Patent application title: V2O5 ELECTRODES WITH HIGH POWER AND ENERGY DENSITIES
Guozhong Cao (Seattle, WA, US)
Guozhong Cao (Seattle, WA, US)
Yanyi Liu (Seattle, WA, US)
UNIVERSITY OF WASHINGTON through its Center for Commercialization
IPC8 Class: AH01M404FI
Class name: Electrode chemically specified inorganic electrochemically active material containing vanadium (v), chromium (cr), niobium (nb), molybdenum (mo), titanium (ti), or tungsten (w) component is active material
Publication date: 2013-09-19
Patent application number: 20130244115
Methods are provided for forming films of orthorhombic V2O5.
Additionally provided are the orthorhombic V2O5 films
themselves, as well as batteries incorporating the films as cathode
materials. The methods use electrodeposition from a precursor solution to
form a V2O5 sol gel on a substrate. The V2O5 gel can
be annealed to provide an orthorhombic V2O5 film on the
substrate. The V2O5 film can be freestanding such that it can
be removed from the substrate and integrated without binders or
conductive filler into a battery as a cathode element. Due to the
improved intercalation properties of the orthorhombic V2O5
films, batteries formed using the V2O5 films have
extraordinarily high energy density, power density, and capacity.
1. A method of forming orthorhombic V2O5 comprising the steps
of: (a) electrodepositing VO2 from a precursor solution onto a
substrate that is cathodic, to provide a plurality of V4+ nucleation
sites on the substrate, wherein the precursor solution comprises
V2O5 and hydrogen peroxide; (b) depositing
V2O.sub.5.nH2O gel from the precursor solution through
catalyzed gelation at the V4+ nucleation sites to provide a mixture
of VO2 and V2O.sub.5.nH2O on the substrate.
2. The method of claim 1 further comprising annealing the mixture of VO2 and V2O.sub.5.nH2O on the substrate to provide dehydrated orthorhombic V2O5 on the substrate.
3. The method of claim 2, wherein the dehydrated orthorhombic V2O5 is a freestanding, continuous film that can be removed from the substrate.
4. The method of claim 2 further comprising separating the dehydrated orthorhombic V2O5 from the substrate to provide a freestanding, continuous orthorhombic V2O5 film.
5. The method of claim 2, wherein annealing comprises heating to a temperature of at least 350.degree. C.
6. The method of claim 2, wherein the dehydrated orthorhombic V2O5 on the substrate is a porous V2O5 film having a plurality of pores formed by tuning a deposition characteristic selected from the group consisting of an applied electrodeposition voltage and an applied electrodeposition current density.
7. The method of claim 2, wherein the dehydrated orthorhombic V2O5 on the substrate is a porous V2O5 film having a plurality of pores formed by tuning a ratio of moles of hydrogen peroxide to V2O5 of the precursor solution.
8. The method of claim 1, wherein the V2O.sub.5.nH2O gel comprises a plurality of particles mixed homogeneously within the V2O.sub.5.nH2O gel, wherein the method further comprises a step of annealing the V2O.sub.5.nH2O gel containing the plurality of particles at a temperature sufficient to remove the plurality of particles to provide a porous V2O5 film.
9. The method of claim 1, wherein the V2O.sub.5.nH2O gel comprises a dopant selected from the group consisting of Mn, Fe, Ni, Co, Cr, Ag, Ti, Zn, Sn, and combinations thereof.
10. The method of claim 1, wherein the V2O.sub.5.nH2O gel comprises an impurity selected from the group consisting of Fe, C, Cr, Na, K, Ca, VO.sub.3.sup.-, Cl-, V3+, V4+, and combinations thereof.
11. The method of claim 1, wherein the substrate is selected from the group consisting of fluorine-doped tin oxide, titanium, platinum, copper, aluminum, and stainless steel.
12. A film comprising V2O5 having: (a) orthorhombic structure; and (b) a thickness of from about 10 nm to about 5 mm.
13. The film of claim 12, wherein the film is a freestanding, continuous film.
14. The film of claim 12 further comprising a dopant selected from the group consisting of Mn, Fe, Ni, Co, Cr, Ag, Ti, Zn, Sn, and combinations thereof.
15. The film of claim 12 further comprising an impurity selected from the group consisting of Fe, C, Cr, Na, K, Ca, VO.sub.3.sup.-, Cl-, V3+, V4+, and combinations thereof.
16. The film of claim 12, wherein the film is on a substrate.
17. The film of claim 16, wherein the substrate is selected from the group consisting of fluorine-doped tin oxide, titanium, platinum, copper, aluminum, and stainless steel.
18. A battery comprising a cathode comprising a V2O5 film of claim 1.
19. The battery of claim 18, wherein the cathode consists of a freestanding, continuous orthorhombic V2O5 film.
20. The battery of claim 18, wherein the cathode does not include a conductive additive in the V2O5 film.
CROSS-REFERENCE TO RELATED APPLICATION
 This application is a continuation of International Application No. PCT/US2011/056583, filed Oct. 17, 2011, which claims the benefit of U.S. Provisional Application No. 61/393,780, filed Oct. 15, 2010, and U.S. Provisional Application No. 61/506,831, filed Jul. 12, 2011, each of which is expressly incorporated herein by reference in its entirety.
 Energy storage technology is incontrovertibly one of the great challenges in the modern society facing environmental and ecological concerns, and the lithium ion battery is regarded as one of the most important energy storage devices due to its extensive applications in many areas including portable electronic devices, electric vehicles and implantable medical devices. As the heart of clean energy devices, the development of energy storage materials holds the key to the new generation of energy storage devices in the 21st century. Nanostructured materials have attracted increasing interests in the field of energy materials due to superior electrochemical properties benefited from the unique nanostructure, such as nanoscale dimension, high surface area and large structural freedom which could provide high energy and power density while holding the mechanical integrity and chemical stability after many intercalation/deintercalation cycles.
 Vanadium oxide is a multi-functional material which has extensive applications in various fields. Since its first investigation as a battery material for lithium ion batteries over 40 years ago, it has been discovered that during Li+ ions intercalation vanadium pentoxide (V2O5) possesses high specific electrochemical capacity (theoretical capacity 450 mA h g-1) with four phase transitions which involves five successive phases of LiXV2O5 (0<x<3): α (x<0.01), ε (0.35<x<0.7), δ (0.9<x≦1), γ (0<x≦2) and the irreversible ω (x>2). Although the Li-ion intercalation voltage is lower than LiCoO2 or LiMn2O4, V2O5 has still been regarded as one of the most popular cathode candidates for Li ion batteries due to these advantages: V2O5 provides higher energy and power density than LiCoO2 and LiFePO4, is easier and more controllable fabrication method than LiMO2 (M=Ni, Mn, Co, Fe), and has higher capacity and better cyclic stability than LiMn2O4. There are various processing methods to prepare nanostructured vanadium pentoxide with high electrochemical performance for lithium ion batteries: self-assembled V2O5 hollow microspheres from nanorods; V2O5 submicro-belts from sol-gel precursor combined with hydrothermal method; Electrospun V2O5 nanofibers; Electrostatic spray-deposited V2O5; co-precipitated macro-plates V2O5 from water/ethanol media and V2O5 nanowires from chemical vapor transport. These nanostructured vanadium pentoxide materials have shown improved electrochemical performance in comparison with conventional cathode materials for lithium ion batteries, however due to the high cost of fabrication and complicated processing method, the broad industrial applications of such nanomaterials are limited.
 Therefore, what is desired is an improved method for forming V2O5 that provides V2O5 films with superior properties when incorporated as cathodes in lithium-ion batteries.
 This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
 In one aspect, a method is provided for forming orthorhombic V2O5. In one embodiment, the method includes the steps of (a) electrodepositing VO2 from a precursor solution onto a substrate that is cathodic, to provide a plurality of V4+ nucleation sites on the substrate, wherein the precursor solution comprises V2O5 and hydrogen peroxide; and (b) depositing V2O5.nH2O gel from the precursor solution through catalyzed gelation at the V4+ nucleation sites to provide a mixture of VO2 and V2O5.nH2O on the substrate.
 In one aspect, a film is provided. In one embodiment, the film is a V2O5 film having: (a) orthorhombic structure; and (b) a thickness of from about 10 nm to about 5 mm.
 In one aspect, a battery is provided. In one embodiment, the battery includes a cathode comprising a V2O5 film as provided in the above aspects.
 In another aspect, lithium iron phosphate/carbon nanocomposites are provided, along with methods for fabricating the nanocomposites and the use of the nanocomposites as cathodes in high energy lithium ion batteries.
DESCRIPTION OF THE DRAWINGS
 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:
 FIG. 1 is a schematic illustration of an apparatus useful for depositing a V2O5 film in accordance with the embodiments provided herein.
 FIG. 2: The relationship of deposition time and thickness of the (a) as-deposited V2O5-x.nH2O films and (b) 500° C. annealed V2O5 films.
 FIG. 3: Thermogravimetric analysis (TGA) curve of as-deposited V2O5-x.nH2O film tested in the air from 100° C. to 600° C. with a heating rate of 2° C. min-1.
 FIG. 4: X-ray diffraction (XRD) pattern of the as-deposited V2O5-x.nH2O film, hydrous V2O5-x.nH2O films annealed at 250° C. and V2O5 films annealed at 500° C. in the air.
 FIG. 5: X-ray photoelectron spectroscopy (XPS) spectrum of high-resolution scan on the V2p3/2 core peaks performed on the films. (A) The as-deposited V2O5-x.nH2O films at room temperature; (B) The V2O5 films after annealing at 500° C. in the air.
 FIG. 6: Scanning electron microscope (SEM) image of the 500° C. annealed V2O5 film: (A) top view, ×40 K, (B) top view, ×100 K, (C) cross-section view, ×40 K, (D) cross-section view, ×100 K.
 FIG. 7: Surface morphology of the films annealed at 500° C. measured by atomic-force microscopy (AFM) on 4 μm×4 μm area and surface roughness distribution along the red line as shown.
 FIG. 8: The cyclic voltammograms of 500° C. annealed V2O5 films with a scan rate of 5 mV s-1 in 1M LiClO4/PC electrolyte solution for the 1st cycle (solid line) and 8th cycle (dash-dot line)
 FIG. 9: Chronopotentiometric curves for the first discharge/charge and second discharge cycles of 500° C. annealed V2O5 thin film cathodes at a current density of 200 mA g-1 (1.3 C) in the potential range of -1.6 V-0.2 V (Vs. Ag+/Ag).
 FIG. 10: The cyclic performance of 500° C. annealed V2O5 thin film cathodes at a current density of 200 mA g-1 (1.3 C). (Inset shows the SEM image of the V2O5 film surface, and a schematic drawing of the enhanced Li+ diffusion in the unique nanostructured V2O5 film with its high surface area and short diffusion path).
 FIG. 11: The cyclic performance of 500° C. annealed V2O5 thin film cathodes at various current densities from 200 mA g-1 (1.3 C) to 12.5 A g-1 (70 C) for up to 177 cycles.
 FIGS. 12A and 12B: SEM images of 500 C annealed porous V2O5 film on fluorine-doped tin oxide (FTO) glasses; FIG. 12C XRD patterns of porous V2O5 film before and after Li+ intercalation. The crystallite size (26.9 nm) calculated from XRD peak is smaller than the V2O5 size (˜100 nm) observed from SEM images, it is likely that SEM shows a secondary aggregated/stacked structure of small crystallites. In combination with BET results, the surface of small crystallites are accessible, therefore it is possible that electrolyte could penetrate through macropores and mesopores, resulting in more intercalation sites at the interface between electrolyte and electrode.
 FIG. 13A: The cyclic voltammograms of 150 nm thick porous V2O5 films at 0.6 V˜-1.1 V (Vs. Ag+/Ag) (scan rate: 2 mV/s) and FIG. 13B chronopotentiometric curves for discharge and charge process of 150 nm thick porous V2O5 film cathodes at 0.6 V˜-1.1 V (Vs. Ag+/Ag) (current density: 180 mA/g).
 FIG. 14A: The rate performance of 150 nm and 500 nm thick porous V2O5 film cathodes at various current densities; FIG. 14B The cyclic performance of 150 nm porous V2O5 thin film cathodes at a current density of 300 mA/g for 40 cycles. FIG. 14C Ragone Plots comparing the energy densities and power densities of porous and folded structured films with different thickness.
 FIG. 15: is a photograph of a freestanding, continuous, orthorhombic V2O5 film in accordance with the embodiments provided herein.
 FIGS. 16A-16C are scanning electron micrograph (SEM) images of representative freestanding V2O5 films in accordance with the embodiments provided herein.
 FIGS. 17A-17C are scanning electron micrograph (SEM) images of representative freestanding V2O5 films in accordance with the embodiments provided herein.
 FIGS. 18A and 18B are scanning electron micrograph (SEM) images of representative freestanding V2O5 films in accordance with the embodiments provided herein.
 FIGS. 19A-19C are scanning electron micrograph (SEM) images of representative freestanding V2O5 films in accordance with the embodiments provided herein.
 FIG. 20 is a capacity comparison chart of battery performance for batteries assembled from freestanding V2O5 films in accordance with the embodiments provided herein.
 FIG. 21 is a Ragone Plot of a representative battery formed using freestanding V2O5 films in accordance with the embodiments provided herein.
 FIGS. 22A-22C are SEM images of porous freestanding V2O5 films templated on a block copolymer in accordance with the embodiments provided herein.
 FIG. 23 is a capacity comparison chart of representative freestanding V2O5 films in accordance with the embodiments provided herein.
 FIG. 24 schematically illustrates a typical method for forming a carbon of a lithium-ion battery.
 FIG. 25 schematically illustrates a lithium-ion batter formed using a V2O5 film in accordance with the embodiments provided herein.
 FIG. 26: Thermogravimetric analysis and differential thermal analysis curve of LiFePO4/C composite powders from room temperature to 800° C. at a heating rate of 2° C./min in nitrogen atmosphere.
 FIG. 27: X-Ray Diffraction patterns of sol-gel derived LiFePO4/C composite powders at room temperature and heat treated at 500° C., 600° C., 700° C. and 800° C.
 FIG. 28: Scanning Electronic Microscopy (SEM) pictures of LiFePO4/C nanocomposite films annealed at 500° C. (A-B), 600° C. (C-D) and 700° C.(E-F).
 FIG. 29: Traditional electrode composed of active materials, conductive additives and binders (left); sol-gel derived LiFePO4/C nanocomposite cathode films in this study, with LiFePO4 nanocrystallites and carbon nanocoating (right).
 FIG. 30: Cyclic voltammetric (CV) curves of LiFePO4/C nanocomposite films derived from (A) 500° C., (B) 600° C., (C) 700° C., (D) 800° C. (Room temperature, 10 mV/s, voltage range: -1.4V˜1.0V (vs. Ag/Ag+)).
 FIG. 31: Discharge capacities of sol-gel derived LiFePO4/c nanocomposite cathode films annealed at 500-800° C. at a discharge rate of 200 mA/g.
 FIG. 32: Lithium ion intercalation capacities of sol-gel derived LiFePO4/C nanocomposite cathode films annealed at 600° C. as a function of cycles under different discharge rates.
 FIG. 33: The first and second charge/discharge curves of sol-gel derived LiFePO4/C nanocomposite cathode films annealed at 600° C. at a discharge rate of 200 mA/g.
 Methods are provided for forming films of orthorhombic V2O5. Additionally provided are the orthorhombic V2O5 films themselves, as well as batteries incorporating the films as cathode materials. The methods use electrodeposition from a precursor solution to form a V2O5 sol gel on a substrate. The V2O5 gel can be annealed to provide an orthorhombic V2O5 film on the substrate. The V2O5 film can be freestanding such that it can be removed from the substrate and integrated, without binders or conductive filler, into a battery as a cathode element. Due to the improved intercalation properties of the orthorhombic V2O5 films, batteries formed using the V2O5 films have extraordinarily high energy density, power density, and capacity.
 In one aspect, a method is provided for forming orthorhombic V2O5. In one embodiment, the method includes the steps of (a) electrodepositing VO2 from a precursor solution onto a substrate that is cathodic, to provide a plurality of V4+ nucleation sites on the substrate, wherein the precursor solution comprises V2O5 and hydrogen peroxide; and (b) depositing V2O5.nH2O gel from the precursor solution through catalyzed gelation at the V4+ nucleation sites to provide a mixture of VO2 and V2O5.nH2O on the substrate.
 Exemplary embodiments of the method are provided further below in Examples 1 and 2. The method includes a first step of electrodepositing VO2 from a precursor solution onto a substrate. The electrodeposition is performed using techniques known to those of skill in the art. Specifically, the substrate is a conducting material, such as a metal or a compound conductor such as fluorine-doped tin oxide (FTO) coated onto a glass slide. The substrate is cathodic in order to deposit VO2 and therefore is held at a negative voltage. A representative voltage range is from about -0.5-4.0 volts. The anode can be any anode known to those of skill in the art, for example, a platinum-coated silicon wafer. The electrodes can be spaced apart at any distance that allows for effective electrodeposition of the VO2 film. The deposition time dictates the amount of film grown, with longer deposition times resulting in thicker film growth.
 The VO2 film is deposited from a precursor solution. The precursor solution includes both V2O5 and hydrogen peroxide. The V2O5 can be provided to the solution in any form, such as a powder or other particulate form. The hydrogen peroxide is in a solution (e.g., aqueous) and the ratio of the moles of V2O5 to hydrogen peroxide can be varied to produce specific film characteristics, as will be discussed further below. The precursor solution may also include water or other solvents or additives (i.e., contaminants or dopants), as long as the additives do not prevent the VO2 film from forming. Such additives will be discussed in more detail below.
 After electrodeposition of VO2 on a substrate, the deposited VO2 forms a plurality of V4+ nucleation sites on the substrate.
 The second step of the method builds off of the V4+ nucleation sites on the substrate to form a V2O5.nH2O gel. The V2O5.nH2O gel is formed through catalyzed gelation at the V4+ nucleation sites. The result is a film ("mixture") of VO2 and V2O5.nH2O on the substrate. The specific chemistry of the electrodeposition and gelation is discussed below in Example 1 and chemical equations 1-8. Essentially, the precursor solution forms a V2O5 sol which nucleates on the V4+ nucleation sites on the substrate to form a sol gel of V2O5.nH2O.
 Referring to FIG. 1, a representative apparatus 100 for depositing a V2O5.nH2O gel from a precursor solution is illustrated. In FIG. 1, a V2O5/hydrogen peroxide precursor solution 105 contacts both an anode 110 and a cathode 115. Upon the cathode 115 is electrodeposited a V2O5.nH2O film 120 from a VO2 film providing a plurality of V4+ nucleation sites.
 In one embodiment, the method further comprises a step of annealing the mixture of VO2 and V2O5.nH2O on the substrate to provide dehydrated orthorhombic V2O5 on the substrate. Annealing comprises heating to a temperature above room temperature. In one embodiment, annealing comprises heating to a temperature of at least 350° C. In another embodiment, annealing comprises heating to a temperature of at least 500° C. From XRD results, it has been determined that the orthorhombic V2O5 phase starts to form at 350° C. Superior crystallinity results at 400° C. or greater.
 Annealing can be in air or any other environment. Annealing transforms the deposited VO2 and V2O5.nH2O on the substrate to form a film of orthorhombic V2O5.
 As illustrated in FIG. 4, wherein the top x-ray diffraction (XRD) pattern is an orthorhombic V2O5 film annealed at 500° C., the orthorhombic 001 peak appears only in the 500° annealed sample, and is not present in the 250° sample and the as-deposited room temperature sample.
 In one embodiment, the dehydrated orthorhombic V2O5 film is a freestanding, continuous film that can be removed from the substrate. Accordingly, in one embodiment, the method further comprises the step of separating the dehydrated orthorhombic V2O5 from the substrate to provide a freestanding, continuous orthorhombic V2O5 film. As illustrated in the photograph of FIG. 15, in certain embodiments, the orthorhombic V2O5 film is continuous and freestanding. Such a film is advantageous, for example, in that it can be integrated into a battery, such as a lithium ion battery, by itself. That is, no backing electrode is required, no binders are required to maintain the structural integrity of the film, and no additional conductive material (e.g., carbon) need be added for the film to function as a cathode. Example 3 provides experimental details of the freestanding orthorhombic V2O5 films.
 As used herein, the term "freestanding" refers to a film that maintains structural integrity when removed from a backing such that the film can be manipulated mechanically (e.g., using tweezers) without fracturing. As used herein, the term "continuous" refers to a film that contains an unbroken path both from one face (surface) of the film to the other, and between any two points on a face of the film.
 In certain embodiments, the dehydrated orthorhombic V2O5 film is a porous
V2O5 film having a plurality of pores. The pores can be formed using a number of techniques, which will be discussed below. The pores range in diameter from about 2 nm to about 5 μm.
 In one embodiment, the pores are formed by tuning a deposition characteristic selected from the group consisting of an applied electrodeposition voltage and an applied electrodeposition current density. By varying the voltage and/or current density during electrodeposition, pores can be created in the film, and the characteristics of the pores can be modified. Specifically, by manipulating the voltage of the electrodeposition, both the pore size and the number of pores will change with the externally applied voltage.
 With regard to current density, by manipulating the current density of the electrodeposition, both the pore size and the number of pores will change with the current density.
 In another embodiment, the pores are formed by tuning the ratio of moles of hydrogen peroxide to moles of V2O5 of the precursor solution. In one embodiment, the ratio of hydrogen peroxide to V2O5 (moles) is from about 2:1 to about 16:1. The ratio of the precursor components will affect the size and number of pores. Similarly, precursor concentration can be used to modify the size and number of pores.
 In another embodiment, the pores are formed by integrating a plurality of particles, or a surfactant, into the V2O5 sol gel. By integrating particles or other polymer compositions (such as block copolymers) into the sol gel, the particles are incorporated into the forming V2O5 gel. If the gel is then annealed to form orthorhombic V2O5, the annealing will eliminate (e.g., by pyrolysis) the particles so as to provide pores templated on the polymer particles.
 Due to the pyrolysis elimination of the particles, some residual carbon, or other byproduct, may remain in the film (e.g., coating the surface of the pores).
 The size of the pores formed by this method will be determined by the size of the polymer particles upon which the film is templated. For example, if 100 nm diameter polymer spheres are used, annealing the film to eliminate these spheres will yield pores in the orthorhombic V2O5 film having a shape similar to that of the polymer particles. That is, the pores will have a diameter of about 100 nm. It will be appreciated that if block copolymers are used, or other particles that have non-spherical shape, these particles for templating are also contemplated by the present disclosure. As long as the particles can be eliminated, either by annealing or some other method that does not disrupt the composition of the orthorhombic V2O5 film, the particles can be used to template pores.
 In one embodiment, the V2O5-x.nH2O gel includes a dopant. In one embodiment, the dopant is selected from the group consisting of Mn, Fe, Ni, Co, Cr, Ag, Ti, Zn, Sn, and combinations thereof. Such dopants can be added to the gel so as to improve the performance of the eventual orthorhombic V2O5 film formed. Dopants may improve the characteristics of the V2O5 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.
 In one embodiment, the V2O5-x.nH2O gel includes one or more impurities. In one embodiment, the impurity is selected from the group consisting of Fe, C, Cr, Na, K, Ca, VO3-, Cl-, V3+, V4+, and combinations thereof. Impurities can be found in the source material (e.g., the V2O5 can include impurities, the hydrogen peroxide can include impurities, and any other additives may also introduce impurities). Allowing impurities in source materials can greatly reduce processing cost, due to the ability to use less-pure (i.e., less expensive) source materials. Impurities are not intentionally added (as dopants are) during film formation, and they are not included in films by any design or intention. Impurities typically do not affect film fabrication and performance. Some impurities, such as Fe, Cr, and C, may have the same benefits to films as dopants of those materials do.
 Dopants are intentionally added during film fabrication. They serve as a functional part in the films, as described in the above comment.
 In one embodiment, the substrate upon which the V2O5 is formed is selected from the group consisting of fluorine-doped tin oxide, titanium, platinum, copper, aluminum, and stainless steel. It will be appreciated that any conductive material can be used; and therefore, the list provided is not meant to be exhaustive.
 In one aspect, a film is provided. In one embodiment, the film is a V2O5 film having: (a) orthorhombic structure; and (b) a thickness of from about 10 nm to about 5 mm.
 The V2O5 film is a thin orthorhombic film. An exemplary method for growing such a film is described above, although it will be appreciated that other methods may be used to form such a film. However, in one embodiment, the orthorhombic V2O5 film is formed using the two-part electrodeposition process described herein.
 The orthorhombic structure and relative thinness of the film provide superior characteristics when the film is used as a cathode in a lithium ion battery. These superior characteristics are discussed further below in Examples 1-3.
 In one embodiment, the film is a freestanding, continuous film. The properties and advantages of such a freestanding, continuous film of orthorhombic V2O5 has been discussed previously above.
 In one embodiment, the orthorhombic V2O5 film has a specific energy density from 400 to 900 W h kg-1. In one embodiment, the orthorhombic V2O5 film has a specific power of from 0.5 to 28 kW kg-1. Both the specific energy density and specific power of the orthorhombic V2O5 films are among the highest reported to date.
 In one embodiment, the orthorhombic V2O5 film is a porous V2O5 film. In one embodiment, the pores have a diameter of from about 2 nm to about 5 μm.
 In one embodiment, the orthorhombic V2O5 film includes a dopant. In one embodiment, the dopant is selected from the group consisting of Mn, Fe, Ni, Co, Cr, Ag, Ti, Zn, Sn, and combinations thereof.
 In one embodiment, the orthorhombic V2O5 film includes a impurity selected from the group consisting of Fe, C, Cr, Na, K, Ca, VO3-, Cl-, V3+, V4+, and combinations thereof.
 In one embodiment, the film is on a substrate. Representative substrates include glass, silicon, metals, and conductors deposited on such substrates (e.g., FTO-coated glass slides). The substrate can be used to support the film during fabrication of the film, such as by the methods provided above, or the substrate can be used as a passive or active element in a device into which the V2O5 film is integrated. For example, if the V2O5 film is integrated into a battery, a substrate may provide a mechanical support for the V2O5 film to act as a cathode, or the substrate may be conducting and act as a charge collector into which charge carriers pass after passing through the V2O5 film acting as a cathode.
 In one aspect, a battery is provided. In one embodiment, the battery includes a cathode comprising a V2O5 film as provided in the above aspects. A typical cathode of a battery (e.g., a lithium-ion battery) includes both the "active material" (i.e., the cathode material) and a binder used to bind the active material into a continuous, cohesive film. Carbon is also added to improve the conductivity of the film. Such a cathode is illustrated in FIG. 24. In the present disclosure, a cathode made entirely of V2O5 is provided, as illustrated in FIG. 25. If the orthorhombic V2O5 disclosed herein is used as a cathode, binder and carbon additives are not necessary for the film to act as an efficient cathode (see results in Examples 1-3).
 However, in certain embodiments, binder and/or carbon can be added to the V2O5 film to further improve the characteristics of the cathode. Exemplary binders include 5%˜15% (wt) PVDF (Polyvinylidene fluoride) dissolved in NMP (N-Methylpyrrolidone). Exemplary carbon additives are added at about 5%˜35% (wt) and include Super P®, graphene, graphite, carbon nanotubes, and acetylene black.
 In one embodiment, the battery is a lithium ion battery.
 In one embodiment, the cathode of the battery consists of a freestanding, continuous orthorhombic V2O5 film, as described elsewhere herein. In one embodiment, the cathode does not include a conductive additive in the orthorhombic V2O5 film. In one embodiment, the cathode does not include a binder in the V2O5 film.
 Particularly with regard to the previous two embodiments, one of the advantages of the freestanding orthorhombic V2O5 film is the ability to integrate the film monolithically into a lithium ion battery as a cathode. Because the film is freestanding, no binder materials need be added to the film for it to be manipulated (placed) into a battery. Further, no conductive (e.g., carbon) additive is necessary in order for it to act as a cathode.
 In another aspect, lithium iron phosphate/carbon nanocomposites are provided, along with methods for fabricating the nanocomposites and the use of the nanocomposites as cathodes in high energy lithium ion batteries. This aspect, and related embodiments are disclosed further below in Example 4.
 The following examples are intended to illustrate, and not limit, the embodiments disclosed herein.
Orthorhombic V2O5 Films
 Sample Preparation:
 The films studied in this research were all prepared by cathodic deposition from diluted vanadium pentoxide solutions which were made according to the recipe reported by Frontenot et al. V2O5 powders (99.8%, Alfa-AESAR) were added into de-ionized water and H2O2 (30 wt. % in H2O, Sigma-Aldrich) to form a solution with a V2O5 concentration (CV) of 0.3M and n(H2O2):n(V) of 8.05:1. The resulting solution was stirred for 15 min and sonicated for 15 min respectively while kept in water at a constant temperature for the reactions. It was observed that the yellow slurry started bubbling vigorously and gradually turned into orange in color. After 5 min a transparent solution was formed with ruby red in color. This solution was later diluted into Cv=0.06 M and then sonicated for 1 hour until the solution turned into brownish red V2O5 gel. This gel was further dispersed and diluted to a Cv of 0.0075 M, and stirred in de-ionized water until a brick red colored and transparent solution was formed. The pH value of this solution is measured to be 2.6 and the cathodic deposition was carried out in this final solution.
 For the preparation of V2O5 films, fluorine doped tin oxide (FTO) coated glass was used as the deposition substrates on the negative side, and Pt plate as a counter electrode on the positive side. The distance between these two electrodes was kept constant as 1.5 cm and the deposition voltage was -2.4 V. The depositions were carried out for 3 min, 5 min, 10 min and 20 min separately to investigate the deposition rate using this method. The films were left in air for one day until completely dried to avoid the cracks induced by drastic volume change; then the films were annealed in ambient atmosphere at 500 C for 3 hours followed by a slow cool-down. All the samples were stored in vacuum before characterizations and property measurements.
 Sample Characterization:
 The thickness of the V2O5 films deposited for different times was measured by Dektak Profilometer 3030 after deposition at room temperature and annealing at 500 C respectively. The rest of the characterizations were conducted on the films deposited for 3 min at -2.4 V. Thermogravimetric properties of the V2O5 films were investigated by thermogravimetric analyzer (TGA 7, PerkinElmer) from room temperature to 600 C in air at a heating rate of 2 C min-1. The phase and crystallite size of the V2O5 films were studied using X-Ray Diffraction (XRD, Philips 1820 X-Ray Diffractometer); the surface morphology and roughness of V2O5 films were detected using scanning electron microscopes (SEM, JEOL, JSM-5200) and atomic force microscopy (AFM, Asylum Research MFP-3D). X-Ray photoelectron spectroscopy (XPS) was used to understand and compare the valence status of vanadium element in V2O5 films before and after annealing and lithium intercalation. All XPS spectra were taken on a Kratos Axis-Ultra DLD spectrometer.
 Electrochemical properties of the V2O5 thin film electrodes were tested using a standard three-electrode setup with 1M LiClO4 in propylene carbonate (PC) as electrolyte, a Pt plate as the counter electrode, and Ag/AgCl as the reference electrode.
 Cyclic voltammetric (CV) curves were measured between 0.6 V˜-1.8 V (Vs. Ag+/Ag) with scan rate of 5 mV 5-1, and the lithium ion intercalation/deintercalation properties and cycling performance were investigated by chronopotentiometric (CP) method in the voltage range of 0.2 V˜-1.6 V (Vs. Ag+/Ag). Both CV and CP tests were performed by electrochemical analyzer (CH Instruments, Model 605B).
 After mixing the V2O5 powders and excessive H2O2 with DI water according to the composition recorded in the experimental section, the yellow slurry mixture experienced a vigorous bubbling with intense exothermic phenomena, which was accompanied with slight color change into orange. Several parallel or sequential chemical reactions would occur associated with the decomposition of excessive H2O2 as detailed in literatures:
V2O5+4H2O2→2[VO(O2)2(OH2)].sup- .-+2H++H2O (1)
V2O5+2H++2H2O2+3H2O→2[VO(O2)(O- H2)3]+ (2)
2[VO(O2)2(OH2)]-+4H++2H2O→2[VO(O.su- b.2)(OH2)3]++O2 (3)
2[VO(O2)(OH2)3]+→2[VO2]++O2+6H- 2O (4)
 The appearance of yellow-orange color could be ascribed to the formation of diperoxovanadate anion [VO(O2)2(OH2)].sup.(Equation 1). After 5 min the slurry transformed into a transparent ruby red solution, which suggests that the main ion species in the solution is the red monoperoxovanadate cation [VO(O2)(OH2)3]+ (Equation 2-3). After adding DI water to dilute the solution into 0.06 M which was followed by an hour of sonication, the solution gradually turned into brownish red with higher viscosity. This could be ascribed to the transformation of ion species into dioxovanadium cation [VO2]+(Equation 4). It should be noted that the vigorous bubbling observed during the mixing of V2O5 and H2O2 is the results of releasing of oxygen gas from reactions 3 and 4; each V2O5 results in the release of 2O2. The increased viscosity and formation of brownish red gel suggests the starting of V2O5.nH2O gelation (Equation 5).
 After sonication, the brownish red mixture of V2O5.nH2O gel and solution was dispersed into 0.0075 M with pH=2.7 for the deposition. During cathodic deposition, electrons move toward the negative side, therefore the V5+ species from V2O5 colloidal particles and dioxovanadate cations VO2+ get reduced on the surface of fluorine-doped tin oxide coated (FTO) glass at negative side (Equation 6-7):
Upon the deposition of VO2 on the surface of FTO substrates, VO2 (with V4+) would serve as a nucleation center that initiates and catalyzes the formation of V2O5.nH2O through low pH condition.
 Consequently, hydrous vanadium oxide would deposit through a combination of parallel yet sequential cathodic deposition and catalyzed gelation. It should be noted that the gelation (Equation 8) without V4+ catalyst typically takes more than 24 hours.
 In spite the fact that above chemical reactions have been well studied and documented, the present study is the first effort to deposit films through the combination of cathodic deposition of VO2 and V4+ catalyzed gelation to form a mixture film of VO2 and V2O5.nH2O, and this deposited thin films on top of FTO glass substrates could directly be applied as cathodes for thin film Li-ion batteries. Although other deposition methods have been studied for the formation of V2O5 films, cathodic deposition is unique as V5+ is simultaneously reduced to V4+ during film fabrication. Consequently the V2O5 films consist of an appreciable amount of V4+ ions that serve three important functions: (1) nucleation centers for phase transition for film deposition, (2) initiators for the sol-gel processing, (3) efficient catalysis for the formation and gelation of hydrous V2O5 films. The cathodic deposition of V2O5 thin films is low cost and easy to control.
 FIG. 2 shows the thickness of the film deposited at negative side as a function of deposition time with a constant voltage of -2.4 V: curve (a) showing the deposition rate for the film before treatment, while curve (b) for the film after annealing at 500° C. for 3 hours. The deposition rates are 65 nm/min and 3 nm/min for the films before and after annealing, respectively. The noticeable reduction in films thickness after heat treatment corresponds to the volume shrinkage and can be attributed to (1) the crystal structure change and (2) partial densification. This is in a good agreement with the structural study of V2O5.nH2O xerogel. Both orthorhombic V2O5 and V2O5.nH2O xerogel have layered structures: the structure for the orthorhombic V2O5 can be described by the packing of VO5 square pyramids with a interlayer distance of ˜4.5 Å along c axis of the orthorhombic cell; while the structure for the V2O5.nH2O xerogel is an assembly of bilayers of single V2O5 layers with VO5 square pyramids with water molecules residing in between, the distance between each slab is 8 Å-21.6 Å depends on the content of the crystalline water in the V2O5.nH2O xerogel. V2O5 has a relatively low melting point and often been used as sintering additives. 500 C is a relatively low temperature for most oxides; however this temperature may allow a noticeable densification for V2O5.
 Moreover it can be observed that with the drastic volume change after thermal treatment, these V2O5 films were well affixed and stayed intact on the FTO glasses, without any macroscopic defects, cracks, pin-holes, etc., not even for large-sized films (1 inch by 1.5 inch in area, 500 nm in thickness). This can be ascribed to the well attachment between the films and the substrates induced by the external electrical field, as well as the fine and homogenous films composed of nanocrystallites in tens of nanometers of size formed by cathodic deposition from V2O5 solution.
 In order to study the crystalline water loss during annealing process, thermogravimetric analysis (TGA) was carried out in flowing air from room temperature up to 600 C with a heating rate of 2 C min-1 and the result is shown in FIG. 3. It should be noted that since the V2O5-x.nH2O films in this research contains V4+ species induced by the cathodic deposition, the films will gain weight from the oxidization reaction when heated up in the air. However the loss of the crystalline water will give a total thermogravimetric trend of weight loss. Therefore in this research, it is inaccurate to use the weight loss from TGA measurement to decide the composition of crystalline water. It can be observed that the TGA curve shows the thermogravimetric change happening in different temperature range in comparison with other references which is due to the various film processing methods applied. In this research the ˜3% weight loss below 250 C can be mainly ascribed to the loss of weakly bound water, and the weight loss between 250 C and 340 C generally involves the loss of crystalline water in V2O5-x.nH2O. Above 340 C the crystallization of V2O5 occurs. This is consistent with XRD results discussed in the following paragraphs.
 FIG. 4 compares the X-Ray Diffraction patterns of the V2O5-x.nH2O films after cathodic deposition from V2O5 resource at room temperature, annealing at 250 C and 500 C respectively in the air. The as-deposited film without any heat treatment shows an intense (001) peak, which indicates the characteristic layered structure of V2O5-z.nH2O. This is in consistency with other research showing a preferential structure of ribbon stacking for V2O5.nH2O gel. The crystallite size calculated by Scherrer Equation is 6.2 nm, and the interlayer distance estimated from Bragg's law is 12.77 Å, which indicates the composition of crystalline water in this sample is n>2.
 When the V2O5-x.nH2O film was heated up to 250 C, the improved crystallinity of layered structural V2O5-x.nH2O film can be confirmed by the appearance of (003) and (004) together with (001) peaks. It is obvious that the (001) peak shifts to the higher angle direction, which results in a decrease in the interlayer distance to 11.31 Å (n≈1.5) due to the loss of crystalline water from the heat treatment. The crystallite size grows slightly larger to 10.0 nm calculated from the XRD pattern. The exhibition of a series of (001) harmonics reflects the nature of the turbostratic stacking of V2O5 ribbons. Moreover the missing peak which is corresponding to the (002) plane suggests the formation of double sheets of V2O5 for each layer.
 After the V2O5-x.nH2O film was annealed at 500 C, the sample was completely dehydrated presenting a pure orthorhombic phase with good crystallinity as shown in the XRD pattern. The interlayer distance along c axis is calculated to be 4.36 Å which is in perfect match with the crystalline structure of orthorhombic V2O5 (JCPDS No. 41-1426). The V2O5 films have preferred orientation which is evidenced by missing diffraction pattern for (010) plane along b axis. The crystallization temperature of orthorhombic phase at 500 C, and V2O5. 1.5H2O at 250 C in this study is higher in comparison with other references. The crystallite size of this orthorhombic V2O5 is calculated to be 35.1 nm from the XRD pattern.
 XPS measurements were carried out on the as-deposited V2O5-x.nH2O films at room temperature and the V2O5 films after annealing in the air at 500 C to investigate the oxidation state of the vanadium as well as to estimate the content of reduced vanadium V4+ in the films. The V2p3/2 core peak spectra for the as-deposited V2O5-x.nH2O films (FIG. 5A) is composed of two components which are located at 517.96 eV and 516.65 eV respectively, as shown in the fitting data. These two binding energy values can be associated to two formal oxidation degrees+5 and +4. However for the 500 C annealed V2O5 films, there is only one V2p3/2 core peak locating at 517.86 eV as shown in FIG. 5B, which is associated to the +5 formal degree for vanadium ions. This difference can be explained by the film preparation conditions: the as-deposited films were formed on the substrate placed on the negative side, as discussed in the film preparation part, some of the V5+ on the surface of substrate got reduced to V4+ which further initiated the gelation hence formed the V2O5-x.nH2O films. Therefore there was noticeable V4+ existing in the as-deposited films, as detected from XPS. After annealing at 500 C in the air, the introduction of oxygen leads to the oxidation and crystallization of the films and therefore the vanadium ions are presented completely in the highest oxidation degree (V5+). The ratio of V4+/V5+ is 15/85, which was decided from the area ratio of fitted spectrum of V2p3/2 (V5+) and V2p3/2 (V4+) as listed in Table 1. These results could well confirm the films color observed in FIG. 1A and the cathodic deposition mechanism discussed in the film preparation session.
TABLE-US-00001 TABLE 1 Binding energy (EB) of the V2p2/3 core peaks taken from the spectrum in FIGS. 5A and 5B V5+ V4+ V5+/ Biding Energy Biding Energy Sample peak area peak area V4+ for V5+ (eV) for V4+ (eV) 5A 3523.41 635.13 85/15 517.96 516.65 5B 3624.30 -- -- 517.86 --
 FIG. 6A-D are the SEM images revealing the surface morphology and microstructures of the V2O5 films annealed at 500 C for 3 hours. The top views of annealed V2O5 films (FIG. 6A-B) shows that the uniform film was homogenously deposited, and composed of small "wrinkled" flakes (domain-like) with 0.5-1.5 μm in diameter placing parallel to the substrate. Each flake is composed of smaller particles of 20-30 nm in diameter, which corroborates very well with the crystallite size calculated from the XRD patterns. The cross-section view of the annealed V2O5 films (FIG. 6C-D) shows the similar nanostructures with 20-30 nm nanoparticles, again agrees very well with the crystallite size calculated from the XRD patterns with 10 nm gaps separating adjacent nanoparticles. It is noted that the nanostructures and the size of nanocrystallites remain the same in the surface and inside the film. It should also be noted that such unique nanostructure was not found in V2O5 thin films deposited on anodic substrates
 The formation of such peculiar domain-nanocrystallite structured thin films may be explained by considering the fact that the film was deposited through a combination of cathodic deposition and catalyzed gelation. The formation of tetravalenced vanadium ions or VO2 by cathodic deposition initiates and catalyzes the formation of gelation of hydrous vanadium pentoxide. Continued reduction and cathodic deposition of vanadium dioxide serves secondary (or new) nucleation, consequently the deposited film consists of many nanoparticles stacking with spaces separating one another. The VO2 could also be regarded as nucleation sites during annealing process, which retards the nanocrystallite growth and suppresses the grain boundary migration (FIG. 6C-D). The AFM image (FIG. 7) on the surface of 500 C annealed V2O5 thin films with an area of 4 μm×4 μm shows that the flake size is about 0.5 μm×1.5 μm in the planar dimension, and the roughness of the film is measured to be +/-20 nm.
 FIG. 8 shows the 1st and 8th cycle of the cyclic voltammogram of 500 C annealed V2O5 thin film electrodes with a thickness within 150-170 nm. It can be clearly observed that there are four cathodic peaks located at -0.192 V, -0.404 V, -1.320 V and -1.797 V respectively, and these four peaks are corresponding to the α/ε, ε/δ, δ/γ, γ/ω phase transitions within the potential range of 0.6 V˜-1.8 V (Vs. Ag+/Ag) respectively according to the other research references. The two anodic peaks at -0.096 V and -0.175 V can be ascribed to the reverse phase transitions of ε/α and δ/ε respectively which still leaves a broad peak after 8 cycles. This is different from other studies which show that when there is more than 2.2 mol Li+ being intercalated into LixV2O5 (x≧2.2) especially at high current densities, there will occur an irreversible phase transition which results in a capacity loss due to the kinetic limitations. However in this research, we were able to observe the partially reversible α/ε, ε/δ phase transitions at a current density of 200 mA g-1 (1.3 C) after 8 cycles. This is a proof of facilitated thermodynamics and kinetics of phase transition, which can be ascribed to the unique "wrinkled" nanostructure of 20-30 nm nanocrystallite separated by 10 nm gaps (FIG. 6). The phase transition during lithium ion intercalation/deintercalation could be favored by the nanoscale dimension as well as the accessibility of the intercalation sites. Nanostructured materials possess huge surface area and excessive surface energy, and thus offer more sites for lithium ion insertion and extraction and allow the phase transition that is otherwise difficult for bulk materials. The broad peak at -0.772 V appears during anodic scanning is in good agreement with the irreversible formation of the w phase, which could be further proved by chronopotentiometric curves (FIG. 9).
 FIG. 9 shows the chronopotentiometric curves for the first discharge/charge and second discharge curves of 500 C annealed V2O5 thin film electrodes of 150-170 nm thick at a current density of 200 mA/g (1.3 C) in the potential range of -1.6 V˜0.2 V (Vs. Ag+/Ag). The initial discharge curve presents four noticeable plateaus: -0.16 V, -0.34 V, -1.25 V and -1.55 V, which are corresponding to the successive appearance of two-phase region: α/ε, ε/δ, δ/γ, γ/ω with Li composition for LixV2O5 in a range of 0<x≦2.68 (related with a capacity of 402 mA h g-1). It can be observed that the first charge and second discharge curves maintain noticeable but shorter plateaus at the same potential positions which are related with the above listed phase transitions. These plateaus solidly prove the enhanced reversibility of phase transitions when more than 2 mols of Li+ ions was inserted into the cathodic deposited V2O5 films in this research. Moreover it is noteworthy that, in the first discharge curve, the vertical drop line connecting the two plateaus related with ε/δ, δ/γ phase transitions becomes a slope in the successive first charge and second discharge curves. This slope shape curve is rather related to a solid solution behavior, which can be related to the formation of a new phase: ω--LixV2O5 (x>2) and it is reported to be irreversible. After the first charge there was 0.68 mol Li+ trapped in the newly formed w phase; however the second discharge achieves a complete intake of the amount of Li+ to form ω--Li2.68V2O5. These CP curves are in good agreement with the CV results (FIG. 8) in explaining the phase transitions of V2O5 films.
 The cyclic performance of the V2O5 thin film electrodes annealed at 500 C was investigated. FIG. 10 shows the discharging capacity at a current density of 200 mA g-1 (1.3 C) for the first 12 cycles, then followed by 170 cycles of discharge/charge tests at various current densities (which will be further discussed in FIG. 11). The last 20 cycles back at current density of 200 mA g-1 (1.3 C) for capacity fading investigation are also shown in FIG. 10. The initial discharge capacity is 402 mA h g-1, which is related to Li2.68V2O5 before the second charge started. Due to the irreversible phase formation from first charge, the second discharge capacity dropped to 368 mA h g-1, and stayed at 325 mA h g-1 for the 12th cycle. The coulombic efficiency is 74.6% for the first cycle and 85.8% for the second cycle. After more than 180 cycles tested at different current densities, the discharge capacity was still as high as 240 mA h g-1. The specific energy densities were calculated to be 900 W h kg-1 for the 1st cycle and 723 W h kg-1 for the 180th cycle when discharged at 200 mA g-1 (1.3 C). This is higher than the data reported on V2O5 for cathode materials in lithium ion batteries. FIG. 11 shows the cyclic discharge capacity of 500 C annealed V2O5 films performed at various current densities at 200 mA g-1 (1.3 C), 450 mA g-1 (3 C), 1.5 A g-1 (10 C), 4.5 A g-1 (30 C) and 10.5 A g-1 (70 C). At fairly high current densities which correspond to fast battery discharge/charge cycles, the film electrode retains high lithium ion storage capacities: 160 mA h g-1 at 4.5 A g-1 (30 C) and 120 mA h g-1 at 10.5 A g-1 (70 C), or with a high specific power of 28 kW kg-1.
 The cathodic deposited V2O5 thin film electrodes show much higher lithium intercalation capacity and energy and power density with better cyclic stability in comparison with other nanostructured V2O5 cathodes reported recently. The high performance could be ascribed to the unique nanostructure in this research (FIG. 10, inset): the 20-30 nm nanocrystallites provide a shorter diffusion path for Li+ ion intercalation/deintercalation, and the 10 nm wrinkled gaps offers a higher surface area with more accessible intercalation sites which favors the electrolyte penetration and interface reactions. This nanostructure could effectively enhance the phase transition during Li+ ion intercalation/deintercalation, and it essentially benefits from the presence of V4+ serving as films initiators and catalysts during cathodic deposition, as well as nucleation sites in the annealing process in air. Since more space freedom is offered by this nanostructure, the film's mechanical integrity and stability during battery test can be well maintained which will result in a good cyclic stability. The external electrical field applied during film deposition helps form a sturdy adhesion to the conductive substrate, which could facilitate a better Li+ ion diffusion and guarantee an excellent energy and power density.
 Nanostructured V2O5 thin film electrodes have been prepared for the first time by cathodic deposition from V2O5 and H2O2 followed by annealing at 500 C in air. The mechanisms and reactions for cathodic depositions of V2O5 thin films are discussed in detail, and the formation of tetravalenced vanadium ions or VO2 by cathodic deposition initiated and catalyzed the formation of gelation of hydrous vanadium pentoxide films. After annealing the as-deposited V2O5-x.nH2O films at 500 C in the air, the V2O5 film shows a preferred oriented orthorhombic phase with a crystallite size of 35.1 nm calculated from XRD patterns. The XPS result reveals that there is 15% V4+ out of Vtotal in the as-deposited V2O5, nH2O films and they all get oxidized to V5+ ions at 500 C.
 The "wrinkled" nanostructure of V2O5 films was detected by SEM to be composed of fine nanocrystallites of 20-30 nm separated by 10 nm gaps. The electrochemistry and phase transitions during Li-ion intercalation and de-intercalation of cathodic deposited V2O5 nanostructured thin films are explicitly discussed in this paper. Electrochemical tests reveal that the nanostructured V2O5 thin film electrodes possess enhanced phase transition reversibility during Li+ ion intercalation/deintercalation. The high energy density (900 W h kg-1 at 200 mA g-1) and power density (28 kW kg-1 at 10.5 A g-1), enhanced phase transitions as well as the good cyclic stability (well functioned over 200 cycles) is ascribed to the unique nanostructure with higher surface area, shorter Li+ ion diffusion path and improved mechanical integrity.
Porous Orthorhombic V205 Films
 The porous structured V2O5 films were prepared by electrodeposition following the same procedure as in Example 1. V2O5 powders (99.8%, Alfa-AESAR) were added into de-ionized water and H2O2 (30 wt. % in H2O, Sigma-Aldrich) at a V2O5 concentration (CV) of 0.3 M and n(H2O2): n(V) of 8.05:1, and the resulting solution was stirred and sonicated for 15 min successively, followed by being diluted to CV=0.06 M and then sonicated for 1 hour until the solution turned into brownish red V2O5 gel. The block copolymer Pluronic P123[(CH2CH2O)20--(CH2CH(CH3)O)70--(CH2CH2O)20] was dissolved into de-ionized water to form a transparent 4 wt % solution, and then mixed with the above V2O5 gel to get the deposition precursor with CV=0.013 M. The V2O5 films were deposited on the fluorine doped tin oxide (FTO) coated glass at a voltage of -2.4 V. The as-deposited films were ambient dried and then annealed at 500° C. for 1 hour in air.
 The surface morphology of porous V2O5 films was observed using scanning electron microscopes (SEM, JEOL, JSM-5200), and phase and crystallite size were studied using X-Ray Diffraction (XRD, Philips 1820 X-Ray Diffractometer). Surface area was determined by nitrogen adsorption-desorption at 77 K (NOVA 4200e, Brunauer-Emmett-Teller (BET)). Electrochemical properties of the V2O5 thin film electrodes were tested using a standard three-electrode setup. The cyclic voltammograms (CV) and chronopotentiometric (CP) measurement were performed using electrochemical analyzer (CH Instruments, Model 605B) in the voltage range of 0.6 V˜-1.1 V (Vs. Ag/Ag+) with 1M LiClO4 in propylene carbonate (PC) as electrolyte, a Pt plate as the counter electrode, and Ag/AgCl as the reference electrode.
Results and Discussion
 Porous V2O5 films were successfully fabricated by electrodeposition as shown in the SEM images in FIGS. 12A and B. The porous V2O5 films compose ofhomogeneously distributed pores of less than 100 nm in diameter, as well as V2O5 size of around 100 nm. Previously we have reported electrodeposition of folded V2O5 film electrodes from V2O5 sol using the similar method. Block copolymer P123 has been reported as porous structure directing agents due to its amphiphilic properties, and it could also reduce or prevent the aggregation of nanocrystallites as well as impede the crystal coarsening. In this research, P123 is homogeneously mixed with V2O5 sol, where thevanadium species, e.g., [VO2]+, VO2, V2O5.nH2O, could be anchored to the surfactant chain on P123 by the combined electrostatic force and hydrogen bonding in a low-pH aqueous solution. After induced gelation and film formation by applying an external electrical voltage, the P123-templated vanadium oxide films could be homogenesouly deposited onto FTO substrates. P123 was then removed by annealing the film in the air at 500 C for 1 hours. The specific surface area of the porous nanostructured V2O5 films was found to be ˜40 m2/g as determined by nitrogen sorption isotherms, which is larger than the surface area of porous structured V2O5 electrodes reported recently. The macropores and ˜100 nm V2O5 discernible from SEM images could not solely account for such a large surface area; in fact the surface area could mainly come from mesopores withpore size distribution centered at a diameter of 3.68 nm from BET result.
 FIG. 12C shows the XRD patterns for the pristine porous V2O5 film and after the films intercalated with 0.76 mol and 1.18 mol Li+, respectively. The porous V2O5 film annealed at 500 C shows pure orthorhombic phase and the crystallite size is calculated to be 26.9 nm from the (001) peak based on Scherrer's equation, which is 8.2 nm smaller than the crystallite size of 35.1 nm in the folded structured V2O5 film electrodeposited from P123-free precursor. The reduced crystallite size could be ascribed to the presence of P123 during film deposition and annealing, where it could effectively impede the crystal growth. The lattice constant along c-axis has also been calculated from (001) peaks in XRD patterns to be 4.32 Å, 4.39 Å and 4.67 Å for V2O5, Li0.76V2O5 and Li1.18V2O5 respectively. During Li+ insertion/extraction in V2O5, Li+ travels along the b-direction between V2O5 layers, which induces the buckled V2O5 planes, and reduces a and b-constants due to the reduction in repulsive Coulumbic force along the ab-plane. In the meantime, c-constant increases as the result of expansion of interlayer distance. The change inc-constant in this study is in good consistency with previous literatures.
 FIG. 13A shows the first 2 cycles of the cyclic votammogram (CV) of porous nanostructured V2O5 film electrodes when tested in 0.6 V˜-1.1 V (Vs. Ag/Ag+). The three pairs of redox peaks in FIG. 13A correspond to the reversible phase transitions among the following four Li+ intercalated phases LixV2O5: α (x<0.1), ε (0.35<x<0.7), δ (0.9<x<1) and γ (1<x<2). Those successive phase transitions were also exemplified in the chronopotentiometric (CP) curves by the presence of three consecutive plateaus in FIG. 13B. It can be calculated that the discharge capacity loss between the first and second cycle was 43 mAh/g, which could be mainly due to the existence of partial phase transition from γ phase to ω phase as marked in FIG. 13B. From both the CV diagrams and CP curves, it can be concluded that the porous V2O5 films show a good reversibility when discharged and charged at 0.6 V˜-1.1 V (Vs. Ag/Ag+).
 FIG. 14A compares the discharge capacities of porous V2O5 films with different thickness when discharged consecutively at various discharge/charge rates. The 150 nm porous V2O5 film delivers a high discharge capacity of over 300 mAh/g in the initial cycle. At the 27th cycle, when a high current density of 9 A/g was applied, the discharge capacity maintains high as 160 mAh/g. When increase the thickness of the porous V2O5 film to 500 nm, it still keeps an excellent rate capability with a discharge capacity of 124 mAh/g at 8 A/g as shown in FIG. 14A. FIG. 14B shows thecyclic stability test at a constant current density of 300 m A/g for 40 cycles for porous V2O5 film with 150 nm in thickness. The initial discharge capacity was measured to be 294 m
 Ah/g, and it stays as high as 240 mAh/g at the 40th cycle. The porous structure with V2O5 nanocrystallites together could offer a benign micro-environment with sufficient flexbility to accommodate volume change during Li+ insertion and extraction, so that a good electrochemical stability and mechanical integrity could be guaranteed after many cycles. FIG. 14C are the Ragone Plots comparing the power densities and energy densities of the porous and folded structured V2O5 films. The 150 nm and 500 nm porous films show high energy density of 843 Wh/kg and 755 Wh/kg respectively, and high power density both of 25.6 kW/kg. The 500 nm folded film shows the worst properties both as in low energy density and power density. The difference of battery performance in altered film structures with various thicknesses could be ascribed to the following rationales. The unique structure in porous films could guarantee a large surface area with sufficient contact between electrode materials and electrolyte, which provides adequate intercalation sites for efficient Li+ intercalation simultaneously. The presence of block copolymer P123 can delay the solid state diffusion and impede fine V2O5 nanocrystallites from agglomeration and coarsening during film formation and growth, therefore a short and fast Li+ diffusion channel during phase propagation could be guaranteed. Whereas for the folded structured films, they could possess large surface area for efficient Li+ intercalation when the films are as thin as 150 nm. However for the thicker folded films, they could become denser, partially losing the features of highly folded nanostructure and also the V2O5 particles could grow larger. The denser films are not able to offer sufficient penetration for electrolyte into all V2O5 particles, thus the Li+ intercalation into thick V2O5 films would rely on and be bottlenecked by slow solid state Li+ diffusion within large V2O5 particles during battery discharge. Similar phenomena of electrochemical performance degradation with increasing film thickness have also been reported in other literatures.
 The porous nanostructured V2O5 films have been fabricated via a simple and low-cost electrode position approach from block copolymer P123 containing V2O5 precursor. P123 is believed to promote the formation of porous structure during film formation. Such V2O5 films demonstrated excellent electrochemical properties because porous V2O5 nanocrystallites possess (1) high surface area permitting enhanced charge transfer kinetics at the interface, (2) efficient Li+ diffusion (3) good electrochemical stability and mechanical integrity.
Freestanding Orthorhombic V2O5 Films
 Freestanding, self-supported, continuous, orthorhombic V2O5 films were fabricated by the electrodeposition method provided in Examples 1 and 2 from a precursor solution having a hydrogen peroxide to V2O5 ratio of 4:1 and 2:1. The concentration of the V2O5 in the precursor solution was 0.1M. The films were deposited on titanium foil, and the sol gel formed by electrodeposition was annealed at 450° C. in air.
 The V2O5 films after annealing were orthorhombic and could be easily peeled off from the titanium foil. FIG. 15 is a photograph of a V2O5 film peeled off of titanium foil after annealing.
 The freestanding film can be readily inserted into an assembly of a lithium ion battery as the cathode. No polymer binder or carbon additive was used.
 In the exemplary battery described herein, the V2O5 film was used as a cathode, and stainless steel was used as the cathode current collector. In the exemplary battery, the anode is metallic lithium. The electrolyte is 1 mol/L LiPF6 in EC/DMC=1:1 (volume ratio). The separator is a Celgard 2400 microporous film.
 FIGS. 16A-16C are SEM micrographs of a V2O5 film formed using a 4:1 ratio of hydrogen peroxide to V2O5 and electrodeposition for 20 minutes using the electrodeposition method described above in Example 1.
 FIGS. 17A-17C are SEM micrographs of a V2O5 film formed using a 4:1 ratio of hydrogen peroxide to V2O5 and electrodeposition for 70 minutes using the electrodeposition method described above in Example 1.
 FIGS. 18A and 18B SEM micrographs of a V2O5 film formed using a 2:1 ratio of hydrogen peroxide to V2O5 and electrodeposition for 20 minutes using the electrodeposition method described above in Example 1.
 FIGS. 19A-19C SEM micrographs of a V2O5 film formed using a 2:1 ratio of hydrogen peroxide to V2O5 and electrodeposition for 70 minutes using the electrodeposition method described above in Example 1.
 As illustrated in the SEM images of FIGS. 16A-19C, films fabricated with different conditions have different characteristics. Particularly, films formed from a 4:1 precursor (hydrogen peroxide to V2O5) illustrated in FIGS. 16A-17C have a higher film-formation efficiency compared to films formed from a precursor solution having a ratio of 2:1, as illustrated in FIGS. 18A-19C. Additionally, films formed from a 4:1 precursor solution are less dense than films formed from a 2:1 precursor solution.
 FIG. 20 graphically illustrates the capacity of "coin cell" batteries assembled using various V2O5 films. Particularly, the films of FIGS. 16A-19C are integrated into batteries and tested. The highest capacity batteries are those that are the thinnest (i.e., grown for the shortest amount of time-20 minutes). Additionally, the 4:1 (hydrogen peroxide to V2O5) precursor solution yields capacity characteristics of the battery superior to the 2:1 film. The estimated thickness of the 20-minute films is 2 μm, and the estimated thickness of the 70-minute films is 10 μm. It will be appreciated that the time of the deposition is related to the thickness of the film, such that a longer deposition time will yield a thicker film. However, the thicker the V2O5 film, the more difficult lithium ion intercalation becomes. As illustrated by FIG. 20, thinner films produce improved battery performance, which is related to the intercalation properties.
 FIG. 21 is a Ragone plot of the 4:1 films grown at 20 and 70 minutes. As illustrated in FIG. 21, the 20-minute (2 μm) films have superior energy and power density compared to the thicker films.
Porous Freestanding V2O5 films
 Additionally, porous freestanding V2O5 films have been fabricated using a modified electrodeposition method as provided above in Example 2. Specifically, a 0.1M precursor solution of 4:1 (hydrogen peroxide to V2O5) was used for the electrodeposition. Block copolymer P123 was added to create a porous nanostructure. The film was grown for about 70 minutes so as to provide a 10 μm film thickness. The films were deposited on titanium foil followed by annealing at 450° C. in air.
 The porous V2O5 films were orthorhombic and were removed from the titanium foil as continuous freestanding films. The freestanding films were directly assembled into a "coin cell" to test the film as a cathode material for a battery.
 FIGS. 22A-22C are SEM micrographs of the freestanding porous V2O5 films.
 FIG. 23 graphically illustrates the capacity of coin cell batteries having the freestanding V2O5 films as cathode materials. As illustrated in FIG. 23, the porous, 10 μm thick films have superior performance to the non-porous 10 μm thick films. However, the 2 μm films exhibit superior performance to both porous and non-porous 10 μm films. From FIG. 23, it can be determined that introducing pores into the V2O5 films improves storage capacity, although only for films of similar thickness. That is, thinner films have superior performance than thicker, yet porous, films.
Lithium Iron Phosphate/Carbon Nanocomposite Film Cathodes for High Energy Lithium Ion Batteries
 Recent increases in demand for oil, with the associated environmental sustainable issues are continuing to exert pressure on an already stretched and strained world energy infrastructure. Significant progress has been made in the development of both renewable energy harvesting and storage technologies, such as solar cells, bio-fuels, fuel cells and batteries. As one of the most promising clean technology for energy storage, lithium-ion batteries are rapidly gaining the market of batteries, and are attracting significant attention from both research and industry communities, due to its highest energy density and environmentally friendly nature. Due to the fact that the energy storage performance of lithium ion batteries is largely limited by the performance of the cathodic materials, more research has been focused on cathodic materials, such as LiCoO2, LiMn2O4 and transitional metal oxides. Since the first report by Goodenough and his co-workers in 1997 on LiFePO4 applied as cathode materials for lithium ion batteries, it has been attracting much interest both in research and industrial fields because of its high theoretical capacity of 170 mAh/g, flat voltage at ˜3.4V, and good thermal and chemical stability. Moreover it offers economic and environmental advantages being low cost and less toxic material. Goodenough and his co-workers showed the possibility of chemically removing lithium from the olivine structure of LiFePO4 thus leaving a new phase FePO4, with a subtle structural change between LiFePO4 and FePO4 leaving the 1D channels for Li+-ion motion intact.
 Since the limited electronic conductivity of LiFePO4, carbon coating, metal particles dispersion, or aliovalent cations doping have been explored to accelerate the Li+ diffusion and intercalation. For example, Huang et al. prepared LiFePO4 and conductive carbon nanocomposites with a particle size of 100-200 nm reaching 90% theoretical discharge capacity at a charge rate of C/2, and they concluded that both particle size minimization and intimate carbon contact are necessary for the optimization of electrochemical redox reaction in batteries. Sides et al. used templates to fabricate nanocomposite fibers of LiFePO4--C with the diameter of 350 nm, the unique structure allows a high capacity as 100% of the theoretical value at 3 C, and 36% at a higher discharge rate of 65 C. It was argued that the unique nanostructure improves the lithium ions diffusion in the solid state and the carbon matrix enhances the electronic conductivity. Huang et al. used 7 wt. % of polypyrrole (PPy) as the conductive additives, and electrochemically deposited Carbon coated LiFePO4 (C-LFP)/PPy composite cathodes on stainless steel substrate with a particle size of 2-5 μm. The composite cathodes demonstrated 92% of the capacity charged at 0.1 C when rapidly discharged at 10 C (within 6 min), which was attributed to the good electrical contact between carbon coated LiFePO4 and PPy, as well as between the particles and the current collector.
 In this example, LiFePO4/C nanocomposite film cathodes were fabricated through sol-gel processing followed with annealing and pyrolysis in nitrogen at elevated temperatures. Poor crystallinity, nanostructures together with uniform distribution of carbon on electrochemical performances of these nanocomposite films were characterized and discussed.
 The LiFePO4 sol was prepared from lithium hydroxide monohydrate LiOH.H2O (≧99.0%, Fluka), ferric nitrate Fe(NO3)3.9H2O (A.C.S. Reagent, Baker Analyzed) and phosphoric acid H3PO4 (A.C.S. Reagent, min. 85%, Spectrum). In order to reduce Fe3+ to Fe2+ during the preparation and form a complex with the iron ions, L-ascorbic acid C6H8O6 (≧99.0%, Sigma) was added to the solution with the molar ratios of 4:1 to the total metal (Li+ and Fe2+). Ascorbic acid also plays the role of providing carbon for the LiFePO4/C nanocomposite films after pyrolysis. The overall molar ratio of Li:Fe:P:ascorbic acid was 1:1:1:4. H3PO4 and Fe(NO3)3.9H2O were first mixed and dissolved in deionized water to form a 1 mol/l solution. LiOH.H2O was then dissolved in the above solution, followed by slowly adding C6H8O6 under constant stirring at room temperature. The obtained mixture was stirred at 60° C. for 1 hour until the solution turned into dark brownish transparent sol, which was then diluted with more deionized water from 1 mol/l to 0.01 mol/l for the film preparation. It is very crucial to follow the above sequence for the chemical reaction, so that the sol will not become unstable and form precipitations during storage at room temperature.
 The LiFePO4/C nanocomposite films were prepared by drop-casting 50 μl of 0.01 mol/l sol onto Pt coated Si wafer and they have a geometric area of approximate 0.2 cm2. The samples were then dried in ambient conditions overnight and then annealed at various temperatures (500° C., 600° C., 700° C., and 800° C.) in N2 atmosphere for 3 hours.
 The un-diluted 1 mol/l sol was poured into a Petri-dish and dried under ambient conditions for 24 hours, and then the residues were collected and ground into fine powders for thermal analysis and X-Ray Diffraction (XRD) measurement. Thermochemical properties of the LiFePO4/C composite powders were investigated by gravimetric analyzer (TGA) and differential thermal analysis (DTA) (PerkinElmer instruments) with the temperature range from room temperature to 800° C. in N2 atmosphere at a heating rate of 2° C./min. The XRD (D8 Diffractometer) method was used to detect the phase of the LiFePO4/C composite powders derived from 800° C. The scanning electron microscopy (SEM) (JEOL JSM-5200) was used to characterize the morphology of LiFePO4/C nanocomposite films after annealed at various temperatures from 500° C. to 800° C.
 Electrochemical properties of the LiFePO4/C nanocomposite films on Pt coated Si wafers were investigated using a standard three-electrode cell setup. 1 mol/l LiClO4 solution in propylene carbonate was used as the electrolyte, a Pt foil as the counter electrode and Ag/AgCl as standard reference electrode respectively. Cyclic voltammetric (CV) and chronopotentiometric measurements (CP) of the LiFePO4/C nanocomposite film cathodes were performed by using an electrochemical analyzer (CH Instruments, Model 605B).
Results and Discussion
 Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the LiFePO4/C composite powders which were heated from room temperature to 800° C. at a rate of 2° C./min in flowing nitrogen is shown in FIG. 26. About 75% weight loss is observed during the temperature sweep to 400° C., and from 400° C. to 800° C., the change of weight loss is 5%. The weight loss can be ascribed to the removal of residual solvent, dehydration, decomposition of ascorbic acid and nitrates and possibly the reduction of some remaining Fe3+ to Fe2+. It can be observed that the first three endothermic peaks between 81.7° C. and 133.4° C. are due to the removal of residual solvent and dehydration of crystalline water; while the endothermic peak at 392° C. shows the pyrolysis of ascorbic acid from the precursor.
 FIG. 27 presents XRD patterns of LiFePO4/C composite powders dried from sol at ambient condition, and then annealed at 500° C., 600° C., 700° C., and 800° C., respectively. The powders without annealing showed no detectable peaks, suggesting the amorphous nature. The patterns of powders annealed at 500° C., 600° C., 700° C., and 800° C. clearly showed the evidence of olivine LiFePO4 phase. Among all these XRD patterns, no evidence of diffraction peaks for crystalline carbon (graphite) appeared throughout the temperature range, which indicates that the carbon generated from ascorbic acid is amorphous and its presence does not have detectable influences on the crystal structure of LiFePO4. The comparison of XRD patterns also revealed that, the samples annealed at different temperatures are in the same phase, except that the peaks are gradually sharpened and intensity increases. This suggests an increase in crystallinity, ordering of olivine LiFePO4 phase, growth of grain size as well as release of lattice strain at higher annealing temperature.
 The crystallite sizes of LiFePO4 in the nano-composite powders treated at different temperatures were calculated using Scherrer's equation and the results are shown in Table 2. The crystallite sizes are below or around 20 nm in samples annealed at 500° C. to 700° C., and grow up to 30.8 nm when annealed at 800° C. The finer LiFePO4 crystallite size compared to the larger crystallite size derived from conventional solid-state synthesis can be ascribed to the sol-gel method applied in this work and the inhibition effect of crystal growth by the presence of carbon nano-coating generated from ascorbic acid intimately mixed in the LiFePO4 sol. This nanostructure with crystallite size under 20 nm could greatly enhance the phase transition during Li-ion intercalation/deintercalation due to the high surface energy, and favored kinetic processes including a short transport pathway and a high and effective contact area with electrolyte.
 Since ascorbic acid was introduced during the sol preparation as a reducing agent of the iron ions, upon gelation and pyrolysis at elevated temperatures, the carbon residues are intimately and homogeneously dispersed in the nanocomposites and might be coated onto the LiFePO4 particle surfaces. The thermal annealing effect on the particle size and morphology is evident from the SEM images (FIGS. 28A-F). It can be observed from FIG. 28 that with the increase of annealing temperature from 500° C. to 700° C., a denser film, and better crystallinity with larger particle size are derived. FIGS. 28A-B are the images under both low and high magnifications of LiFePO4/C nanocomposite films annealed at 500° C. It can be observed that small particles with loose structures are obtained at 500° C., and lower crystallinity is derived at this temperature which is in consistent with XRD results. FIGS. 28C-D show SEM pictures of 600° C. heat treated films, which composes of two distinct phases with different particle sizes. An energy-dispersive X-ray spectroscopy (EDAX) check of each phase shows that small particles are carbon phase while large particles are carbon coated LiFePO4 phase. It can also be seen from FIG. 28D that, the carbon particles are homogeneously distributed in the films and some are coated on the surface of LiFePO4 particles, which well guarantees the effective conductive network in the whole film thus improve the electrochemical performance of LiFePO4/C nanocomposite films. The surface carbon could also exist as surface defect which serves as nucleation sites to promote phase transition. The three-phase interface of LiFePO4--C-electrolyte could offer a lower nucleation activation energy, therefore the phase transition during Li-ion intercalation/deintercalation is greatly enhanced. Further increase the annealing temperature to 700° C., the morphology of films was examined and shown in FIGS. 28E-F. It can be observed that a denser film with better crystallinity and trace of carbon was attained at this temperature. It is also found that both LiFePO4 and carbon particles grow larger and show distinct crystallites morphology when the annealing temperature increases.
 A schematic (shown as FIG. 29) demonstrating the distribution and co-existence of carbon with LiFePO4 is proposed based on the XRD, SEM and EDS results discussed above. The carbon residue from ascorbic acid forms an amorphous nano-network in LiFePO4/C nanocomposite films, connecting the individual LiFePO4 particles; the carbon may also wrap around the LiFePO4 particles, and act as both nano-coating to improve the electrical conductivity and surface defect to enhance the lithium ion diffusions. There is also a possibility that porous carbon webs can reside in the interior of the particles, as reported by Chung et al. The conventional electrode process adds 15-20 wt % of conductive additives (carbon black etc.) and binder (PVdF etc.) to the active materials with particles size of micrometer scale, which often gives an inadequate contact between particles thus impedes the lithium ion from diffusing effectively in certain areas. In addition, the additives and binders bring in noticeable mass which further results in a low specific energy and power density counted for the whole electrode. In contrast to the conventional configuration, the carbon network and nanocoating introduced by sol-gel chemistry in this work guarantees a better electrical conductivity, enhanced lithium ion diffusion and higher electrochemical performance as discussed below.
 The cyclic voltammetric (CV) curves of LiFePO4/C nanocomposite film cathodes annealed at different temperatures from 500° C. to 800° C. are shown in FIGS. 30A-D, which shows distinct redox peaks for intercalation/de-intercalation of lithium ions corresponding to the two-phase charge/discharge reaction of Fe2+/Fe3+ redox couple. The anodic oxidation peak for sample that annealed at 500° C. as shown in FIG. 30A appears at -0.04V vs. Ag/Ag+ and cathodic reduction peak at -0.33V, and the peaks are -0.03V and -0.31V for sample that was treated at 600° C. For the films treated at 700° C. and 800° C., the CV curves show a wider gap between redox peaks. It was argued by Kim et al. that the smaller gap between redox peaks is more efficient for redox reactions. It is likely that the LiFePO4/C nanocomposite films annealed at 600° C. has more desirable crystallinity as well as nano and micro structure that facilitates redox reactions at the interface and affects the kinetics of transport processes. This result is in consistent with the chronopotentiometric results analyzed in the next paragraphs.
 The charge-discharge performances of LiFePO4/C nanocomposite film cathodes derived at different temperatures (500-800° C.) at 200 mA/g are summarized and compared in FIG. 31. The film annealed at 600° C. shows better capacity and cycle stability, as it delivers higher discharge capacity as 312 mAh/g for the initial cycle, and stays 218 mAh/g after 20 cycles. This prominent electrochemical property of LiFePO4/C nanocomposite films treated at 600° C. could be explained by the SEM pictures (FIGS. 28C-D) and XRD results (FIG. 27 and Table 2): the poor crystalline LiFePO4 phase is less compact and more disordering in comparison with well crystallized phase, thus it provides a more flexible structure which could accommodate more lithium ions and facilitate the diffusion within this structure. The LiFePO4 nanocrystallites below 20 nm could also favor the kinetics of phase transition during Li-ion intercalation/deintercalation. Moreover the carbon residing on the surface of LiFePO4 particles could perform as surface defect and buffer material, thereby enhancing the electrochemical capacity and improving cyclic stability.
TABLE-US-00002 TABLE 2 Crystallite size of LiFePO4/C composite powders treated at various temperatures calculated using Scherrer's equation. Temperature(° C.) Crystallite Size (nm) 500 16.1 600 19.4 700 21.1 800 30.8
 For the film annealed at 500° C., the initial discharge capacity is similarly high as 600° C. sample, which could be ascribed to the amorphous LiFePO4 phase with carbon surface coating that exists in this low temperature treated sample. However a drastic drop of the discharge capacity and poor cyclic performance are detected in this 500° C. film, which shows 139 mAh/g after 13 cycles. This poor cyclic property could be due to the loosely packed microstructure annealed at low temperatures; with increased cycles, the structure may experience irreversible change or loose contact with current collector--similar observations in samples annealed at low temperatures are often found in literature.
 The initial discharge capacities for 700° C. and 800° C. films are 228 mAh/g and 120 mAh/g, which decrease to 148 mAh/g and 99 mAh/g after 20 cycles. The SEM pictures (FIGS. 28E-F) and XRD patterns (FIG. 27) show that more compact and well crystallized structures are obtained in higher temperature annealed films, which gives less freedom and open space for lithium ion diffusion, thus lower discharge capacities are measured from this research. The poorer electrochemical performances at higher annealing temperatures could also be ascribed to the enlarged particle size with the increase of temperature. Since charge transfer resistance is related to the difference of particle size. A decrease in particle size will decrease the polarization associated with electronic and/or ionic resistance, thus improve the reversible capacity. The larger particles present as transport limitation both for lithium ions and electron diffusion, which results in capacity loss.
 The charge-discharge performance at different charging rate of LiFePO4/C nanocomposite film cathodes annealed at 600° C. is shown in FIG. 32. In this experiment, we conducted the intercalation and deintercalation at the same rate for a specific sample and all samples were measured between -1.6 V˜1.0 V (Vs Ag/Ag+). The as-prepared LiFePO4/C nanocomposite film cathodes demonstrate a high initial specific discharge capacity of 327 mAh/g at the current density of 100 mA/g (0.6 C). When the current density is 200 mA/g (1.2 C), the initial capacity is 312 mAh/g, and the initial capacities show 171 mAh/g and 139 mAh/g at higher rate of 300 mA/g (1.8 C) and 500 mA/g (3 C) respectively. This high discharge capacity at a high rate could be ascribed to the surface defect and enhanced electronic conductivity due to the carbon nano-coating at the LiFePO4 particle surface. This carbon coating can well provide a better connecting network for electron diffusion. Moreover the shortened transportation path as well as the enhanced phase transition kinetics of lithium ion intercalation/de-intercalation could be ascribed to the nanoscaled structure.
 The sol-gel derived LiFePO4/C nanocomposite film cathodes demonstrated a discharge capacity of over 300 mAh/g, exceeding the theoretical value of 170 mAh/g reported in literature. FIG. 33 presents the first charge and discharge curve at a rate of 200 mA/g, and it could be observed that the charge capacity of the first cycle is 167 mAh/g, which almost equals theoretical value of well crystallized bulk LiFePO4, indicating that the initial sol-gel derived LiFePO4/C nanocomposite films consist of stoichiometric chemical composition with an atomic ratio of Li+:Fe2+:PO43+=1:1:1 as it was designed in the sol processing and sample preparation. This result is in good agreement with the XRD patterns as shown in FIG. 27, and it also validates that during the first charge step, all the Li+ ions extracted from the LiFePO4/C nanocomposite films, as was measured to be 168 mAh/g in capacity. However at the subsequent discharge process, a capacity of 312 mAh/g was measured, which shows that the amount of Li ions that intercalate into the film exceeds the theoretical value for a stoichiometric crystalline LiFePO4. Although there is a gradual degradation of the electrochemical performances with increase cycles, the capacity of LiFePO4/C nanocomposite films stays above the theoretical limit within the number of cycles conducted in this study. The lack of well-defined plateau for the discharge curve in FIG. 33 in comparison with other work on LiFePO4 could also be an indication of the poor crystallinity at high discharge rate of 1.2 C. This experimental result has shown its reproducibility and all the measurements conditions are carefully verified.
 The exact explanation for such a high lithium ion intercalation capacity is not known and a number of experiments are underway to get insights for a fundamental understanding, however, capacities higher than theoretical limit observed in other nanostructured electrode materials have also been reported in literatures by other authors. For example, it has been observed that the VOTPP-based VOR nanotubes exhibited remarkable charge capacities of 437 mAh/g, which exceeds the reported theoretical value of 240 mAh/g, and they believe that it is the increased volumetric density of nanotubes for ion intercalation and shorter diffusion paths which provide better freedom for dimensional change that occurs during intercalation and de-intercalation reactions. Some have fabricated TiO2-graphne hybrid nanostructured materials and tested them as anode materials for Li-ion batteries. It was observed high Li-ion intercalation capacities of ˜200 mAh/g at C/5 for rutile TiO2-0.5 wt % graphene, and ˜200 mAh/g at 1 C for rutile TiO2-10 wt % graphene hybrid materials during the first 10 cycles, which exceeds the theoretical capacity of 168 mAh/g for bulk rutile TiO2 materials. They believed that the high intercalation properties and enhanced kinetics in TiO2-graphene hybrid materials can be attributed to the improved conductivity with the incorporation of highly conducting graphene, and this self-assembled hybrid materials are more effective compared with the conventional electrodes fabricated with conductive additives and binders. Some have observed high Li-ion storage capability, high rate performance and cyclability in nanometer-sized rutile TiO2 electrode, with ˜378 mAh/g of Li-ion intercalation capacity for the initial cycle, which is corresponding to more than 1 Li+ being inserted into TiO2. For rutile TiO2, Li-ion diffusion occurs mainly through c channels and the sluggish Li diffusion in the a-b planes is the bottleneck for further Li-ion insertion. It is believed that the limit of Li-ion diffusion in a-b planes was weakened in nanometer-sized rutile TiO2, which means that more thermodynamically stable octahedral sites in a-b planes can be reached by Li ions, providing more pronounced intercalation sites for Li-ions. It has been reported that the mesoporous hydrous manganese dioxide nanowall arrays achieved a stable high intercalation capacity of 256 mAh/g, exceeding the theoretical limit of 150 mAh/g for manganese dioxide bulk film. They argued that such high capacity is ascribed to the hierarchically structured macro- and mesoporosity of MnO2.0.5H2O nanowall arrays, which provides a large surface to volume ratio favoring interface Faradaic reactions, short solid-state diffusion paths, and freedom to permit volume change during lithium ion intercalation and de-intercalation. Based on quantum theory, It has been proposed that there is no noticeable net charge change of the oxidation state of a transition metal in a crystal lattice changes associated with lithium ion intercalation, and instead the intercalation is due to the change of hybridization as a result of the change of its energy level relative to the surrounding atoms (e.g., oxygen in transition metal oxides). Therefore the irrelevant relationship between static charges of transition metal and its oxidation status change upon removal or addition of electrons could bring a re-examination of the theoretical capacity value to electrode materials for lithium ion batteries. The excellent performance of the sol-gel derived LiFePO4/C nanocomposite cathode films observed in this study may be attributed to the relatively poor crystallinity of LiFePO4 nanocrystallites offering more available sites for Li-ion intercalations, as well as the intimate contact of carbon to LiFePO4 crystallites, serving as both surface defects and electronic conductive coatings and networks, which effectively enhances the conductivity of composite film electrodes. This unique nanocomposite structure could result in an enhanced electrochemical performance with much improved transport properties and storage capacity through facilitating the phase transition during Li-ion intercalation/deintercalation processes.
 LiFePO4/carbon nanocomposite film cathodes are readily fabricated by sol-gel processing with excessive polymer additive followed with annealing and pyrolysis in an inert gas at elevated temperatures for lithium ion batteries, with carbon serving as both defects and conductive nanocoating on the surface of LiFePO4 particles. Crystal, nano and microstructure of the LiFePO4/C nanocomposite films can be tuned through controlling the subsequent annealing process. High electrochemical performance with initial discharge capacity of 312 mAh/g and good cyclic stability (218 mAh/g after 20 cycles) were observed for LiFePO4/C nanocomposite film cathodes annealed at 600° C. when tested within 1.0 V˜-1.6 V (Vs. Ag+/Ag). The exceptionally high electrochemical performances could be ascribed to the LiFePO4 nanocrystallites with large surface to volume ratio and possible surface defects, and the relatively poor crystallinity which provides a less packed structure to accommodate more lithium ions. Furthermore, the carbon surface defects and conductive
 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.
Patent applications by Guozhong Cao, Seattle, WA US
Patent applications by UNIVERSITY OF WASHINGTON through its Center for Commercialization
Patent applications in class Vanadium (V), chromium (Cr), niobium (Nb), molybdenum (Mo), titanium (Ti), or tungsten (W) component is active material
Patent applications in all subclasses Vanadium (V), chromium (Cr), niobium (Nb), molybdenum (Mo), titanium (Ti), or tungsten (W) component is active material