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WO2017113125A1 - 作为锂离子电池阳极材料的V2O5-C-SnO2杂化纳米带及其制备方法 - Google Patents

作为锂离子电池阳极材料的V2O5-C-SnO2杂化纳米带及其制备方法 Download PDF

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WO2017113125A1
WO2017113125A1 PCT/CN2015/099581 CN2015099581W WO2017113125A1 WO 2017113125 A1 WO2017113125 A1 WO 2017113125A1 CN 2015099581 W CN2015099581 W CN 2015099581W WO 2017113125 A1 WO2017113125 A1 WO 2017113125A1
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nanobelt
sno
hybrid
glucose
preparation
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French (fr)
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程春
张林飞
张圣亮
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南方科技大学
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • 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

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  • the present invention belongs to the field of lithium ion battery, particularly to a high-performance V as an anode material for lithium ion batteries 2 O 5 -C-SnO 2 (i.e., V 2 O 5 - carbon -SnO 2) hybrid nanoribbons.
  • the nanostructured active material has a short lithium ion diffusion distance, easy strain relaxation during electrochemical cycling, and a very large surface to volume ratio when in contact with the electrode, which can improve LIB Capacity and cycle life 13-16 .
  • nanomaterials often self-aggregate due to high surface energy, which reduces the effective contact area of the active material, the conductive agent, and the electrolyte. How to maintain the effective contact area and make full use of the advantages of nano-active materials remains a challenge and is of great significance.
  • V 2 O 5 due to its high specific capacity, the natural abundance and relatively low cost material for a lithium anode is applied 17, 18 in-depth study.
  • V 2 O 5 is also an ideal material for high energy anodes. If V 5+ can be reduced to V 0 , it exhibits a high theoretical capacity of 1472 mA h g -1 and a maximum capacity of 19-22 among all metal oxides.
  • limited data is available for the V 2 O 5 anode, where the potential high capacity cannot be achieved 22-24 with stable cycle performance.
  • Liu et al. Reported that V 2 O 5 -SnO 2 nanocapsule double-shell, which shows a reversible capacity 600mA h g-1 at 16 after 50 cycles 250mA g -1.
  • SnO 2 because of its abundance secure lithiated potential and a high theoretical capacity (782mA h g -1) is one of the most intensively studied of the anode material 25.
  • SnO 2 is usually due to alloying Li- / alloying process to the large volume expansion (up to 250%) and agglomerated, pulverized lead electrodes 26 and rapid capacity fade.
  • One of the mitigation strategies is to establish a heterostructure of SnO 2 with other materials that can buffer excessive volume changes. Due to the low volume change during lithiation/delithiation, V 2 O 5 has been proposed as a promising candidate for the mechanical support of SnO 2 by forming nanocapsules 16 , nanosheets 27 , and core-shell nanowires 28 .
  • One of the objects of the present invention is to provide a V 2 O 5 -C-SnO 2 (i.e., V 2 O 5 -carbon-SnO 2 ) hybrid nanobelt as a high performance anode for a lithium ion battery.
  • the hybrid nanoribbon provided by the present invention when used as an anode material for a lithium ion battery (LIB), exhibits a much higher reversible capacity and structural stability than the carbon-V 2 O 5 hybrid nanobelt.
  • a V 2 O 5 -C-SnO 2 hybrid nanobelt for a lithium ion battery anode material the ultra-dispersed SnO 2 nanocrystal is tightly attached to the V 2 O 5 surface by amorphous carbon.
  • the nanostructured V 2 O 5 functions not only as a support matrix but also as an active electrode component, and when used as an anode material of a lithium ion battery (LIB), exhibits a specific ratio of carbon-V 2 O 5 .
  • the nanoribbons have much higher reversible capacity and structural stability.
  • the cycle performance of the excellent VCSN can be attributed to the synergistic effect of SnO 2 and V 2 O 5 .
  • the SnO 2 nanocrystals have a diameter of less than 10 nm, preferably 3-6 nm.
  • the hybrid nanobelt has a lattice period of 0.33 ⁇ 0.02 nm.
  • the hybrid nanobelt has a thickness of 5 to 20 nm, for example, 8 nm, 13 nm, 18 nm or the like, and preferably 7 to 15 nm.
  • the ultra-thin features of the hybrid nanoribbons of the present invention can increase electron transfer and shorten the lithium diffusion path, resulting in increased power density.
  • the mass ratio of the SnO 2 , V 2 O 5 , and carbon is: 0.015-0.045:0.065-0.2:0.08-0.25, for example, 0.015-0.04:0.07-0.2:0.1-0.2, 0.02-0.03 : 0.07-0.15: 0.15-0.25, 0.03-0.04: 0.15-0.2: 0.08-0.15, and the like.
  • the ratio of this range the hybrid nanobelt has good dispersibility and is ideal for use as an electrode material. Beyond this range, the electrical properties are gradually attenuated, and the nanoribbon structure also begins to decompose and fracture.
  • the method first dissolves SnCl 2 in a solution of V 2 O 5 nanobelts to culture the seed crystal; then, the seed crystal is adsorbed onto the surface of the V 2 O 5 nanobelt by means of glucose.
  • the method comprises the steps of:
  • Glucose plays an important role in the formation of hybrid nanoribbons with ideal morphology.
  • the reaction in the absence of glucose results in irregular and broken nanoribbons.
  • a conventional nanomaterial synthesis additive such as polyethylene glycol 2000 (PEG2000)
  • the resulting nanobelts appear as small, agglomerated blocks having a length of 10 nm to 500 nm. Therefore, the introduction of glucose not only immobilizes the SnO 2 seed on the V 2 O 5 nanobelt, which enables the in-situ growth of the superdisperse SnO 2 nanocrystals, but also serves as an effective physical support for V 2 O 5 has the form of nanoribbons integrity.
  • the V 2 O 5 nanobelts can be prepared using methods in the prior art.
  • the method 29 using the modified Zhu is synthesized from a V 2 O 5 powder. Briefly, V 2 O 5 powder, H 2 O 2 and deionized water were mixed until a clear solution was obtained, and then the mixture was placed in a reactor and maintained at 150-250 ° C for 15 hours or more to form V 2 O 5 nm. band. The resulting brick red floc was collected by separation and washed with absolute ethanol. Finally, the resulting V 2 O 5 nanobelts were dispersed in deionized water for later use.
  • SnCl 2, V 2 O 5 as the mass ratio of the three glucose: 0.01-0.06:0.05-0.208:0.2-0.8, for example 0.01-0.05:0.1-0.208:0.4-0.8,0.02-0.06:0.05 -0.108: 0.2-0.5, 0.03-0.05: 0.15-0.208: 0.3-0.6, and the like.
  • the ratio of this range the final product obtained by the synthesis has good dispersibility, and the nanobelt is uniform and intact, and is not damaged, and is preferably used as an electrode material. Beyond this range, the electrical properties are gradually attenuated, and the nanoribbon structure also begins to decompose and fracture.
  • the mass concentration of V 2 O 5 in the solution of the V 2 O 5 nanobelt in the step (1) is 5-20 mg/mL, for example, 8 mg/mL, 13 mg/mL, 16 mg/mL, and 19 mg/mL.
  • Etc. preferably 10-15 mg/mL, more preferably 12 mg/mL.
  • the concentration of glucose in the aqueous glucose solution in the step (1) is 0.02-0.10 mol/L, for example, 0.03 mol/L, 0.07 mol/L, 0.095 mol/L, etc., preferably 0.04-0.06 mol/L. More preferably, it is 0.05 mol/L.
  • the aqueous glucose solution is added to the step (1) with stirring.
  • the heating temperature in the step (2) is 170-200 ° C, for example, 170 ° C, 175 ° C, 189 ° C, 195 ° C, etc., preferably 170-180 ° C, more preferably 170 ° C; heating time It is 4h or more, for example, 4.5h, 5.5h, 6.0h, 8.5h, 10h, 15h, etc., Preferably it is 5-12h, More preferably, it is 8h.
  • the cooling in step (3) is to cool to room temperature.
  • the collection in step (3) is carried out by centrifugation.
  • the rotational speed of the centrifugation is 4,000-8000 rpm, preferably 6000 rpm; the time of centrifugation is 3 min or more, preferably 4-6 min, more preferably 5 min.
  • the washing in the step (3) is carried out sequentially using distilled water and absolute ethanol to remove ions and possible residues, preferably 2 times or more, more preferably 3-6 times, particularly preferably 4 times.
  • the drying in step (3) is carried out under vacuum.
  • the drying temperature in the step (3) is 50-100 ° C, for example, 55 ° C, 70 ° C, 85 ° C, 92 ° C, 98 ° C, etc., preferably 60-90 ° C, more preferably 80 ° C;
  • the drying time is 3 h or more, for example, 3.6 h, 4.5 h, 5.5 h, 6.0 h, 8.5 h, 10 h, 15 h, etc., preferably 6-12 h, more preferably 8 h.
  • the method comprises the steps of:
  • the black product was collected by centrifugation; then washed with distilled water and absolute ethanol at least four times in sequence, and dried at 50-100 ° C for more than 3 h under vacuum.
  • the present invention provides a simple two-step hydrothermal process for the preparation of ultra-thin V 2 O 5 -C-SnO 2 hybrid nanoribbons (denoted as VCSN).
  • VCSN ultra-thin V 2 O 5 -C-SnO 2 hybrid nanoribbons
  • Incorporated by excellent carbonate linking agent and agent interaction glucose overcome the difference between the 2 O 5 SnO 2 and V.
  • the resulting VCSN showed a highly stable cycle with a highly reversible capacity of 800 mA h g -1 after 100 cycles at a current density of 200 mA g -1 .
  • the improved cycle stability and rate performance of these hybrid nanoribbons can be attributed to their unique structural design and synergistic effects between SnO 2 and V 2 O 5 .
  • the ultra-thin features of VCSN can increase electron transfer and shorten the lithium diffusion path, resulting in increased power density.
  • the ultrathin V 2 O 5 -carbon-SnO 2 hybrid nanobelts of the present invention can be prepared by a solution-based method having a high yield. These nanoribbons provide a short lithium ion path with a stable structure and high electron and ion conductivity. This property is achieved by using glucose as a carbonic acid agent for the formation of monodisperse SnO 2 nanocrystals on the surface of the V 2 O 5 nanobelt and the linker which delays structural fracture. As anode materials for LIB, these hybrid nanobelts exhibit extremely high reversible capacity, excellent cycle performance, and good rate performance.
  • the controlled growth strategy of the multicomponent metal oxides of the present invention can motivate new ways to fabricate nanostructures for functional nanocomposites with improved performance in applications such as solar light conversion, energy storage, and water splitting. Reasonable design of the material.
  • Figure 1 (A) is a TEM image of ultra-thin V 2 O 5 nanobelts dispersed in water; (B) is an XRD pattern of pure V 2 O 5 nanoribbons;
  • Figure 2 is a glucose-induced transformation pathway for preparing VCSN
  • FIG. 3 (A) is a TEM image of VCSN, (B) and (C) are HRTEM images of VCSN, and (D) is a V 2 O 5 -based nanocomposite synthesized by hydrothermal method at 170 ° C for 8 hours. XRD image;
  • Figure 4 is a TEM image of a sample synthesized by adding different amounts of SnCl 2 ; wherein, (A) 10 mg, (B) 60 mg, (C) 80 mg, (D) 100 mg;
  • FIG. 5 shows the cyclic voltammetry curve of VCSN at 0.01-3.0 V at a scan rate of 0.2 mV s -1 ;
  • (B) is the charge-discharge curve,
  • (C) is the cycle of the VCSN base electrode at 200 mAg -1 Performance,
  • (D) is the rate performance of VCSN at different current densities;
  • FIG. 6 are TEM images of different magnifications of the VCSN base electrode after complete discharge at 200 mAg -1 ;
  • Figure 7 is a low magnification TEM image of VCSN synthesized in the absence of glucose
  • Figure 8 is an EDX spectrum of VCSN
  • Figure 9 is a nitrogen adsorption/desorption isotherm of VCSN, and V 2 O 5 /SnO 2 samples;
  • Figure 10 is a TEM image of a V 2 O 5 /SnO 2 nanocomposite synthesized without glucose (A) and with PEG2000 (B);
  • Figure 11 is a graph showing the charge and discharge capacity versus cycle number of a V 2 O 5 /SnO 2 nanocomposite at a current density of 200 mAg -1 ;
  • Fig. 12(A) shows the charge-discharge voltage distribution
  • (B) shows the carbon-V 2 O 5 core-shell under the voltage range of 0.01-3.0 V at a current density of 200 mAg -1 and a cycle number of 100 times. Cyclic performance of nanobelts;
  • Figure 13 is an impedance diagram of an electrode composed of a VCSN and a V 2 O 5 /SnO 2 composite material
  • Figure 14 is an XPS spectrum of complete discharge ((A) and (B)) and full charge ((C) and (D)) of VCSN.
  • V 2 O 5 thin nanoribbons using a modified method of synthesizing Zhu 29 from V 2 O 5 powder.
  • the resulting brick red floes were collected by centrifugation (8,000 rpm for 5 min) and washed three times with absolute ethanol.
  • the resulting V 2 O 5 nanobelts were dispersed in 70 mL of deionized water for later use.
  • V 2 O 5 -C-SnO 2 Hybrid Nanobelts (VCSN)
  • VCSN is prepared by simple hydrothermal action.
  • 0.04 g of SnCl 2 ⁇ 2H 2 O was dissolved in a solution of 30 mL of V 2 O 5 nanobelts, and then 40 mL of a 0.05 mol/L aqueous glucose solution was added with stirring. After 30 minutes, a brown suspension appeared, which was transferred to a 100 mL lined Teflon autoclave, sealed in an oven at 170 ° C for 8 hours, and then naturally cooled to room temperature.
  • the obtained black product was collected by centrifugation (6,000 rpm for 5 min), and then washed with distilled water and absolute ethanol at least four times in order to remove ions and possible residues, and finally, dried at 80 ° C for 6 hours under vacuum.
  • V 2 O 5 /SnO 2 hybrid preparation process was similar to the above VCSN synthesis except that glucose was not introduced into the final reaction solution.
  • Ni-filtered Cu K ⁇ radiation An X-ray diffraction (XRD) pattern was performed on a Bruker D8 advanced X-ray diffractometer at 40 kV and 25 mA.
  • TEM Transmission electron microscopy images
  • HRTEM high-resolution transmission electron microscopy images
  • EDS energy dispersive X-ray spectroscopy
  • Nitrogen adsorption measurements were performed using a Micromeritics ASAP 2020 system at 77 K using Barrett-Emmett-Teller (BET) to calculate surface area. Nitrogen adsorption measurements were taken on Autosorb 6B at liquid nitrogen temperature.
  • Electrochemical testing was performed in a 2032 button cell.
  • the working electrode consisted of 80 wt% active material, 10 wt% conductive carbon black (Super-P-Li), and 10 wt% polymer binder (polyvinylidene fluoride, PVDF).
  • the electrolyte was 1 M LiPF 6 in a mixture of ethylene carbonate and diethyl carbonate (1:1 by volume).
  • Lithium foil is used as a counter electrode which is separated from the working electrode by glass fibers.
  • Battery assembly was performed in a glove box with a humidity and oxygen concentration below 1.0 ppm. The charge and discharge test was performed on the NEWARE battery detector.
  • the cells were charged/discharged in voltage windows of 0.01-3.0 V at different current densities.
  • Cyclic voltammogram (CV) measurements were performed on a CH instrument model 600C electrochemical workstation at a scan rate of 0.2 mV s -1 .
  • Electrochemical impedance spectroscopy (EIS) measurements were performed on the working electrode in the frequency range of 100 kHz to 0.01 Hz with 5 mV AC disturbance. The EIS data is analyzed using a Nyquist map representing the virtual portion (Z') and the real portion (Z") of the impedance.
  • Figure 1 (A) is a TEM image of the ultra-thin V 2 O 5 nanobelts dispersed in water prepared in Example 1; (B) is an XRD pattern of pure V 2 O 5 nanoribbons; (A in Figure 1) The TEM image shows that the newly prepared V 2 O 5 nanoribbon substrate has a width of 50-80 nm and a length of up to several tens of micrometers, and is characterized by flexibility, smoothness, thinness, and almost transparency.
  • Figure 2 is a glucose-induced transformation pathway for the preparation of VCSN. Fig.
  • FIG. 3 (A) is a TEM image of VCSN prepared in Example 1, (B) and (C) are HRTEM images of VCSN, and (D) is V 2 synthesized by hydrothermal method at 170 ° C for 8 hours. An XRD image of the O 5 -based nanocomposite; the thickness of the carbon coating as shown in (C) is about 2 nm.
  • Figure 4 is a TEM image of a sample synthesized by adding different amounts of SnCl 2 ; (A) 10 mg, (B) 60 mg, (C) 80 mg, (D) 100 mg.
  • FIG. 5 (A) is prepared in Example 1 at a scan rate of 0.2mVs -1 0.01-3.0V VCSN in the cyclic voltammetry; (B) is a charge-discharge curve, (C) as 200mAg -1 The cycle performance of the lower VCSN base electrode, (D) is the rate performance of VCSN at different current densities.
  • Fig. 6 (A) and (B) are TEM images of different magnifications of the base electrode prepared in VCSN Example 1 after complete discharge at 200 mAg -1 .
  • V 2 O 5 nanobelt synthesized by a hydrothermal method was used as a starting template material.
  • TEM Transmission electron microscopy
  • XRD X-ray diffraction
  • the XRD pattern shows a strong peak which can be classified as orthorhombic V 2 O 5 (JCPDS No. 40-1296).
  • SnCl 2 is first dissolved in a solution of V 2 O 5 nanobelts to culture the seed crystals. These seeds are then adsorbed onto the surface of the V 2 O 5 nanoribbon by means of glucose, which occurs due to the affinity of SnO 2 and V 2 O 5 for the -OH group (Fig. 2) 30,31 .
  • FIG. 3 shows a TEM image of the prepared VCSN.
  • the hybrid nanoribbon has a length of a few microns and a width of 50-80 nm.
  • the aggregate morphology of the hybrid nanoribbons as shown in Figure 7 shows excellent uniformity and dispersibility.
  • Typical high resolution TEM (HRTEM) analysis ((B) and (C) of Figure 3) on these hybrid nanoribbons clearly shows the dense growth of SnO 2 nanocrystals on the V 2 O 5 surface .
  • the fixed SnO 2 nanocrystals have a diameter of less than 5 nm.
  • An enlarged TEM image recorded on the edge of the nanoribbon in (C) of Figure 3 indicates that the entire surface of the nanoribbon is covered with a continuous amorphous carbon layer having a thickness of about 2 nm.
  • the X-ray diffraction (XRD) pattern of the hybrid nanobelts ((D) of Fig. 2) shows that all of the XRD peaks can be well indexed into a tetragonal SnO 2 phase (JCPDS No. 41-1445) and orthorhombic V 2 . O 5 phase (JCPDS No.
  • the XRD peak of VCSN is relatively wider and weaker than the synthesized V 2 O 5 nanoribbon template (Fig. 1 (B)). And some peaks are incorporated into the background. This is attributable to the smaller size of the V 2 O 5 and SnO 2 nanocrystals in the composite as determined by the TEM study above ((B) of Figure 3).
  • the energy dispersive X-ray spectroscopy (EDS) pattern ( Figure 8) shows that the hybrid nanoribbon consists of Sn, V, C, and O, which is consistent with the above TEM and XRD measurements, with a weight ratio of V to Sn of 10; EDS analysis confirmed There is a representative peak corresponding to the Sn and O elements and an atomic ratio of Sn/O of about 30:66.
  • the surface area of the prepared hybrid nanoribbons was investigated using an N 2 adsorption isotherm. As shown in FIG. 9, with having found that nano hybrid 132.9m 2 / g of Barrett-Emmett-Teller (BET) surface area, than V 2 O 5 / SnO 2 samples (28.3m 2 / g) to about 4.7 times.
  • BET Barrett-Emmett-Teller
  • the introduction of glucose not only immobilizes the SnO 2 seed crystal on the V 2 O 5 nanobelt, which enables the in-situ growth of the ultra-dispersed SnO 2 nanocrystals, but also serves as an effective physical support for V 2 O
  • the 5 nanoribbons have morphological integrity.
  • Figure 4 shows the TEM image using the product prepared SnCl 2 when other conditions remain unchanged plus different amounts.
  • the amount of SnCl 2 is less than 60 mg, a hybrid nanobelt having a desired morphology can be obtained in high yield ((A) and (B) of Fig. 4).
  • the amount of SnCl 2 is more than 60 mg ((C) and (D) of Fig. 4), a hybrid nanobelt having a pore diameter of 10 to 50 nm is formed, sometimes even broken.
  • FIG. 5 shows a cyclic voltammogram (CV) of the first 5 consecutive cycles in a voltage window of 0.01 - 3.0 V at a scanning rate of 0.2 mV s -1 .
  • This CV characteristic is basically consistent with that reported in the literature 33-35 , indicating the same electrochemical reaction pathway.
  • (B) of FIG. 5 shows a charge and discharge curve of a Li/V 2 O 5 -carbon-SnO 2 battery. At a current density of 200 mAg -1 , the first discharge and charge capacities were 2075 and 1205 mAh g -1 , respectively .
  • SEI solid electrolyte interface
  • FIGS. 11 and 12 show the cycle performance of the anode composite cycled 100 times at a current density of 200 mAg -1 .
  • the hybrid nanoribbon still showed a high reversible capacity of 930 mAhg -1 and a capacity retention rate of 84.5% from the tenth cycle.
  • the nanocomposite maintained a reversible capacity of 800 mAhg -1 , indicating excellent cycle stability of the VCSN.
  • the cycle performance of the V 2 O 5 /SnO 2 composite without the carbon layer and the carbon-V 2 O 5 core-shell nanoribbon is provided in FIGS. 11 and 12.
  • VCSN was found to exhibit much lower resistance than the V 2 O 5 /SnO 2 composite, as evidenced by a significant decrease in the diameter of the semicircle in the high frequency region in the electrochemical impedance spectroscopy (EIS) pattern (Fig. 13). Lower contact and charge transfer impedance facilitates Li + diffusion and electron transfer, which results in greatly improved electrochemical performance of VCSN.
  • the VCSN was cycled at a voltage window of 0.01-3.0 V ((D) of Figure 5) at different current densities of 100 to 800 mAg -1 .
  • V voltage window
  • VCSN still reversible capacity can be achieved in about 620mAhg -1.
  • VCN still maintains a reversible capacity of about 1005 mAhg -1 when the current rate drops back to 200 mAg -1 after more than 60 cycles, indicating excellent rate performance of VCSN.
  • VCN still maintains a reversible capacity of about 1005 mAhg -1 when the current rate drops back to 200 mAg -1 after more than 60 cycles, indicating excellent rate performance of VCSN.
  • V 2 O 5 powder 0.26 g of V 2 O 5 powder, 5 mL of 30% H 2 O 2 , and 30 mL of deionized water until a clear solution is obtained, then place 35 mL of this mixture in a 100 mL Teflon autoclave and hold at 190 ° C for 15 hours. To form a V 2 O 5 nanobelt. The resulting brick red floes were collected by centrifugation (8,000 rpm for 5 min) and washed three times with absolute ethanol. Finally, the resulting V 2 O 5 nanobelts were dispersed in 140 mL of deionized water for later use.
  • V 2 O 5 powder 0.85 g of V 2 O 5 powder, 5 mL of 30% H 2 O 2 , and 30 mL of deionized water until a clear solution is obtained, then place 35 mL of this mixture in a 100 mL Teflon autoclave and hold at 150 ° C for 30 hours. To form a V 2 O 5 nanobelt. The resulting brick red floes were collected by centrifugation (8,000 rpm for 5 min) and washed three times with absolute ethanol. Finally, the resulting V 2 O 5 nanobelts were dispersed in 140 mL of deionized water for later use.
  • V 2 O 5 -C-SnO 2 hybrid nanobelts prepared in the above Examples 2-5 have similar morphology and structure to the V 2 O 5 -C-SnO 2 hybrid nanoparticle prepared in Example 1, and equivalent Electrochemical performance.
  • the improved cycle stability and rate performance of the hybrid nanoribbons of the present invention can be attributed to the unique design of the nanostructure compositions mentioned in the present invention.
  • the ultrathin nanobelt subunit has a short distance for efficient Li + ion diffusion and a large electrode-electrolyte contact area for high Li + ion flux across the interface, resulting in improved rate performance 35,37 .
  • the soft carbon layer acts as an excellent physical support in which the ultra-thin nanobelt subunits are tightly attached or embedded.
  • Electrode material made in this way may have some outstanding advantages, such as good cycle for the volume change resistance, and a high electron and ion conductivity 43.
  • ultrathin V 2 O 5 -carbon-SnO 2 hybrid nanoribbons were prepared by a solution-based process with high yield. These nanostructures provide a short lithium ion path with a stable structure and high electron and ion conductivity. This result was achieved by using glucose as a carbonic acid agent for the formation of monodisperse SnO 2 nanocrystals on the surface of the V 2 O 5 nanobelt and the linker which retards structural fracture. As anode materials for LIB, these hybrid nanobelts exhibit extremely high reversible capacity, excellent cycle performance, and good rate performance. Our multi-component metal oxide controlled growth strategy can inspire new ways to fabricate nanostructures for functional nanocomposites with improved performance in applications such as solar light conversion, energy storage and water splitting. Reasonable design.

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Abstract

一种用于锂离子电池阳极材料的V2O5-C-SnO2杂化纳米带及其制备方法，所述杂化纳米带为超分散的SnO2纳米晶体通过无定形碳连接在V2O5表面上。所述制备方法是通过葡萄糖连接，将SnO2负载到V2O5超薄纳米带上。本发明的V2O5-碳-SnO2杂化纳米带阳极材料显示出高度稳定的循环性。本发明利用简单的两步水热法用于制备超薄V2O5-碳-SnO2杂化纳米带，通过引入作为特殊的连接剂和碳化剂的葡萄糖，克服了SnO2和V2O5之间相互作用差的难题。

Description

作为锂离子电池阳极材料的V2O5-C-SnO2杂化纳米带及其制备方法 技术领域
本发明属于锂离子电池领域，特别涉及一种作为锂离子电池高性能阳极材料的V2O5-C-SnO2(即V2O5-碳-SnO2)杂化纳米带。
背景技术
作为最重要的能量存储装置之一，由于锂离子电池(LIB)的诸多优点，如高能量密度、环境友好和轻的重量，近几年来已经对其进行了深入研究1-3。尽管石墨是用于商业LIB的主要阳极材料，但是其相对低的理论容量(372mA h g-1)大大地阻碍了具有高能量密度的LIB的发展4，5。当用作锂离子电池中的阳极时，过渡金属氧化物由于高的理论容量和丰富的原料来源已经比商业石墨引起了更多的关注6-12。为了用作LIB的阴极或阳极，纳米结构的活性材料在电化学循环时具有短的锂离子扩散距离、易应变弛豫，且与电极接触时非常大的表面和容积比，这可提高LIB的容量和循环寿命13-16。
然而，在普通电池中，由于高的表面能，纳米材料经常自聚集，这降低了活性材料、导电剂和电解液的有效接触面积。如何保持所述的有效接触面积并充分利用纳米活性材料的优势仍是一个挑战并具有重要意义。
V2O5由于其高的比容量、天然丰度和相对低成本是用于锂阳极应用深入研究的材料17，18。此外，V2O5还是用于高能量阳极的理想材料。如果可将V5+还原为V0，则它呈现出1472mA h g-1的高的理论容量，在所有金属氧化物中最高的容量19-22。然而，对于V2O5阳极有限的数据可用，其中潜在的高容量不能在稳定的循环性能下实现22-24。例如，Liu等人报道了双层壳的V2O5-SnO2纳米胶囊，其在250mA g-1下50次循环后显示600mA h g-1的可逆容量16。对氧化钒气凝胶最近的研究显示在118mA g-1的速率下仅30次循环1000mA h g-1的高容量 22。此外，结构劣化，差的电化学动力学和低的电子导电性已经严重阻碍了它们进一步的发展。例如，Sun等人通过原子层沉积法将石墨烯涂覆到无定形V2O5上以增强电子导电性和电化学活性19。
SnO2由于其丰度、安全的锂化电势和高的理论容量(782mA h g-1)是最深入研究的阳极材料之一25。然而，SnO2通常由于其在Li-合金化/去合金化过程中大的体积膨胀(高达250％)和团聚，导致电极粉碎和快速的容量衰减26。缓解策略之一是建立SnO2与能够缓冲过度的体积变化的其他材料的异质结构。由于在锂化/去锂化过程中低的体积变化，已经提议V2O5作为有前景的候选者通过形成纳米胶囊16、纳米片27、核壳纳米线28用于SnO2的机械支撑。
受以前研究的启发，我们开发了一种通过葡萄糖连接将SnO2涂覆到V2O5纳米带上的简单的策略以实现高功率密度和高能量密度LIB。
发明内容
本发明目的之一在于提供一种作为用于锂离子电池的高性能阳极的V2O5-C-SnO2(即V2O5-碳-SnO2)杂化纳米带。本发明提供的杂化纳米带用作锂离子电池(LIB)的阳极材料时，显示比碳-V2O5杂化纳米带高得多的可逆容量和结构稳定性。
为达上述目的，本发明采用如下技术方案：
一种用于锂离子电池阳极材料的V2O5-C-SnO2杂化纳米带，超分散的SnO2纳米晶体通过无定形碳紧紧地连接在V2O5表面上。本发明的杂化纳米带中，纳米结构的V2O5不仅充当支持基质还充当活性电极组分，当用作锂离子电池(LIB)的阳极材料时，显示比碳-V2O5杂化纳米带高得多的可逆容量和结构稳定性。优异的VCSN的循环性能可归因于SnO2和V2O5的协同效应。
作为优选，所述SnO2纳米晶体的直径小于10nm，优选为3-6nm。
优选地，所述杂化纳米带的晶格周期为0.33±0.02nm。
作为优选，所述杂化纳米带的厚度为5～20nm，例如为8nm、13nm、18nm等，优选为7～15nm。本发明的杂化纳米带的超薄特征可提高电子转移并缩短锂扩散路径，导致提高的功率密度。
优选地，所述SnO2、V2O5、碳三者的质量比为：0.015-0.045∶0.065-0.2∶0.08-0.25，例如为0.015-0.04∶0.07-0.2∶0.1-0.2、0.02-0.03∶0.07-0.15∶0.15-0.25、0.03-0.04∶0.15-0.2∶0.08-0.15等。选择此范围的比例，杂化纳米带的分散性好，用作电极材料最理想。超出此范围，可导致电学性能的逐渐衰减，且纳米带结构也开始分解断裂。
本发明的目的之一还在于提供一种用于锂离子电池的V2O5-C-SnO2杂化纳米带的制备方法，所述方法通过葡萄糖连接将SnO2负载到V2O5纳米带上。
作为优选，所述方法先将SnCl2溶解在V2O5纳米带的溶液中以培养晶种；然后，所述晶种借助于葡萄糖吸附到V2O5纳米带的表面上。
作为优选，所述方法包括如下步骤：
(1)将SnCl2溶解在V2O5纳米带的溶液中，然后加入葡萄糖水溶液；
(2)出现悬浮物后，将所得混合物密封加热；
(3)冷却后收集黑色产物；然后洗涤，干燥。
葡萄糖在具有理想形态的杂化纳米带的形成中起着重要作用。在不存在葡萄糖的反应导致了不规则和破碎纳米带。当将葡萄糖替换为普通的纳米材料合成添加剂如聚乙二醇2000(PEG2000)时，所得纳米带表现为具有10nm至500nm长度的，小的和团聚的块。因此，引进葡萄糖不仅使SnO2晶种固定在V2O5纳米带上，这使得能够进行的超分散SnO2纳米晶体的原位生长，而且还通过 用作有效的物理支撑，使V2O5纳米带具有形态完整性。
其中，所述V2O5纳米带可使用现有技术中的方法进行制备。例如使用改进的Zhu的方法29从V2O5粉末合成。简略地，混合V2O5粉末，H2O2和去离子水直至得到澄清溶液，然后将该混合物放置在反应器中并在150-250℃下保持15小时以上以形成V2O5纳米带。通过分离收集所得的砖红色絮凝物并用无水乙醇洗涤。最后，将所得的V2O5纳米带分散在去离子水中以备后用。
作为优选，SnCl2、V2O5、葡萄糖三者的质量比为：0.01-0.06∶0.05-0.208∶0.2-0.8，例如为0.01-0.05∶0.1-0.208∶0.4-0.8、0.02-0.06∶0.05-0.108∶0.2-0.5、0.03-0.05∶0.15-0.208∶0.3-0.6等。选择此范围的比例，合成得到的最后产物分散性好，纳米带均匀完整，不受破坏，用作电极材料最理想。超出此范围，可导致电学性能的逐渐衰减，且纳米带结构也开始分解断裂。
作为优选，步骤(1)中所述V2O5纳米带的溶液中V2O5的质量浓度为5-20mg/mL，例如为8mg/mL、13mg/mL、16mg/mL、19mg/mL等，优选为10-15mg/mL，更优选为12mg/mL。
优选地，步骤(1)中所述葡萄糖水溶液中葡萄糖的浓度为0.02-0.10mol/L，例如为0.03mol/L、0.07mol/L、0.095mol/L等，优选为0.04-0.06mol/L，更优选为0.05mol/L。
优选地，步骤(1)中加入葡萄糖水溶液在搅拌下加入。
作为优选，步骤(2)中所述加热的温度为170-200℃，例如为170℃、175℃、189℃、195℃等，优选为170-180℃，更优选为170℃；加热的时间为4h以上，例如为4.5h、5.5h、6.0h、8.5h、10h、15h等，优选为5-12h，更优选为8h。
优选地，步骤(3)中所述冷却为冷却至室温。
优选地，步骤(3)中所述收集通过离心分离进行。
优选地，所述离心分离的转速为4,000-8000rpm，优选6000rpm；离心的时间为3min以上，优选为4-6min，更优选为5min。
优选地，步骤(3)中所述洗涤依次使用蒸馏水和无水乙醇进行以去除离子和可能的残留物，优选进行2次以上，更优选进行3-6次，特别优选4次。
优选地，步骤(3)中所述干燥在真空下进行。
优选地，步骤(3)中所述干燥的温度为50-100℃，例如为55℃、70℃、85℃、92℃、98℃等，优选为60-90℃，更优选为80℃；干燥的时间为3h以上，例如为3.6h、4.5h、5.5h、6.0h、8.5h、10h、15h等，优选为6-12h，更优选为8h。
作为优选，所述方法包括如下步骤：
(1)将SnCl2溶解在5-20mg/mL的V2O5纳米带的溶液中，然后加入浓度为0.02-0.10mol/L的葡萄糖水溶液；SnCl2、V2O5、葡萄糖三者的质量比为：0.01-0.06∶0.05-0.208∶0.2-0.8；
(2)出现棕色悬浮物后，将所得混合物转移至高压锅中，在170-200℃下加热4h以上；
(3)冷却至室温后离心分离收集黑色产物；然后依次用蒸馏水和无水乙醇洗涤至少四次，在真空下在50-100℃下干燥3h以上。
本发明提供一种简单的两步水热法用于制备具有超薄V2O5-C-SnO2杂化纳米带(表示为VCSN)。通过引入作为优异的连接剂和碳酸剂的葡萄糖克服了SnO2和V2O5之间差的相互作用。所得的VCSN显示出高度稳定的循环性，在200mA g-1的电流密度下100次循环后具有800mA h g-1的高度可逆容量。这些杂化纳米带改进的循环稳定性和倍率性能可归因于它们独特的结构设计和SnO2与V2O5之间的协同效果。此外，VCSN的超薄特征可提高电子转移并缩短锂扩散路径，导致提高的功率密度。
本发明的超薄V2O5-碳-SnO2杂化纳米带可通过具有高收率的基于溶液的方法制备。这些纳米带提供具有稳定结构的短锂离子路径和高的电子和离子传导性。该性能通过使用葡萄糖作为碳酸剂用于单分散SnO2纳米晶体在V2O5纳米带表面上的形成以及延缓结构破碎的连接剂来实现。作为LIB的阳极材料，这些杂化纳米带表现出极高的可逆容量，优异的循环性能，以及良好的倍率性能。本发明的多组分金属氧化物的控制生长的策略可激发出新的方式来制作纳米结构，用于在应用中如太阳能光转换、能量储存和水分解等具有提高的性能的功能性纳米复合材料的合理设计。
附图说明
图1中(A)为分散在水中的超薄V2O5纳米带的TEM图像；(B)为纯V2O5纳米带的XRD图谱；
图2为制备VCSN的葡萄糖诱导的转化路径；
图3中(A)为VCSN的TEM图像，(B)、(C)为VCSN的HRTEM图像，(D)为使用水热法在170℃下保持8小时合成的V2O5基纳米复合材料的XRD图像；
图4为外加不同量的SnCl2合成的样品的TEM图像；其中，(A)10mg，(B)60mg，(C)80mg，(D)100mg；
图5中(A)为在0.2mVs-1的扫描速率下VCSN在0.01-3.0V的循环伏安曲线；(B)为充放电曲线，(C)为在200mAg-1下VCSN基电极的循环性能，(D)为在不同的电流密度下VCSN的倍率性能；
图6中(A)、(B)为在200mAg-1下完全放电后VCSN基电极不同放大倍数的TEM图像；
图7为在不存在葡萄糖下合成的VCSN的低放大率TEM图像；
图8为VCSN的EDX光谱；
图9为VCSN，和V2O5/SnO2样品的氮吸附/解吸等温线；
图10为不用葡萄糖(A)和用PEG2000(B)合成的V2O5/SnO2纳米复合材料的TEM图像；
图11为在200mAg-1的电流密度下，V2O5/SnO2纳米复合材料的充电和放电容量对循环数；
图12的(A)为充放电电压分布，(B)为在0.01-3.0V的电压范围内，在电流密度200mAg-1，循环次数100次的条件下测试碳-V2O5核-壳纳米带的循环性能；
图13为由VCSN和V2O5/SnO2复合材料组成的电极的阻抗图；
图14为VCSN的完全放电((A)和(B))和完全充电((C)和(D))的XPS光谱。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅用于帮助理解本发明，不应视为对本发明的具体限制。
本发明中所有的化学品都是分析级的并不经进一步纯化使用。
实施例1
超薄V2O5纳米带的合成
首先，超薄V2O5纳米带使用改进的Zhu的方法从V2O5粉末合成29。混合0.36g的V2O5粉末，5mL的30％H2O2，和30mL的去离子水直至得到澄清溶液，然后将35mL的该混合物放置在100mL Teflon高压锅中并在190℃下保持20小时以形成V2O5纳米带。通过离心分离(8,000rpm持续5min)收集所得的砖红色絮凝物并用无水乙醇洗涤三次。最后，将所得的V2O5纳米带分散在70mL的去离子水中以备后用。
V2O5-C-SnO2杂化纳米带(VCSN)的合成
VCSN通过简单的水热作用制备。在典型的合成中，将0.04g SnCl2·2H2O溶解在30mL的V2O5纳米带的溶液中，然后在搅拌下加入40mL的0.05mol/L的葡萄糖水溶液。30分钟后，出现棕色悬浮，将其转移至100mL有内衬的Teflon高压锅中，在烘箱中在170℃下密封加热8小时，然后自然冷却至室温。通过离心分离(6,000rpm持续5min)收集所得的黑色产物，然后依次用蒸馏水和无水乙醇洗涤至少四次以去除离子和可能的残留物，最后，在真空下在80℃下干燥6小时。
对比例1
V2O5/SnO2杂化物的合成
V2O5/SnO2杂化物制备过程与上面VCSN合成的过程相似，除了没有将葡萄糖引入最终反应溶液中。
材料表征
使用具有Ni滤过的Cu K α辐射(
Figure PCTCN2015099581-appb-000001
)的Bruker D8高级X射线衍射仪在40kV电压和25mA电流下进行X射线衍射(XRD)图。通过具有200kV的加速电压的JEOL-2010显微镜捕获透射电子显微镜图像(TEM)、高分辨率透射电子显微镜图像(HRTEM)、和能量色散X射线光谱(EDS)分析。使用Micromeritics ASAP 2020系统在77K下利用Barrett-Emmett-Teller(BET)计算表面积进行氮吸附测量。在Autosorb 6B上在液氮温度下进行氮吸附测量。
电化学表征
在2032扣式电池中进行电化学试验。工作电极由80wt％的活性材料，10wt％的导电炭黑(Super-P-Li)，和10wt％的聚合物粘合剂(聚偏二氟乙烯，PVDF)构成。电解液是碳酸亚乙酯和碳酸二乙酯的混合物(体积比1∶1)中的1M LiPF6。 锂箔用作对电极，其通过玻璃纤维与工作电极分开。在具有低于1.0ppm的湿度和氧浓度的手套式操作箱中进行电池装配。在NEWARE电池检测器上进行充放电试验。对于阳极性能测量，电池在不同电流密度下在0.01-3.0V的电压窗口中充电/放电。在CH仪器型号600C电化学工作站上在0.2mVs-1的扫描速率下进行循环伏安图(CV)测量。对于工作电极在具有5mV交流扰动的100kHz至0.01Hz的频率范围中进行电化学阻抗谱(EIS)测量。使用表示阻抗的虚拟部分(Z′)和真实部分(Z″)的Nyquist图分析EIS数据。
图1中(A)为实施例1中制备的分散在水中的超薄V2O5纳米带的TEM图像；(B)为纯V2O5纳米带的XRD图谱；图1中的(A)TEM图像显示新制备的V2O5纳米带基底具有50-80nm的宽度和高达几十微米的长度，具有柔韧、光滑、薄和几乎透明的特征。图2为制备VCSN的葡萄糖诱导的转化路径。图3中(A)为实施例1中制备的VCSN的TEM图像，(B)、(C)为VCSN的HRTEM图像，(D)为使用水热法在170℃下保持8小时合成的V2O5基纳米复合材料的XRD图像；如(C)中显示的碳覆盖层的厚度为约2nm。图4为外加不同量的SnCl2合成的样品的TEM图像；其中，(A)10mg，(B)60mg，(C)80mg，(D)100mg。图5中(A)为在0.2mVs-1的扫描速率下实施例1中制备的VCSN在0.01-3.0V的循环伏安曲线；(B)为充放电曲线，(C)为在200mAg-1下VCSN基电极的循环性能，(D)为在不同的电流密度下VCSN的倍率性能。图6中(A)、(B)为在200mAg-1下完全放电后VCSN实施例1中制备的基电极不同放大倍数的TEM图像。
通过水热法合成的超薄V2O5纳米带用作起始模板材料。透射电子显微镜(TEM)研究显示这些V2O5纳米带高度均匀，具有4nm的厚度和800nm至几个微米的长度，这意味着＞200(图1的(A))的大的长宽比。由于高的均匀性和相对大的长宽比，V2O5纳米带可用作优异的模板以通过简单的葡萄糖辅助的水热法 支撑SnO2纳米晶体的生长。如从图1的(B)中的X射线衍射(XRD)图中观察到的，XRD图显示可归为正交晶V2O5(JCPDS No.40-1296)的强的峰。为了使纳米晶体生长，首先将SnCl2溶解在V2O5纳米带的溶液中以培养晶种。然后，这些晶种借助于葡萄糖吸附到V2O5纳米带的表面上，这由于SnO2和V2O5对-OH基团的亲和性而发生(图2)30，31。
图3的(A)显示制备的VCSN的TEM图像。杂化纳米带长度为几微米和宽度为50～80nm。如图7中示出的杂化纳米带的集合形态学显示优异的均匀性和分散性。在这些杂化纳米带上进行典型的高分辨率TEM(HRTEM)分析(图3的(B)和(C))，其清楚地显示在V2O5表面上SnO2纳米晶体的稠密的生长。固定的SnO2纳米晶体的直径小于5nm。在图3的(B)中清楚地观察到0.33nm的晶格周期，对应于四角形SnO2的(110)晶体平面的中间翼间距。在图3的(C)中在纳米带的边缘上记载的放大TEM图像表明纳米带的整个表面覆盖有厚度约2nm的连续无定形碳层。杂化纳米带的X射线衍射(XRD)图谱(图2的(D))显示所有的XRD峰可很好地索引为四角形的SnO2相(JCPDS No.41-1445)和正交晶V2O5相(JCPDS No.40-1296)。同等的，VCSN的XRD峰比合成的V2O5纳米带模板的(图1的(B))相对地更宽和更弱。且一些峰并入背景中。这可归因于如由上面TEM研究确定的复合材料中V2O5和SnO2纳米晶体的更小的尺寸(图3的(B))。能量色散X射线光谱(EDS)图谱(图8)显示杂化纳米带由Sn、V、C和O组成，这与上面的TEM和XRD测量一致，V和Sn的重量比为10；EDS分析证实，存在对应于Sn和O元素的代表性峰和Sn/O原子比为约30∶66。使用N2吸附等温线研究制备的杂化纳米带的表面积。如在图9中示出的，发现杂化纳米带具有132.9m2/g的Barrett-Emmett-Teller(BET)表面积，这比V2O5/SnO2样品的(28.3m2/g)大约4.7倍。
结果发现，葡萄糖在具有理想形态的VCSN(图7)的形成中起着重要作用。在不存在葡萄糖的反应导致了不规则和破碎纳米带(图10中的(A))。当将葡萄糖替换为普通的纳米材料合成添加剂如聚乙二醇2000(PEG2000)时，所得纳米带表现为具有10nm至500nm长度的小的和缠结的块(图10中的(B))。因此，引进葡萄糖不仅使SnO2晶种固定在V2O5纳米带上，这使得能够进行的超分散SnO2纳米晶体的原位生长，而且还通过用作有效的物理支撑，使V2O5纳米带具有形态完整性。
此外，SnCl2的初始量显著影响杂化纳米带的最终形态。图4显示使用当其它条件保持不变时外加不同量的SnCl2制备的产物的TEM图像。当SnCl2的量小于60mg时，可以以高产率得到具有理想形态的杂化纳米带(图4的(A)和(B))。当SnCl2的量大于60mg时(图4的(C)和(D))，形成具有10-50nm孔径的杂化纳米带，有时甚至破裂。这些高孔隙度杂化纳米带的形成可以归因于V2O5纳米带通过选择性阳离子交换与过量的Sn2+阳离子反应的事实。对于通过阳离子交换反应水热制备的纳米多孔CdxZn1-xS纳米片也报道了类似的现象32。
我们随后研究了这些VCSN作为LIB的阳极材料的电化学性能。图5的(A)示出了在0.2mVs-1的扫描速率下在0.01-3.0V的电压窗口中第一个5个连续循环的循环伏安图(CV)。该CV特性与文献中报道的基本一致33-35，表明相同的电化学反应路径。图5的(B)示出Li/V2O5-碳-SnO2电池的充放电曲线。在200mAg-1的电流密度下，第一放电和充电容量分别是2075和1205mAh g-1。在初始循环过程中，出现大的不可逆容量和初始库仑效率为58％，这可归因于在VCSN电极表面上固体电解质界面(SEI)层的形成。
由于与锂插入/析出相关联的不同的氧化还原反应，可在第一个充放电曲线(图5的(A)，(B))中观察到多个电压平台。虽然理论上SnO2具有782mAhg-1的 高容量25，但是这些VCSN的容量大多数来自于V2O5，因为只有10wt％的复合材料是SnO2。如果假定当该复合材料放电至0V，V2O5可被还原成金属V，则Li插入反应的理论容量为1472mAhg-1，这可以解释这种纳米复合材料作为阳极材料高的可逆容量19-22。
图5的(C)示出该阳极复合材料在200mAg-1的电流密度下循环100次的循环性能。50次循环后，杂化纳米带仍显示930mAhg-1的高可逆容量，且从第十次循环容量保持率高达84.5％。100次循环后，纳米复合材料保持800mAhg-1的可逆容量，这表明VCSN的出色的循环稳定性。作为比较，在图11和12中提供没有碳层的V2O5/SnO2复合材料和碳-V2O5核壳纳米带的循环性能。在相同的试验条件下，这两个样品表现出其容量快得多的衰减，并且在200mAg-1下50次循环后保持仅约518mAhg-1(对于V2O5/SnO2复合材料)和411mAhg-1(碳-V2O5核壳纳米带)的容量。发现VCSN比V2O5/SnO2复合材料表现出低得多的电阻，如由在电化学阻抗谱(EIS)图(图13)中在高频区半圆的直径显著减小证明的。较低的接触和电荷转移阻抗有利于Li+扩散和电子转移，这导致VCSN大大提高的电化学性能。
为了评估倍率性能，VCSN在100至800mAg-1的不同电流密度下在0.01-3.0V(图5的(D))的电压窗口循环。随着电流密度增加VCSN只经历了容量的小幅下降。例如，在800mAg-1的高电流密度下，VCSN仍然可实现约620mAhg-1的可逆容量。值得注意的是，超过60次循环后当电流率降低回200mAg-1时，VCSN仍保持约1005mAhg-1的可逆容量，这表明VCSN优异的倍率性能。我们通过XPS光谱还研究了来自完全充电和放电的V和Sn的价态。如图14中的(A)和(B)中所示，XPS光谱在完全放电中没有明显的V和Sn峰。然而，在完全充电中，Sn 3d5/2在487.7eV中心的结合能归属于Sn4+。同样，出现了位于516.9 和525eV的结合能处的V5+2p3/2和2p1/2频带的特性的附属物，可以清楚地知道，在我们的阳极材料中形成了V2O5和SnO2(图14中的(C)和(D))36。
实施例2-3
超薄V2O5纳米带的合成
混合0.26g的V2O5粉末，5mL的30％H2O2，和30mL的去离子水直至得到澄清溶液，然后将35mL的该混合物放置在100mL Teflon高压锅中并在190℃下保持15小时以形成V2O5纳米带。通过离心分离(8,000rpm持续5min)收集所得的砖红色絮凝物并用无水乙醇洗涤三次。最后，将所得的V2O5纳米带分散在140mL的去离子水中以备后用。
实施例2中V2O5-C-SnO2杂化纳米带(VCSN)的合成
将0.015g SnCl2·2H2O溶解在30mL的V2O5纳米带的溶液中，然后在搅拌下加入40mL的0.003mol/L的葡萄糖水溶液。30分钟后，出现棕色悬浮，将其转移至100mL有内衬的Teflon高压锅中，在烘箱中在180℃下密封加热10小时，然后自然冷却至室温。通过离心分离(8,000rpm持续3min)收集所得的黑色产物，然后依次用蒸馏水和无水乙醇洗涤至少四次以去除离子和可能的残留物，最后，在真空下在50℃下干燥10小时。
实施例3中V2O5-C-SnO2杂化纳米带(VCSN)的合成
将0.06g SnCl2·2H2O溶解在30mL的V2O5纳米带的溶液中，然后在搅拌下加入40mL的0.1mol/L的葡萄糖水溶液。30分钟后，出现棕色悬浮，将其转移至100mL有内衬的Teflon高压锅中，在烘箱中在200℃下密封加热4小时，然后自然冷却至室温。通过离心分离(4,000rpm持续8min)收集所得的黑色产物，然后依次用蒸馏水和无水乙醇洗涤至少四次以去除离子和可能的残留物，最后，在真空下在100℃下干燥3小时。
实施例4-5
超薄V2O5纳米带的合成
混合0.85g的V2O5粉末，5mL的30％H2O2，和30mL的去离子水直至得到澄清溶液，然后将35mL的该混合物放置在100mL Teflon高压锅中并在150℃下保持30小时以形成V2O5纳米带。通过离心分离(8,000rpm持续5min)收集所得的砖红色絮凝物并用无水乙醇洗涤三次。最后，将所得的V2O5纳米带分散在140mL的去离子水中以备后用。
实施例4中V2O5-C-SnO2杂化纳米带(VCSN)的合成
将0.02g SnCl2·2H2O溶解在30mL的V2O5纳米带的溶液中，然后在搅拌下加入40mL的0.03mol/L的葡萄糖水溶液。30分钟后，出现棕色悬浮，将其转移至100mL有内衬的Teflon高压锅中，在烘箱中在190℃下密封加热5小时，然后自然冷却至室温。通过离心分离(6,000rpm持续5min)收集所得的黑色产物，然后依次用蒸馏水和无水乙醇洗涤至少四次以去除离子和可能的残留物，最后，在真空下在70℃下干燥12小时。
实施例5中V2O5-C-SnO2杂化纳米带(VCSN)的合成
将0.05g SnCl2·2H2O溶解在30mL的V2O5纳米带的溶液中，然后在搅拌下加入40mL的0.08mol/L的葡萄糖水溶液。30分钟后，出现棕色悬浮，将其转移至100mL有内衬的Teflon高压锅中，在烘箱中在170℃下密封加热12小时，然后自然冷却至室温。通过离心分离(6,000rpm持续5min)收集所得的黑色产物，然后依次用蒸馏水和无水乙醇洗涤至少四次以去除离子和可能的残留物，最后，在真空下在90℃下干燥5小时。
上述实施例2-5制备的V2O5-C-SnO2杂化纳米带具有与实施例1制备的V2O5-C-SnO2杂化纳米类似的形貌和结构，以及相当的电化学性能。
本发明的杂化纳米带改进的循环稳定性和倍率性能可归因于在本发明中所提到的纳米结构组合物独特的设计。首先，超薄纳米带亚基对于有效的Li+离子扩散具有短的距离且对于穿过界面的高的Li+离子流具有大的电极-电解液接触面积，从而导致提高的倍率性能35，37。其次，已经报道使用纯V2O5纳米材料或其纳米复合材料的阳极的形态和结构趋向于塌陷，因为Li+离子频繁的插入/释放过程导致循环稳定性严重下降38。然而，在本文情况下，软碳层充当优异的物理支撑，其中超薄纳米带亚基紧紧连接或嵌入。这有效地抵消了V2O5基纳米复合材料形态和结构的破碎。因此，这些VCSN的容量保持与许多其他V2O5基纳米结构相比显著提高39-42。此外，Sn纳米颗粒(当纳米复合材料用作阳极时在SnO2的还原过程中产生的)被嵌入在V2O5基质中并形成超细金属氧化物电极(图6)。用这种方法制成的电极材料可具有一些突出的优点，如对于循环体积变化良好的耐受性，和高的电子和离子传导性43。
总之，超薄V2O5-碳-SnO2杂化纳米带通过具有高收率的基于溶液的方法制备。这些纳米结构提供具有稳定结构的短锂离子路径和高的电子和离子传导性。该结果通过使用葡萄糖作为碳酸剂用于单分散SnO2纳米晶体在V2O5纳米带表面上的形成以及延缓结构破碎的连接剂来实现。作为LIB的阳极材料，这些杂化纳米带表现出极高的可逆容量，优异的循环性能，以及良好的倍率性能。我们的多组分金属氧化物的控制生长的策略可激发出新的方式来制作纳米结构，用于在应用中如太阳能光转换、能量储存和水分解等具有提高的性能的功能性纳米复合材料的合理设计。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺 流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。
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Claims (10)

  1. 一种用于锂离子电池阳极材料的V2O5-C-SnO2杂化纳米带，其特征在于，超分散的SnO2纳米晶体通过无定形碳连接在V2O5表面上。
  2. 根据权利要求1所述的杂化纳米带，其特征在于，所述SnO2纳米晶体的直径小于10nm，优选为3-6nm；
    优选地，所述杂化纳米带的晶格周期为0.33±0.02nm。
  3. 根据权利要求1或2所述的杂化纳米带，其特征在于，所述杂化纳米带的厚度为5～20nm，优选为7～15nm；
    优选地，所述SnO2、V2O5、碳三者的质量比为：0.015-0.045∶0.065-0.2∶0.08-0.25。
  4. 一种用于锂离子电池阳极材料的V2O5-C-SnO2杂化纳米带的制备方法，其特征在于，通过葡萄糖连接将SnO2负载到V2O5纳米带上。
  5. 根据权利要求4所述的制备方法，其特征在于，先将SnCl2溶解在V2O5纳米带的溶液中以培养晶种；然后，所述晶种借助于葡萄糖吸附到V2O5纳米带的表面上。
  6. 根据权利要求4或5所述的制备方法，其特征在于，包括如下步骤：
    (1)将SnCl2溶解在V2O5纳米带的溶液中，然后加入葡萄糖水溶液；
    (2)出现絮状悬浮物后，将所得混合物密封加热；
    (3)冷却后收集黑色产物；然后洗涤，干燥。
  7. 根据权利要求5或6所述的制备方法，其特征在于，SnCl2、V2O5、葡萄糖三者的质量比为0.01-0.06∶0.05-0.208∶0.2-0.8。
  8. 根据权利要求6或7所述的制备方法，其特征在于，步骤(1)中所述V2O5纳米带的溶液中V2O5的质量浓度为5-20mg/mL，优选为10-15mg/mL；
    优选地，所述葡萄糖水溶液中葡萄糖的浓度为0.02-0.10mol/L，优选为 0.04-0.06mol/L；
    优选地，加入葡萄糖水溶液在搅拌下加入。
  9. 根据权利要求6-8任一项所述的制备方法，其特征在于，步骤(2)中所述加热的温度为170-200℃，优选为170-180℃；加热的时间为4h以上，优选为8-12h；
    优选地，步骤(3)中所述冷却为冷却至室温；
    优选地，所述收集通过离心分离进行；
    优选地，所述离心分离的转速为4,000-8000rpm；离心的时间为3min以上，优选为4-6min；
    优选地，所述洗涤依次使用蒸馏水和无水乙醇进行，优选进行2次以上，更优选进行3-6次；
    优选地，所述干燥在真空下进行；
    优选地，所述干燥的温度为50-100℃，优选为60-90℃；干燥的时间为3h以上，优选为6-12h。
  10. 根据权利要求6-9任一项所述的制备方法，其特征在于，包括如下步骤：
    (1)将SnCl2溶解在5-20mg/mL的V2O5纳米带的溶液中，然后加入浓度为0.02-0.10mol/L的葡萄糖水溶液；SnCl2、V2O5、葡萄糖三者的质量比为：0.01-0.06∶0.05-0.208∶0.2-0.8；
    (2)出现棕色悬浮物后，将所得混合物转移至高压锅中，在170-200℃下加热4h以上；
    (3)冷却至室温后离心分离收集黑色产物；然后依次用蒸馏水和无水乙醇洗涤至少四次，在真空下在50-100℃下干燥3h以上。
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