capacity, and excellent volume stability by preventing the aggregation of nanoparticles, thereby reducing the resistivity of the electrode surface to induce an effective electrochemical reaction.
  • the G / M complex of the present invention is a metal nanoparticle; And a graphene sheet formed by surrounding the metal nanoparticles. This structure prevents the agglomeration and particle growth of the metal nanoparticles and can uniformly disperse the metal nanoparticles in the carbon nanofiber matrix.
  • the metal nanoparticles may be one or more selected from the group consisting of Si, Sn, Ge, Al, Pb, Zn, Co, Cu, Ti, Ni, Li, Ag, Au, the silicon (Si) -based negative electrode material
  • the theoretical capacity is about 4,200 mAh / g, which is the most promising material because it is 10 times larger than graphite material, but the silicon anode material causes a large change in crystal structure when absorbing and storing lithium, resulting in a large volume change of more than 300%.
  • Si silicon
  • the G / M complex of the present invention was conceived that the graphene oxide is negatively charged and the metal nanoparticles are positively charged. As a result of the experiment, the metal nanoparticles and the graphene oxide sheet are strongly bound by electrostatic attraction to oxidize the metal nanoparticles. It was confirmed that the G / M composite formed by wrapping with the graphene sheet was kept fairly stable.
  • the metal nanoparticles may be modified to have -NH 2 groups.
  • the size of the metal nanoparticles can be controlled as desired.
  • the G / M composite may have a size of 50 nm or less so as to be uniformly dispersed in the carbon nanofiber composite. It can be formed to have.
  • the G / M complex of the present invention can be prepared as follows.
  • the graphene oxide sheet may be formed by any known method, and in the present invention, a carboxyl group (COOH) or a hydroxyl group (OH) group is introduced into graphite by using the Hummers method (negative charge).
  • Graphene oxide sheet (GO) having a compound was synthesized (Chem. Mater. 1999, 11 (3), 771-778).
  • the graphene oxide sheet may have a structure of 20 layers or less, more preferably, a single layer structure or a 10 layer structure.
  • the silicon nanoparticles can enhance the positive charge by a known method, for example, can be modified to amino-funtionalized silicon, which is a silicon nanoparticle having -NH 2 groups using APS.
  • APS Angew. Chem. Int. Ed. 2010, 49, 8408-8411.
  • modified Amino-funtionalized silicon has a positive charge, it is possible to prepare a G / Si composite in which GO is strongly bound through GO and electrostatic attraction and reduced by GO.
  • the G / M composite of the present invention is electrically conductive when the carbon nanofiber composite in which the G / M composite is uniformly dispersed as an electrode is formed by complexing graphene having excellent thermal conductivity, mechanical strength and electrical properties with metal nanoparticles. It can have excellent and excellent mechanical properties.
  • Carbon nanofiber composite of the present invention is carbon nanofibers; And a graphene-metal nanoparticle composite constituting a part of the carbon nanofibers.
  • the graphene-metal nanoparticle composite has the same characteristics as described above and thus goes to the description above.
  • the carbon nanofiber composite including the G / M composite has a diameter of 100 to 300 nm, a specific surface area of 300 m 2 / g or less, and an average pore diameter of 1 to 2 nm.
  • the carbon nanofiber composite of the present invention can be pulverized to form a powder form in a state in which the G / M composite is maintained, so that the carbon nanofiber composite may be used as it is, that is, as a web, but can be used by pulverizing into a powder form You can increase your chances.
  • the inclusion of the G / M complex in the carbon nanofiber matrix exhibits a certain synergistic effect, but when the G / M complex is uniformly dispersed and positioned, it showed better characteristics.
  • Carbon nanofiber composite manufacturing method of the present invention comprises the steps of preparing a spinning solution comprising a G / M complex and a carbon fiber precursor; Electrospinning the spinning solution to obtain precursor spinning fibers; Oxidative stabilizing the precursor spun fiber to obtain a flame resistant fiber; And carbonizing the flame resistant fiber to obtain a carbon nanofiber composite.
  • the spinning solution contains the graphene-metal nanoparticle composite within 30 parts by weight per 100 parts by weight of the carbon nanofiber precursor and the graphene-metal nanoparticle composite.
  • the spinning solution content ratio of the G / M composite is experimentally determined as the content ratio of electrospinning well. In other words, if the concentration is higher than the upper limit, it is difficult to spin due to the influence of the spinning solution viscosity and the fibers are not formed well.
  • the carbon nanofiber precursor and the graphene-metal nanoparticle composite may be included in a weight ratio of 4: 1 to 20: 1.
  • the polymer for carbon nanofiber precursor is polyacrylonitrile (PAN, polyacrylonitrile), polyvinyl alcohol (PVA, polyvinylachol), polyimide (PI, polyimide), polybenzimidazole (PBI, polybenzimidazol), phenol resin (phenol resin), epoxy resin, polyethylene (PE, polyethylene), polypropylene (PP, polypropylene), polyvinylchloride (PVC, polyvinylchloride), polystyrene (PS, polystyrene), polyaniline (PA, polyanaline), Polymethyl methacrylate (PMMA, polymethylmethacrylate), polyvinylidene chloride (PVDC, polyvinylidence chloride), polyvinylidene fluoride (PVDF, povinylidene fluoride) and various pitch (pitch) and the like can be used.
  • PAN polyacrylonitrile
  • PVA polyvinyl alcohol
  • PI polyimide
  • PBI polybenzimidazole
  • the type of the polymer for carbon nanofiber precursor for the production of the spinning solution can be used by selecting a suitable solvent that can dissolve the polymer. That is, the solvent in which the carbon fiber precursor is dissolved in the spinning solution is not limited so long as it can disperse all the prepared carbon fiber precursor and the G / M composite.
  • the solvent in which the carbon fiber precursor is dissolved in the spinning solution is not limited so long as it can disperse all the prepared carbon fiber precursor and the G / M composite.
  • at least one of dimethyformamide (DMF), dimethysulfoxide (DMSO) and tetrahydrofuran (THF) was used.
  • Polyacrylonitrile (PAN, molecular weight 160,000) was used as the carbon nanofiber precursor, and a modified acrylic containing 5-15% copolymer as well as 100% homopolymer can be used.
  • As the composition of the copolymer itaconic acid or methylacrylate may be used as the copolymer.
  • Oxidation stabilization may be carried out by supplying compressed air at a flow rate of 5-20 mL per minute using a hot air circulating fan and maintaining at 200-300 ° C. for 30 minutes or more at a temperature increase rate of 1 ° C. per minute.
  • the carbonization may be performed by maintaining the temperature in an inert gas atmosphere for 30 minutes to 2 hours after heating up to 750 to 850 ° C. at a rate of 5 ° C. per minute.
  • At least one of the size and distribution of the graphene-metal nanoparticle composites included in the carbon nanofiber composites by controlling the concentration of the graphene-metal nanoparticle composites contained in the spinning solution during the manufacture of the carbon nanofiber composites of the present invention. Can be controlled. That is, graphene forms a G / M complex surrounding the metal nanoparticles in order to prevent the metal nanoparticles from growing too large or aggregated to become large particles and exposed to the outside of the carbon nanofibers, and the G / M complex contained in the spinning solution. This is because the carbon nanofiber composite having the metal nanoparticles controlled to the desired size can be uniformly distributed in the carbon nanofiber matrix by controlling the concentration of.
  • the electrode of the present invention includes the above-described carbon nanofiber composite as an electrode active material.
  • the carbon nanofiber composite used in the electrode of the present invention includes a G / M composite, for example, the electrode of the present invention may be used as a negative electrode in a secondary battery.
  • the carbon nanofiber composite may be used as the web state prepared by electrospinning, or may be used after being pulverized into a powder form.
  • the secondary battery of the present invention includes an electrode including a carbon nanofiber composite as an electrode active material.
  • the electrode active material contained in the electrode is not separated from the substrate even after 100 cycles of charge and discharge, and the discharge capacity is maintained at 600 mAh / g even after 100 cycles of charge and discharge.
  • This characteristic is due to the structure of the carbon nanofiber composite used as the electrode active material, since the metal nanoparticles dispersed in the carbon nanofiber matrix are in the form of a G / M composite, the graphene surrounding the metal nanoparticles suppresses the volume expansion of the metal nanoparticles. It is expected to act as a support.
  • the silicon nanoparticles were modified with amino-funtionalized silicon having -NH 2 groups using APS.
  • the modified nanoparticles were positively charged.
  • the Amino-funtionalized silicon nanoparticles have a positive charge and GO has a negative charge, the Amino-funtionalized silicon nanoparticles are strongly bound through electrostatic attraction.
  • amino-funtionalized silicon nanoparticles with positive charges can prevent agglomeration and large growth due to repulsion between positive charges.
  • Example 1 The GO obtained in Example 1 was observed with an electron microscope, and the photograph is shown in FIG. 5 as a result.
  • SEM (FIG. 5A) and TEM (FIG. 5B) photographs show that GO synthesized by the Hammers method is composed of thin layers of GO with graphite peeled off, and the number of GO layers is about 1-10. .
  • the surface of GO has been reported to be negatively charged and easy to disperse in polar solvents.
  • the G / Si composite obtained in Example 3 was observed with an electron microscope, and the photograph is shown in FIG. 6 as a result.
  • the SEM (FIGS. 6A and B) photos show that the silicon nanoparticles are covered with graphene sheets
  • the TEM (FIGS. 6C and d) photos show that about 3 nm of thin, pliable and corrugated graphene is formed of the silicon nanoparticles. It can be seen from the edge that the graphene layer surrounds the silicon nanoparticles well. In addition, it was confirmed that the graphene layer is well connected to the separated particles without agglomeration of the adjacent silicon nanoparticles through the TEM (Fig. 6c and d) photograph.
  • the carbon nanofiber precursor was prepared by preparing a PAN pure polymer and a G / Si composite, dissolving the PAN and G / Si composites in DMF prepared as a solvent, and dispersing the same by dispersing using ultrasonic waves as follows.
  • G / Si composite (20 wt%: 0.60 g) was added to the polymer solution, and then ultrasonically dispersed for 2 hours to increase the dispersion of silicon. It was dissolved for 4 hours at °C to prepare a spinning solution (G / Si / PAN solution).
  • the homogenized spinning solution (G / Si / PAN solution) was electrospun using an electrospinner. At this time, the spinning condition was put into the 30 ml syringe attached to a 0.5 mm needle and the fiber precursor solution was electrospun by applying a voltage of 20 kV. In this case, the distance between the needle and the current collector was maintained at 15 cm, and the dissolution rate of the fiber precursor solution was 3 ml / h. When the fibers were accumulated in the current collector, the nonwoven fabric was removed to separate the precursor spinning fiber.
  • the precursor spinning fiber (G / Si / PAN-based spinning fiber) obtained by electrospinning was supplied at a flow rate of 5-20 mL per minute using a hot air circulation fan at 200-300 ° C. at a temperature rising rate of 1 ° C. per minute. Stabilized by maintaining for 1 hour to obtain a G / Si / PAN-based flame resistant fiber.
  • GSP G / Si / PAN-based Carbon Nanofiber Composite
  • G / Si / PAN-based carbon nanofiber composite (20-GSP) was prepared by carbonizing the G / Si / PAN-based flame resistant fiber obtained through stabilization at 800 ° C. under an inert gas (N 2 , Ar gas) atmosphere. It was.
  • a G / Si / PAN-based carbon nanofiber composite (10-GSP) was prepared in the same manner as in Example 1 except that 10 wt% (0.30 g) of G / Si composite was used as the spinning solution.
  • a G / Si / PAN-based carbon nanofiber composite (5-GSP) was prepared in the same manner as in Example 1 except that 5 wt% (0.15 g) of G / Si composite was used as the spinning solution.
  • a Si / PAN-based carbon nanofiber composite (20-SP) having a silicon content of 20 wt% of Comparative Example was prepared in the same manner as in Example 1 except that Si was used instead of the G / Si composite when preparing the spinning solution.
  • Comparative Example carbon nanofibers were obtained in the same manner as in Example 1 except that the G / Si composite was not used in the preparation of the spinning solution.
  • the average diameter range of the obtained carbon nanofiber composite was 250-350 nm, and 5-GSP having a low concentration of the G / Si composite had a smooth surface without generating particles or beads, whereas the concentration of the G / Si composite was It can be seen that as is increased, clusters are present in the middle segment of the fiber and the number of clusters increases.
  • the energy dispersive X-ray spectroscopy (EDX) of the 10-GSP surface revealed that the C, O, and Si elements were present in an atomic ratio of 78.83%, 6.18%, and 15.96%, respectively.
  • high magnification SEM images show that 20-GSP has clusters in the fiber, while 20-SP shows that the clustered nanoparticles of the nanoparticles aggregated are exposed on the surface of the carbon fiber. there was.
  • FIGS. 9A and 9C From (a), (b), and (c) of FIGS. 9A and 9C, in which TEM images of 10-GSP, 20-GSP, and 20-SP are shown, nanoparticles having a size of 50 nm or less are well dispersed in a carbon nanofiber matrix.
  • 20-SP has cluster clusters on the surface of carbon nanofibers.
  • the superlattice diffraction points in the form of (110), (220), and (311) appear in the diffraction pattern of the limited field electron diffraction (SAED) (FIG. 9d) of the nanoparticles present in the 10-GSP to know the internal structure of the material. Through this, the crystalline diffraction pattern of the silicon nanoparticles was confirmed.
  • SAED limited field electron diffraction
  • graphite exhibits a 2 ⁇ value at 26.5 kV, which is known as a representative crystal peak observed in the extra structure (002) of graphite.
  • functional groups such as carboxyl groups or hydroxyl groups containing oxygen are bound between the graphite layers in the (001) plane. It can be seen that the result of inducing phase shift by increasing graphite interlayer distance (Polymer, 2011, 35 (6), 565-573.).
  • 20-GSP, 10-GSP and 5-GSP which are the G / Si / PAN carbon nanofiber composites obtained in Examples 2 to 4, were cut to prepare a negative electrode material, and the prepared negative electrode and LiPF 6 1: 1 vol% Coin cells composed of ethylene carbonate (EC) / dimethyl carbonate (DMC) liquid electrolyte were prepared to prepare secondary batteries 1 to 3 (20-GSP, 10-GSP, 5-GSP).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • a coin cell was prepared in the same manner as in Example 5, except that SP-20 obtained in Comparative Example 1 was used as a negative electrode, to prepare Comparative Example Secondary Battery 1 (SP-20).
  • a coin cell was prepared in the same manner as in Example 5 except that the CNF nonwoven fabric obtained in Comparative Example 2 was used as a negative electrode, to prepare Comparative Example Secondary Battery 2 (CNP).
  • CNP Comparative Example Secondary Battery 2
  • the secondary batteries obtained in Examples 5 to 7 were charged and discharged using a WBCS3000L charging / discharging device manufactured by Won-A tech, and the charge and discharge capacity and cycle characteristics of the lithium secondary batteries manufactured as negative electrodes were investigated. 11 is shown. Charging and discharging was performed at a voltage range of 0.02 to 1.50 V at a current of 100 mA / g.
  • the electrolyte is decomposed to form a coating SEI (Solid Electrolyte Interface or Solid Electrolyte Inter-phase) on the electrode surface.
  • SEI Solid Electrolyte Interface or Solid Electrolyte Inter-phase
  • electrolyte decomposition due to electron transfer between the electrode and the electrolyte is suppressed, and only insertion and removal of lithium ions can be selectively performed.
  • Li x Si is formed in which Si crystals are crystallized due to the reaction of silicon and lithium by electrochemical reaction, and the reaction peak of Li x Si appears at a low voltage of 0.1 V.
  • Example 6 In order to determine the interfacial properties of 10-GSP, 20-GSP, and CNF obtained in Example 5, Example 6, and Comparative Example 4, analysis was performed by electrochemical impedance spectroscopy (EIS), and the results are shown in FIG. It is shown in (b). Impedance measurement was performed using Jahner Electrik IM6e, and the frequency range was tested by applying 100 kHz-10 mHz and AC signal 10 mV mV.
  • EIS electrochemical impedance spectroscopy
  • Figure 12 (b) is a Nyquist plot showing the characteristics of the carbon nanofiber composite electrode in the imaginary term and real term impedance according to the frequency. According to the frequency of the AC potential, a straight line with a constant slope appears in the high frequency region where the semicircle is low. At this time, the semicircle is controlled by the reaction rate due to charge transfer, but the straight portion is controlled by the diffusion of the reactants. (The Korean Institute of Electrical and Electronic Material Engineers, 2011, 24 (4), 333-339).
  • the small R f value in the 20-GSP electrode is also related to the formation of the SEI film.
  • the film formed by the solvent decomposition reaction acts as a protective film on the electrode surface, so that the smooth insertion / reinsertion of lithium ions into the electrode is achieved without large resistance. It can be seen that it shows excellent discharge capacity.
  • 20-GSP shows a large slope of the straight line, which shows that the diffusion rate of lithium ions is fast because the solid state diffusion resistance due to diffusion of lithium ions into the bulk cathode is low due to the electrical conductivity of graphene. .
  • 20-SP shows the highest cathode initial capacity, but after 50 charge / discharge cycles, GSP electrodes showed better cycle characteristics than Comparative Example 3.
  • the carbon nanofiber composite 20-SP prepared by mixing only silicon and polyacrylonitrile without graphene is exposed to the surface of the carbon nanofibers because the particles become larger due to the attraction between the silicon.
  • the cycle characteristics were reduced due to the volume expansion of silicon. This shows that due to the miscibility between PAN and silicon nanoparticles, agglomeration of metals occurs, which makes it difficult to uniformly disperse the silicon nanoparticles.
  • 10-GSP and 20-GSP which are samples prepared by adding a G / Si composite, exhibit stable capacity reduction because the graphene encloses the silicon, thereby suppressing the agglomeration of silicon particles into larger particles. Dispersed evenly within the nanofibers, it not only buffers the large volume change of silicon nanoparticles due to the charging and discharging of the existing lithium ion battery, but also reduces the resistivity of the electrode surface of the lithium ion battery, thereby making it an effective electrochemical reaction during battery charging and discharging. This can be induced.
  • graphene plays a role in buffering the agglomeration of silicon particles in 10-GSP and 20-GSP electrodes, so that silicon is dispersed in the CNF matrix, so that electrochemically active sites are increased and carbon nanofibers maintain electrical conductivity. As such, the electrochemical properties are expected to be very excellent.
  • FIG. 14 is a photograph of the electron scanning microscope results of 5-GSP, 10-GSP, and 20-GSP after 50 cycles of charging and discharging. Therefore, it can be seen from FIG.
  • the G / Si / PAN-based carbon nanofiber composite obtained in Examples 2 to 4 is used as an electrode in a fibrous web state as in Examples 5 to 7 as compared with the conventional case using a particulate form, electrons move by themselves. This is very fast and does not require an active material, a binder and a conductive agent, other solvents, auxiliary facilities, etc., and has the advantage of eliminating the process of preparing and coating a slurry. In addition, the expected effect is expected to be very large as a cathode material to replace the graphite in the future because of its easy handling.
  • 20-GSP of the web form obtained in Example 2 was ground to prepare a powder.
  • Super-P was used as the conductive material and polyacrylic acid was used as the binder.
  • the composition of the electrode was mixed at 80 wt% of the negative electrode active material, 10 wt% of the conductive material, and 10 wt% of the binder.
  • a coin cell consisting of the prepared negative electrode and LiPF 6 1: 1 vol% ethylene carbonate (EC) / dimethyl carbonate (DMC) liquid electrolyte was prepared to prepare a secondary battery 4 (grinded 20-GSP).
  • a coin cell was prepared in the same manner as in Example 8 except that silicon nanoparticles were used as a negative electrode active material, thereby preparing Comparative Example Secondary Batteries 3 (Si NPs).
  • the grinded 20-GSP prepared in Example 8 and Si NPs prepared in Comparative Example 5 were charged and discharged using a WBCS3000L charge / discharge device of Won-A tech. Charging and discharging were performed at a voltage range of 0.005 to 2.0 V at a current of 100 mA / g. As a result of charge and discharge of the lithium secondary batteries according to Example 8 and Comparative Example 5, cycle characteristics and coulombic efficiencies are shown in FIG. 15.
  • the initial capacity of the silicon nanoparticles shows a very high high capacity close to 4000 mA / g, but the crystalline silicon nanoparticles shows a rapid decrease in capacity as the cycle increases. This seems to be a phenomenon caused by rapid volume expansion because lithium does not reversibly move due to the affinity between the two materials in the silicon.
  • grinded 20-GSP maintains higher capacity than silicon nanoparticles even after 100 charge / discharge results, and also shows better cycle characteristics and Klong efficiency.
  • 20-GSP not only prevents graphene from agglomeration of silicon, but also disperses it evenly in carbon nanofibers, and also inhibits volume expansion by buffering carbon nanofibers acting as a matrix. As the cycle increases, the capacity decreases more stably than silicon nanoparticles.
  • the surface photograph of the grinded 20-GSP obtained before charging and discharging shows a clean and uniform surface
  • the surface photograph of silicon nanoparticles shows a relatively uniform surface although there are some cracks on the surface. Can be.
  • the silicon nanoparticles are cracked as the volume increased during the alloying process with lithium decreases when recharged, compared to grinded 20-GSP. You can see that they form a surface.
  • 20-GSP showed no cracks or the active material falling from the current collector through 100 SEM images before and after 100 cycles, and the substrate under the active material was not exposed. It can be explained that it exhibits excellent cycle characteristics compared to nanoparticles.
  • the lithium ion battery manufactured using the carbon nanofiber composite including the G / M composite of the present invention can expect excellent charge / discharge characteristics, high capacity, and excellent volume stability.
  • the carbon nanofiber composite including the G / M composite of the present invention is used only in a lithium ion battery, the cell performance is improved even when used as an electrode active material in an energy storage device including other types of secondary batteries. It can be expected that long term driving performance can be improved as well.

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Abstract

La présente invention concerne un composite de nanofibre de carbone, et plus particulièrement un composite de nanoparticule de graphène et de métal, un composite de nanofibre de carbone contenant ce composite, et une batterie secondaire contenant le composite de nanoparticule de carbone.
PCT/KR2014/005507 2014-04-07 2014-06-23 Composite de nanoparticule de graphène et de métal, composite contenant un composite de nanofibre de carbone, et batterie secondaire contenant un composite de nanoparticule de carbone WO2015156446A1 (fr)

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KR102570543B1 (ko) * 2021-05-26 2023-08-28 (주)나노제네시스 그래핀-금속 입자 복합체를 포함하는 전고체전지용 음극 및 이를 포함하는 전고체전지

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CN109768250A (zh) * 2019-01-07 2019-05-17 华南理工大学 一种静电纺丝法制备锂硫电池复合正极材料的方法及应用
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