WO2013176363A1 - Procédé permettant de préparer un nanocomposite comprenant une nanostructure à plusieurs phases à base d'étain et du carbone amorphe, et matériau actif de cathode contenant ce nanocomposite - Google Patents

Procédé permettant de préparer un nanocomposite comprenant une nanostructure à plusieurs phases à base d'étain et du carbone amorphe, et matériau actif de cathode contenant ce nanocomposite Download PDF

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WO2013176363A1
WO2013176363A1 PCT/KR2012/011355 KR2012011355W WO2013176363A1 WO 2013176363 A1 WO2013176363 A1 WO 2013176363A1 KR 2012011355 W KR2012011355 W KR 2012011355W WO 2013176363 A1 WO2013176363 A1 WO 2013176363A1
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tin
bacteria
amorphous carbon
nanocomposite
transition metal
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English (en)
Korean (ko)
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김동완
심현우
임아현
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아주대학교산학협력단
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on 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 method for producing a nanocomposite composed of polyphase nanostructures and amorphous carbon based on a tin element, and a negative electrode active material comprising the same.
  • Batteries a device that converts chemical energy into electrical energy, are classified into primary cells, secondary batteries, fuel cells, and solar cells, depending on the types and characteristics of basic materials.
  • the secondary battery can be recharged and used several times when discharged.
  • primary batteries although they have large capacities such as alkali batteries, mercury batteries, and manganese batteries, they are limited in terms of primary batteries and are not recycled and thus not environmentally friendly.
  • Recyclable secondary batteries such as cadmium batteries, nickel metal hybrid batteries, lithium metal batteries, and lithium ion batteries are not only energy efficient and environmentally friendly due to their higher voltage than primary batteries, but also have a low energy density and have many technical advantages. Unlike constraints, secondary batteries have high capacity and high energy density and are currently commercialized in various industrial fields.
  • lithium ion secondary batteries among the various secondary batteries have attracted great attention in recent years due to applications ranging from small to medium and large.
  • the lithium ion secondary battery is largely composed of a positive electrode and a negative electrode, an electrolyte and a separator, and utilizes electrical energy generated by a redox reaction when lithium ions are inserted / desorbed between the positive electrode and the negative electrode. That is, based on the principle that lithium ions and electrons carrying charge reciprocate between the positive electrode and the negative electrode, during discharge, the lithium ions and electrons move to the positive electrode and are inserted into the negative electrode active material, and when charged, they are detached from the negative electrode active material. Thus, the process of being inserted into the positive electrode active material is repeated.
  • High performance of lithium-ion secondary batteries is closely related to the development of electrode active materials and improvement of physical properties, which are key factors.
  • innovative ideas and advanced nanotechnology are appropriate to avoid development of simple materials and process technologies. Fusion is necessary. That is, in order for a lithium ion battery to have a large capacity and excellent cycle stability, an anode and a cathode active material to be used must have an appropriate crystal structure and excellent electrical properties to react with lithium. In addition, there should be no side-reaction between the active material and the electrolyte, and the volume change of the active material lattice generated during charging and discharging should be small.
  • the negative electrode active material based on the insertion / desorption reaction of the lithium ion of the carbon-based material is the core in the negative electrode material field of the lithium ion secondary battery technology.
  • the capacity commercialized with a small theoretical capacity (372 mAh / g) is basically smaller than this. Therefore, in recent years, studies on new anode active materials to replace carbon-based materials and researches for improving performance of anode active materials having nanostructures have been actively conducted, and many research cases have been reported.
  • CuO which expresses its capacity through a reaction (alloying reaction) using Si, Ge, Sn, etc., which forms an alloy with lithium, or a conversion reaction between metal / metal oxides, rather than a conventional insertion / desorption process
  • transition metal oxides such as CoO, Fe 2 O 3 , NiO, MnO 2, etc.
  • Such a negative electrode active material may be made by preparing a material having a nanostructure rather than a conventional micro-sized bulk material, which may react with lithium due to the high specific surface area, which is one of the biggest features of the nanostructure. This is because it can exhibit the characteristics as an improved negative electrode active material based on the advantage that the number of sites, the diffusion movement distance of lithium ions can be shortened.
  • attempts have been made to achieve high performance of lithium-ion secondary batteries using the advantages of each nanostructure by preparing nanocomposites through complexing of nanostructures, as well as simple application of a negative electrode active material using nanostructures.
  • the preparation of the negative electrode active material for the high performance of the lithium ion secondary battery is to improve the electrical conductivity through nano-structured or nano-composite material capable of realizing high capacity characteristics, small volume change between reaction with lithium, interparticle
  • nanostructures of various compositions as well as to manufacture various forms of nanostructures in a simple process.
  • the preparation of a negative electrode active material through nanostructure of elements such as Sn, Ge, and Si, which realizes high capacity characteristics through an alloy reaction with lithium is considered to be important as a negative electrode active material material capable of achieving high performance of a lithium ion secondary battery.
  • the problem of rapid capacity reduction due to large volume change, low electrical conductivity, and the like should be considered together, and the complexion with other nanomaterials of the nanostructure having the alloy reaction with lithium is also considered. Need to be.
  • the nanostructures have a variety of properties depending on the shape produced, there is also a need for a manufacturing method that can easily control the shape of the nanostructures during synthesis.
  • the present inventors have developed a negative electrode active material consisting of nanocomposites composed of high carbon element-based nanostructures and amorphous carbons that can provide enhanced electrical conductivity through application of bacterial templates as a medium and through thermochemical reduction. .
  • the present invention is not only a simple manufacturing process in the production of the nanocomposite, but also easy to mass production of bacteria as a medium, the tube shape through a simple thermochemical reduction in the hydrogen atmosphere of the complex consisting of bacteria / tin oxide It is an object of the present invention to provide a method for producing a nanostructure consisting of a multi-phase tin element having a nanostructure and an amorphous carbon.
  • It provides a method for producing a nanostructure / amorphous carbon nanocomposite based transition metal element comprising a.
  • the present invention provides a tube-shaped nanocomposite composed of a transition-phase element-based multi-phase nanostructures and amorphous carbon derived from bacteria attached to the bacterial surface due to the thermochemical reduction of the nanocomposites. do.
  • the present invention provides a negative electrode active material for a secondary battery comprising the nanocomposite.
  • the present invention provides a secondary battery employing a negative electrode including the negative electrode active material.
  • Tube-shaped nanocomposites can be prepared that are complexed with amorphous carbon derived from bacteria.
  • the present invention can be easily obtained through simple thermochemical reduction and easy to mass production based on the bacteria / tin oxide complex which can be easily obtained at low temperature by applying bacteria as a template.
  • the manufacturing method of the present invention has the advantage of economical and time-saving effect because the manufacturing process is simple.
  • the production method of the present invention has the advantage of obtaining a tubular nanocomposite composed of a multiphase low-dimensional nanostructure and amorphous carbon in one manufacturing process.
  • the nanocomposites composed of multiphase nanostructures and amorphous carbon based on the tin element presented in the present invention have a simple and economical manufacturing process and are easy to obtain a large amount of intermediate bacteria / tin oxides. With the advantage of being able to produce, various applications are possible across industries such as lithium secondary batteries, electric double layer super capacitors, and similar super capacitors.
  • Figure 1 is a schematic diagram showing a tube-shaped nanocomposite manufacturing process consisting of amorphous carbon / tin element-based multi-phase nanostructures prepared through the use of the bacterial template and tin precursor presented in the present invention.
  • FESEM field emission scanning electron microscope
  • Figure 3 is a transmission electron microscopy (TEM) picture of the composite consisting of bacteria / tin oxide (SnO2) prepared by the intermediate medium in the present invention ((a) transmission electron micrograph, (b) high resolution Transmission electron micrograph].
  • TEM transmission electron microscopy
  • Figure 4 is an X-ray Diffraction patterns (XRD) of the composite consisting of bacteria / tin oxide (SnO2) prepared in the intermediate medium in the present invention.
  • XRD X-ray Diffraction patterns
  • FIG. 5 is a result of a thermogravimetry analyzer (TGA) of a complex composed of bacteria / tin oxide (SnO 2) prepared as an intermediate medium in the present invention.
  • TGA thermogravimetry analyzer
  • Figure 6 is a field emission scanning electron micrograph showing the shape of the tube-shaped nanocomposite consisting of the amorphous carbon / tin element-based multiphase nanostructures of the present invention.
  • FIG. 7 is a transmission electron micrograph showing a shape of a tube-shaped nanocomposite composed of the amorphous carbon / tin element-based multiphase nanostructure of the present invention, a high resolution transmission electron micrograph, and a selected area electron diffraction (SAED) pattern photograph. .
  • SAED selected area electron diffraction
  • FIG. 8 is an X-ray powder diffraction pattern of a tube-shaped nanocomposite composed of the amorphous carbon / tin element based multiphase nanostructures of the present invention.
  • Example 9 is a scanning electron micrograph showing the shape of the nanocomposite prepared according to Examples 2 to 4 of the present invention ((a) Example 2, (b) Example 3, (c) Example 4).
  • Example 10 is a field emission scanning electron micrograph showing the shape of the nanocomposite prepared according to Example 5 of the present invention.
  • Example 12 is a field emission scanning electron microscope, a transmission electron microscope, and a high resolution transmission electron micrograph of a nanocomposite shape prepared according to Example 8 of the present invention ((a) field emission scanning electron micrograph, (b) transmission electron Micrograph, (c) high resolution transmission electron micrograph].
  • Example 13 is a scanning electron micrograph showing the shape of the nanocomposite prepared according to Example 10 of the present invention.
  • Example 14 is a cycle-shaped nanocomposite composed of amorphous carbon / tin element-based multi-phase nanostructures prepared in the present invention and various current density changes of the negative electrode active materials prepared using the powders of Example 8 and Comparative Example 1 This is a result of comparing the measured dose change curves.
  • It provides a method for producing a nanostructure / amorphous carbon nanocomposite based transition metal element comprising a.
  • the present invention provides a tube-shaped nanocomposite composed of a transition-phase element-based multi-phase nanostructures and amorphous carbon derived from bacteria attached to the bacterial surface due to the thermochemical reduction of the nanocomposites. do.
  • the present invention provides a negative electrode active material for a secondary battery comprising the nanocomposite.
  • the present invention provides a secondary battery employing a negative electrode including the negative electrode active material.
  • It provides a method for producing a transition metal-based nanostructure / amorphous carbon nanocomposite comprising a.
  • the transition metal used in the present invention is not particularly limited, and Cu, Co, Fe, Ni, Mn, Ti, which are the four periodic elements on the periodic table, and Y, Zr, Nb, Mo, Tc, Ru, and Rh, which are the five periodic elements on the periodic table.
  • Pd, Ag, Cd, In, Sn, Sb, Te and the like can be used. More preferably, it is a 5 period element, Most preferably, it is Sn.
  • the present invention binds tin element-based oxide nanostructures capable of realizing high capacity properties to the Bacillus bacterial surface and thermochemically reduces the obtained bacteria / tin oxide complexes under hydrogen atmosphere, thereby removing from bacteria with high capacity properties.
  • the present invention relates to a method of manufacturing a nanocomposite that can mitigate volume change during reaction with lithium through a tube shape by providing high electrical conductivity by induced amorphous carbon.
  • the present invention provides a method for preparing a bacterial / tin oxide complex which is an intermediate step; And obtaining a final nanocomposite through thermochemical reduction of the obtained composite.
  • the bacterium / tin oxide composite obtained in the intermediate step has the advantage of increasing the yield of tin oxide nanostructures that are combined with the simple synthesis, low temperature, and increase of bacteria used as a template. This gives the possibility of mass production of the nanocomposites finally obtained.
  • Such a process for synthesizing a bacterial / tin oxide complex is similarly made by the inventors, focusing on incorporating a transition metal oxide on the surface of the Bacillus bacterium, which has been previously patented [Korean Patent Application, Application No. 10-2009-0011628]. Can lose.
  • tin precursor solution in which tin precursor is dissolved in deionized water to the solution of step 1 and stiring at 20 to 30 ° C. for 0.5 to 2 hours to uniformly disperse bacteria and tin precursors;
  • It relates to a method for producing a nanocomposite consisting of a multi-phase nanostructure / amorphous carbon based on a tin element comprising a.
  • the tin precursor used in the present invention is not particularly limited according to the number of divalent and tetravalent oxidized numbers, and examples thereof include nitrate, chloride, acetate, and the like.
  • Synthesis of the bacterial / tin oxide complex is carried out by hydrazine (N 2 H 4 ⁇ H 2 O) using tin ions of cations attached to the bacterial surface as a reducing agent through electrostatic attraction in solution. It can be obtained on the basis of a liquid phase synthesis method, which is used to reduce and simultaneously oxidize. In general, the liquid phase synthesis method is not excellent in crystallinity, but the crystalline material can be obtained at a low temperature according to the synthesis method, and there is an advantage that particles of uniform and small size can be obtained.
  • the synthesis process of the bacterial / tin oxide composite presented in the present invention is a simple process, it is possible to obtain a nano powder consisting of uniformly sized tin oxide nanostructures with crystallinity at room temperature (20 ⁇ 30 °C) It has the advantage that mass production is possible.
  • FIG. 1 A series of synthesis methods used to prepare the nano-composite composed of the tin phase-based polyphase nanostructure and amorphous carbon according to the present invention is well illustrated in FIG. 1, and a detailed description based on FIG. 1 is as follows.
  • the concentration control of the bacterial template solution may be performed through the optical absorbance (Optical Density, OD) measured at 600 nm wavelength using an UV spectrometer, the concentration of the bacterial template applied in the present invention is 600 nm It is preferable to use the thing of the range whose optical absorbance is 1.0-2.0 in wavelength.
  • optical absorbance Optical Density, OD
  • the tin precursor While maintaining the bacteria dispersion solution in the proper concentration range while stirring at room temperature, the tin precursor is added to deionized water to prepare a tin chloride precursor in the range of 10 to 100 mM, and dissolve so that the tin precursor is sufficiently dispersed during the stirring process. After that, the tin precursor solution, which has been dissolved, is slowly added to the bacterial dispersion solution that is being stirred at room temperature while the stirring is maintained. At this time, when the tin precursor solution is rapidly added, the transition metal precursor of the cation may not be adhered evenly to the surface of the dispersed bacteria, and thereafter, it may be reduced or reduced in the aqueous solution by the reducing agent of hydrazine. Partial reflux in the course of spontaneous oxidation at may make it difficult to achieve agglomerate and a well-shaped single rod shape between the bacteria, so it is preferable to add slowly using a burette if possible.
  • a sufficient sterling time of 0.5 to 2 hours is maintained at 20 to 30 ° C. to allow sufficient adhesion and even distribution and dispersion between the tin precursor of the cation and the bacteria.
  • hydrazine which can act as a reducing agent, is added to deionized water to prepare a hydrazine solution in the range of 10 to 1000 mM and the sterling process is performed. Dissolve to ensure sufficient dispersion. Thereafter, the hydrazine solution, which has been dissolved, is slowly added to the mixed solution being stirred at room temperature in the state where the sterling is maintained. At this time, the amount of about 10 ml per minute is added using a burette as in the case of adding the tin precursor solution.
  • the mixed solution added to the reducing agent hydrazine is refluxed for 10 to 15 hours while continuously stirring at 20 °C to 30 °C, after which the supernatant and the precipitate is separated by centrifugation, the supernatant is removed and The precipitate is washed with deionized water and acetone (acetone). At this time, the precipitate is a state in which the tin oxide is evenly distributed and attached to the bacterial surface. Thereafter, the obtained precipitate is subjected to a drying process in a vacuum oven.
  • the vacuum drying proceeded in the present invention was carried out at a temperature of 60 ⁇ 70 °C, pressure range of 10 -2 to 10 -3 torr for 6 to 8 hours.
  • the shape of the bacteria / tin oxide composite powder obtained after the vacuum drying is 500 ⁇ 800 nm in diameter, 1 ⁇ 2 ⁇ m Bacillus bacteria surface of 2 ⁇ 5 nm evenly surrounded by tin oxide nanostructures, oxide nanostructures Has a very uniform and fine particle size distribution.
  • the shape of the prepared bacterial / tin oxide complex can be observed through field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). 2, 3].
  • FESEM field emission scanning electron microscopy
  • TEM transmission electron microscopy
  • the phase type and crystal structure of the synthesis result of the prepared bacterial / tin oxide complex can be confirmed using X-ray diffraction patterns (XRD) [FIG. 4].
  • XRD X-ray diffraction patterns
  • the synthesized bacterial / tin oxide composite powder shows the same X-ray diffraction pattern as SnO 2 (JCPDS card No. 41-1445).
  • Figure 5 shows the quantitative characteristics of the tin oxide bound to the bacterial / tin oxide complex synthesized by thermal gravimetric analysis (TGA).
  • the synthesized bacteria / tin oxide complex is prepared through the thermochemical reduction under a hydrogen atmosphere to prepare a tubular nanocomposite consisting of tin-based multi-phase nanostructures and amorphous carbon derived from bacteria.
  • the advanced thermochemical reduction process is maintained for 12 hours after reaching 400 °C at a temperature rising rate of 10 °C per minute under a hydrogen atmosphere, if the conditions of the gas atmosphere, temperature, time does not satisfy the desired tin base Since it is impossible to obtain a tube-shaped nanocomposite composed of polyphase nanostructures and amorphous carbon, it is preferable to comply with the conditions.
  • the shape of the final powder obtained after the thermochemical reduction process can be observed through field emission scanning electron microscopy and transmission electron microscopy, and it can be seen that the diameter is reduced by 100 to 200 nm compared to the bacterial / tin oxide composite shown after vacuum drying. 6 and 7. Moreover, according to FIG. 7, it can be seen through the high resolution transmission electron micrograph that after the thermochemical reduction, multiphase nanostructures based on tin elements were formed. In addition, according to FIG. 8, the phase and crystal structures of the resultant obtained after thermodynamic reduction were confirmed by using an X-ray diffraction pattern [FIG. 8].
  • tube-shaped nanocomposites composed of microstructured nanostructures and amorphous carbon based on tin element through bacteria / tin oxides and thermochemical reduction are electrochemical devices, more specifically lithium-ion in the art. It can be used for secondary batteries, electric double layer super capacitors and the like.
  • the present invention provides a nanocomposite powder composed of a multi-phase tin element-based nanostructure / amorphous carbon in a tubular shape obtained through thermochemical reduction, as well as the intermediate complex composed of the bacteria / tin oxide.
  • an electrode for a lithium battery was separately prepared and a half cell was constructed to evaluate electrochemical properties.
  • the lithium ion secondary battery exhibits better electrochemical performance as the number of lithium charges that can react per unit molecular weight of the negative electrode active material used, and the particle aggregation phenomenon during charging and discharging are limited.
  • the inert powder and the conductive additive and binder composed of the bacteria / tin oxide prepared as the intermediate step or the tubular tin element based polyphase nanostructure / amorphous carbon obtained after thermochemical reduction are finally obtained.
  • Lithium metal is used as a negative electrode, and the prepared electrode is used as an anode.
  • An electrolyte and a separator are inserted between two electrodes to complete a half cell.
  • the manufactured battery was evaluated for charging and discharging cycles while varying the current density flowing in the voltage range of 0.01 to 3.0V.
  • electrochemical characteristics were measured only for powders subjected to thermochemical reduction at 400 ° C., and electrochemical characteristics were also obtained for bacteria / tin oxides prepared in an intermediate step as a control and powders subjected to thermochemical reduction at 500 ° C. Were measured and compared with each other.
  • the powder of the tin element-based multiphase nanostructure / amorphous carbon proposed in the present invention exhibits a higher capacity than the measured results of the controls, and has a high current. Higher capacity also showed better stability in density.
  • 5 ⁇ l were taken from the stock solution of Bacillus subtilis, which was stored frozen, and then inoculated into a test tube containing 5 ml LB liquid medium (Luria-Bertani, LB broth) and rotating at 200 rpm at 37 ° C. Were initially cultured in an incubator. After 10 to 12 hours from the initial incubation, 500 ⁇ l was collected from the culture solution and passaged in 5 Erlenmeyer flasks each containing 200 ml of liquid medium. Bacteria culture 5 hours after subculture were centrifuged at 12,000 rpm for 20 minutes to separate bacteria and supernatant. The sunk bacteria separated from the supernatant were washed twice with deionized water and centrifuged.
  • LB liquid medium Lia-Bertani, LB broth
  • the precipitate is deposited in the state that the tin oxide is evenly distributed on the surface of the Bacillus bacteria, the synthesized precipitate was vacuum dried for 6 hours under the temperature of 60 °C, pressure condition of 10 -2 torr, intermediate step Bacteria / tin oxide complexes were prepared.
  • the prepared bacteria / tin oxide composite was subjected to thermochemical reduction under a hydrogen atmosphere.
  • 0.2 to 0.3 g of the prepared bacteria / tin oxide composite powder was weighed and subjected to thermochemical reduction in a tubular high temperature electric furnace.
  • a purge process is performed by flowing argon gas at a flow rate of 100 sccm for 30 minutes while the vacuum pump is operated.
  • hydrogen gas was flowed at a flow rate of 40 sccm for 30 minutes to create a reducing atmosphere.
  • a thermochemical reduction process was performed at 400 ° C. for 12 hours.
  • Synthesis method is the same as in Example 1, but after fixing the concentration of the tin chloride precursor in Table 1 to 10 mM, to change the concentration of N 2 H 4 ⁇ H 2 O reducing agent to 100, 500, 1000 mM, respectively.
  • the bacterial / tin oxide complexes thus obtained as intermediate steps of the present invention were prepared.
  • 9 shows scanning electron micrographs of the bacterial / tin oxide complexes prepared according to the conditions of Examples 2, 3, and 4, respectively.
  • Synthesis method is the same as in Example 1, but obtained by the intermediate step of the present invention with the concentration of the tin chloride precursors shown in Table 1 to 100 mM, the concentration of the N 2 H 4 ⁇ H 2 O reducing agent to 100 mM
  • the resulting bacterial / tin oxide complex was prepared.
  • Field emission scanning electron micrographs of the bacterial / tin oxide complexes prepared according to Example 5 are shown in FIG. 10.
  • thermochemical Nanocomposites consisting of amorphous carbon and multiphase nanostructures based on tin elements with final tube shapes obtained through reduction cannot be prepared. Therefore, suitable forms of bacterial / tin oxide composite intermediate stage mediators should be prepared through the above examples.
  • thermochemical reduction processes in order to produce a nanocomposite having a tube shape which is the final form of the present invention between the thermochemical reduction processes through the above embodiments, and consisting of polyphase nanostructures and amorphous carbon on the basis of tin element, the temperature between the thermochemical reduction processes, Conditions such as time and mood must be adequately set.
  • the shape of the nanocomposite prepared in Example 8 is shown in FIG. 12 using a field emission scanning electron microscope, a transmission electron microscope, and a high resolution transmission electron microscope.
  • the nanostructures based on amorphous carbon and tin elements derived from bacteria after the thermochemical reduction process are not evenly distributed, but a recrystallized reduction to tin metal due to a high reduction temperature is achieved. It can be seen that the increase significantly. These results later showed lower capacity characteristics in composites with tin-based multiphase nanostructures in secondary battery tests with lithium.
  • the synthesis was carried out in the same manner as in Example 1, except that the precipitate in the intermediate step was obtained without using a bacterial template as described in Table 1 below.
  • a scanning micrograph of the obtained precipitate is shown in FIG. 13, and when the bacterial template identified in FIG. 13 is not applied, it is not formed on a template of tin oxide obtained in an intermediate step, and thus a desired rod shape cannot be obtained.
  • the nanocomposite consisting of amorphous carbon and multiphase nanostructures based on tin element having the final tube shape of the present invention cannot be produced.
  • Example 2 In order to compare and analyze the secondary battery characteristics of the tubular nanocomposite consisting of the tin element-based polyphase nanostructure and amorphous carbon prepared in Example 1, the same synthesis as in Example 1 as a control as shown in Table 2 below. Secondary battery characteristics were compared by using the nanopowder prepared in Example 8 and the intermediate bacteria / tin oxide complex which was performed by the method but did not undergo the thermochemical reduction process.
  • the negative electrode active material of the anode active material of the tube-shaped nanocomposite composed of the tin element-based polyphase nanostructure and amorphous carbon prepared in Example 1 and the nanopowder prepared in Comparative Example 1 and the powder prepared in Example 8 In order to compare and evaluate as an active material, the capacity of the half battery was measured after producing an electrode.
  • nano-powder negative electrode active material prepared in Example 1 was weighed to have a mass ratio of 70: 15: 15 and graphite (MMM Cabon) and a binder, Kynar 2801 (PVdF-HFP), and then inert. It was prepared in the form of a slurry by dissolving in N-methyl- pitolidon (NMP), an organic solvent. Thereafter, the slurry was applied to a copper foil as a current collector, dried in a vacuum oven at 100 ° C. for 4 hours to volatilize an organic solvent, and then pressed into a circular shape having a diameter of 1 cm.
  • NMP N-methyl- pitolidon
  • the nano powders prepared in Comparative Examples 1 and 8 were also weighed 0.5 to 1 mg as a negative electrode active material, and the mass ratio of graphite as a conductive agent and Kynar 2801 as a binder was 70:15:15, and then inert. It was dissolved in organic solvent to form a slurry. The subsequent process is the same as the manufacturing process of the electrode presented through the sample of Example 1.
  • the electrodes prepared in (a) as lithium metal ions as the cathode and the anode An electrolyte and a separator (Celgard 2400) were inserted between the two, and a half cell of a Swagelok type was configured.
  • the electrolyte used was a material in which LiPF6 was dissolved in a solution in which a volume ratio of ethylene carbonate (EC) and dimethyl carbonate (dimethyl carbonate, DMC) was 1: 1. All procedures of the half cell preparation presented above were carried out in a glove box filled with argon, an inert gas.
  • the manufactured half-slave type half cell uses a charge / discharge cycler (WBCS 3000, WonA Tech., Korea) to change the voltage to 0.03 mV / sec between 0.01 and 3.0 V voltages and is in a positive static mode.
  • the current density was 78 mA / g, 157 mA / g, 235 mA / g, 392 mA / g, and the current density was changed to galvanostatic mode.
  • the electrochemical characteristics were evaluated by changing the current density while performing 10 cycle charge / discharge tests.
  • the graph analyzed according to the constant current method is shown in FIG. 14.
  • the bacteria / tin oxide (SnO 2) obtained in the intermediate step of the present invention.
  • Sn amorphous carbon / single-phase tin metal
  • Table 3 shows the discharge capacity when 10 charge and discharge cycle tests were performed at each current density in the secondary battery characteristics evaluation of the powders prepared in Examples 1, 9 and Comparative Example 1. .
  • Table 3 is a negative electrode using the powders prepared in Example 8 and Comparative Example 1 is the negative electrode active material of the tube-shaped nanocomposite composed of the amorphous carbon / tin element-based multi-phase nanostructures prepared in Example 1 of the present invention It has much higher capacity characteristics than active materials, and shows cycle stability with high capacity characteristics even at high current densities. From this, the material of the tube-shaped nanocomposite composed of amorphous carbon / tin element-based multiphase nanostructures raised in the present invention can achieve high capacity due to low dimensional nanostructures composed of polyphase tin elements.
  • the present invention is directed to polyphase tin oxides having a 0-dimensional shape and tin metal and bacteria by thermochemically reducing the powder of bacteria / tin oxide obtained by directly binding tin oxide to the Bacillus bacterial surface in a hydrogen atmosphere.
  • the present invention relates to a tube-shaped nanocomposite complexed with amorphous carbon.
  • Bacteria are used as a template for low capacity and low output (low capacity for high current density), which have been pointed out as a disadvantage in the conventional negative electrode active material for lithium secondary batteries, and the capacity greatly decreases due to large volume change when reacting with lithium.
  • it is possible to solve the problem by manufacturing a tubular nanocomposite composed of amorphous carbon / tin element based multi-dimensional low dimensional nanostructures, which are manufactured through thermochemical reduction by combining tin oxide, which can realize high capacity, with the bacterial surface. Do.
  • thermochemical reduction process is simple, economical, and it is possible not only to obtain various types of complexes depending on the shape of the bacterium template used, but also to facilitate low-temperature synthesis and synthesis of intermediate media. Because of the ease of production, it is expected to be practically applicable not only to lithium secondary batteries but also to electric double layer super capacitors.

Abstract

La présente invention se rapporte à un nanocomposite tubulaire qui comprend : des oxydes d'étain à plusieurs phases ayant une forme à zéro dimension grâce à la réduction thermochimique, dans une atmosphère d'hydrogène, d'une poudre de bactéries/oxyde d'étain obtenue par liaison directe d'un oxyde d'étain sur la surface de bactéries du genre Bacillus ; et un complexe de carbone amorphe dérivé d'étains métaux et de bactéries. Il est possible d'éliminer les points faibles d'un matériau actif de cathode classique destiné à une batterie secondaire au lithium, c'est-à-dire la faible capacité et le faible rendement (faible capacité à une densité de courant élevée), ainsi que l'importante diminution de capacité au fil des cycles en raison d'un grand changement de volume au cours de la réaction avec le lithium. Pour y parvenir, on prépare un nanocomposite tubulaire qui comprend des nanostructures à plusieurs phases et à faible dimension basées sur du carbone amorphe/un élément étain en utilisant des bactéries comme modèle, en liant sur la surface de ces bactéries un oxyde d'étain qui peut donner une grande capacité, et en les soumettant à une réduction thermochimique. La réduction thermochimique selon la présente invention est simple et économique à préparer, elle permet la préparation de différentes formes de composite suivant la forme du modèle de bactéries à utiliser, et elle facilite la synthèse à basse température, la synthèse intermédiaire ainsi que la production en série. Par conséquent, la présente invention peut avoir une applicabilité pratique dans le domaine des batteries secondaires au lithium et celui des condensateurs électriques à double couche.
PCT/KR2012/011355 2012-05-22 2012-12-24 Procédé permettant de préparer un nanocomposite comprenant une nanostructure à plusieurs phases à base d'étain et du carbone amorphe, et matériau actif de cathode contenant ce nanocomposite WO2013176363A1 (fr)

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