WO2010059749A1 - Matériaux d'anode revêtue de carbone - Google Patents

Matériaux d'anode revêtue de carbone Download PDF

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WO2010059749A1
WO2010059749A1 PCT/US2009/065022 US2009065022W WO2010059749A1 WO 2010059749 A1 WO2010059749 A1 WO 2010059749A1 US 2009065022 W US2009065022 W US 2009065022W WO 2010059749 A1 WO2010059749 A1 WO 2010059749A1
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sno
carbon
nano
colloids
nanospheres
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Lynden A. Archer
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Cornell University
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Priority to US13/129,610 priority Critical patent/US20110300447A1/en
Priority to CN200980154835XA priority patent/CN102282704A/zh
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Priority to US14/337,003 priority patent/US20150030930A1/en
Priority to US16/703,289 priority patent/US20200112022A1/en

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • 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
    • H—ELECTRICITY
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    • 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
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to carbon-coated SnO 2 nano-colloids and coaxial SnO 2 @carbon nanospheres.
  • the present invention also describes anodes of a Li- ion battery coated with either SnO 2 nano-colloids or the coaxial SnO 2 @carbon nanospheres.
  • Lithium-ion batteries are unmatched among energy storage technologies in terms of power density per unit volume or per unit mass. Tarascon et al. Nature :414359 (2001); Idota et al. 276:1395 Science (1997), Hassoun et al., Adv. Mater.. 19:1632
  • SnO 2 -based nanostructured materials are attracting growing research attention as high-capacity negative electrodes for LIBs for a variety of reasons, including their high theoretical capacity, low-cost, low toxicity, and widespread availability. Idota et al.
  • the theoretical reversible lithium storage capacity for the second reaction is readily calculated to be 790 niA h/g, which is more than twice the theoretical capacity, 372 mA h/g, for currently used graphite.
  • NYDOCS:43711.2 nano-painting with carbon has recently been found effective for improving cyclability, where carbon functions as a physical buffering layer for the large volume change (cushion effect).
  • a new type of nano-architecture, coaxial Sn ⁇ 2@carbon hollow nanosphere is described.
  • Anodes comprised of this structure exhibit exceptional cycling performance and charge-rate capabilities.
  • SnO 2 nano-colloids exhibiting similar improved properties over the art are also described.
  • a simple green-chemical method for large-scale synthesis of nearly monodisperse SnO 2 hybrid particles coated selectively with/without carbon is also described. The procedure utilizes widely available stannates and glucose as precursors. Glucose not only mediates the rapid precipitation of colloidal SnO 2 particles, but also serves as a carbon precursor for SnO 2 @carbon core-shell particles.
  • the invention describes nano-colloids, comprising carbon-coated SnO 2 nano- colloids.
  • the nano-colloids may be monodisperse or polydisperse and may comprise two carbon shells.
  • the carbon may be derived from a polysaccharide such as glucose.
  • An anode from a Li-ion battery may be coated with the nano-colloids.
  • the nano-colloids may be spherical in shape and have a diameter ranging from about 150 nm to about 400 nm.
  • a method of synthesizing SnO 2 nano-colloids comprising the steps of (a) dissolving potassium stannate in a glucose solution; (b) heating the glucose solution to a temperature ranging from about 160 0 C to about 200 0 C for about 2 hours to about 8 hours to obtain a powder; and (c ) carbonizing the powder by heating to a temperature ranging from about 450 0 C to about 700 0 C for about 2 hours to about 8 hours. Carbonizing may be done under N 2 .
  • the glucose solution can have a concentration ranging from about 0.2 M to about 1.0 M or from about 0.5 M to about 0.8 M.
  • the invention also discloses coaxial SnO 2 @carbon hollow nanospheres, comprising a hollow SnO 2 shell having an outer shell of carbon.
  • the carbon is derived from a polysaccharide such as glucose.
  • the SnO 2 shell may be a double shell of SnO 2 .
  • a method for making the coaxial SnO2@carbon hollow nanospheres comprising the steps of: (a) synthesizing substantially monodisperse silica nanospheres; (b) coating SnO 2 double-shells on the silica nanospheres; (c) coating the SnO 2 @silica with a polysaccharide such as glucose; (d) carbonizing the glucose under an inert atmosphere; and (e) removing the silica nanospheres by addition of acid or base.
  • the silica nanospheres are removed by addition of NaOH or HCl.
  • An anode of a Li-ion battery may be coated with a plurality of coaxial SnO2@carbon hollow nanospheres.
  • the mesoporous SnO 2 hollow nanospheres can have pores ranging from about 3 nm to about 5nm in diameter.
  • Figure l(a) is an TEM image as-synthesized SnO 2 nano-colloids coated with a thin layer of glucose-derived carbon-rich polysaccharide (18O 0 C, 0.8 M glucose).
  • Figure l(b) is an TEM image as-synthesized SnO 2 colloids with no coating of carbon materials observed (16O 0 C, 0.8 M glucose).
  • Figure l(d) is a magnified FESEM image of the rectangular area indicated in Figure l(c).
  • Figure l(e) provides a digram of a typical Lithium- ion battery.
  • Figure 2 is a plot of a TGA curve of carbon-coated SnO 2 nano-colloids shown in Figures l(c) and l(d).
  • Figure 3 is a collection of XRD patterns.
  • Plot (a) is an XRD of as-synthesized
  • Plot (b) is an XRD of the nanocolloids after carbonization at 45O 0 C.
  • Plot (c) is an XRD of the nanocolloids after calcination in air at 500 0 C for 1 hour.
  • Figure 4(a) is FESEM (a, c) and TEM (b, d) images of SnO 2 nano-colloids obtained after calcination in air at 400 0 C.
  • Figure 4(b) is TEM (a, c) and TEM (b, d) images of SnO 2 nano-colloids obtained after calcination in air at 400 0 C.
  • Figure 4(d) is TEM (a, c) and TEM (b, d) images of SnO 2 nano-colloids obtained after calcination in air at 500 0 C.
  • Figure 5 (a) shows a first-cycle discharge-charge voltage profile of the carbon- coated SnO 2 nano-colloids depicted in Figure l(c) at a current density of 120 mA/g.
  • Figure 5(b) shows a cyclic voltammogram for first and second cycles between 2
  • Figure 5(c) shows a plot of discharge capacity (lithium insertion) versus cycle number between 2 V and 5 mV.
  • Figure 6(a) is an TEM image of carbon-coated SnO 2 /Sn nanospheres obtained after carbonization at 55O 0 C.
  • Figure 6(b) is a FESM image of carbon-coated SnO 2 /Sn nanospheres obtained after carbonization at 55O 0 C.
  • Figure 6(c) is a TEM image of carbon hollow nanospheres obtained after carbonization at 700 0 C.
  • Figure 6(d) a TEM image of carbon-coated Sn nanospheres obtained after H 2 reduction at 55O 0 C.
  • Figure 7 is a collection of XRD patterns.
  • Plot (a) is an XRD of as-synthesized SnO 2 /polysaccharide nanospheres (180 0 C, 1.0 M glucose).
  • Plot (b) is an XRD of the nanocolloids after carbonization at 550 0 C.
  • Plot (c) is an XRD of the nanocolloids after H 2 reduction at 55O 0 C.
  • FIG 8 shows TGA curves for the following: plot (a) corresponds to the carbon- coated Sn(VSn nanospheres shown in Figure 6(a); plot (b) corresponds to the carbon- coated Sn nanospheres shown in Figure 6(d).
  • Figure 9(a) shows first-cycle discharge-charge voltage profiles for Sn ⁇ 2@carbon (I, see Fig. 6(a)) and Sn@carbon (II, see Fig. 6(d)).
  • Figure 9(b) shows discharge capacities (lithium storage) versus cycle number between 2 V and 5 mV at the same current density of 120 mA/g.
  • Figure 10 is a schematic of the formation sequence for Sn ⁇ 2@carbon coaxial hollow spheres.
  • Figure 1 l(a) shows an FESEM image of Sn ⁇ 2@carbon hollow spheres of Example 3.
  • Figure 1 l(b) shows an FESEM image of Sn ⁇ 2@carbon hollow spheres of Example 3.
  • Figure 1 l(c) shows a TEM image of Sn ⁇ 2@carbon hollow spheres of Example 3.
  • Figure 1 l(d) shows a TEM image of Sn ⁇ 2@carbon hollow spheres of Example 3.
  • Figure 1 l(e) shows FESM of Sn ⁇ 2@carbon hollow spheres of Example 3.
  • Figure 1 l(f) shows TEM Sn ⁇ 2@carbon hollow spheres of Example 3.
  • Figure 12(a) shows Cyclic vo Mammograms of Sn ⁇ 2@carbon coaxial hollow spheres of Example 3 depicting the first two cycles between 3 V and 5 mV at a scan rate of 0.05 mV/s.
  • Figure 12(c) shows cycling performance of the same cell at various rates after cycled for 100 cycles shown in Figure 12(b) for the spheres of Example 3.
  • Figure 13 shows XRD patterns Of SnO 2 (a) and SnO 2 @carbon (b) hollow spheres of Example 3 after dissolving silica templates in 2M NaOH at 50 0 C.
  • Figure 14 shows a TGA curve in air flow of 60 mL/min with a temperature ramp of 3 °C/minute for the spheres of Example 3.
  • the weight loss below 150 0 C rises primarily from water evaporation since the sample is found not completely dry.
  • Figure 15 shows a low-magnification FESEM image of SnO 2 hollow spheres of Example 3 after dissolving silica templates in 2M NaOH with the broken ones indicated by white frames.
  • Figure 16 shows a plot of a typical discharge-charge voltage profile for the first cycle at a current density of 0.32 C for the spheres of Example 3.
  • Figure 17 shows a plot of the cycling performance of SnO 2 @carbon hollow spheres of Example 3 measured between 3 V and 5 mV at a current density of 0.8 C for the spheres.
  • Figure 18 shows a plot comparing cycling performances between SnO 2 and SnO 2 @carbon hollow spheres of Example 3 under the same testing conditions.
  • Figure 19 shows a schematic illustration of the synthetic procedure for making SnO 2 /carbon composite hollow spheres, and derived carbon double-shelled hollow spheres.
  • Figure 20(b) shows an SEM of the SnO 2 hollow nanospheres in Example 4.
  • Figure 20(c) shows a TEM of the SnO 2 hollow nanospheres of Example 4.
  • Figure 20(d) shows a TEM of the SnO 2 hollow nanospheres of Example 4.
  • Figure 20(e) shows an N2 adsorption-desorption isotherm at 77 K for the SnO 2 hollow nanospheres of Example 4.
  • Figure 20(f) shows corresponding pore size distributions calculated by BJH method from both branches for the SnO 2 hollow nanospheres of Example 4.
  • Figure 21 shows XRD patterns of SnO 2 hollow nanospheres (a) and SnO2/carbon composite hollow spheres (b) of Example 4.
  • Figure 22(a) shows an SEM image of a SnO 2 /carbon composite hollow spheres of Example 4.
  • Figure 22 (b) shows a TGA curve under air with a ramp of 10 °C/minute of a SnO2/carbon composite hollow spheres of Example 4.
  • Figure 22 (c) shows a TEM image of a SnO 2 /carbon composite hollow spheres of Example 4.
  • Figure 22 (d) shows a TEM image of a SnO 2 /carbon composite hollow spheres of Example 4.
  • Figure 22 (f) shows a TEM image showing double-shelled carbon hollow spheres after focused electron beam irradiation with some remaining Sn nanoparticles indicated by black arrows.
  • Figure 23(a) shows a discharge-charge voltage profiles of SnCVcarbon composite hollow spheres for I 51 and 2 nd cycles at a current density of 100 mA/g.
  • Figure 23 (b) shows a cycling performance of SnCVcarbon composite hollow spheres at a current density of 100 mA/g and SnO2 hollow nanospheres at a current density of 160 mA/g.
  • the first type of particle is carbon-coated SnO 2 nano-colloid.
  • the nano-colloids may be monodisperse or polydisperse and may comprise two carbon shells.
  • the carbon may be derived from a polysaccharide such as glucose.
  • An anode from a Li- ion battery may be coated with the nano-colloids.
  • the nano-colloids may be spherical in shape and have a diameter ranging from about 150 nm to about 400 nm.
  • the carbon- coated SnO 2 nano-colloid may be SnO 2 /carbon composite hollow spheres which is prepared by a template-free route based on an inside-out Ostwald ripening mechanism. Lou et al., Adv. Mater. 18:2325 (2006). Since the hollow interior space is created by spontaneous evacuation of the interior materials through the shell, the shell is highly porous.
  • a method of synthesizing the SnO 2 nano-colloids may comprise the steps of (a) dissolving potassium stannate in a glucose solution; (b) heating the glucose solution to a temperature ranging from about 160 0 C to about 200 0 C for about 2 hours to about 8 hours to obtain a powder; and (c ) carbonizing the powder by heating to a temperature ranging from about 450 0 C to about 700 0 C for about 2 hours to about 8 hours. Carbonizing may be done under N 2 .
  • the glucose solution can have a concentration ranging from about 0.2 M to about 1.0 M or from about 0.5 M to about 0.8 M.
  • a glucose-derived polysaccharide (PS) carbon precursor is efficiently infiltrated into the mesoporous SnO 2 shells through 3D interconnected "nano-channels" (i.e., pores), and deposited onto both its interior and exterior surfaces.
  • the PS is carbonized under inert atmosphere to produce a 3D carbon network in the SnO 2 shell sandwiched by two carbon shells.
  • the SnO 2 /carbon mixture is then heated forming a Sn-carbon composite or colloid containing carbon and Sn.
  • Pores may be introduced into the nano-colloids as described in He et al. , Appl. Surf. Sci. 255:183 (2008), Kobayashi et al. Appl. Surf Sci. 255: 191 (2008) and Gidley et al. Annu. Rev. Mater. Res. 36: 49 (2006).
  • the SnO 2 nano-colloids of the present invention are useful as anode materials for lithium-ion (Li-ion) batteries.
  • the carbon-coated SnO 2 nano-colloids of the present invention exhibit significantly improved cycling performance in such anodes as compared to conventional SnO 2 -based anodes.
  • the SnO 2 /carbon composite hollow spheres of the present invention are made up of a hollow SnO 2 microsphere core and a layer of carbon on the outside surface of the core and optionally another carbon layer inside the core.
  • the SnO 2 /carboncomposite hollow spheres are manufactured as discussed below in the examples.
  • the SnO 2 hollow spheres range in size from about 150 to about 400 nm. In general, the pore size is less than about 5 nm, although other ranges are possible, including from about 3 nm to about 5 nm and about 4 nm.
  • the mesoporous structure has a Brunauer-Emmettt-Teller (BET) specific surface area of at least about 110 m 2 /g, although higher and lower numbers are also possible.
  • BET Brunauer-Emmettt-Teller
  • the spheres may be mono or polydisperse.
  • the second type of nanoparticle encompassed by the present invention is a SnO 2 @carbon coaxial hollow nanospheres.
  • the coaxial SnO 2 @carbon hollow nanospheres may comprise a hollow SnO 2 shell having an outer shell of carbon.
  • the carbon may be derived from a polysaccharide such as glucose.
  • the SnO 2 shell may be a double shell of SnO 2 .
  • An anode of a Li- ion battery may contain or be coated with a plurality of the coaxial SnO2@carbon hollow nanospheres.
  • a method for making the coaxial SnO2@carbon hollow nanospheres may comprise the steps of: (a) synthesizing substantially monodisperse silica nanospheres; (b) coating SnO 2 double-shells on the silica nanospheres; (c) coating the SnO 2 @silica with a polysaccharide such as glucose; (d) carbonizing the glucose under an inert atmosphere; and (e) removing the silica nanospheres by addition of acid or base.
  • the silica nanospheres may be removed by addition of NaOH or HCl.
  • An anode of a Li-ion battery may be coated with a plurality of coaxial SnO2@carbon hollow nanospheres.
  • substantially monodisperse refers to nanospheres that are greater than about 60% monodisperse, greater than about 70% monodisperse, greater than about 80% monodisperse, or greater than about 90% monodisperse.
  • step 10 provides an outline of the synthetic pathway for these nanoparticles.
  • silica nanospheres (ranging in size from about 240 to about 250 nm in diameter) are coated with uniform SnO 2 double shells. Lou et al. Small, 3:261 (2007).
  • the double- shelled architecture increases not only the structural integrity, but also the weight fraction of the electrochemically active component (SnO 2 ) of the designed component anode.
  • SnO 2 electrochemically active component
  • step 2 these core-shelled silica@SnO 2 nanospheres are further coated with glucose- derived carbon-rich polysaccharide (GCP) by a simple hydrothermal approach.
  • GCP glucose- derived carbon-rich polysaccharide
  • These nanospheres may have a variety of pore size openings typically ranging from about 0.1 nm to about 10 nm and more typically from about 0.12 nm to about 6 nm, and most typically from about 0.15 nm to about 0.55 nm.
  • the size of the pores may be the same or different, i.e., the distribution of pore size may have a variety of different distributions, normal, binomial, etc.
  • the pore size may be varied by adjusting the pH of the either the acid or base used to dissolve or remove the silica core.
  • Silica nanospheres may be synthesized in a wide range of sizes (ranging from about 5 nm to about 2000 nm) using multiple sol-gel approaches, including the Stober method. Stober et al. J.
  • the methods of the present invention are also useful for large-scale synthesis of monodisperse SnO 2 nano-colloids coated selectively with/without carbon using inexpensive stannate and one or more PS, e.g., glucose, as precursors.
  • PS e.g., glucose
  • the nano-colloids may be polydisperse, i.e., have an uneven shape distribution.
  • PS Glucose-derived polysaccharides
  • carbon-derived materials are useful as carbon precursors in the method of the present invention.
  • PS include, but are not limited to, the following: glucose, fructose, maltose, lactose, dextrose, sucrose, or other polysaccharides; a preferred polysaccharide (PS) is glucose.
  • any water or alcohol dispersable carbon source may be used.
  • the PS are employed in the form of a solution in a solvent such as water in which the PS is soluble.
  • Aqueous solutions of PS, especially glucose, in the range from about 0.2 M to about 1 M and preferably about 0.5 M to about 0.8 M may be used, although both higher and lower ranges may be used as well, e.g., ranging from about 0.01 M to about 0.2 M and from 0.8 M to about 8 M.
  • Other examples of carbon-derived materials include, polyacrylonitrile (PAN) and its water-dispersable copolymers, citric acid, gallic acid, and fumaric acid.
  • Li-ion battery may comprise either type of nanoparticle.
  • a general diagram of a Lithium- ion battery is shown below in Figure l(e).
  • the material may be polydisperse, having a variety of different size distributions.
  • the geometry of the particles may vary from a cube, sheet, rhomboid to encompass a wide range of different geometries as well as size distributions.
  • Examples 1 and 2 Carbon-coated SnO 2 nano-colloids were synthesized in large scale by a simple hydrothermal method followed by carbonization under inert atmosphere. The resulting
  • NYDOCS:43711.2 nanocolloids may be monodisperse, i.e., having the same size, or polydisperse.
  • the overall structure and synthetic pathway of the carbon-coated SnO 2 nano-colloids is shown in Figure 19 (see, Wen et al., Hollow Micro-/Nanostructures:Synthesis and Applications, Adv. Matter. 20:1-33 (2008)).
  • 1.0 gram of potassium stannate trihydrate (K 2 Sn ⁇ 3-3H 2 O, Aldrich, 99.9%) was dissolved in 20 mL of 0.8 M (concentrations in the range of about 0.2 to about 1.0 M were investigated) aqueous glucose solution.
  • Other molar concentrations of glucose may be used, including from about 0.0 IM to about 0.2 and from about 0.5 M to about 8M and from aboutl .0 M to about 8 M may also be used.
  • the solution was transferred to a Teflon-lined stainless steel autoclave (40 mL in volume) and hydrothermally treated in an air- flow electric oven at 18O 0 C (temperatures in the range of 16O 0 C - 200 0 C were investigated) for 4 hours. The times may also range from about 2 hours to about 8 hours, from about 4 to about 8 hours and from about 6 to about 8 hours.
  • the dark-grey precipitate was harvested by centrifugation and washed thoroughly with ethanol and deionized water. After vacuum-drying at room temperature, about 0.75 gram of brown-grey powder was obtained.
  • the powder was loaded into a tube furnace and heated under high-purity N 2 at 45O 0 C (temperatures in the range of 45O 0 C - 700 0 C were also investigated and found to work for 4 hours with a temperature ramp of 4°C/minute (carbonization may also be for about 2 to about 6 g hours and for about 4 to about 6 hours).
  • a mixed H 2 /N 2 (6% H 2 ) gas flow was used instead of pure N 2 gas.
  • the brown-grey powder was calcined in air at about 35O 0 C to about 500 0 C for about 1 hour.
  • thermogravimetric analysis was carried out under an air flow of 60 niL/minute
  • Electrochemical measurements were carried out using homemade two-electrode Swagelok-type cells with lithium metal as the counter and reference electrodes at room temperature.
  • the working electrode consisted of 80 wt% of the active material (e.g., Sn ⁇ 2 @C), 10 wt% of conductivity agent (carbon black, Super-P-Li), and 10 wt% of binder (polyvinylidene difluoride, PVDF, Aldrich).
  • the active material loading in each electrode disc (about 13 mm in diameter) was typically 1 - 2 mg.
  • the electrolyte was 1 M LiPF 6 in a 50:50 w/w mixture of ethylene carbonate and diethyl carbonate.
  • Cell assembly was carried out in a Argon- filled glove box with the concentrations of moisture and oxygen below 1 ppm. Charge-discharge cycles of the half-cells were measured between 5 mV and 2.0 V (or 3.0 V) at a constant current density with a Maccor 4304 battery tester.
  • Uniform-sized carbon-coated SnO 2 nano-colloids were synthesized in large scale using inexpensive stannate and glucose as precursors (note, nonuniform nanocolloids may also be used). The synthesis is based on a hydrothermal method followed by carbonization under inert atmosphere.
  • Figure l(a) displays as-synthesized SnO 2 nanocolloids coated with a thin layer of GCP under hydrothermal conditions at 18O 0 C. As can be seen, these discrete core-shell nano-colloids are nearly monodisperse with a diameter of about 100 nm. Each individual SnO 2 colloid is composed of numerous fine nanoparticles.
  • SnO 2 nano-colloids synthesized at 16O 0 C did not appear to have as notable GCP coating as shown in Figure l(b). Formation of SnO 2 nanospheres can be mediated by using a mild acidic condition created as a result of hydrothermal treatment of glucose. When the glucose concentration is increased to 0.5 M, the product consisted of small nanoparticles and nanospheres with a broad size
  • GCP can be carbonized at a temperatures as low as 400 0 C.
  • Figure l(c) and l(d) show carbon-coated SnO 2 nano-colloids obtained by carbonizing the as-synthesized SnO 2 (S)GCP nano-colloids at 450 0 C. As can be seen, the morphology is largely unaltered. The carbon content in these carbon-coated SnO 2 nano-colloids can be readily determined by thermo-gravimetric analysis (TGA). As shown in TGA curve in Figure 2, the combustion of carbon begins around 26O 0 C, and is nearly complete around 400 0 C. (In Figure 2, the weight is normalized at 100 0 C since the weight loss below 100 0 C is mainly caused by water evaporation).
  • the mean crystallite size is estimated to be about 4 nm only using Scherrer's formula based on the (110) peak. According to previous reports, carbothermal reduction of SnO 2 becomes substantial only when the carbonization temperature reaches around 600 0 C.
  • Figure 4 shows the resulting SnO 2 nano-colloids after calcination at 400 0 C and 500 0 C. At higher calcination temperatures, nanospherical morphology is maintained and the crystallite size (compare 4(d) with 4(b)), leading to a more porous structure.
  • the other peak was at about 1.28 V, which might indicate partial reversibility of reaction (1).
  • both cathodic peaks shifted to higher voltages (about 0.14 V and 1.0 V), and the peak current decreased substantially. This result indicates occurrence of irreversible processes during the first cathodic sweep.
  • irreversible decomposition of electrolyte could occur at low voltages (for example, formation of solid electrolyte interface (SEI)).
  • SEI solid electrolyte interface
  • There is no noticeable current change at both anodic peaks which suggests that the alloying/de- alloying reaction between Sn and Li takes place to the same extent. In other words, the reaction is highly reversible (otherwise, a significant reduction in anodic peaks during 2 nd cycle would be observed). Reversibility from cathodic and anodic peaks in the same cycle might be possible.
  • Figure 5(c) shows the cycling performance of the carbon-coated SnO 2 nano- colloids.
  • the current densities used for SnO 2 @Carbon and SnO 2 are 300 and 400 mA/g, respectively, by taking the carbon mass of SnO 2 @Carbon into account.
  • the capacity retention significantly improved compared to cycling performance of previously known SnO 2 -based materials. Specifically, while the capacity still decayed gradually over cycling, a high capacity of 440 mA h/g could be retained over at least 100
  • FIGS 6(a) and 6(b) show particles synthesized with a glucose concentration of 1.0 M and carbonized at 55O 0 C.
  • the SnO 2 /polysaccharide nanospheres were synthesized at 18O 0 C with a glucose concentration of 1.0 M.
  • the SnO 2 nanospheres were completely embedded in thick carbon shells. From the corresponding XRD analysis ( Figure 7(b)), carbothermal reduction took place to a small extent as suggested by the emerging small peaks (compared to Figure 7(a)), which can be assigned to SnO and Sn.
  • Catalytic decomposition of electrolyte by pure Sn crystallites might also be responsible for an anomalous high- voltage (> 1.0 V) irreversible capacity observed in Sn electrodes. This possibility, however, can be ruled out in present instance since the capacity contribution above 1.0 V is insignificant.
  • Figure 9(b) shows the comparative cycling performance.
  • the initial total capacity of Sn@carbon (around 560 mA - 600 mA h/g) was generally consistent with the additive contributions by weight fraction from Sn (about 430 mA h/g) and carbon matrix (about 160 mA h/g).
  • the capacity of Sn@carbon faded gradually to about 560 mA h/g after 20
  • the confined Sn nanospheres of 50 - 80 nm in size may be too large, and in addition there appears to be no interior hollow space for accommodating the large volume change during discharging-charging cycles.
  • each carbon-coated porous SnO 2 nanosphere was composed of numerous small crystallites (see Figure 6(a)).
  • the SnO 2 @carbon nanospheres can deliver a capacity higher than the theoretical capacity of graphite (372 mA h/g) for at least a 100 cycles.
  • a greater number of cycles may also be possible, including 100, 200, 400, 800, 1600 and 3200 cycles. Higher order of cycling ranges including greater than 50,000 or 100,000 are also possible.
  • Silica nanospheres (ranging from about 240 to about 250 nm in diameter) were synthesized by the St ⁇ ber's method. Stober et al, J. Colloid Interface Sci.. 26:62 (1968) using the one-pot protocol described in Lou et al., Small, 3:261 (2007). Stober synthesis is the ammonia-catalyzed reactions of tetraethylorthosilicate with water in Io w- molecular- weight alcohols. This reaction produces nearly monodisperse, spherical silica nanoparticles with sizes ranging from 5-2000 nm. R.K. Her, The Chemistry of Silica:
  • Etching of silica with base or acid is fully detailed in Her et al., The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties, and Biochemistry, Wiley, New York (1979), Brinker et al., Sol-Gel Science: The Physics and Chemistry of Sol-gel Processing, Academic, San Diego (1990) and Liang et al, Chemistry of Materials, 20:1451 (2008).
  • the product was harvested by centrifugation and washed with deionized water and ethanol for at least five times. After drying at 5O 0 C, the resulting brown powder was carbonized at 500 0 C for 4 hours under inert atmosphere. Finally, SnO 2 @carbon coaxial hollow spheres were obtained by dissolving the silica nanotemplates in a 2 M NaOH solution at 5O 0 C for 8 hours (HCl may also be used).
  • thermogravimetric analysis was carried out under air flow of 60 mL/min using TA Instrument Q500 from room temperature to 55O 0 C with a heating rate of 3°C/minute.
  • the electrochemical measurements were carried out using homemade Swagelok- type cells with lithium metal as the counter and reference electrodes at room temperature.
  • the working electrode consisted of active material (e.g., Sn ⁇ 2@carbon hollow spheres), conductivity agent (carbon black, Super-P-Li), and polymer binder (polyvinylidene difluoride, PVDF, Aldrich) in a weight ratio of around 80:10:10.
  • active material e.g., Sn ⁇ 2@carbon hollow spheres
  • conductivity agent carbon black, Super-P-Li
  • polymer binder polyvinylidene difluoride, PVDF, Aldrich
  • the active material loading in each electrode disc (about 12 mm in diameter) is typically 1 - 2 mg, corresponding to about 1.5 mg/cm 2 .
  • the electrolyte was 1 M LiPF 6 in a 50:50 w/w mixture of ethylene carbonate and diethyl carbonate.
  • Cell assembly was carried out in an Argon- filled glove box with the concentrations of moisture and oxygen below 1 ppm. Charge-discharge cycles of the cells were measured in a fixed voltage window (see main text) at a constant current density with a Maccor 4304 battery tester. Both the C rate and specific capacity were corrected based on the mass of Sn ⁇ 2@carbon coaxial hollow spheres while excluding possible impurities such as remnant silica and base from elemental analysis. 1C is defined as 625 niA/g for easy denotation.
  • Figure 1 l(a) - (d) shows the FESEM (a,b) and TEM (c,d) images of Sn ⁇ 2@carbon hollow spheres.
  • the arrows in (c) and (d) indicate carbon shells;
  • (e) and (f) show double-shelled SnO 2 hollow spheres.
  • FESEM field emission scanning electron microscopy
  • TEM transmission electron microscopy
  • hydrothermally derived GCP is advantageous because it can be carbonized at a temperature as low as 400 0 C, while carbothermal reduction of SnO 2 takes place only when the temperature reaches about 600 0 C. Park et al. Adv. Funct. Mater.. 18:455 (2008).
  • Figure 12a shows the cyclic vo Mammograms (CV) for the first two cycles at a scan rate of 0.05 mV/s in the potential window of 3 V - 5 mV.
  • the CV behavior is generally consistent with literature,
  • the SnO 2 @carbon coaxial hollow spheres manifest superior cycling performance, namely, a stable capacity of about 500 niA h/g for at least about 200 cycles. Higher order to cycles are also possible, including about 200, 400, 500, 1000, 10,000 and 100,000.
  • Mesoporous SnO 2 hollow nanospheres may also be synthesized as follows. Lou et al. Chem. Mater. 20:6562 (2008). Urea and potassium stannate trihydrate, K 2 SnO 3 3H 2 0 (Aldrich, 99.9%) were dissolved in a mixed solvent of ethano I/water (37.5 % ethanol by volume) to achieve concentrations of 0.1 M and 16 mM, respectively. Afterwards, the solution was transferred to Teflon-lined stainless steel autoclaves, and hydrothermally treated in an airflow electric oven at 150° C for 24 hours to produce a white precipitate, which was then harvested by centrifugation and washed with ethanol and deionized water followed by vacuum drying at room temperature.
  • SnO 2 /polysaccharide composite hollow spheres 0.2 g of as-synthesized mesoporous Sl 102 hollow nanospheres was dispersed by ultrasonication in 20 mL of 1 .0 M aqueous glucose solution. The suspension was transferred to a 40 mL Teflon-lined autoclave, which was then heated in an air- flow electric oven at 180 0 C for 3 hours. The product was again harvested by centrifugation and washed with deionized water and ethanol for at least five times. After drying at 50 0 C, the resulting brown powder was carbonized at 550 0 C for 3 hours under inert atmosphere to obtain SnO 2 /carbon composite hollow spheres.
  • Electrochemical Measurement The electrochemical measurements were carried out using homemade two- electrode cells with lithium metal as the counter and reference electrodes at room temperature.
  • the working electrode consisted of active material (e.g., SnO 2 /carbon composite hollow spheres), conductivity agent (carbon black, Super-P), and polymer binder (polyvinylidene difluoride, PYDF, Aldrich) in a weight ratio of around 80: 10:10.
  • active material e.g., SnO 2 /carbon composite hollow spheres
  • conductivity agent carbon black, Super-P
  • polymer binder polyvinylidene difluoride, PYDF, Aldrich
  • the electrolyte was 1 M LiPF 6 in a 50:50 w/w mixture of ethylene carbonate and diethyl carbonate.
  • Cell assembly was carried out in an Argon-filled glove box with the concentrations of moisture and oxygen below 1 ppm.
  • Charge-discharge cycles of the cells were measured between 2.0 V and 0.005 V at a constant current density of 100 mA/g based on the active material with a Maccor-Series-2000 battery tester. Similar measurement was also carried out for pure SnO 2 hollow nanospheres at a current rate of 160 mA/g.
  • the mesoporous SnO 2 hollow spheres with size in the range of 150 - 400 nm are prepared by a template-free route based on an inside-out Ostwald ripening mechanism. Lou et al. Adv. Mater. 20:3987 (2008); Lou et al. Adv. Mater. 18:2325 (2006). Since the hollow interior space is created by spontaneous evacuation of the interior materials through the shell, it follows that the as-formed SnO 2 shell must be highly porous. Here we confirm this structural feature by N 2 sorption measurements. As shown in Figure 20(e), the N 2 adsorption-desorption isotherm is characteristic of type IV with a relatively unusual type H4 hysteresis loop, which might
  • pore size distribution from the desorption branch is less reliable and such a sharp peak may be an artifact corresponding to capillary evaporation at the lower end of the hysteresis loop with a relative pressure of about 0.4 - 0.5. Nonetheless, from the pore size distributions, it can be concluded that the pores are generally smaller than 5 nm. As expected, such a mesoporous structure gives rise to a relatively high Brunauer-Emmett-Teller (BET) specific surface area of about 110 m 2 /g. The pores may be randomly or evenly distributed on the surface; the pores may also be distributed in one area.
  • BET Brunauer-Emmett-Teller
  • Tin oxide could be carbothermally reduced to metallic tin when the carbonization temperature reaches 600 0 C.
  • An initial attempt to incorporate carbon networks from a polymer precursor (e.g., PAN) by vapor deposition polymerization was not successful. McCann et al., Nano Lett. 7:2740 (2007); Johnson et al. Science 283:963 (1999). Therefore, in this work, carbonization is carried out at 55O 0 C to avoid destruction of the nanostructure.
  • XRD x-ray diffraction
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • thermogravimetric analysis (TGA) is carried out.
  • Figure 22(b) shows the TGA curve under air with a temperature ramp of 10°C/min. From the observation that the TGA curve is monotonic, and since the weight loss mainly takes place below 600 0 C, the possible carbothermal reduction of SnO 2 and re-oxidation of Sn by oxygen can be ruled out. Therefore, the carbon content in the SnO 2 /carbon nanocomposite is simply determined to be about 33.5% by weight.
  • the hollow spherical nature of these SnO 2 /carbon composite particles is clearly revealed by the low magnification TEM image (Fig.
  • Figure 22(d) shows a TEM image displaying a representative single hollow sphere. From the relative light contrast, it can be clearly observed that a thin carbon layer is coated uniformly on the outer surface of the SnO 2 sphere. It is further proven that the carbon precursor deposits not only on the outer surface but also penetrate into the mesoporous SnO 2 shell. When the particles are irradiated by focused electron beams during the TEM examination, SnO 2 could be reduced to form melted metallic Sn, which could evaporate easily under vacuum. As a result, it is interesting to occasionally observe that double-shelled carbon spheres (Fig.
  • Figure 23(a) and 23(b) show the results in terms of the discharge-charge voltage profiles for the first two cycles and cycling performance (i.e., capacity retention vs. cycle number) at a constant current density of 100 mA/g.
  • the voltage profiles are characteristic of SnO 2 -based materials.
  • the initial discharge and charge capacities are 2157 and 983 mA h/g, respectively.
  • the capacity of the SnO 2 /carbon composite anode is comparable to that of SnO 2 in the course of the first 30 cycles, despite the fact that one-third of its mass is composed of low-activity amorphous carbon. This observation suggests that the introduction of a carbon matrix to form a truly mixed nanocomposite increases the utilization efficiency of the active component, and improves the cycle life of Li-metal alloying electrodes by reducing the pulverization problem.
  • the extent of improvement in capacity retention can be lower than expected due to two factors: carbon materials completely fill in the pores, and the central cavity is too small (in other words, the shell is too thick).

Abstract

L'invention porte sur des nano-colloïdes de SnO2 revêtu de carbone, presque monodispersés. L'invention porte également sur des nanoparticules de SnO2 revêtu de carbone. L'invention porte également sur des sphères creuses composites SnO2/carbone ainsi que sur une anode d'une batterie lithium-ion comprenant les nano-colloïdes. L'invention porte également sur un procédé de synthèse de nano-colloïdes de SnO2. L'invention porte également sur des nanosphères creuses de SnO2 revêtu de carbone, sur un procédé de fabrication de nanosphères creuses de SnO2 revêtu de carbone coaxial et sur une anode d'une batterie lithium-ion formée à partir des nanosphères creuses de SnO2 revêtu de carbone coaxial.
PCT/US2009/065022 2008-11-18 2009-11-18 Matériaux d'anode revêtue de carbone WO2010059749A1 (fr)

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