WO2013151282A1 - Procédé pour la préparation de nanocomposite d'oxyde de métal de transition-carbone - Google Patents

Procédé pour la préparation de nanocomposite d'oxyde de métal de transition-carbone Download PDF

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Publication number
WO2013151282A1
WO2013151282A1 PCT/KR2013/002664 KR2013002664W WO2013151282A1 WO 2013151282 A1 WO2013151282 A1 WO 2013151282A1 KR 2013002664 W KR2013002664 W KR 2013002664W WO 2013151282 A1 WO2013151282 A1 WO 2013151282A1
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transition metal
carbon
metal oxide
precursor
carbon nanocomposite
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PCT/KR2013/002664
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English (en)
Korean (ko)
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현택환
이지은
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서울대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • 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
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 preparing a transition metal oxide-carbon nanocomposite. More specifically, the present invention comprises the steps of (i) heating the mixture of the transition metal precursor and the surfactant to prepare a transition metal oxyhydroxide nanoparticles; (ii) adding a carbon precursor to the product mixture solution obtained in step (i) to form a carbon precursor layer on the surface of the transition metal oxyhydroxide nanoparticles; And (iii) calcining the product mixture solution obtained in step (ii).
  • LIB Rechargeable lithium ion batteries
  • various portable electronic devices such as digital cameras, mobile phones and laptops.
  • LIBs have also received great attention as important elements of hybrid vehicles, implantable medical devices and clean energy storage devices.
  • the explosive market demand for LIBs places increasing demands on higher energy and power densities, improved cycle stability and lower costs.
  • transition metal oxides usually have the problem of large volume expansion / reduction associated with lithium ion insertion and extraction, which leads to rapid capacity fading and poor cycling ability. .
  • Nanomaterials can effectively accommodate strain due to volume changes and improve cycle performance.
  • reducing the size to nanoscale significantly increases the electrode / electrolyte contact area and significantly reduces the travel distance of lithium ions, allowing the cell to operate at greater power.
  • porous structures In addition to nanoscale materials, porous structures also have the same advantages as nanomaterials (N. Du, H. Zhang, B. Chen, J. Wu, X. Ma, Z. Liu, Y. Zhang, D. Yang). , X. Huang, J. Tu Adv. Mater. 2007 , 19 , 4505; T. Yoon, C. Chae, Y.-K. Sun, X. Zhao, HH Kung, JK Lee J. Mater. Chem . 2011 , 21 , 17325; K. Zhong, B. Zhang, S. Luo, W. Wen, H. Li, X. Huang, L. Chen J. Power Sources 2011 , 196 , 6802).
  • the void space in the porous structure buffers the local volume change of the lithium ion insertion / release process, thereby improving cycling performance.
  • Another strategy to improve the performance of the cathode is to coat or encapsulate the active material with carbon, which acts as a buffer layer, which buffers the stress due to volume expansion / contraction by its elasticity. Mitigation to allow for better capacity retention.
  • the buffer layer may increase the electronic conductivity of the electrode and reduce the pulverization and aggregation of the electrode material (W.-M. Zhang, X.-L. Wu, J.). .-S. Hu, Y.-G. Guo, L.-J. Wan Adv.Funct . Mater. 2008 , 18 , 3941; Y. Piao, HS Kim, Y.-E. Sung, T. Hyeon Chem. Commun.
  • iron oxide is used as a LIB electrode due to its rich reserves, environmental friendliness, low cost and high theoretical capacity (928 mAh / g for Fe 3 O 4 and 1007 mAh / g for ⁇ -Fe 2 O 3 ).
  • One of the most attractive materials T. Yoon, C. Chae, Y.-K. Sun, X. Zhao, HH Kung, JK Lee J. Mater. Chem . 2011 , 21 , 17325; W.-M. Zhang, X.-L. Wu, J.-S. Hu, Y.-G. Guo, L.-J. Wan Adv.Funct.Mate . 2008 , 18 , 3941; Y.
  • mesoporous silica Compared to mesoporous silica, alumino-silicates in terms of porous structure, it is much more difficult to produce mesoporous transition metal oxides.
  • Soft template synthesis can be used for some transition metal oxides such as TiO 2 , ZrO 2 , Nb 2 O 5, and WO 3 , but there are few reports on iron oxides.
  • Hard mold synthesis is successful in the synthesis of various ordered and crystalline metal oxides, but this method requires complex reaction steps, including the synthesis and removal of the template. Pyrolysis of some metal precursors also makes it possible to produce porous structures, but metal precursors are expensive. Thus neither of these methods is suitable for synthesizing porous materials of a particular shape.
  • the inventors have developed a simple, economical and scalable sea urchin-like transition metal oxide-carbon nanocomposite synthesis method that does not require an autoclave. It was.
  • An object of the present invention is to prepare a transition metal oxyhydroxide nanoparticles by (i) heating a mixture of a transition metal precursor and a surfactant; (ii) adding a carbon precursor to the product mixture solution obtained in step (i) to form a carbon precursor layer on the surface of the transition metal oxyhydroxide nanoparticles; And (iii) to provide a method for producing a transition metal oxide-carbon nanocomposite comprising calcining the product mixture solution obtained in step (ii).
  • the object of the present invention described above is to prepare a transition metal oxyhydroxide nanoparticle by (i) heating a mixture of a transition metal precursor and a surfactant; (ii) adding a carbon precursor to the product mixture solution obtained in step (i) to form a carbon precursor layer on the surface of the transition metal oxyhydroxide nanoparticles; And (iii) it can be achieved by providing a transition metal oxide-carbon nanocomposite manufacturing method comprising the step of calcining the product mixture solution obtained in step (ii).
  • transition metal oxide-carbon nanocomposite refers to a nano-composite having a core-shell structure in which transition metal oxide nanoparticles are coated with a carbon layer.
  • the transition metal precursor of the method according to the invention is a precursor of a transition metal such as Fe, Mn, Ni, Co, Cr or In, and may be a transition metal chloride, a transition metal hydroxide, a transition metal sulfide, a transition metal oxide, or the like.
  • the surfactant is an anionic surfactant such as sodium dodecy sulfate, sodium dodecybenzenesulfonate, ammonium lauryl sulfate or sodium stearate, cetyl Cationic surfactants such as cetyltrimethylammonium bromide, cetyltriethylammonium chloride, benzalkonium chloride or benzethonium chloride, or poloxamer or triton X Neutral surfactant such as -100 (Triton X-100).
  • anionic surfactant such as sodium dodecy sulfate, sodium dodecybenzenesulfonate, ammonium lauryl sulfate or sodium stearate
  • cetyl Cationic surfactants such as cetyltrimethylammonium bromide, cetyltriethylammonium chloride, benzalkonium chloride or benzethonium chloride, or poloxamer or tri
  • the heating temperature of step (i) of the process according to the invention is preferably from 20 ° C. to 300 ° C., and the heating time is from 30 minutes to 24 hours.
  • the size of the transition metal oxyhydroxide produced in step (i) of the method according to the invention may be 0.1 ⁇ m to 1 ⁇ m.
  • the carbon precursor of step (ii) of the process according to the invention is pyrrole, sucrose, furfuryl alcohol, thiophene, aniline, 1-perferyl pyrrole (1 -furfuryl pyrrole), or polymers thereof.
  • the calcination temperature of step (iii) of the process according to the invention may be 250 ° C. to 350 ° C., and the calcination time may be 2 to 10 hours.
  • the carbon precursor layer is converted into a carbon layer by the calcination, and the thickness of the carbon layer may be 5 nm to 20 nm.
  • the transition metal oxyhydroxide can be produced without using high temperature and high pressure conditions, the production cost of the transition metal oxide-carbon nanocomposite is low.
  • transition metal ions of the transition metal oxyhydroxide serve as a catalyst in the step of forming the carbon layer by polymerization of the carbon precursor, a separate polymerization catalyst is not required.
  • the method of the present invention can reduce the cost of manufacturing equipment investment because it is possible to produce the transition metal oxide-carbon nanocomposites with only one reactor.
  • the method of the present invention is easy to scale up and is suitable for mass production of transition metal oxide-carbon nanocomposites.
  • FIG. 1 is a sea urchin FeOOH synthesized in Example 1 of the present invention (FIG. 1A, high degree of insertion), FeOOH coated with polypyrrole of sea urchin (FIG. 1B), sea urchin Fe 3 O 4 -C nanocomposite after calcination ( Figure 1c, inset is high magnification) and TEM image of the cut Fe 3 O 4 -C nanocomposite.
  • Figure 2a shows the XRD pattern for (i) sea urchin FeOOH and (ii) Fe 3 O 4 -C nanocomposite synthesized in Example 1 of the present invention
  • Figure 2b is the Fe 3 O 4 -C nanocomposite Shows the N 2 adsorption-desorption isotherm (inset is pore size distribution curve).
  • Figure 3 shows the Raman spectrum of the sea urchin Fe 3 O 4 -C nanocomposites synthesized in Example 1 of the present invention.
  • Example 4 is a TEM photograph of sea urchin-like Fe 3 O 4 particles without a carbon shell synthesized in Example 1 of the present invention.
  • FIG. 5 shows TEM images (FIG. 5A) and XRD spectra (FIG. 5B) of sea urchin ⁇ -Fe 2 O 3 particles synthesized in Example 1 of the present invention.
  • FIG. 6A is a charge-discharge profile of sea urchin Fe 3 O 4 -C nanocomposites synthesized in Example 1 of the present invention at a current density of 100 mA / g
  • FIG. 6B is the present invention at a scan rate of 0.1 mV / s. Cyclic voltammogram of the sea urchin Fe 3 O 4 -C nanocomposite synthesized in Example 1.
  • FIG. 7 shows sea urchin Fe 3 O 4 -C nanocomposites (squares, blue) synthesized in Example 1 of the present invention at a current density of 100 mA / g (FIG. 7A) and various current densities (FIG. 7B), The cycle performance of Fe 3 O 4 (circle, red) and Fe 2 O 3 (triangle, green) without carbon shell is shown.
  • Iron (III) chloride and sodium dodecyl sulfate (surfactant) were heated at 70 ° C. under atmospheric pressure to synthesize ⁇ -FeOOH as a precursor.
  • the ⁇ -FeOOH particles are sea urchinous spherical particles and have a diameter of 200 nm to 500 nm (FIG. S1).
  • the ⁇ -FeOOH particles are surrounded by needles of about 2.5 nm thick and about 45 nm long.
  • a pyrrole monomer was added to the reaction solution as a carbon source without undergoing a separation process or a washing process.
  • Fe 3+ in the solution acted as a polymerization catalyst of the pyrrole monomer.
  • pyrrole was polymerized on the ⁇ -FeOOH particle surface. Further pyrrole monomers could be added during the polymerization of the pyrrole, and synthesis of sea urchin ⁇ -FeOOH and polypyrrole coating could be carried out in one reactor without purification. The reaction proceeded at a relatively low temperature of 70 ° C. and atmospheric pressure.
  • the chemical composition of the resulting Fe 3 O 4 -C nanocomposite can be adjusted according to the amount of pyrrole monomer, and in this example, Fe 3 O 4 -C nanocomposites containing 12 wt% of carbon were investigated.
  • pyrrole was not added, sea urchin Fe 3 O 4 without a carbon shell was obtained (FIG. 4).
  • sea urchin phase ⁇ -Fe 2 O 3 particles were obtained (FIG. 5).
  • the needle-like material on the particle surface was thickened.
  • the nitrogen adsorption-desorption isotherm and corresponding Barrett-Joyner-Halenda (BJH) pore size distributions were identified for each step.
  • the surface areas of sea urchin ⁇ -FeOOH, polypyrrole-coated ⁇ -FeOOH and Fe 3 O 4 -C nanocomposites after calcination are 149.41 m 2 / g, 51.29 m 2 / g and 77.73 m 2 / g, respectively.
  • the surface area of the sea urchin ⁇ -FeOOH was due to thin needle-like material and internal pores, and decreased after polypyrrole coating.
  • Example 2 Fe 3 O 4 -C nanocomposite performance as LIB anode material
  • Example 1 The use of the sea urchin Fe 3 O 4 -C nanocomposite synthesized in Example 1 as a LIB anode material was investigated. Electrochemical testing of the nanocomposites was performed using a galvanostatic charge-discharge cycle method of 10 mV to 3.0 V at a current density of 100 mA / g (FIG. 6A). In the first cycle, the discharge curve showed a high plateau at about 0.8 V (vs. Li / Li + ), which was Fe 3 O 4 , carbon-Fe 3 O 4 composite and graphene-Fe 3 O 4 This is in good agreement with the results of the literature on the complex.
  • the sea urchin phase Fe 3 O 4 -C nanocomposite electrode has a first discharge capacity and charge capacity of 1228 mAh / g and 821 mAh / g, respectively.
  • the Coulombic efficiency in the first cycle is about 67%.
  • the irreversible capacity loss in the first cycle is due to the formation of a solid electrolyte interface (SEI) layer.
  • SEI solid electrolyte interface
  • cyclic voltammetry (CV) was performed at a scan rate of 0.1 mV / s (Fig. 6b) . As a result, the difference between the reduction potential and the oxidation potential was found to be large.
  • the large cathodic peak at 0.64 V corresponds to the reduction of Fe 3+ and Fe 2+ to Fe 0 with SEI layer formation. Thereafter, multiple anodic peaks between 1.6 V and 1.9 V are due to the oxidation of Fe 0 to Fe 2+ and Fe 3+ .
  • the CV curves of the Fe 3 O 4 -C nanocomposites agree well, which means that the electrochemical reversibility is good.
  • FIG. 7A shows the cycle performance of the Fe 3 O 4 -C nanocomposite up to 40 cycles at a current density of 100 mA / g, with the results and sea urchin phase Fe 3 O 4 and ⁇ -Fe 2 O 3 without carbon shell
  • the CV curves of the particles were compared in FIG.
  • the capacity of ⁇ -Fe 2 O 3 is the largest of the three electrodes.
  • the capacity of ⁇ -Fe 2 O 3 decreases very rapidly before stabilization after 30 cycles, due to the large volume change in the course of the cycle.
  • the capacity of Fe 3 O 4 decreases relatively slowly before stabilizing after 20 cycles.
  • the Fe 3 O 4 -C nanocomposite exhibits a charge capacity of about 745 mAh / g at a current density of 400 mA / g, which is about 90% of the charge capacity at a current density of 100 mA / g.
  • Fe 3 O 4 and ⁇ -Fe 2 O 3 show about 56% and 37% of the charge capacity at a current density of 100 mA / g, respectively.
  • the Fe 3 O 4 -C nanocomposite shows better rate performance compared to the Fe 3 O 4 and ⁇ -Fe 2 O 3 .

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Abstract

La présente invention porte sur un procédé pour la préparation d'un nanocomposite d'oxyde de métal de transition-carbone. Plus précisément, la présente invention porte sur un procédé pour la préparation du nanocomposite d'oxyde de métal de transition-carbone, comprenant les étapes consistant à : (i) chauffer un mélange d'un précurseur à métal de transition et d'un tensioactif pour préparer des nanoparticules d'oxyhydroxyde de métal de transition ; (ii) former une couche de précurseur de carbone sur la surface des nanoparticules d'oxyhydroxyde de métal de transition par ajout d'un précurseur de carbone à une solution mélangée du produit obtenu à partir de l'étape (i) ; et (iii) calciner une solution mélangée du produit obtenu à partir de l'étape (ii).
PCT/KR2013/002664 2012-04-06 2013-04-01 Procédé pour la préparation de nanocomposite d'oxyde de métal de transition-carbone WO2013151282A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN108636338A (zh) * 2018-05-11 2018-10-12 杭州诚洁环保有限公司 一种Fe/C复合固体吸附剂及其制备方法和应用
US10232347B2 (en) * 2016-12-28 2019-03-19 Soochow University Hollow mesoporous carbon nanosphere composite material loaded with gold nanoparticles, and preparation method thereof and application in continuous processing of CO
CN114180620A (zh) * 2021-11-30 2022-03-15 陕西科技大学 一种聚吡咯为模板制备二氧化钛/碳负极的制备方法
CN114534742A (zh) * 2022-02-24 2022-05-27 海南大学 一种高熵单原子催化剂及其制备方法
US12027700B2 (en) * 2019-02-13 2024-07-02 Lg Energy Solution, Ltd. Positive electrode comprising goethite for lithium secondary battery and lithium secondary battery comprising same

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10232347B2 (en) * 2016-12-28 2019-03-19 Soochow University Hollow mesoporous carbon nanosphere composite material loaded with gold nanoparticles, and preparation method thereof and application in continuous processing of CO
CN108636338A (zh) * 2018-05-11 2018-10-12 杭州诚洁环保有限公司 一种Fe/C复合固体吸附剂及其制备方法和应用
CN108636338B (zh) * 2018-05-11 2020-09-29 杭州诚洁环保有限公司 一种Fe/C复合固体吸附剂及其制备方法和应用
US12027700B2 (en) * 2019-02-13 2024-07-02 Lg Energy Solution, Ltd. Positive electrode comprising goethite for lithium secondary battery and lithium secondary battery comprising same
CN114180620A (zh) * 2021-11-30 2022-03-15 陕西科技大学 一种聚吡咯为模板制备二氧化钛/碳负极的制备方法
CN114534742A (zh) * 2022-02-24 2022-05-27 海南大学 一种高熵单原子催化剂及其制备方法

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