EP2121184A2 - Nanotubes auto-ordonnés d'oxydes de titane et d'oxydes d'alliages de titane pour applications de stockage d'énergie et d'accumulateurs - Google Patents

Nanotubes auto-ordonnés d'oxydes de titane et d'oxydes d'alliages de titane pour applications de stockage d'énergie et d'accumulateurs

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Publication number
EP2121184A2
EP2121184A2 EP07869155A EP07869155A EP2121184A2 EP 2121184 A2 EP2121184 A2 EP 2121184A2 EP 07869155 A EP07869155 A EP 07869155A EP 07869155 A EP07869155 A EP 07869155A EP 2121184 A2 EP2121184 A2 EP 2121184A2
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EP
European Patent Office
Prior art keywords
oxide
titanium
nanotubes
substrate
titanium alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07869155A
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German (de)
English (en)
Inventor
Manoranjan Misra
Krishnan S. Raja
Kangnian Zhong
Vishal K. Mahajan
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University of Nevada Reno
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University of Nevada Reno
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Publication date
Application filed by University of Nevada Reno filed Critical University of Nevada Reno
Publication of EP2121184A2 publication Critical patent/EP2121184A2/fr
Withdrawn legal-status Critical Current

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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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/005—Epitaxial layer growth
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

  • This invention relates to synthesis and use of self-ordered arrays of nanotubular oxides of titanium and titanium alloys.
  • the arrays can be used in energy storage applications, such as in Li-ion batteries.
  • Nanocrystalline titanium dioxides have been investigated as potential anode materials for Li-ion insertion. See, for example, V. Subramanian et al., /. Power Sources, 159 (2006) 186-192; S.W. Oh et al., /. Power Sources, 161 (2006) 1314-1318; A.R. Armstrong et al., Advanced Materials 17 (2005) 862-65; CO. Avellanda et al., Electrochimic acta 46 (2001) 1977-81; and Q.-H. wu et al., Surface Science 578 (2005) 203-212, all of which are herein incorporated by reference in their entirety.
  • the nanostructured TiO 2 materials are prepared via the sol-gel or hydrothermal
  • nano-phosphate particles as anode materials has also been disclosed in S. Chung et al., Nature Materials, 2 (2002) 123-128, herein incorporated by reference in its entirety.
  • a combination of TiO 2 and nanocarbon materials has also been investigated as a possible anode material by different research groups. See, for example, H. Huang et al., Materials Letters, 61 (2007) 296-299, and L. J. Fu et al., /. Power Sources, 159 (2006) 219-222, both of which have herein been incorporated by reference in their entirety.
  • the nanocomposite TiO 2 -carbon materials are prepared using doctor-blade or pelletization techniques.
  • This invention relates to an electrode capable of storing energy.
  • the electrode comprises an anodized and oxidatively- annealed titanium oxide or titanium alloy oxide substrate having a plurality of self-ordered oxide nanotubes.
  • the electrode may be used in energy storage application, such as a component of a lithium-ion battery.
  • the invention also relates to a method of manufacturing an anodized and annealed titanium oxide or titanium alloy oxide substrate.
  • the method involves (a) anodizing a titanium or titanium alloy substrate under conditions sufficient to form anodized titanium oxide or titanium alloy oxide having a plurality of self-ordered oxide nanotubes on the anodized surface, and (b) annealing the oxide nanotubes in a controlled gaseous
  • the invention also relates to an anodized titanium alloy oxide substrate having a plurality of self-ordered oxide nanotubes.
  • the substrate may be annealed in oxygen or another gaseous atmosphere.
  • the substrate is suitable as an electrode or a component of a battery, as well as in other applications, such as the photo-electrolysis of water.
  • This invention also relates to a method of using an anodized and oxidatively- annealed titanium oxide or titanium alloy oxide substrate in an energy storage application.
  • the method involves contacting an anodized and oxidatively- annealed titanium oxide or titanium alloy oxide substrate having a plurality of self-ordered oxide nanotubes with an energy source and an electric current, and receiving ions from the energy source in the oxide nanotubes.
  • Fig. 1 depicts a schematic of an anodization process flow.
  • Fig. 2 depicts a top view of an anodized titanium surface (2(a)), and various views of anodized TiMn (2(b-d)).
  • Fig. 3 depicts top views of an anodized Ti-Mn surface at different magnifications.
  • Fig. 4 depicts SEM images of nanocomposite structures of carbon nanotubes grown on a titanium oxide nanotubular template at different magnitudes.
  • Fig. 5 depicts a schematic arrangement of a Li-ion charge-discharge experiment.
  • Fig. 6 depicts a schematic arrangement of a Li-ion multiple charge-discharge experiment using a two-electrode configuration.
  • Fig. 7 depicts a cyclic voltamogram of oxidatively annealed titanium oxide nanotubes.
  • Fig. 8 depicts a cyclic voltamogram showing the capacity of (TiMn)O 2 associated with Li-ion insertion and de-insertion.
  • Fig. 9 depicts the potential variation during charging (8(a)) and discharging (8(b)) of lithium ions using TiO 2 and (TiMn)O 2 substrates.
  • Fig. 10 depicts potential variation during discharge cycles using TiO 2 and (TiMn)O 2 substrates.
  • Fig. 11 depicts SEM images of nanotubular oxide of Ti-Mn after Li charge- discharge experiments.
  • Figs. 12 and 13 depict the specific capacity shown in exemplified Ti-Mn substrates.
  • Fig. 14 depicts a cross-section of anodized (TiMn)O 2 .
  • Fig. 15 depicts the oxygen K-edge electron loss spectrum of an anodized single nanotube of Ti-Mn oxide.
  • Fig. 16 shows the electron energy loss spectroscopy results of the Ti-Mn oxide nanotubes after Li-insertion.
  • Fig. 17 shows a typical potential profile of Ti-Mn oxide discharge using a two- electrode configuration.
  • the invention relates to a method of manufacturing an anodized and annealed titanium oxide or titanium alloy oxide substrate.
  • the method involves (a) anodizing a titanium or titanium alloy substrate under conditions sufficient to form anodized titanium oxide or titanium alloy oxide having a plurality of self-ordered oxide nanotubes on the anodized substrate, and (b) annealing the oxide nanotubes in a controlled gaseous atmosphere, for example, when the substrate is annealed in an oxygen or other oxidizing atmosphere.
  • the anodized and oxidatively- annealed titanium oxide or titanium alloy oxide substrates of the invention have a surface area sufficient to incorporate ions for energy storage.
  • the anodization may take place using electrochemical techniques known in the art.
  • the titanium or titanium alloy material may be electrochemically anodized in an aqueous or non-aqueous acidified electrolyte solution containing a fluoride salt.
  • the anodization process can be set up in a system similar to the schematic shown in Fig. 1.
  • titanium metal Any type of titanium metal may be used as the titanium substrate.
  • the only limitation on the titanium metal is the ability to anodize to form the titanium oxide
  • the titanium substrate may be titanium foil, a titanium sponge or a titanium metal layer on an other substrate, such as, for example, a semiconductor substrate, plastic substrate, and the like, as known in the art.
  • Titanium metal may be deposited on a substrate using conventional film deposition techniques known in the art, including but not limited to, sputtering, evaporation using thermal energy, E-beam evaporation, ion assisted deposition, ion plating, electrodeposition (also known as electroplating), screen printing, chemical vapor deposition, molecular beam epitaxy (MBE), laser ablation, and the like.
  • the titanium substrate and/or its surface may be formed into any type of geometry or shape known in the art.
  • the titanium substrate may be planar, curved, tubular, non-linear, bent, circular, square, rectangular, triangular, smooth, rough, indented, etc.
  • size of the titanium substrate depends only upon the size of the annodization tank. For example, sizes ranging from less than a square centimeter to up to square meters are contemplated.
  • thickness may be any thickness.
  • the titanium substrate may be as thin as a few nanometers.
  • any type of titanium alloy may be used as the titanium alloy substrate, provided the titanium alloy has the ability to anodize to form the titanium alloy oxide nanotubes on the surface of the substrate.
  • Preferred titanium alloys include Ti-Mn, Ti- Nb, Ti-Zr, Ti-Si, and Ti-Al-V, however other titanium alloys known in the art may also be used. Titanium alloys may be purchased from commercial suppliers, such as Titanium Metals Corporation (TIMET), based in the U.S., or KOBELCO, based in Japan.
  • the content of the elements in the alloy vary as known in the art. Generally, the titanium alloy contains from about 0.1-50 wt% of elements other than titanium, with the balance of the alloy being titanium.
  • a Ti-Mn alloy will typically contain 3-8 wt% manganese, with the balance titanium; a Ti-Al-V alloy will typically contain 3-8 wt% aluminum, 2-4 wt% vanadium, with the balance titanium (a Ti-6A1-4V contains 6 wt% Al, 4 wt% V, with the balance Ti).
  • the titanium— either by itself or with the other metal(s) in the alloy— will become oxidized during the anodization process.
  • the titanium and manganese typically oxidize, thus forming oxide nanotubes having both titanium oxide and
  • the oxide stoichiometry of the nanotubes can change depending on how easily the non-titanium metals in the alloy form a solid solution with the titanium upon anodization. In titanium-manganese alloys, both the titanium and manganese form a solid solution together, and the resulting nanotubes have a composition where the manganese oxide is distributed throughout the nanotubular structure.
  • the self-ordered oxide nanotubes will contain two or more regions of varying oxide stoichiometries.
  • the oxide nanotubes when anodizing Ti-Si alloy with Si content varying from 2-28%, the oxide nanotubes have two distinct chemistries, where the top layer is predominately TiO 2 and bottom layer is predominantly SiO 2 .
  • This dual oxide layer is mainly attributed to the large difference in transference numbers of Ti 4+ and Si 4+ ions in the oxide layer.
  • the titanium or titanium alloy substrate may be cleaned and polished using standard metallographic cleaning and polishing techniques known in the art.
  • the material surface may be cleaned using soap and distilled water.
  • the titanium or titanium alloy metal substrate is chemically and/or mechanically cleaned and polished prior to anodization. Mechanical cleaning is preferably done by sonication.
  • a titanium metal surface may be incrementally polished by utilizing 120 grit emery paper down to 1200 grit emery paper followed by wet polishing in a 15 micron alumina slurry. After polishing, the metal substrate may be thoroughly washed with distilled water and sonicated for about 10 minutes in isopropyl alcohol, as known in the art.
  • Performing such optional cleaning and polishing aids in consistency of the titanium and titanium alloy metal substrates used in the invention and better ensures that the substrates have uniform starting points (e.g., planar surfaces when desired). While it is preferred to use clean or polished surfaces, there may be instances when the material is clean prior to use or using a clean material is otherwise undesirable or unnecessary.
  • An acidified fluoride electrolyte may be used in the anodization step.
  • the electrolyte may be an aqueous electrolyte, an organic electrolyte solution, or a mixture thereof.
  • Fluoride compounds which may be used in the electrolytes are those known in the art and include, but are not limited to, hydrogen fluoride, HF; lithium fluoride, LiF; sodium fluoride, NaF; potassium fluoride, KF, ammonium fluoride, NH 4 F; and the like.
  • It is preferred that the fluoride electrolytes have a pH below 5, with a pH range of 4-5 being most preferred. Adjusting the pH may be done by adding acid, as is known in the art.
  • Suitable acidified fluoride electrolytes include, for example, a 0.5 M H 3 PO 4 + 0.14 M NaF solution, a 0.5 -2.0 M Na(NO 3 ) + 0.14 M NaF solution, a 0.5-2.0 M NH 4 NO 3 + 0.14 M NH 4 F, or a combination of 0.5 M H 3 PO 4 + 0.14 M NaF + 0.05-1.0 M Na(NO 3 ).
  • any organic solvent, or mixture of organic solvents, which is capable of solvating fluoride ions and is stable under the anodization conditions may be used as an organic electrolyte.
  • the organic electrolyte may also be a miscible mixture of water and an organic solvent. It is preferred that about 0.16 wt% to about 95% wt% water be present in an organic electrolyte because water participates in the initiation and/or formation of the nanotubes.
  • the organic solvent is a polyhydric alcohol such as glycerol, ethylene glycol (EG) or diethylene glycol (DEG).
  • organic electrolyte is that during the annealing step, the organic solvent is volatized and decomposes under the annealing conditions but also results in carbon doping of the titanium dioxide or titanium alloy nanotubes.
  • the incorporation of carbon in the TiO 2 lattices increases the conductivity of the nanotubes and improves the charge-discharge performance as an anode material in Li-ion batteries.
  • Preferred electrolyte solutions containing a non-aqueous solution include ethylene glycol + 0.2-0.5 wt% NH 4 F, and glycerol + 0.2-0.5 wt% NH 4 F.
  • Various elements in the electrolyte solution may be doped into the oxide nanotubes, such as carbon, nitrogen, phosphorus, sulfur, or fluorine. If desired, doping may be accomplished through the interaction with the electrolyte, as discussed above, or by conventional means known in the art, such as solid source diffusion, gas diffusion, or via a thermal treatment, such as in the annealing step. Incorporation of fluorine in the
  • titanium and titanium alloy oxides is believed to expand the lattice structure, in some cases significantly. This expanded lattice, in turn, is believed to lead to increase in the concentration of ions that can be stored in the oxide lattice.
  • incorporating or doping the oxide nanotubes with fluorine is a preferred embodiment of this invention.
  • Various combinations of solutions can be employed in order to tailor the morphology of the nanotubes, such as surface with ridges or without ridges (straight nanotubes). Different electrolyte solutions can be used depending on the compatibility with the materials being anodized, as appreciated by one of skill in the art. For example 0.5 M H 3 PO 4 + 0.14 M NaF solution can be used for creating titanium oxide nanotubes with ridges.
  • Such a solution appears to work adequately for all titanium and titanium alloy materials, such as Ti-6A1-4V.
  • Ti-6A1-4V titanium and titanium alloy materials
  • anodization in 0.5 M H 3 PO 4 + 0.14 M NaF results in nonotubes with ridges
  • using a Ti-Mn alloy anodization in 0.5 M H 3 PO 4 + 0.14 M NaF results in nanoparticle morphology.
  • the electrolyte solution can also be varied depending on the length of the nanotube that is desired. For instance, a 2.0 M Na(NOs) 2 + 0.14 M NaF solution with a pH of 3.8-6.0 can be used for growing relatively long nanotubes.
  • the electrolyte solution may also contain a complexing agent, e.g. EDTA, tri- sodium citrate (CeHsNa 3 O ? 2H 2 O), citric acid, sodium pyrophosphate (Na 4 P 2 ⁇ 7 10H 2 O), gluconate, gluconic acid, tartarate, malate, glycine, and other complexing agents known in the art.
  • EDTA tri- sodium citrate
  • Na 4 P 2 ⁇ 7 10H 2 O citric acid
  • sodium pyrophosphate Na 4 P 2 ⁇ 7 10H 2 O
  • gluconate gluconic acid
  • tartarate malate
  • glycine glycine
  • the complexing agent which is preferably added in the amount of 0.1-5.0 wt%, with 0.5-1.0 wt% being most preferred, allows for the formation of improved nanopores at a faster rate. It is believed that the addition of EDTA in aqueous electrolyte solutions increases the kinetics of nano
  • the formation of the nanotubes may be improved by mixing or stirring the electrolyte during anodization.
  • Conventional techniques for mixing or stirring the electrolyte may be used, e.g. mechanical stirring, magnetic stirring, etc.
  • the electrolyte solution should preferably be stirred continuously during the entire anodization process, or at least until a steady state is reached.
  • the mixing is achieved by ultra-sonicating the electrolyte solution during annodization. Sonication may be done using commercially
  • Ultra- sonicating the electrolyte during anodization aids in nanotube formation giving more uniform and smooth nanotubes than achieved with other mixing techniques. Ultra- sonication also provides more uniform concentration of radicals and pH preventing or at least minimizing the existence of concenteration and pH gradients which may occur during anodization.
  • Various ultra-sonication techniques may be found in PCT Application No. PCT/US06/35252, filed September 11, 2006 and PCT Application No. PCT/US06/47349, filed December 13, 2006, both of which are herein incorporated by reference in their entirety.
  • the container of the electrolyte may be placed inside an ultrasonication bath.
  • an ultrasonic field may be introduced near the anode surface by immersing an ultrasonicator horn/probe in the solution.
  • the ultrasonication frequency typically ranges from 16-50 kHz and the power intensity typically varies from 0.1-10 W/cm 2 .
  • Self-ordered oxide nanotubes can typically be obtained more quickly with ultrasonic mixing than conventional mixing techniques (i.e. 20 minutes), for example, when under an applied external potential of 20 V in phosphoric acid and sodium fluoride electrolytes.
  • the effect of different synthesis parameters viz., synthesis medium (inorganic, organic and neutral), fluoride source, applied voltage and synthesis time are discussed below.
  • the pore diameters can generally be tuned from 30-120 nm by changing the annodization process parameters such as anodization potential and temperature.
  • the pore diameter generally increases with anodization potential and fluoride concentration, and the diameter generally decreases with the electrolyte temperature.
  • a 300-1000 nm thick self-ordered porous titanium dioxide or titanium alloy layer can be prepared by this procedure relatively quickly.
  • Anodization by ultrasonic mixing is also more efficient than the conventional magnetic stirring.
  • the anodizing approach discussed above is able to build a porous titanium oxide film of controllable pore size, good uniformity, and conformability over large areas at low cost.
  • the anodization step occurs over period of 1-30 hours.
  • the anodization time can be reduced by more than 50%. It also leads to better ordered and more uniform titanium oxide and
  • titanium alloy oxide nanotubes compared to nanotubes prepared using conventional magnetic stirring.
  • nanotubes can be improved as anodization time increases. For example, after about 120 seconds of anodization, small pits start to form on the surface of titanium and titanium alloy. These pits increase in size after about 600 seconds, though still retaining the inter-pore areas. After about 900 seconds, most of the surface is covered with an oxide layer, however the pores are not well distinct. After about 1200 seconds, the surface is completely or almost completely filled with self-ordered nanotubes. Anodizing from about 1200 to about 7200 seconds will increase the size of the nanotubes and increase the pore diameter. Further increase in time past 7200 seconds generally does not affect the pore diameters or the length of the nanotubes.
  • the applied potential can affect nanotubes formation and pore size. Generally, 10 V is sufficient to prepare the titanium oxide or titanium alloy oxide nanotubes, with typical voltages ranging from 5-60 V. However, pore uniformity and order have been found to increase upon an application of increased applied potentials, such as 15 V to 20 V, to the system.
  • the power source in the anodization reaction is a direct current power source that can supply 40 V of potential and support 20 mA/cm current density.
  • the anodization voltage may be applied in steps (0.5 V/min) or the voltage may be continuously ramped at a rate of 1-10 V/min from open circuit potential to higher values. It is believed that this process results in pre-conditioning of the surface to form nanoporous surface layer. After reaching the final desired anodization potential, the voltage is generally maintained at constant value. The anodization process is continued for approximately 20 minutes or more after the current has reached a plateau value. [0049] Pore size also increases with the application of the higher applied potentials.
  • the pore openings of the titanium oxide and titanium alloy oxide nanotubes can be tuned as desired by changing the synthesis parameters, including applied voltage and/or fluoride ion concentrations.
  • the surface of the material forms nanopores and nanotubes ranging from 10-150 nm diameter, more preferably 60-100 nm.
  • the anodization process produces oxide nanotubes that appear on the suface of the material being anodized.
  • Figs. 2 and 3 show titanium oxide nanotubes produced on a titanium surface after anodization, the anodization being carried out in ethylene glycol (2.5 wt% water) and 0.5 wt % NH 4 F solution, 20V, Ih.
  • the diameter of the nanotube varies from 30-100 nanometers and the length varies from 400-800 nm.
  • the nanotubes can be increased up to 25 micron in length.
  • anodization of Ti-Mn alloys at 52 V in an ethylene glycol solution containing 2 wt% water and 3 wt% NH 4 F for 17 hours produced nanotubes about 12 micron in length. Nanotubes more than 20 micron in length were obtained after anodization time was increased to 20 hours.
  • anodization of Ti-Mn alloys at 30-60 V in an ethylene glycol solution containing 2 wt% water and 3 wt% NH 4 F for 3-20 hours represents a preferred embodiment of the invention capable of producing nanotubes having preferred morphologies.
  • nanotubes Longer nanotubes may be desired for certain purposes while shorter nanotubes may be desired for other purposes.
  • nanotubes ranging from 10- 20 micron in length is preferred, while in other embodiments, for instance the embodiments of the invention relating to CNT growth in the nanotubes, the nanotubes are preferably 3-4 micron in length.
  • the samples may be cleaned by means known in the art. To sufficiently clean the samples, it is preferred that they are thoroughly washed with distilled water and ultrasonicated in acetone for at least 2 minutes. The cleaned samples may then be dried in air or nitrogen stream and stored in a desiccator.
  • the nanotubes are annealed in an gaseous atmosphere under conditions known by those of skill in the art.
  • the gaseous atmosphere can be under oxidizing conditions or reducing conditions, as known in the art. If a titanium substrate was used, then the gaseous atmosphere should be an oxidizing atmosphere so that the substrate is oxidatively-annealed. If a titanium alloy substrate was used, the gaseous atmosphere may be include gases known in the art that can be used during annealing, such as oxygen, nitrogen, hydrogen, cracked ammonia, argon, helium,
  • the titanium alloy is annealed in an oxidizing atmosphere such as oxygen.
  • Annealing in an oxidizing atmosphere is preferred when the substrate is used in an energy storage application. Unlike processes used to prepare nanotubes with oxygen vacancies, where annealing in an oxidizing atmosphere is avoided, it has been found that annealing in an oxidizing atmosphere leads to unexpected advantages in energy storage applications, such as increased capacity.
  • any conventional annealing techniques and heating apparatus may be used.
  • the annealing typically takes place at temperatures of approximately 300 0 C or higher, preferably 350-650 0 C, and more preferably from about 450-550 0 C. As appreciated by those of skill in the art, certain temperature ranges will be preferred for certain substrates. For instance, for Ti-Mn alloy substrates, the preferred temperature range is 300-500 0 C.
  • the reaction may take place for a time period of approximately 1-10 hours.
  • the annealing process is preferably conducted at a heating and cooling rate of about 1- 50 °C/min, preferably about 1-10 °C/min.
  • An embodiment of this invention relates to growing carbon nanotubes (CNT) in the titanium oxide and titanium alloy oxide nanotubes.
  • the nanotubular oxide samples may be used as templates to grow the CNT.
  • a plurality of catalyst particles should first be deposited in the oxide nanotubes to provide nucleation sites for carbon nanotube growth. Any catalyst particle suitable for CNT growth via chemical vapor deposition may be used.
  • the catalyst is cobalt, nickel, iron, or combinations thereof. Cobalt sulfate is a particularly preferred catalyst.
  • the electrolyte composition containing the catalyst is preferably maintained at a pH ranging from 3-7, and is preferably maintained at temperatures ranging from 20-50 0 C.
  • the catalyst particles may be deposited through any technique known in the art.
  • the catalyst is electrochemically deposited in the nanotubes via a computer-controlled pulse-reverse electrochemical deposition process, using equipment such as a pulse reverse DC rectifier. See U.S. Patent Application No. 11/033,839, filed January 13, 2005, herein incorporated by reference in its entirety, for suitable pulse-reverse electrodeposition techniques.
  • a short cathodic pulse can be given for the potential drop across the semi-conducting barrier layer, while maintaining the current density at a high density.
  • the cathodic pulse assists in making the cathode work piece (for instance, the nanoporous titania) and the high current density assists in depositing the catalyst into the pores in a high-aspect ratio and depositing the catalyst in areas that have high chemical potential.
  • a short anodic pulse is applied.
  • the pulse has a three fold objective: It discharges the capacitance developed in the barrier layer, stops the catalyst deposition immediately, and removes or depletes any extra catalyst deposited other than at bottom of the nanopores. Lastly, a delay time is introduced when no pulse is applied.
  • the metal ions migrate from the outer solution to inside of the pores, thereby replenishing the depleted regions with the catalyst.
  • the entire process is repeated several times. For instance, the process may be repeated for at least 500 cycles or at least 5 minutes, thus providing a minimum of 4 cathodic seconds of deposition time. This process preferentially deposits the catalyst at the bottom of the pores to support CNT growth.
  • CVD chemical vapor deposition
  • the nanoporous template having the catalyst at the bottom of the pores may be loaded into the chamber of a suitable CVD furnace (typically a quartz chamber) and heated in an inert atmosphere.
  • CVD furnace typically a quartz chamber
  • CNT growth may be accomplished by introducing a carbon source, hydrogen gas, and an inert gas onto the titanium oxide or titanium alloy oxide substrate under typical CVD process conditions. More particularly, the carbon- containing gas that acts as the carbon source is introduced into the CVD chamber with hydrogen and the inert gas.
  • the carbon source is preferably acetylene, methane, or carbon monoxide.
  • the inert gas is preferably argon.
  • Preferred chemical vapor deposition conditions include temperatures ranging from 500-700 0 C, more preferably from 600-650 0 C; reaction times starting at about one minute or longer; and flow rates ranging from about 10-200 seem for the carbon source, about 5-50 seem for the hydrogen, and about 100-300 seem of the inert gas.
  • This invention also relates to an electrode capable of storing energy.
  • the electrode comprises an anodized and oxidatively- annealed titanium oxide or titanium alloy oxide substrate having a plurality of self-ordered oxide nanotubes.
  • the electrode may be used in an energy storage application, such as a component of a lithium-ion battery.
  • None of the available techniques known in the art employ a self-ordered nanotubular array structure or disclose electrodes having a plurality of self-ordered oxide nanotubes that can be used for energy storage applications.
  • the ordered arrays of the nanotubes present in the electrodes provide a large surface area for enhanced incorporation of the lithium ions and an easy pathway for unhindered transportation of ions.
  • the anodized and oxidatively-annealed substrate is either a titanium oxide substrate or a titanium alloy oxide substrate. Any alloy that contains titanium may be used. Preferred titanium alloys include Ti-Mn, Ti-Nb, Ti-Zr, Ti-Si, and Ti-Al-V, as discussed above. Nanotubular oxide of alloys such as Ti-Mn, where oxides of Ti and Mn are present, have been shown to produce a multifold increase in discharge capacity. [0066]
  • the electrode may contain a plurality of catalyst particles deposited at the bottom of the oxide nanotubes to provide nucleation sites for carbon nanotube growth. Preferred catalyst particles include Co, Ni, Fe, and combinations thereof. The catalyst particles may be used to grow carbon nanotubes in the oxide nanotubes.
  • This invention also relates to an anodized titanium alloy oxide substrate having a plurality of self-ordered oxide nanotubes.
  • the substrate may be annealed in a gaseous atmosphere, preferably oxygen, as discussed above.
  • the substrate may be used in an energy storage application, or it may be used in other applications, such as in the photo- electrolysis of water and other applications known in the art.
  • This invention also relates to a method of using the electrode in an energy storage application.
  • Suitable energy storage applications include as an anode or cathode for batteries.
  • the method involves contacting an anodized and oxidatively-annealed titanium oxide or titanium alloy oxide substrate having a plurality of self-ordered oxide nanotubes with a cell and an electric current, and receiving ions from the energy source in the oxide nanotubes.
  • the cell may be a fuel cell or a battery, for instance, a lithium-ion battery or other hydride batteries.
  • the substrate may be contacted to or connected with the cell by any means known in the art, such as that of a conventional battery arrangement where the substrate acts as an electrode, preferably the anode, when the electric current is passed through the cell.
  • the substrate can receive ions, store them, and take on the customary functions of an electrode, as appreciated by those of skill in the art.
  • the electrode components are typically prepared in an initial step and then assembled onto a current collector as a second step. However, in this invention, the oxide nanotubes and substrate are formed as a single component.
  • one embodiment of this invention is directed towards a battery housed in a container having at least one titanium oxide or titanium alloy oxide inner surface of the container; the surface of the container is anodized under sufficient conditions to grow oxide nanotubes on the surface that can act as the anode to the battery.
  • This invention also relates to a lithium-ion battery that contains an electrode that comprises an anodized and oxidatively- annealed titanium oxide or titanium alloy oxide substrate having a plurality of self-ordered oxide nanotubes.
  • Lithium-ion batteries having the above-referenced electrodes have been shown to exhibit improved storage capacities and ability to carry lithium load.
  • the battery When the electrode contains an anodized and oxidatively- annealed titanium oxide substrate, the battery has been shown to have a storage capacity of at least 555 mAh/g and a lithium load of at least 1.68 moles per mole of titanium oxide.
  • the electrode When the electrode contains an anodized and oxidatively- annealed titanium oxide substrate containing carbon nanotubes grown in the oxide nanotubes, the battery has been shown to have a storage capacity of at least 1.7 Ah/g.
  • the battery When the electrode contains an anodized and oxidatively- annealed titanium alloy oxide, such as an oxide of a titanium-manganese alloy, the battery has been shown to have a storage capacity of at least 1.5 Ah/g.
  • the lithium load for preferred batteries ranges from 3.6-4.3 moles per mole of oxide.
  • the electrode preferably has a storage capacity of at least 500 mAh/g, more preferably has a storage capacity of at least 1.0 Ah/g, and most preferably has a storage capacity of 1.5 Ah/g or higher. Additionally, the electrode preferably has a lithium load of at least 1.5 moles per mole of oxide, more preferably a lithium load of at least 3.6 moles per mole of oxide.
  • a direct current power source that can supply 40 V of potential and support 20 mA/cm 2 current density.
  • a platiumn foil Pt rod/mesh
  • An external volt meter and an ammeter may be connected to the circuit in parallel and series respectively for measuring the actual potential and current during anodization.
  • the distant between material and the metal foil is maintained, typically at about 4 cm.
  • ultrasonication of the electrolyte can be carried out during anodization.
  • the container of the electrolyte is placed inside an ultrasonication bath or an ultrasonic field is introduced near the anode surface by immersing a ultrasonicator horn/probe.
  • the ultrasonication frequency can be 16-50 kHz and the power intensity can vary from 0.1-10 W/cm 2 .
  • the samples are thoroughly washed with plenty of distilled water and ultrsonicated in acetone for 2 minutes.
  • the cleaned samples are dried in air or nitrogen stream and stored in a desiccator for further annealing.
  • Annealing of the anodized specimens is carried out in a controlled oxidizing atmosphere furnace with continuous gas purging.
  • the annealing temperature varies from 350-650 0 C and the annealing time varies from 1-10 h.
  • the heating and cooling rates are controlled at 1-50 °C/min.
  • DC rectifier was used for electrodeposition.
  • An 8 msec cathodic pulse (with current control) was given for the potential drop across the semi-conducting barrier layer.
  • the current density was limited to -70mA/cm 2 .
  • An anodic pulse was applied for 2 msec with the current density restricted to +70mA/cm 2 .
  • a delay time of 600 msecs is given when no pulse is applied.
  • the CNTs were produced by chemical vapor deposition (CVD).
  • the nanoporous titania template with Co at the bottom of the pores was loaded into the quartz chamber of a CVD furnace and heated in argon atmosphere at a flow rate of 200 standard cubic centimeters (seem) for 5 min to reach a stable temperature of 635°C. After this, a mixture of acetylene, hydrogen, and argon was introduced into the chamber at flow rates of 40, 20 and 200 seem, respectively, for 3 min at the same temperature.
  • FIGS. 4(a)-(d) illustrate the SEM images of the nanocomposite structure of CNT and TiO 2 nanotubes.
  • FIG. 5 schematically illustrates the experimental arrangement for Li-ion charging-discharging studies.
  • Li foil (1 mm thick) and Li wire (3 mm diameter) were used as counter electrode and reference electrode respectively.
  • the experiments were carried out in a tightly sealed environment by controlling the oxygen and moisture level below 1 ppm. This was achieved by using a
  • the preparatory work of the experiments such as mixing the electrolyte and electrical connections is generally carried out only after achieving the desired atmospheric condition.
  • the electrolyte typically contains 1 M of lithium salt such as LiPF 6 , LiClO 4 , LiBF 4 , LiAlCl 4 , lithium perfluoromethylsulfonimide (Li(CF 3 SO 2 ) 2 N), lithium perfluoromthylsulfomethanide (Li(C 2 F 5 SO 2 ) 2 N), or lithium perfluoromethylsulfomethanide (Li(CF 3 SO 2 ) S C).
  • LiPF 6 was used.
  • the solvent is typically a mixture of alkyl carbonates such as propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), or diethyl carbonate (DEC).
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • PC + DEC or EC + DMC.
  • PC + DMC with 1:1 v/v ratio was used.
  • Charge-Discharge cycles were carried out on the nanotubular oxide samples using the similar set up described in Fig. 5.
  • the samples investigated were (1) pure TiO 2 nanotubular arrays annealed at 500 0 C in oxygen for 6 h, and (2) anodized Ti-Mn alloy annealed at 500 0 C for 6 h in oxygen.
  • Fig. 7 illustrates a cyclic voltammogram of TiO 2 nanotubes annealed at 500 0 C for six hours in oxygen.
  • the electrolyte is 1 M LiPF6 with lithium as counter and reference electrode.
  • Two anodic and cathodic peaks indicate presence of lower symmetry phase in the TiO 2 nanotubes.
  • the peak at 1.5 V corresponds to Li-Ti-O spinel and peak at higher potential is associated with lower symmetry anatase.
  • a similar cyclic voltammogram for (TiMn)O 2 is shown in Fig. 8.
  • the cathodic and anodic peaks occurred at similar potentials as that of TiO 2 shown in Fig. 7. This may indicate that the manganese is not directly involved in the electrochemical reaction. Under one theory, it is believed that the manganese instead acts to expand the lattice of the titanium oxide.
  • Fig. 9(a) illustrates the potential variation during the charging cycles. Discharging was carried out by applying a negative current density of -0.1 mA/cm 2 . The potential of the nanotubular sample was recorded continuously during the discharge as shown in Fig. 9(b). The initial potential during discharge was about 4 V, which is closer to the open circuit potential of the nanotubular oxide in 1 M lithium solution. The potential deceased rapidly during first 200 seconds and the decay was almost steady. The capacity was calculated factoring in the amount of discharge that occurred above 2 V. [0090] Fig. 10 shows the discharge behavior of titanium oxide and a titanium-manganese alloy oxide until 2 V. No fading of capacity was observed with number of cycles. After 200 seconds of discharge, a quasi plateau potential region was observed. In view of the
  • the lithium insertion was calculated to be 1.68 mole per mole of TiO 2 .
  • the discharge capacity of the titanium oxide nanotubes was calculated as 1.3 Ah/g.
  • the discharge capacity of titanium- manganese oxide nanotubes was found to be about three times that of titanium oxide substrate based on the 2 V cutoff potential. For example, TiO 2 nanotubes took about 500 seconds to reach 2 V, whereas Ti-Mn oxide nanotubes took about 1500 seconds.
  • the weight of the nanotubes present on the metal substrate was theoretically estimated based on the geometry. The estimated weight of the nanotubes was about 0.01 mg/cm 2 . Even considering only rapid discharge behavior for capacity determination that occurred within 200 seconds, the capacity of TiO 2 nanotubes would still be 555 mAh/g.
  • Example 2a (TiMn)O 2 as a Negative Electrode
  • Charge current Charge: 0.45 mA for 1000s or maximum 4.3V, 9000s at constant voltage cut off at 0.10 mA.
  • Example 2b (TiMn)O 2 as a Negative Electrode [00100] 1: Conditions: a) Material: Ti8Mn. b) Anodizing time: 3.0hr at 20V. c) Anneal time: 500 0 C 5 hr in O 2 . d) Thickness of nanotube: 1.2 ⁇ m, area of electrode: 0.85 cm 2
  • Charge current Charge: 0.4OmA for 1000s or maximum 4.3V, 9000s at constant voltage cut off at 0.10 mA.
  • Charge current Charge: 2.0 mA for 1000s cut off at 4.3V, 9000s at constant voltage cut off at 0.10 mA.
  • Table 1 shows a comparison of the output current voltage, specific capacity, specific energy, and specific power of various battery materials using tests similar to those described above.
  • the table compares the following cathodes: (a) a conventional graphite/LiCo ⁇ 2 electrode; (b) a nano-phosphate prepared in accordance with the disclosure set forth in Chung et al., Nature Materials, 2 (2002) 123-128, described above; (c) a titanium oxide nanoparticles electrode, prepared in accordance with the disclosure set forth in Subramanian et al., /. Power Sources, 159 (2006) 186- 192, described above; (d) a titanium dioxide nanotubular array, prepared in accordance with this invention; and (e) titanium manganese nanotubular array, prepared in accordance with this invention.
  • the electrode prepared in accordance with the invention demonstrated an improvement over the convention electrodes for specific capacity, specific energy, and specific power, while also demonstrating the same or about the same output current voltage.
  • the table confirms that the titanium oxide and titanium alloy oxide nanotubes of this invention outperform titanium oxide nanoparticles for important battery measurements. It is believed that the better current transport and easy diffusion pathways for Li-ions provided by the titanium oxide and titanium alloy oxide nanotubes enables this improvement. Additionally, the titanium oxide and titanium alloy oxide nanotubes exhibit a diffusion length of a half of wall thickness.
  • Fig. 14 shows a cross-section of anodized (TiMn)O 2 showing the length of the nanotubes.
  • Fig. 15 depicts the oxygen K-edge electron energy loss spectrum of an anodized single nanotube of Ti-Mn oxide. The identified peaks, shown as (a), (b), (c), and (d) suggest (Ti, Mn)O 2 stoichiometry in the anodized conditions.
  • Fig. 16 shows the electron energy loss spectroscopy results of the Ti-Mn oxide nanotubes after Li-insertion. The inset figure indicates Li-insertion is present in the nanotubes. The ability of the nanotubes to receive and store a charge, as confirmed in this figure, indicates that the nanotubes are acting as an battery rather than as a super capacitor.
  • Fig. 17 depicts an electrode on an 8.3 micro 0.28 cm 2 cycle.
  • the electrode is a TiMn substrate, anodized at 51.5 V for 17 hours at 350 0 C.
  • the substrate was annealed for five hours producing nanotubes having a thickness of 8.3 micron and weighing 0.47 mg.
  • the charge cycle was 2.0 mA for 1000 s, cut off at 4.3 V, 9000 at constant V, cut off at 0.1 mA.
  • the discharge cycle was 850 mA/g or 0.40 mA for 20,000 s, cut off at 2.8 V.
  • the specific capacity of the electrode was calculated at 2.44 mAh/cm or 1470 mAh/g.
  • the graph in Fig. 17 shows the potential profile of the Ti-Mn oxide discharge using a two-electrode configuration where the cathode was a commercial-grade LiCoO 2 electrode having an anode-to-cathode mass ratio of 1:50.
  • the plateau potential of discharge is shown to be around 3.5 V.

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Abstract

L'invention concerne des nanotubes d'oxyde que l'on forme par anodisation et recuit oxydatif d'un substrat en titane ou en alliage de titane avec ou sans sonication aux ultrasons. Le cas échéant, des nanotubes de carbone peuvent être obtenus par croissance dans les nanotubes d'oxyde. Les substrats précités possèdent une capacité spécifique et des vitesses de charge-décharge améliorées lorsqu'ils sont utilisés comme électrodes dans des accumulateurs aux ions lithium.
EP07869155A 2006-12-12 2007-12-12 Nanotubes auto-ordonnés d'oxydes de titane et d'oxydes d'alliages de titane pour applications de stockage d'énergie et d'accumulateurs Withdrawn EP2121184A2 (fr)

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