Polycrystalline vanadium oxide nanosheets

Abstract

Improved V.sub.2O.sub.5 materials are disclosed herein in the form of 2D leaf-like nanosheets. Methods of forming the V.sub.2O.sub.5 nanosheets and batteries (e.g., lithium-ion) incorporating the V.sub.2O.sub.5 nanosheets are also provided.

Claims

1. A method of forming polycrystalline V.sub.2O.sub.5 nanosheets comprising the steps of: (a) providing a V.sub.2O.sub.5 gel by sonicating a solution of hydrogen peroxide and V.sub.2O.sub.5 powder; (b) freezing the V.sub.2O.sub.5 gel to provide a pre-frozen V.sub.2O.sub.5 gel; (c) lyophilizing the pre-frozen V.sub.2O.sub.5 gel to provide lyophilized V.sub.2O.sub.5; and (d) annealing the lyophilized V.sub.2O.sub.5 by heating to a temperature of at least 350 C. to provide polycrystalline V.sub.2O.sub.5 nanosheets, wherein the hydrogen peroxide and the V.sub.2O.sub.5 powder are present in a molar ratio of H.sub.2O.sub.2:V.sub.2O.sub.5 of about 16:1.

2. The method of claim 1, wherein the freezing step lasts at least one day at 20 C.

3. The method of claim 1, wherein the lyophilizing step is a temperature of 50 C. or less and a vacuum of 0.1 Torr or less.

4. The method of claim 1, wherein the annealing step is performed in an atmosphere selected from the group consisting of air, oxygen, nitrogen, carbon monoxide, carbon dioxide, argon, and combinations thereof.

5. The method of claim 1, further comprising adding a carbon source to the solution and performing the annealing step in an oxygen-free atmosphere to provide polycrystalline V.sub.2O.sub.5 nanosheets with a continuous carbon network throughout the nanosheets.

6. The method of claim 1, wherein the V.sub.2O.sub.5 gel comprises a dopant selected from the group consisting of Mn, Fe, Ni, Co, Cr, Ag, Ti, Zn, Sn, Cu, Al, K, Mg, Ca, B, Bi, and combinations thereof.

Description

DESCRIPTION OF THE DRAWINGS

(1) The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:

(2) FIG. 1. A schematic illustration of the synthesis route of 2D leaf-like V.sub.2O.sub.5 nanosheets according to the disclosed embodiments.

(3) FIGS. 2A-2D. Low- (FIG. 2A) and high-magnification (FIG. 2B) FESEM images of a V.sub.2O.sub.5 nanosheet; FIG. 2C: TEM image of a V.sub.2O.sub.5 nanosheet; FIG. 2D: high resolution TEM (HRTEM) image of an area of FIG. 2C.

(4) FIGS. 3A and 3B. FIG. 3A: XRD pattern of leaf-like V.sub.2O.sub.5 nanosheets. The vertical lines on the x-axis correspond to the standard XRD reflections of orthorhombic V.sub.2O.sub.5 and the inset shows crystalline structure of layered V.sub.2O.sub.5. FIG. 3B: N.sub.2 adsorption/desorption isotherm and corresponding BJH pore-size distribution curves (inset) of leaf-like V.sub.2O.sub.5 nanosheets.

(5) FIGS. 4A-4D. FIG. 4A: CV curves of the first two cycles of leaf-like V.sub.2O.sub.5 nanosheet electrodes at a scan rate of 0.2 mV s.sup.1. FIG. 4B: Discharge capacities of leaf-like V.sub.2O.sub.5 nanosheet electrodes at various current densities. FIG. 4C: Charge/discharge curves of leaf-like V.sub.2O.sub.5 nanosheet electrodes at various current densities. FIG. 4D: Cycling performance of leaf-like V.sub.2O.sub.5 nanosheet electrodes at a current density of 500 mA g.sup.1. Inset shows the charge/discharge curves corresponding to different cycles.

(6) FIGS. 5A and 5B. FIG. 5A: Nyquist plots of leaf-like V.sub.2O.sub.5 nanosheet electrodes measured at various depths of discharge (DOD). FIG. 5B: The calculated R.sub.sf+R.sub.ct values at the different depth of discharge states.

(7) FIGS. 6A and 6B. Low- (FIG. 6A) and high-magnification (FIG. 6B) FESEM images of V.sub.2O.sub.5 nanosheets.

(8) FIG. 7. XRD pattern of V.sub.2O.sub.5 nanosheets.

(9) FIG. 8. Ragone plot of 2D leaf-like V.sub.2O.sub.5 nanosheet electrodes.

DETAILED DESCRIPTION

(10) Improved V.sub.2O.sub.5 materials are disclosed herein in the form of 2D leaf-like nanosheets. Methods of forming the V.sub.2O.sub.5 nanosheets and batteries (e.g., lithium-ion) incorporating the V.sub.2O.sub.5 nanosheets are also provided.

(11) The particulars shown herein are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for the fundamental understanding of the invention, the description taken with the drawings and/or examples making apparent to those skilled in the art how the several forms of the invention may be embodied in practice.

(12) The following definitions and explanations are meant and intended to be controlling in any future construction unless clearly and unambiguously modified in the following examples or when application of the meaning renders any construction meaningless or essentially meaningless.

(13) As used herein and unless otherwise indicated, the terms a and an are taken to mean one, at least one or one or more. Unless otherwise required by context, singular terms used herein shall include pluralities and plural terms shall include the singular.

(14) V.sub.2O.sub.5 Nanosheets

(15) In one aspect, a V.sub.2O.sub.5 nanosheet is provided having a thickness of from about 3 nm to 1000 nm and a specific surface area of from about 1 m.sup.2 g.sup.1 to about 500 m.sup.2 g.sup.1; wherein the V.sub.2O.sub.5 nanosheet comprises a plurality of crystalline domains.

(16) The nanosheets are referred to herein as 2D and/or leaf-like due to their unusual shape in the form of sheets. The nanosheets are not formed from a single crystalline domain, but are polycrystalline. This polycrystallinity results from the formation of the nanosheets from annealed aggregates of nanoribbons or nanorods of V.sub.2O.sub.5.

(17) The form of V.sub.2O.sub.5 as nanosheets is beneficial to their use as electrode material (e.g., as cathodes in LIBs). Particularly, the nanosheets provide large surface area, but are thin enough to permit transfer of ions through the sheet. The polycrystalline nature of the nanosheets enhances the ion permeability by providing a looser packing of the V.sub.2O.sub.5 lattice compared to a single-crystalline material.

(18) In one embodiment, the V.sub.2O.sub.5 nanosheets have a thickness of from about 3 nm to 1000 nm. In one embodiment, the V.sub.2O.sub.5 nanosheets have a thickness of from about 3 nm to 100 nm. In one embodiment, the V.sub.2O.sub.5 nanosheets have a thickness of from about 60 nm to 80 nm. The thickness of V.sub.2O.sub.5 can be controlled by tuning the concentration of the V.sub.2O.sub.5 sol. The higher concentration of the V.sub.2O.sub.5 sol during synthesis, the thicker the V.sub.2O.sub.5 nanosheets.

(19) As noted above, the relatively thin nanosheets provide high surface area but facilitate ion transfer across the thickness of the sheet, which provides benefits when incorporated into LIBs.

(20) In one embodiment, the nanosheets have a specific surface area of from about 1 m.sup.2 g.sup.1 to about 500 m.sup.2 g.sup.1. In one embodiment, the nanosheets have a specific surface area of from about 25 m.sup.2 g.sup.1 to about 30 m.sup.2 g.sup.1. Specific surface area can be obtained through Brunauer-Emmett-Teller (BET) testing. The specific surface area is an important characteristic for LIB electrode materials because it determines the contact area between an active material and an electrolyte in a LIBs; and it determines the number of reaction sites of lithium ion intercalation/deintercalations. The large specific surface area also determines the surface energy and, thus, affects the phase transition involved with lithium ion intercalation/deintercalation process

(21) In one embodiment, the plurality of crystalline domains are orthorhombic. The orthorhombic phase of V.sub.2O.sub.5 is preferred because batteries formed using orthorhombic V.sub.2O.sub.5 nanosheets have extraordinarily high energy density, power density, and capacity.

(22) In one embodiment, the plurality of crystalline domains comprise V.sub.2O.sub.5 nanorods. The nanosheet structure include nanorod-shaped sub-domains due to the method of fabrication, as discussed below. The nanorod shape of the V.sub.2O.sub.5 sub-domains provides the basis for the polycrystallinity of the nanosheets that results in the extraordinary properties of the provided nanosheets.

(23) In one embodiment, the nanosheet has a power density from about 20 W kg.sup.1 to 16,000 W kg.sup.1. In one embodiment, the nanosheet has a power density from about 100 W kg.sup.1 to 8500 W kg.sup.1.

(24) In one embodiment, the nanosheet has an energy density from about 50 Wh kg.sup.1 to 1500 Wh kg.sup.1. In one embodiment, the nanosheet has an energy density from about 200 Wh kg.sup.1 to 900 Wh kg.sup.1.

(25) FIG. 8 is a Regone plot that illustrates exemplary energy and power density data obtained from nanosheets in accordance with the disclosed embodiments. See the EXAMPLES below for a further discussion of FIG. 8.

(26) In one embodiment, the nanosheet further includes a continuous carbon network throughout the nanosheet. The carbon coating is very thin, with a thickness of 0.5 nm to 20 nm. The carbon coatings are either nanocrystalline or amorphous, and either dense or porous. By incorporating a continuous carbon network into the nanosheet, the electrochemical performance of the nanosheets can be improved. The continuous carbon network of the V.sub.2O.sub.5 nanosheet can improve the electrical conductivity of V.sub.2O.sub.5 and affect the thermodynamics and enhance the kinetics of lithium insertion/extraction in LIBs. In addition, the continuous carbon network can also increase the stability of the V.sub.2O.sub.5 material by reducing the surface reactions of V.sub.2O.sub.5 with the electrolyte and accommodating volume variation during charge-discharge cycling.

(27) In one embodiment, the nanosheet further includes a dopant selected from the group consisting of Mn, Fe, Ni, Co, Cr, Ag, Ti, Zn, Sn, Cu, Al, K, Mg, Ca, B, Bi, and combinations thereof. Such dopants can be added to the gel so as to improve the performance of the eventual orthorhombic V.sub.2O.sub.5 film formed. Dopants may improve the characteristics of the V.sub.2O.sub.5 films in a number of ways. First, dopants can improve electrical conductivity, such that doped films have improved Li-ion intercalation properties, such as rate capability and cyclic stability. Second, dopants can serve as nucleation sites that facilitate film formation during electrodeposition. Third, dopants can impede crystallite growth during annealing, such that the crystallite size of doped films can be smaller than undoped films. Fourth, dopants will facilitate the phase transition during lithium ion intercalation and deintercalation, and thus enhance energy storage capacity. Finally, the incorporation of appropriate dopants can improve the cyclic stability.

(28) In another aspect, a battery is provided comprising a cathode comprising a V.sub.2O.sub.5 nanosheet as disclosed herein. In one embodiment, the battery is a lithium ion battery. The integration of materials such as the nanosheets into batteries as cathode materials is well known to those of skill in the art. An exemplary LIB is fabricated and characterized in the EXAMPLES section below.

(29) V.sub.2O.sub.5 Nanosheet Fabrication Method

(30) In one aspect, a method of forming polycrystalline V.sub.2O.sub.5 nanosheets is provided. In one embodiment, the method includes the steps of: (a) providing a V.sub.2O.sub.5 gel; (b) freezing the V.sub.2O.sub.5 gel to provide a pre-frozen V.sub.2O.sub.5 gel; (c) lyophilizing the pre-frozen V.sub.2O.sub.5 gel to provide lyophilized V.sub.2O.sub.5; and (d) annealing the lyophilized V.sub.2O.sub.5 to provide polycrystalline V.sub.2O.sub.5 nanosheets.

(31) The method is a simple, green approach to V.sub.2O.sub.5 nanosheet growth, as illustrated in FIG. 1. The method begins with the step of providing a V.sub.2O.sub.5 gel. Methods of forming such gels are known to those of skill in the art. An exemplary method of providing a V.sub.2O.sub.5 gel is to combine a V.sub.2O.sub.5 powder (e.g., commercially available) that is reacted with H.sub.2O.sub.2 in combination with ultrasonic treatment to generate the V.sub.2O.sub.5 gel.

(32) The method continues with a step of freezing the V.sub.2O.sub.5 gel to provide a pre-frozen V.sub.2O.sub.5 gel. The freezing step does not take place under vacuum and is referred to as pre-freezing because it precedes the lyophilizing (freeze-drying) step. The freezing step is performed at a sufficiently low temperature and for a sufficient amount of time so as to freeze the V.sub.2O.sub.5 gel. In one embodiment, the freezing step lasts at least one day at 20 C.

(33) The method continues with a step of lyophilizing the pre-frozen V.sub.2O.sub.5 gel to provide lyophilized V.sub.2O.sub.5. The time, temperature, and vacuum of this step are sufficient to lyophilize the pre-frozen V.sub.2O.sub.5 gel. In one embodiment, the lyophilizing step is a temperature of 50 C. or less and a vacuum of 0.1 Torr or less.

(34) The method concludes with a step of annealing the lyophilized V.sub.2O.sub.5 to provide polycrystalline V.sub.2O.sub.5 nanosheets. In one embodiment, annealing comprises heating to a temperature of at least 350 C. If the annealing temperature is below 350 C., pure orthorhombic phase V.sub.2O.sub.5 cannot be obtained.

(35) In one embodiment, the V.sub.2O.sub.5 gel comprises a dopant selected from the group consisting of Mn, Fe, Ni, Co, Cr, Ag, Ti, Zn, Sn, Cu, Al, K, Mg, Ca, B, Bi, and combinations thereof. Accordingly, an additional step of the method is to provide a dopant to the V.sub.2O.sub.5 gel. As noted previously, dopants can be used to provide additional properties (e.g., conductivity).

(36) In one embodiment, providing the V.sub.2O.sub.5 gel comprises sonicating a solution of hydrogen peroxide and V.sub.2O.sub.5 powder. In one embodiment, the V.sub.2O.sub.5 powder and the hydrogen peroxide are present to provide a ratio of n(H.sub.2O.sub.2):n(V) of about 8:1.

(37) In one embodiment, the annealing step is performed in an atmosphere selected from the group consisting of air, oxygen, nitrogen, carbon monoxide, carbon dioxide, argon, and combinations thereof. This treatment can be used to tailor the valence state of the vanadium ions and oxygen vacancies in the final V.sub.2O.sub.5 nanosheets. For example, when annealed in air, very little V.sup.4+ can be retained in the final V.sub.2O.sub.5 nanosheets because most of the V.sup.4+ is oxidized during the process of annealing. When annealed in oxygen free atmosphere (nitrogen), most of the V.sup.4+ and oxygen vacancies in cryogel can be retained in the final V.sub.2O.sub.5 nanosheets. When annealed in reducing atmosphere (carbon monoxide), more V.sup.4+ and/or V.sup.3+ will be generated in the V.sub.2O.sub.5 nanosheets. This low valence state vanadium ions and the accompanied oxygen vacancies play very important roles in modifying lithium-ion storage capability and electron conductivity of the V.sub.2O.sub.5.

(38) In one embodiment, the method further includes a step of adding a carbon source to the solution and performing the annealing step in an oxygen-free atmosphere to provide polycrystalline V.sub.2O.sub.5 nanosheets with a continuous carbon network throughout the nanosheets. During the sol-gel process, carbon sources (organic molecules, such as glucose) can be introduced. In the following annealing process in oxygen free atmosphere, organic molecules will be decomposed and produce carbon coatings on the surface of V.sub.2O.sub.5 nanosheets. Because V.sub.2O.sub.5 is a poor electron conductor, the electrochemical performance of V.sub.2O.sub.5 nanosheets could be significantly improved by carbon coatings. The carbon coating is very thin, with a thickness of 0.5 nm to 20 nm. The carbon coatings are either nanocrystalline or amorphous, and either dense or porous.

(39) The following examples are intended to illustrate, and not limit, the embodiments disclosed herein.

EXAMPLES

2D Leaf-Like V2O5 Nanosheets

(40) The method of forming the nanosheets is a simple, green approach, as illustrated in FIG. 1. The method begins with a V.sub.2O.sub.5 powder (e.g., commercially available) that is reacted with H.sub.2O.sub.2 in combination with ultrasonic treatment to generate V.sub.2O.sub.5 gel.

(41) The V.sub.2O.sub.5 gel is optionally diluted, frozen, lyophilized (i.e., freeze-dried), and annealed to obtain V.sub.2O.sub.5 nanosheets. A comprehensive description of the exemplary method is described below in the Experimental section. The low-cost raw materials (commercial V.sub.2O.sub.5 powder and H.sub.2O.sub.2 can be used) and facile experimental procedures favorably enable the method suitable for large-scale production.

(42) FIGS. 2A-2D present FESEM and TEM images of the V.sub.2O.sub.5 nanosheets annealed at 450 C. for 1 h in air. It can be clearly seen that the prepared V.sub.2O.sub.5 has a large-area 2D leaf-like structure (FIG. 2A). The thickness of the V.sub.2O.sub.5 nanosheets is 60-80 nm (FIG. 2B). To the best of our knowledge, this is the first time that such large-area 2D leaf-like V.sub.2O.sub.5 nanosheets have been obtained. From the SEM image shown in FIG. 2B, one can find that the V.sub.2O.sub.5 nanosheet actually is polycrystalline and consists of small nanorods. The TEM image (FIG. 2C) further confirms the 2D sheet structure of the prepared V.sub.2O.sub.5. The high resolution (HR) TEM image (FIG. 2D) of the V.sub.2O.sub.5 nanosheet displays clear lattice fringes with a spacing of 0.26 nm and is indexed to the (310) planes of orthogonal V.sub.2O.sub.5 (JCPDS card No. 41-1426).

(43) Without being bound by theory, the mechanism for the formation of this 2D V.sub.2O.sub.5 nanosheet can be described as follows. During the process of freeze drying, the ribbon-like V.sub.2O.sub.5 fibers intertwine into sheets V.sub.2O.sub.5 during the removal of solvent from the V.sub.2O.sub.5 gel. The freeze-dried V.sub.2O.sub.5 cryogel consists of long nanobelts that are less than 100 nm wide (FIGS. 6A and 6B). The nanobelt morphology could be related to the formation of hydrous V.sub.2O.sub.5 as previously reported in the literature, and this is in good agreement with the XRD diffraction results (FIG. 7). When the V.sub.2O.sub.5 cryogel was annealed in air at 450 C., the hydrous V.sub.2O.sub.5 nanobelts grew into small nanorods and formed orthorhombic leaf-like V.sub.2O.sub.5 nanosheets.

(44) FIG. 3A shows the XRD pattern of the V.sub.2O.sub.5 nanosheets annealed at 450 C. for 1 h in air. All diffraction peaks can be indexed to an orthorhombic phase V.sub.2O.sub.5 (JCPDS card No. 41-1426) with the lattice parameters of a=11.488 , b=3.559 , c=4.364 , agreeing well with literature values. No secondary phase was observed. The orthorhombic phase V.sub.2O.sub.5 has a layered structure consisting of V.sub.2O.sub.5 layers stacking along the c-axis (inset of FIG. 3A). Nitrogen adsorption/desorption isotherm measurements were carried out and the results are shown in FIG. 3B. The Barrett-Joyner-Halenda (BJH) pore size distribution obtained from the isotherm revealed that the sample contains relatively mesoscale pores. The Brunauer-Emmett-Teller (BET) specific surface area has been estimated to be 28 m.sup.2 g.sup.1.

(45) FIG. 4A presents the cyclic voltammetry (CV) profiles of 2D leaf-like V.sub.2O.sub.5 nanosheet electrodes for the first two cycles at a scan rate of 0.2 mV s.sup.1. In the first cycle, the three intensive reduction peaks located at 3.30, 3.08, and 2.17V, corresponding to the phase transitions /, /, and /, respectively. Three obvious oxidation peaks appeared during anodic scanning, at 2.57, 3.35, and 3.48 V, respectively. An additional cathodic peak observed in the high potential region (at 3.56 V) could be ascribed to the irreversible phase transition of the / system. The symmetrical features of the CV curve suggest good reversibility of the cycling process. FIG. 4B gives the cycling response of 2D leaf-like V.sub.2O.sub.5 nanosheet electrodes at various charge/discharge current densities. The discharge capacities measured in the voltage window from 2.0 V to 4.0 V are 303, 273, 251, 219, and 160 mA h g.sup.1 at current densities of 50, 200, 500, 1000, and 2000 mA h g.sup.1, respectively. Even at a very high current density of 5000 mA g.sup.1, the 2D leaf-like V.sub.2O.sub.5 nanosheet electrode can still deliver high capacity of 104 mA h g.sup.1. Note that this rate capability is better than those of carbon-coated V.sub.2O.sub.5 and other V.sub.2O.sub.5 nanostructured electrodes reported in literature to date (Table 1).

(46) TABLE-US-00001 TABLE 1 A comparison of C-rate results between electrodes of the present disclosure (Exemplary Electrodes) and other reported V.sub.2O.sub.5 based electrodes. All data are second discharge capacities. Samples discharge capacity/mAh g.sup.1 Current Exemplary Ref. Ref. Ref. Ref. Ref. density Electrodes 1 2 3 4 5 50 mA g.sup.1 303 250 120 mA g.sup.1 261 200 mA g.sup.1 273 500 mA g.sup.1 251 140 580 mA g.sup.1 135 735 mA g.sup.1 146 1000 mA g.sup.1 219 190 1764 mA g.sup.1 103 2000 mA g.sup.1 160 150 Ref. 1: J. Liu, H. Xia, D. Xue, L. Lu, J. Am. Chem. Soc. 2009, 131, 12086-12087. Ref. 2: A. Sakunthala, M. V. Reddy, S. Selvasekarapandian, B. V. R. Chowdari, P. Christopher Selvin, Energy Environ. Sci. 2011, 4, 1712-1725. Ref. 3: J. Liu, Y. Zhou, J. Wang, Y. Pan, D. Xue, Chem. Commun. 2011, 47, 10380-10382. Ref. 4: S. Wang, Z. Lu, D. Wang, C. Li, C. Chen, Y. Yin, J. Mater. Chem. 2011, 21, 6363-6369. Ref. 5: Y. Wang, H. J. Zhang, K. W. Siah, C. C. Wong, J. Lin, A. Borgna, J. Mater. Chem. 2011, 21, 10336-10341.

(47) The results described in the present disclosure show that the 2D leaf-like V.sub.2O.sub.5 nanosheet structure favorably reduces the diffusion length for lithium ions and enables high-rate performance of LIBs. With the charge/discharge current density increasing from 50 to 5000 mA g.sup.1, the powder density increases from 142 W kg.sup.1 to 8410 W kg.sup.1 (FIG. 8). These compare to supercapacitors, which are addressing the extremes of power-density needs (1000-20000 W kg.sup.1) of commercially available devices, though their energy density is only about 1-20 Wh kg.sup.1. The 2D leaf-like V.sub.2O.sub.5 nanosheets may be used for novel and superior electrochemical energy-storage devices with both high-power and high-energy densities. FIG. 4C presents the charge/discharge curves of the 2D leaf-like V.sub.2O.sub.5 nanosheet electrodes at various current densities in the range 2.0-4.0 V. Reversible plateau regions can be observed at all the current densities. The discharge/charge plateaus agree well with the redox peaks shown in the CV curve of FIG. 4A. With an increase in current density, especially at very high current densities (2000 and 5000 mA g.sup.1), the discharge voltage decreases and the charge voltage increases due to an increasing polarization effect. FIG. 4D shows the cycling performance of the 2D leaf-like V.sub.2O.sub.5 nanosheet electrodes at a current density of 500 mA g.sup.1. After 100 cycles, a specific discharge capacity of 206 mAh g.sup.1 can be retained. The capacity fading rate is about 0.22% per cycle, which is lower than the results reported for this material. The 2D leaf-like V.sub.2O.sub.5 nanosheet electrodes maintained a well-defined reversible plateau region even at the 60.sup.th cycle. It is noticeable that the capacity loss with the plateau of about 3.15 V is much larger than those of others. Therefore, it can be inferred that leaf-like V.sub.2O.sub.5 processes relatively poor reversibility for lithium ion intercalation/de-intercalation with the voltage plateau of about 3.15 V, which is considered a main reason for capacity fading. The excellent high-rate performance of leaf-like V.sub.2O.sub.5 nanosheet electrodes is believed to be based on their unique architecture results from at least the following aspects: The large specific area of the 2D leaf-like V.sub.2O.sub.5 nanosheets facilitate the electrolyte to transport the intercalation and de-intercalation of the lithium ions; and the hierarchical porous structure of the V.sub.2O.sub.5 nanosheets relax the mechanical strain generated upon the charge/discharge cycling.

(48) FIG. 5A provides the Nyquist plots of the 2D leaf-like V.sub.2O.sub.5 nanosheet electrode at various depth of discharge (DOD) after the electrode was activated at 20 mA g.sup.1 for 4 cycles. The semicircle in the high frequency region relates to the combined process of surface film (R.sub.sf) and the charge transfer resistance (R.sub.ct). The low frequency semicircle (for 76%, 90%, and 100% DOD) corresponds to a bulk phenomenon, which arises from electronic conductivity of active material and ionic conductivity of the electrolyte filled in the pores of composite electrode. FIG. 4B presents the calculated R.sub.sf+ct values (diameter of semicircle at high frequency) under various DOD states. With DOD increasing from 0% to 62%, the R.sub.sf+ct value initially decreases from 853 to 637 at 28% DOD and then slightly increases to 660 at 62% DOD. Further increasing DOD from 76% to 100% leads the R.sub.sf+ct value abruptly increased from 740 to 1660. Such a large increase of R.sub.sf+ct value suggests that the electrochemical reaction under high DOD became much more difficult than under low DOD, due to the change of phase structure. Another important feature of the EIS plots is the appearance of bulk resistance (R.sub.b, the second semicircle at low frequency, FIG. 8) under high DOD (76%, 90%, and 100% DOD) states. This suggests that under those states the electrode is a poor electronic conductor. While under low DOD (from 0% DOD to 62% DOD) states, the bulk resistance (R.sub.b) is negligibly small, indicating that electrodes are good electronic conductors. This result is in good agreement with the four-probe current-voltage characteristics for Li.sub.xV.sub.2O.sub.5 nanoribbons reported previously. Large changes in R.sub.b values have also been observed in some other cathode materials, depending on the DOD, and are attributed to reversible semiconductor-metal transformations during cycling.

(49) In summary, we have developed a facile, green, and low-cost synthesis of 2D leaf-like V.sub.2O.sub.5 nanosheets. The unique nanoscale characteristics, including 2D morphology, hierarchical porous structure, large specific surface, of these 2D V.sub.2O.sub.5 nanosheets leads to the superior electrochemical performance in terms of their specific capacity, rate capability, and cyclability when they are used as cathode material for LIBs. The obtained excellent performance opens up new opportunities in the development of high performance next-generation LIBs.

(50) Experimental

(51) Material Preparation:

(52) Vanadium pentoxide gel was prepared using a known method. In brief, V.sub.2O.sub.5 powders (99.8%, Alfa-AESAR) were added into de-ionized water and H.sub.2O.sub.2 (30 wt. % in H.sub.2O, Sigma-Aldrich) to form a solution with a V.sub.2O.sub.5 concentration (C.sub.V) of 0.3 M and n(H.sub.2O.sub.2):n(V) of 8:1. The resulting solution was stirred for 15 min while kept in a water bath at a room temperature and then sonicated for 15 min for the reactions. This solution was later diluted to C.sub.V=0.056 M and then sonicated for about 80 min until the solution turned into brownish red V.sub.2O.sub.5 gel. This gel was further dispersed and diluted to a C.sub.V of 0.03 M, and stirred in de-ionized water until a homogenous red-colored, viscous solution was formed. This solution was pre-frozen in a freeze refrigerator at 20 C. for 1 day and then freeze-dried under vacuum at 50 C. for 3 days in a Labconco FreeZone 1 L freeze dryer. After drying, the V.sub.2O.sub.5 cryogel was annealed in ambient atmosphere at 450 C. for 1 h to form 2D leaf-like V.sub.2O.sub.5 nanosheets.

(53) Material Characterization:

(54) The phase structure and morphology of the as-prepared samples were characterized by X-ray diffraction (XRD, Philips 1820 X-ray diffractometer), field emission scanning electron microscopy (FESEM, JEOL, JSM-7000), and transmission electron microscopy (TEM, Tecnai G2 F20 S-Twin). The Brunauer-Emmett-Teller (BET) specific surface areas and pore size distributions were measured with QuantaChrome NOVA 4200e analyzer (working gas N.sub.2, 77 K).

(55) Electrochemical Measurements:

(56) The electrochemical properties of the 2D leaf-like V.sub.2O.sub.5 nanosheets were tested in coin-cells with metallic lithium as the anode and polypropylene (PP) film as separator. The coin-cells were assembled in an argon-filled glove-box. The cathodes were fabricated by mixing V.sub.2O.sub.5 nanosheets, super P carbon black, and poly(vinyldifluoride) (PVDF) at a weight ratio of 70:20:10 in n-methyl-2-pyrrolidone (NMP) solvent. The resulting mixture was then uniformly spread on an aluminum foil current collector. Finally, the electrode was dried at 80 C. for 12 h. The electrode loading was about 2 mg cm.sup.2. The electrolyte solution was made of 1 M LiPF.sub.6 in a 1:1 (V:V) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC). The cells were galvanostatically charged and discharged under different current densities between 2.0 V and 4.0 V (vs Li/Li.sup.+) using Arbin BT-2000 battery tester at room temperature. Cyclic voltammetry (CV) studies were carried out on an electrochemical workstation (CHI 605 C) between 2.0 and 4.0 V at a scan rate of 0.2 mV s.sup.1. Electrochemical impedance spectroscopies (EIS) were performed using the Solartron 1287A in conjunction with a Solartron 1260FRA/impedance analyzer. In EIS measurement, the frequency ranged from 100 kHz to 5 mHz and the AC amplitude was 5.0 mV.

(57) While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.