Patent Publication Number: US-7722787-B2

Title: Metal vanadium oxide particles

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation of commonly assigned U.S. patent application Ser. No. 09/246,076, filed Feb. 5, 1999, now U.S. Pat. No. 6,225,007 to Horne et al., entitled “Metal Vanadium Oxide Particles,” incorporated herein by reference. 
    
    
     FIELD OF THE INVENTION 
     The invention relates to particles of metal vanadium oxide compositions. In particular, the invention relates to nanoscale metal vanadium oxide particles, such as silver vanadium oxide particles, and corresponding methods for producing nanoscale metal vanadium oxide particles. 
     BACKGROUND OF THE INVENTION 
     Lithium based batteries have become commercially successful due to their relatively high energy density. Suitable positive electrode materials for lithium based batteries include materials that can intercalate lithium atoms into their lattice. The negative electrode can be lithium metal, lithium alloys or compounds that can reversibly intercalate lithium atoms into their lattice. Batteries formed from lithium metal or lithium alloy negative electrodes are referred to as lithium batteries while batteries formed with an anode (negative electrode) active material that can intercalate lithium ions are referred to as lithium ion batteries. 
     In order to produce improved batteries, various materials have been examined for use as cathode (positive electrode) active materials for lithium based batteries. A variety of materials, generally chalgogenides, are useful in lithium based batteries. For example, vanadium oxides in certain oxidation states are effective materials for the production of positive electrodes for lithium based batteries. Also, metal vanadium oxide compositions have been identified as having high energy densities and high power densities, when used in positive electrodes for lithium based batteries. Silver vanadium oxide has a particularly high energy density and high power densities, when used in lithium based batteries. Silver vanadium oxide batteries have found particular use in the production of implantable cardiac defribulators where the battery must be able to recharge a capacitor to deliver large pulses of energy in rapid succession, within ten seconds or less. 
     SUMMARY OF THE INVENTION 
     In a first aspect, the invention pertains to a collection of particles comprising metal vanadium oxide, the particles having an average diameter less than about 500 nm. 
     In another aspect, the invention pertains to a method of producing particles of metal vanadium oxide comprising heating a mixture of vanadium oxide particles with a non-vanadium metal compound, the vanadium oxide particles having an average diameter less than about 500 nm. 
     In a further aspect, the invention pertains to a battery comprising a positive electrode having active particles comprising metal vanadium oxide within a binder, the active particles having an average diameter less than about 500 nm. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic, sectional view of an embodiment of a laser pyrolysis apparatus, where the cross section is taken through the middle of the laser radiation path. The upper insert is a bottom view of the collection nozzle, and the lower insert is a top view of the delivery nozzle. 
         FIG. 2  is a schematic view of a reactant delivery apparatus for the delivery of vapor reactants to the laser pyrolysis apparatus of  FIG. 1 . 
         FIG. 3  is schematic, side view of a reactant delivery apparatus for the delivery of an aerosol reactant to the laser pyrolysis apparatus of  FIG. 1 . 
         FIG. 4  is a schematic, perspective view of an elongated reaction chamber for the performance of laser pyrolysis, where components of the reaction chamber are shown as transparent to reveal internal structure. 
         FIG. 5  is a sectional view of the reaction chamber of  FIG. 4  taken along line  5 - 5 . 
         FIG. 6  is a schematic, sectional view of an apparatus for heat treating nanoparticles, in which the section is taken through the center of the apparatus. 
         FIG. 7  is a schematic, sectional view of an oven for reacting nanoparticles under heat, in which the section is taken through the middle of the oven. 
         FIG. 8  is a schematic, perspective view of an embodiment of a battery of the invention. 
         FIG. 9  is an x-ray diffractogram of crystalline VO 2  nanoparticles. 
         FIG. 10  is an x-ray diffractogram of crystalline V 2 O 5  nanoparticles produced by heat treating nanoparticles of crystalline VO 2 . 
         FIG. 11  is a transmission electron microscope view of crystalline V 2 O 5  nanoparticles. 
         FIG. 12  is a plot depicting the distribution of particle sizes for the crystalline V 2 O 5  nanoparticles depicted in  FIG. 11 . 
         FIG. 13  is a plot of four x-ray diffractograms of silver vanadium oxide produced by heat treating nanocrystalline V 2 O 5  with silver nitrate in an oxygen atmosphere, where each diffractogram was produced with materials formed under different conditions. 
         FIG. 14  is a plot of three x-ray diffractograms of silver vanadium oxide produced by heat treating nanocrystalline V 2 O 5  with silver nitrate in an argon atmosphere, where each diffractogram was produced with materials formed under different conditions. 
         FIG. 15  is a transmission electron microscope view of silver vanadium oxide nanoparticles. 
         FIG. 16  is a transmission electron microscope view of the V 2 O 5  nanoparticle samples used to produce the silver vanadium oxide particles shown in  FIG. 15 . 
     
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Vanadium oxide nanoparticles can be used to form metal vanadium oxide nanoparticles, such as silver vanadium oxide nanoparticles. Vanadium oxide nanoparticles with various stoichiometries and crystal structures can be produced by laser pyrolysis alone or with additional processing. These various forms of vanadium oxide nanoparticles can be used as starting materials for the formation of metal vanadium oxide nanoparticles. The nanoparticles are formed by mixing the vanadium oxide nanoparticles with a compound of the metal to be introduced into the vanadium oxide to form a material with both metals in the lattice. By using appropriately selected processing conditions, the particles incorporating both metals can be formed without losing the nanoscale character of the initial vanadium oxide nanoparticles. 
     Preferred collections of metal vanadium oxide particles have an average diameter less than a micron and a very narrow distribution of particle diameters. In particular, the distribution of particle diameters preferably does not have a tail. In other words, there are effectively no particles with a diameter an order of magnitude greater than the average diameter such that the particle size distribution rapidly drops to zero. 
     To generate vanadium oxide nanoparticle starting materials for further processing into metal vanadium oxides, laser pyrolysis is used either alone or in combination with additional processing. Specifically, laser pyrolysis has been found to be an excellent process for efficiently producing vanadium oxide nanoparticles with a narrow distribution of average particle diameters. In addition, nanoscale vanadium oxide particles produced by laser pyrolysis can be subjected to heating under mild conditions in an oxygen environment or an inert environment to alter the crystal properties of the vanadium oxide particles without destroying the nanoparticle size. The stoichiometry and crystal structure of the vanadium oxide nanoparticles produced by laser pyrolysis can be modified by heat processing in an oven. Thus, a variety of different types of vanadium oxide based nanoparticles can be produced. 
     A basic feature of successful application of laser pyrolysis for the production of vanadium oxide nanoparticles is production of a reactant stream containing a vanadium precursor, a radiation absorber and an oxygen source. The reactant stream is pyrolyzed by an intense light beam, such as a laser beam. The laser pyrolysis provides for formation of phases of materials that are difficult to form under thermodynamic equilibrium conditions. As the reactant stream leaves the light beam, the vanadium oxide particles are rapidly quenched. 
     The metal vanadium oxide particles are formed by a thermal process. A second metal precursor comprises a non-vanadium transition metal. Preferred second metal precursors include compositions with copper, silver or gold. The second metal precursor compound is mixed with a collection of vanadium oxide nanoparticles and heated to form the particles incorporating both metals. Under suitably mild conditions, the heat processing is effective to produce the particles while not destroying the nanoscale of the initial vanadium oxide particles. 
     As noted above, lithium atoms and/or ions can intercalate into various forms of vanadium oxide and metal vanadium oxide particles. To form a positive electrode, which acts as a cathode upon discharge of the cell, the metal vanadium oxide nanoparticles can be incorporated into a film with a binder such as a polymer. The film preferably incorporates additional electrically conductive particles held by a binder along with the metal vanadium oxide particles. The film can be used as a positive electrode in a lithium battery or a lithium ion battery. 
     A. Vanadium Oxide Nanoparticle Production 
     Laser pyrolysis has been discovered to be a valuable tool for the production of nanoscale vanadium oxide particles. In addition, the particles produced by laser pyrolysis are a convenient material for further processing to expand the pathways for the production of desirable vanadium oxide particles. Thus, using laser pyrolysis alone or in combination with additional processes, a wide variety of vanadium oxide particles can be produced. 
     The reaction conditions determine the qualities of the particles produced by laser pyrolysis. The reaction conditions for laser pyrolysis can be controlled relatively precisely in order to produce particles with desired properties. The appropriate reaction conditions to produce a certain type of particles generally depend on the design of the particular apparatus. Specific conditions used to produce vanadium oxide particles in a particular apparatus are described below in the Examples. Additional information on the production of vanadium oxide nanoparticles by laser pyrolysis is provided in copending and commonly assigned U.S. patent application Ser. No. 08/897,778 to Bi et al. now U.S. Pat. No. 6,106,798, entitled “Vanadium Oxide Nanoparticles,” incorporated herein by reference. Furthermore, some general observations on the relationship between reaction conditions and the resulting particles can be made. 
     Increasing the laser power results in increased reaction temperatures in the reaction region as well as a faster quenching rate. A rapid quenching rate tends to favor production of high energy phases, which may not be obtained with processes near thermal equilibrium. Similarly, increasing the chamber pressure also tends to favor the production of higher energy structures. Also, increasing the concentration of the reactant serving as the oxygen source in the reactant stream favors the production of particles with increased amounts of oxygen. 
     Reactant flow rate and velocity of the reactant gas stream are inversely related to particle size so that increasing the reactant gas flow rate or velocity tends to result in smaller particle size. Also, the growth dynamics of the particles have a significant influence on the size of the resulting particles. In other words, different forms of a product compound have a tendency to form different size particles from other phases under relatively similar conditions. Laser power also influences particle size with increased laser power favoring larger particle formation for lower melting materials and smaller particle formation for higher melting materials. 
     Laser pyrolysis has been performed generally with gas phase reactants. The use of exclusively gas phase reactants is somewhat limiting with respect to the types of precursor compounds that can be used. Thus, techniques have been developed to introduce aerosols containing reactant precursors into laser pyrolysis chambers. The aerosol atomizers can be broadly classified as ultrasonic atomizers, which use an ultrasonic transducer to form the aerosol, or as mechanical atomizers, which use energy from one or more flowing fluids (liquids, gases, or supercritical fluids) themselves to form the aerosol. Improved aerosol delivery apparatuses for reactant systems are described further in copending and commonly assigned U.S. patent application Ser. No. 09/188,670, now U.S. Pat. No. 6,193,936, filed on Nov. 9, 1998, entitled “Reactant Delivery Apparatuses,” incorporated herein by reference. 
     Using aerosol delivery apparatuses, solid precursor compounds can be delivered by dissolving the compounds in a solvent. Alternatively, powdered precursor compounds can be dispersed in a liquid\solvent for aerosol delivery. Liquid precursor compounds can be delivered as an aerosol from a neat liquid, a liquid/gas mixture, liquid mixtures or a liquid solution, if desired. Aerosol reactants can be used to obtain significant reactant throughput. The solvent, if any, can be selected to achieve desired properties of the solution. Suitable solvents include water, methanol, ethanol and other organic solvents. The solvent should have a desired level of purity such that the resulting particles have a desired purity level. 
     If the aerosol precursors are formed with a solvent present, the solvent is rapidly evaporated by the laser beam in the reaction chamber such that a gas phase reaction can take place. Thus, the fundamental features of the laser pyrolysis reaction are unchanged. However, the reaction conditions are affected by the presence of the aerosol. Suitable conditions for the formation of manganese oxide nanoparticles by laser pyrolysis with aerosol precursors is described in copending and commonly assigned U.S. patent application Ser. No. 09/188,770, filed on Nov. 9, 1998, now U.S. Pat. No. 6,506,493, entitled “Metal Oxide Particles,” incorporated herein by reference. Suitable vanadium precursors for aerosol production include, for example, vanadium trichloride (VCl 3 ), vanadyl chloride (VOCl), and vanadyl dichloride (VOCl 2 ), which is soluble in absolute alcohol. 
     The compounds are dissolved in a solution preferably with a concentration greater than about 0.5 molar. Generally, the greater the concentration of precursor in the solution the greater the throughput of reactant through the reaction chamber. As the concentration increases, however, the solution can become more viscous such that the aerosol has droplets with larger sizes than desired. Thus, selection of solution concentration can involve a balance of factors in the selection of a preferred solution concentration. 
     Appropriate vanadium precursor compounds for vapor delivery generally include vanadium compounds with reasonable vapor pressures, i.e., vapor pressures sufficient to get desired amounts of precursor vapor in the reactant stream. The vessel holding the precursor compounds can be heated to increase the vapor pressure of the vanadium precursor, if desired. Suitable vanadium precursors include, for example, VCl 4 , VCCl, V(CO) 6  and VOCl 3 . The chlorine in these representative precursor compounds can be replaced with other halogens, e.g., Br, I and F. 
     Preferred secondary reactants serving as oxygen source include, for example, O 2 , CO, CO 2 , O 3  and mixtures thereof. The secondary reactant compound should not react significantly with the vanadium precursor prior to entering the reaction zone since this generally would result in the formation of large particles. 
     Laser pyrolysis can be performed with a variety of optical light frequencies. Preferred light sources include lasers, especially lasers that operate in the infrared portion of the electromagnetic spectrum. CO 2  lasers are particularly preferred sources of light. Infrared absorbers for inclusion in the molecular stream include, for example, C 2 H 4 , NH 3 , SF 6 , SiH 4  and O 3 . O 3  can act as both an infrared absorber and as an oxygen source. Alternatively, a solvent, such as isopropyl alcohol, in a liquid delivered by aerosol can absorb light from the light beam. The radiation absorber, such as the infrared absorber, absorbs energy from the radiation beam and distributes the energy to the other reactants to drive the pyrolysis. 
     Preferably, the energy absorbed from the radiation beam increases the temperature at a tremendous rate, many times the rate that energy generally would be produced even by strongly exothermic reactions under controlled condition. While the process generally involves nonequilibrium conditions, the temperature can be described approximately based on the heat in the absorbing region. The laser pyrolysis process is qualitatively different from the process in a combustion reactor where an energy source initiates a reaction, but the reaction is driven by energy given off by an exothermic reaction. 
     An inert shielding gas can be used to reduce the amount of reactant and product molecules contacting the reactant chamber components. Appropriate shielding gases include, for example, Ar, He and N 2 . Inert gas can also be mixed with the reactant stream to moderate the reaction. 
     An appropriate laser pyrolysis apparatus generally includes a reaction chamber isolated from the ambient environment. A reactant inlet connected to a reactant supply system produces a reactant stream through the reaction chamber. A light beam path intersects the reactant stream at a reaction zone. The reactant stream continues after the reaction zone to an outlet, where the reactant stream exits the reaction chamber and passes into a collection system. Generally, the light source is located external to the reaction chamber, and the light beam enters the reaction chamber through an appropriate window. 
     Referring to  FIG. 1 , a particular embodiment  100  of a laser pyrolysis apparatus involves a reactant supply system  102 , reaction chamber  104 , collection system  106 , light source  108  and shielding gas delivery system  110 . Two alternative reaction supply systems can be used with the apparatus of  FIG. 1 . The first reaction supply system is used to deliver exclusively gaseous reactants. The second reactant supply system is used to deliver one or more reactants as an aerosol. Variations on these reaction supply systems can also be used. 
     Referring to  FIG. 2 , a first embodiment  112  of reactant supply system  102  includes a source  120  of precursor compound. For liquid or solid precursors, a carrier gas from carrier gas source  122  can be introduced into precursor source  120  to facilitate delivery of the precursor as a vapor. The carrier gas from source  122  preferably is either an infrared absorber or an inert gas and is preferably bubbled through a liquid precursor compound or delivered into a solid precursor delivery system. Inert gas used as a carrier gas can moderate the reaction conditions. The quantity of precursor vapor in the reaction zone is roughly proportional to the flow rate of the carrier gas. 
     Alternatively, carrier gas can be supplied directly from infrared absorber source  124  or inert gas source  126 , as appropriate. The secondary reactant is supplied from reactant source  128 , which can be a gas cylinder or other suitable container. The gases from the precursor source  120  are mixed with gases from reactant source  128 , infrared absorber source  124  and inert gas source  126  by combining the gases in a single portion of tubing  130 . The gases are combined a sufficient distance from reaction chamber  104  such that the gases become well mixed prior to their entrance into reaction chamber  104 . 
     The combined gas in tube  130  passes through a duct  132  into rectangular channel  134 , which forms part of an injection nozzle for directing reactants into the reaction chamber. Portions of reactant supply system  112  can be heated to inhibit the deposition of precursor compound on the walls of the delivery system. 
     Flow from sources  122 ,  124 ,  126  and  128  are preferably independently controlled by mass flow controllers  136 . Mass flow controllers  136  preferably provide a controlled flow rate from each respective source. Suitable mass flow controllers include, for example, Edwards Mass Flow Controller, Model 825 series, from Edwards High Vacuum International, Wilmington, Mass. 
     Referring to  FIG. 3 , an alternative embodiment  150  of the reactant supply system  102  is used to supply an aerosol to channel  134 . Channel  134  forms part of an injection nozzle for directing reactants into the reaction chamber and terminates at the reactant inlet. Reactant supply system  150  includes an aerosol generator  152 , carrier gas supply tube  154  and junction  156 . Channel  134 , aerosol generator  152  and carrier gas supply tube  154  meet within interior  158  within junction  156 . Carrier gas supply tube  154  is oriented to direct carrier gas along channel  134 . 
     Aerosol generator  152  is mounted such that an aerosol  160  is generated in the volume of chamber  158  between the opening into channel  134  and the outlet from supply tube  154 . In a preferred embodiment, aerosol generator  152  generates an aerosol with momentum roughly orthogonal to the carrier gas flow from tube  154  to channel  134 . Thus, carrier gas from supply tube  154  directs aerosol precursor generated by aerosol generator  152  into channel  134 . 
     Aerosol generator  152  can operate based on a variety of principles. For example, the aerosol can be produced with an ultrasonic nozzle, with an electrostatic spray system, with a pressure-flow or simplex atomizer, with an effervescent atomizer or with a gas atomizer where liquid is forced under significant pressure through a small orifice and fractured into particles by a colliding gas stream. Suitable ultrasonic nozzles can include piezoelectric transducers. Ultrasonic nozzles with piezoelectric transducers and suitable broadband ultrasonic generators are available from Sono-Tek Corporation, Milton, N.Y., such as model 8700-120. Suitable aerosol generators are described further in copending and commonly assigned, U.S. patent application Ser. No. 09/188,670, now U.S. Pat. No. 6,193,936 to Gardner et al., entitled “REACTANT DELIVERY APPARATUSES,” incorporated herein by reference. Additional aerosol generators can be attached to junction  156  through other ports  162  such that additional aerosols can be generated in interior  158  for delivery into the reaction chamber. 
     Junction  156  includes ports  162  to provide access from outside junction  156  to interior  158 . Thus, channel  134 , aerosol generator  152  and tube  154  can be mounted appropriately. In one embodiment, junction  156  is cubic with six cylindrical ports  162 , with one port  162  extending from each face of junction  156 . Junction  156  can be made from stainless steel or other durable, noncorrosive material. A window  161  preferably is sealed at one port  162  to provide for visual observation into interior  158 . The port  162  extending from the bottom of junction  156  preferably includes a drain  163 , such that condensed aerosol that is not delivered through channel  134  can be removed from junction  156 . 
     Carrier gas supply tube  154  is connected to gas source  164 . Gas source  164  can include a plurality of gas containers that are connected to deliver a selected gas or gas mixture to supply tube  154 . Thus, carrier gas supply tube  154  can be used to deliver a variety of gases desired within the reactant stream including, for example, laser absorbing gases, reactants, and/or inert gases. The flow of gas from gas source  164  to supply tube  154  is controlled by one or more mass flow controllers  166 . Liquid supply tube  168  is connected to aerosol generator  152 . Liquid supply tube  168  is connected to liquid supply  170 . 
     In operation, carrier gas flow directs the aerosol delivered within chamber  158  into channel  134 . In this way, the delivery velocity of the aerosol is determined by the flow rate of the carrier gas. In alternative embodiments, the aerosol generator is placed at an upward angle relative to the horizontal, such that a component of the forward momentum of the aerosol is directed along channel  134 . In a preferred embodiment, the output directed from the aerosol generator is placed at about a 45° angle relative to the normal direction defined by the opening into channel  134 , i.e. the direction of the flow into channel  134  from supply tube  154 . 
     Referring to  FIG. 1 , shielding gas delivery system  110  includes inert gas source  190  connected to an inert gas duct  192 . Inert gas duct  192  flows into annular channel  194 . A mass flow controller  196  regulates the flow of inert gas into inert gas duct  192 . If reactant delivery system  112  is used, inert gas source  126  can also function as the inert gas source for duct  192 , if desired. 
     The reaction chamber  104  includes a main chamber  200 . Reactant supply system  102  connects to the main chamber  200  at injection nozzle  202 . Reaction chamber  104  can be heated to keep the precursor compound in the vapor state. Similarly, the argon shielding gas preferably can be heated. The chamber can be examined for condensation to ensure that precursor is not deposited in the chamber. 
     The end of injection nozzle  202  has an annular opening  204  for the passage of inert shielding gas, and a reactant inlet  206  for the passage of reactants to form a reactant stream in the reaction chamber. Reactant inlet  206  preferably is a slit, as shown in  FIG. 1 . Annular opening  204  has, for example, a diameter of about 1.5 inches and a width along the radial direction from about ⅛ in to about 1/16 in. The flow of shielding gas through annular opening  204  helps to prevent the spread of the reactant gases and product particles throughout reaction chamber  104 . 
     Tubular sections  208 ,  210  are located on either side of injection nozzle  202 . Tubular sections  208 ,  210  include ZnSe windows  212 ,  214 , respectively. Windows  212 ,  214  are about 1 inch in diameter. Windows  212 ,  214  are preferably cylindrical lenses with a focal length equal to the distance between the center of the chamber to the surface of the lens to focus the beam to a point just below the center of the nozzle opening. Windows  212 ,  214  preferably have an antireflective coating. Appropriate ZnSe lenses are available from Janos Technology, Townshend, Vt. Tubular sections  208 ,  210  provide for the displacement of windows  212 ,  214  away from main chamber  200  such that windows  212 ,  214  are less likely to be contaminated by reactants and/or products. Window  212 ,  214  are displaced, for example, about 3 cm from the edge of the main chamber  200 . 
     Windows  212 ,  214  are sealed with a rubber o-ring to tubular sections  208 ,  210  to prevent the flow of ambient air into reaction chamber  104 . Tubular inlets  216 ,  218  provide for the flow of shielding gas into tubular sections  208 ,  210  to reduce the contamination of windows  212 ,  214 . Tubular inlets  216 ,  218  are connected to inert gas source  138  or to a separate inert gas source. In either case, flow to inlets  216 ,  218  preferably is controlled by a mass flow controller  220 . 
     Light source  108  is aligned to generate a light beam  222  that enters window  212  and exits window  214 . Windows  212 ,  214  define a light path through main chamber  200  intersecting the flow of reactants at reaction zone  224 . After exiting window  214 , light beam  222  strikes power meter  226 , which also acts as a beam dump. An appropriate power meter is available from Coherent Inc., Santa Clara, Calif. Light source  108  preferably is a laser, although it can be an intense conventional light source such as an arc lamp. Preferably, light source  108  is an infrared laser, especially a CW CO 2  laser such as an 1800 watt maximum power output laser available from PRC Corp., Landing, N.J. 
     Reactants passing through reactant inlet  206  in injection nozzle  202  initiate a reactant stream. The reactant stream passes through reaction zone  224 , where reaction involving the vanadium precursor compound takes place. Heating of the gases in reaction zone  224  generally is extremely rapid, roughly on the order of 10 5  degree C./sec depending on the specific conditions. The reaction is rapidly quenched upon leaving reaction zone  224 , and particles  228  are formed in the reactant stream. The nonequilibrium nature of the process allows for the production of nanoparticles with a highly uniform size distribution and structural homogeneity. 
     The path of the reactant/product stream continues to collection nozzle  230 . Collection nozzle  230  is spaced about 2 cm from injection nozzle  202 . The small spacing between injection nozzle  202  and collection nozzle  230  helps reduce the contamination of reaction chamber  104  with reactants and products. Collection nozzle  230  has a circular opening  232 . Circular opening  232  feeds into collection system  106 . 
     The chamber pressure is monitored with a pressure gauge attached to the main chamber. The preferred chamber pressure for the production of the desired oxides generally ranges from about 80 Torr to about 500 Torr. 
     Reaction chamber  104  has two additional tubular sections not shown. One of the additional tubular sections projects into the plane of the sectional view in  FIG. 1 , and the second additional tubular section projects out of the plane of the sectional view in  FIG. 1 . When viewed from above, the four tubular sections are distributed roughly, symmetrically around the center of the chamber. These additional tubular sections have windows for observing the inside of the chamber. In this configuration of the apparatus, the two additional tubular sections are not used to facilitate production of particles. 
     Collection system  106  preferably includes a curved channel  270  leading from collection nozzle  230 . Because of the small size of the particles, the product particles follow the flow of the gas around curves. Collection system  106  includes a filter  272  within the gas flow to collect the product particles. Due to curved section  270 , the filter is not supported directly above the chamber. A variety of materials such as Teflon, glass fibers and the like can be used for the filter as long as the material is inert and has a fine enough mesh to trap the particles. Preferred materials for the filter include, for example, a glass fiber filter from ACE Glass Inc., Vineland, N.J. and cylindrical Nomex® fiber filters from AF Equipment Co., Sunnyvale, Calif. 
     Pump  274  is used to maintain collection system  106  at a selected pressure. A variety of different pumps can be used. Appropriate pumps for use as pump  274  include, for example, Busch Model B0024 pump from Busch, Inc., Virginia Beach, Va. with a pumping capacity of about 25 cubic feet per minute (cfm) and Leybold Model SV300 pump from Leybold Vacuum Products, Export, Pa. with a pumping capacity of about 195 cfm. It may be desirable to flow the exhaust of the pump through a scrubber  276  to remove any remaining reactive chemicals before venting into the atmosphere. The entire apparatus  100  can be placed in a fume hood for ventilation purposes and for safety considerations. Generally, the laser remains outside of the fume hood because of its large size. 
     The apparatus is controlled by a computer. Generally, the computer controls the laser and monitors the pressure in the reaction chamber. The computer can be used to control the flow of reactants and/or the shielding gas. The pumping rate is controlled by either a manual needle valve or an automatic throttle valve inserted between pump  274  and filter  272 . As the chamber pressure increases due to the accumulation of particles on filter  272 , the manual valve or the throttle valve can be adjusted to maintain the pumping rate and the corresponding chamber pressure. 
     The reaction can be continued until sufficient particles are collected on filter  272  such that the pump can no longer maintain the desired pressure in the reaction chamber  104  against the resistance through filter  272 . When the pressure in reaction chamber  104  can no longer be maintained at the desired value, the reaction is stopped, and filter  272  is removed. With this embodiment, about 1-300 grams of particles can be collected in a single run before the chamber pressure can no longer be maintained. A single run generally can last up to about 10 hours depending on the type of particle being produced and the type of filter being used. 
     The reaction conditions can be controlled relatively precisely. The mass flow controllers are quite accurate. The laser generally has about 0.5 percent power stability. With either a manual control or a throttle valve, the chamber pressure can be controlled to within about 1 percent. 
     The configuration of the reactant supply system  102  and the collection system  106  can be reversed. In this alternative configuration, the reactants are supplied from the top of the reaction chamber, and the product particles are collected from the bottom of the chamber. In this configuration, the collection system may not include a curved section so that the collection filter is mounted directly below the reaction chamber. 
     An alternative design of a laser pyrolysis apparatus has been described in copending and commonly assigned U.S. patent application Ser. No. 08/808,850 now U.S. Pat. No. 5,958,348, entitled “Efficient Production of Particles by Chemical Reaction,” incorporated herein by reference. This alternative design is intended to facilitate production of commercial quantities of particles by laser pyrolysis. The reaction chamber is elongated along the laser beam in a dimension perpendicular to the reactant stream to provide for an increase in the throughput of reactants and products. The original design of the apparatus was based on the introduction of purely gaseous reactants. Alternative embodiments for the introduction of an aerosol into an elongated reaction chamber is described in copending and commonly assigned U.S. patent application Ser. No. 09/188,670 to Gardner et al., filed on Nov. 9, 1998, now U.S. Pat. No. 6,193,936, entitled “Reactant Delivery Apparatuses,” incorporated herein by reference. 
     In general, the alternative pyrolysis apparatus includes a reaction chamber designed to reduce contamination of the chamber walls, to increase the production capacity and to make efficient use of resources. To accomplish these objectives, an elongated reaction chamber is used that provides for an increased throughput of reactants and products without a corresponding increase in the dead volume of the chamber. The dead volume of the chamber can become contaminated with unreacted compounds and/or reaction products. 
     The design of the improved reaction chamber  300  is shown schematically in  FIGS. 4 and 5 . A reactant inlet  302  enters the main chamber  304 . Reactant inlet  302  provides for the introduction of gaseous and/or aerosol reactants into main chamber  304 . Reactant inlet  302  conforms generally to the shape of main chamber  304 . Main chamber  304  includes an outlet  306  along the reactant/product stream for removal of particulate products, any unreacted gases and inert gases. Shielding gas inlets  310  are located on both sides of reactant inlet  302 . Shielding gas inlets are used to form a blanket of inert gases on the sides of the reactant stream to inhibit contact between the chamber walls and the reactants and products. 
     Tubular sections  320 ,  322  extend from the main chamber  304 . Tubular sections  320 ,  322  hold windows  324 ,  326  to define a laser beam path  328  through the reaction chamber  300 . Tubular sections  320 ,  322  can include inert gas inlets  330 ,  332  for the introduction of inert gas into tubular sections  320 ,  322 . 
     The dimensions of elongated reactant inlet  316  preferably are designed for high efficiency particle production. Reasonable dimensions for the reactant inlet for the production of vanadium oxide nanoparticle, when used with a 1800 watt CO 2  laser, are from about 5 mm to about 1 meter. 
     The improved apparatus includes a collection system to remove the nanoparticles from the molecular stream. The collection system can be designed to collect a large quantity of particles without terminating production or, preferably, to run in continuous production by switching between different particle collectors within the collection system. The collection system can include curved components within the flow path similar to curved portion of the collection system shown in  FIG. 1 . A particular preferred collection system for particle production systems operating in a continuous collection mode is described in copending and commonly assigned U.S. patent application Ser. No. 09/107,729, now U.S. Pat. No. 6,270,732 to Gardner et al., entitled “Particle Collection Apparatus And Associated Methods,” incorporated herein by reference. A batch collection system for use with the improved reaction system is described in copending and commonly assigned U.S. patent application Ser. No. 09/188,770, filed on Nov. 9, 1998, now U.S. Pat. No. 6,506,493, entitled “Metal Oxide Particles,” incorporated herein by reference. The configuration of the reactant injection components and the collection system can be reversed such that the particles are collected at the top of the apparatus. 
     As noted above, properties of the vanadium oxide particles can be modified by further processing. The starting material for the heat treatment can be any type of solid vanadium oxide compound. Suitable materials include, for example, VO, VO 1.27 , VO 2 , V 2 O 3 , V 3 O 5  and amorphous V 2 O 5 . The starting materials generally can be particles of any size and shape. In addition, particles used as starting material can have been subjected to one or more prior heating steps under different conditions. 
     Nanoscale particles are preferred starting materials. The nanoscale particles have an average diameter of less than about 1000 nm and preferably from about 5 nm to about 500 nm, and more preferably from about 5 nm to about 150 nm. Suitable nanoscale starting materials have been produced by laser pyrolysis. 
     The vanadium oxide particles are preferably heated in an oven or the like to provide generally uniform heating. The processing conditions generally are mild, such that significant amounts of particle sintering does not occur. The temperature of heating preferably is low relative to the melting point of both the starting material and the product material. For nanoparticles, the processing temperature generally ranges from about 50° C. to about 500° C., and more preferably from about 60° C. to about 400° C. 
     The heating preferably is continued for greater than about 5 minutes, and generally is continued for from about 2 hours to about 100 hours, preferably from about 2 hours to about 50 hours. For certain target product particles, additional heating does not lead to further variation in the particle composition. The atmosphere for the heating process can be an oxidizing atmosphere or an inert atmosphere. In particular, for conversion of amorphous particles to crystalline particles or from one crystalline structure to a different crystalline structure of essentially the same stoichiometry, the atmosphere generally can be inert. The atmosphere over the particles can be static, or gases can be flowed through the system. 
     Appropriate oxidizing gases include, for example, O 2 , O 3 , CO, CO 2 , and combinations thereof. The O 2  can be supplied as air. Oxidizing gases optionally can be mixed with inert gases such as Ar, He and N 2 . When inert gas is mixed with the oxidizing gas, the gas mixture can be from about 1 percent oxidizing gas to about 99 percent oxidizing gas, and more preferably from about 5 percent oxidizing gas to about 99 percent oxidizing gas. Alternatively, either essentially pure oxidizing gas or pure inert gas can be used, as desired. 
     The precise conditions can be altered to vary the type of vanadium oxide product produced. For example, the temperature, time of heating, heating and cooling rates, the gases and the exposure conditions with respect to the gases can all be changed, as desired. Generally, while heating under an oxidizing atmosphere, the longer the heating period the more oxygen that is incorporated into the material, prior to reaching equilibrium. Once equilibrium conditions are reached, the overall conditions determine the crystalline phase of the powders. 
     A variety of ovens or the like can be used to perform the heating. An example of an apparatus  400  to perform this processing is displayed in  FIG. 6 . Apparatus  400  includes a jar  402 , which can be made from glass or other inert material, into which the particles are placed. Suitable glass reactor jars are available from Ace Glass (Vineland, N.J.). The top of glass jar  402  is sealed to a glass cap  404 , with a Teflon® gasket  405  between jar  402  and cap  404 . Cap  404  can be held in place with one or more clamps. Cap  404  includes a plurality of ports  406 , each with a Teflon® bushing. A multiblade stainless steel stirrer  408  preferably is inserted through a central port  406  in cap  404 . Stirrer  408  is connected to a suitable motor. 
     One or more tubes  410  are inserted through ports  406  for the delivery of gases into jar  402 . Tubes  410  can be made from stainless steel or other inert material. Diffusers  412  can be included at the tips of tubes  410  to disburse the gas within jar  402 . A heater/furnace  414  generally is placed around jar  402 . Suitable resistance heaters are available from Glas-col (Terre Haute, Ind.). One port preferably includes a T-connection  416 . The temperature within jar  402  can be measured with a thermocouple  416  inserted through T-connection  416 . T-connection  416  can be further connected to a vent  418 . Vent  418  provides for the venting of gas circulated through jar  402 . Preferably vent  418  is vented to a fume hood or alternative ventalation equipment. 
     Preferably, desired gases are flowed through jar  402 . Tubes  410  generally are connected to an oxidizing gas source and/or an inert gas source. Oxidizing gas, inert gas or a combination thereof to produce the desired atmosphere are placed within jar  402  from the appropriate gas source(s). Various flow rates can be used. The flow rate preferably is between about 1 standard cubic centimeters per minute (sccm) to about 1000 sccm and more preferably from about 10 sccm to about 500 sccm. The flow rate generally is constant through the processing step, although the flow rate and the composition of the gas can be varied systematically over time during processing, if desired. Alternatively, a static gas atmosphere can be used. 
     VO 2 , a material with a high melting point, is relatively easy to form in the laser pyrolysis apparatuses described above. VO 2  is a suitable starting product for oxidation to other forms of vanadium oxide. Some empirical adjustment may be required to produce the conditions appropriate to generate a desired material. In addition, the heat processing can result in an alteration of the crystal lattice and/or removal of adsorbed compounds on the particles to improve the quality of the particles. 
     For the processing of vanadium oxide, for example, the temperatures preferably range from about 50° C. to about 500° C. and more preferably from about 60° C. to about 400° C. The particles preferably are heated for about 5 minutes to about 100 hours. Some empirical adjustment may be required to produce the conditions appropriate for yielding a desired material. The use of mild conditions avoids interparticle sintering resulting in larger particle sizes. Some controlled sintering of the particles can be performed at somewhat higher temperatures to produce slightly larger, average particle diameters. 
     The conditions to convert crystalline VO 2  to orthorhombic V 2 O 5  and 2-D crystalline V 2 O 5 , and amorphous V 2 O 5  to orthorhombic V 2 O 5  and 2-D crystalline V 2 O 5  are describe in copending and commonly assigned U.S. patent application Ser. No. 08/897,903, to Bi et al. now U.S. Pat. No. 5,989,514, entitled “Processing of Vanadium Oxide Particles With Heat,” incorporated herein by reference. 
     B. Formation of Metal Vanadium Oxide Particles 
     It has been discovered that heat processing can be used to form nanoscale metal vanadium oxide particles. In a preferred approach to the thermal formation of metal vanadium oxide particles, vanadium oxide nanoscale particles first are mixed with a non-vanadium metal compound. The resulting mixture is heated in an oven to form a metal vanadium oxide composition. The heat processing to incorporate metal into the vanadium oxide lattice can be performed in an oxidizing environment or an inert environment. In either type of environment, the heating step generally results in alteration of the oxygen to vanadium ratio. In addition, the heat processing can result in an alteration of the crystal lattice and/or removal of adsorbed compounds on the particles to improve the quality of the particles. 
     The use of sufficiently mild conditions, i.e., temperatures well below the melting point of the vanadium oxide particles, results in metal incorporation into the vanadium oxide particles without significantly sintering the particles into larger particles. The vanadium oxide particles used for the process preferably are nanoscale vanadium oxide particles. It has been discovered that metal vanadium oxide compositions can be formed from vanadium oxides with an oxidation state of +5 or less than +5. In particular, vanadium oxides with an oxidation states from +2 (VO) to +5 (V 2 O 5 ) can be used to form metal vanadium oxide particles. 
     Generally, the metal incorporated into the metal vanadium oxide particle is any non-vanadium transition metal. Preferred metals for incorporation into the vanadium oxide include, for example, copper, silver, gold, and combinations thereof. Suitable silver compounds include, for example, silver nitrate (AgNO 3 ). Suitable copper compounds include, for example, cupric nitrate (Cu(NO 3 ) 2 ). Alternatively, silver metal powder, copper metal powder or gold metal powder can be used as sources of the respective metals. 
     Appropriate oxidizing gases include, for example, O 2  (supplied as air, if desired), O 3 , CO, CO 2  and combinations thereof. The reactant gas can be diluted with inert gases such as Ar, He and N 2 . Alternatively, the gas atmosphere can be exclusively inert gas. Silver vanadium oxide particles have been produced with either an inert atmosphere or an oxidizing atmosphere, as described in the Examples below. 
     A variety of apparatuses can be used to perform the heat processing for lithiation and/or annealing of a sample. An embodiment of a suitable apparatus  400  is described above with respect to  FIG. 6  for the heat processing of vanadium oxides produced by laser pyrolysis. An alternative apparatus  430  for the incorporation of a metal into the vanadium oxide lattice is shown in  FIG. 7 . The particles are placed within a small vial  432 , boat or the like within tube  434 . Preferably, the desired gases are flowed through tube  434 . Gases can be supplied for example from inert gas source  436  or oxidizing gas source  438 . 
     Tube  434  is located within oven or furnace  440 . Oven  440  can be adapted from a commercial furnace, such as Mini-Mite™ 1100° C. Tube Furnace from Revco/Lindberg, Asheville, N.C. Oven  436  maintains the relevant portions of the tube at a relatively constant temperature, although the temperature can be varied systematically through the processing step, if desired. The temperature can be monitored with a thermocouple  442 . 
     To form metal vanadium oxide particles in the heating step, a mixture of vanadium oxide particles and the metal compound can be placed in tube  434  within a vial  432 . Preferably, a solution of the metal compound is mixed with the vanadium oxide nanoparticles and evaporated to dryness prior to further heating in the oven. The evaporation can be performed simultaneously with the heating to form the metal vanadium oxide composition, if desired. For example, silver nitrate and copper nitrate can be applied to the vanadium oxide particles as an aqueous solution. Alternatively, vanadium oxide nanoparticles can be mixed with a dry powder of the metal compound or elemental metal powder, thereby avoiding the evaporation step. A sufficient amount of the metal compound or elemental metal powder is added to yield the desired amount of incorporation of the metal into the vanadium oxide lattice. This incorporation into the vanadium oxide lattice can be checked, for example, through the use of x-ray diffractometry, as described below. 
     The precise conditions including type of oxidizing gas (if any), concentration of oxidizing gas, pressure or flow rate of gas, temperature and processing time can be selected to produce the desired type of product material. The temperatures generally are mild, i.e., significantly below the melting point of the materials. The use of mild conditions avoids interparticle sintering resulting in larger particle sizes. Some controlled sintering of the particles can be performed in the oven at somewhat higher temperatures to produce slightly larger, average particle diameters. 
     For the metal incorporation into vanadium oxide, the temperature generally ranges from about 50° C. to about 500° C., preferably from about 80° C. to about 400° C., and more preferably from about 80° C. to about 325° C. The processing temperature can range from about 80° C. to about 250° C. The particles preferably are heated for about 5 minutes to about 100 hours. Some empirical adjustment may be required to produce the conditions appropriate for yielding a desired material. 
     C. Particle Properties 
     A collection of particles of interest, comprising metal vanadium oxide compounds, generally has an average diameter for the primary particles of less than about 500 nm, preferably from about 5 nm to about 100 nm, more preferably from about 5 nm to about 50 nm, and even more preferably from about 5 nm to about 25 nm. The primary particles usually have a roughly spherical gross appearance. Upon closer examination, crystalline particles generally have facets corresponding to the underlying crystal lattice. Nevertheless, crystalline primary particles tend to exhibit growth that is roughly equal in the three physical dimensions to give a gross spherical appearance. In preferred embodiments, 95 percent of the primary particles, and preferably 99 percent, have ratios of the dimension along the major axis to the dimension along the minor axis less than about 2. Diameter measurements on particles with asymmetries are based on an average of length measurements along the principle axes of the particle. 
     Because of their small size, the primary particles tend to form loose agglomerates due to van der Waals and other electromagnetic forces between nearby particles. Nevertheless, the nanometer scale of the primary particles is clearly observable in transmission electron micrographs of the particles. The particles generally have a surface area corresponding to particles on a nanometer scale as observed in the micrographs. Furthermore, the particles can manifest unique properties due to their small size and large surface area per weight of material. For example, vanadium oxide nanoparticles generally exhibit surprisingly high energy densities in lithium batteries, as described in copending and commonly assigned U.S. patent application Ser. No. 08/897,776 now U.S. Pat. No. 5,952,125, entitled “Batteries With Electroactive Nanoparticles,” incorporated herein by reference. 
     The primary particles preferably have a high degree of uniformity in size. Laser pyrolysis, as described above, generally results in particles having a very narrow range of particle diameters. Furthermore, heat processing under mild conditions does not alter the very narrow range of particle diameters. With aerosol delivery, the distribution of particle diameters is particularly sensitive to the reaction conditions. Nevertheless, if the reaction conditions are properly controlled, a very narrow distribution of particle diameters can be obtained with an aerosol delivery system, as described above. As determined from examination of transmission electron micrographs, the primary particles generally have a distribution in sizes such that at least about 95 percent, and preferably 99 percent, of the primary particles have a diameter greater than about 40 percent of the average diameter and less than about 160 percent of the average diameter. Preferably, the primary particles have a distribution of diameters such that at least about 95 percent, and preferably 99 percent, of the primary particles have a diameter greater than about 60 percent of the average diameter and less than about 140 percent of the average diameter. 
     Furthermore, in preferred embodiments no primary particles have an average diameter greater than about 4 times the average diameter and preferably 3 times the average diameter, and more preferably 2 times the average diameter. In other words, the particle size distribution effectively does not have a tail indicative of a small number of particles with significantly larger sizes. This is a result of the small reaction region and corresponding rapid quench of the particles. An effective cut off in the tail of the size distribution indicates that there are less than about 1 particle in 10 6  have a diameter greater than a specified cut off value above the average diameter. Narrow size distributions, lack of a tail in the distributions and the roughly spherical morphology can be exploited in a variety of applications. 
     In addition, the nanoparticles generally have a very high purity level. The crystalline metal vanadium oxide nanoparticles produced by the above described methods are expected to have a purity greater than the reactants because the crystal formation process tends to exclude contaminants from the lattice. Furthermore, crystalline vanadium oxide particles produced by laser pyrolysis have a high degree of crystallinity. Similarly, the crystalline metal vanadium oxide nanoparticles produced by heat processing have a high degree of crystallinity. Impurities on the surface of the particles may be removed by heating the particles to achieve not only high crystalline purity but high purity overall. 
     Vanadium oxide has an intricate phase diagram due to the many possible oxidation states of vanadium. Vanadium is known to exist in oxidation states between V +2  and V +5 . The energy differences between the oxides of vanadium in the different oxidation states is not large. Therefore, it is possible to produce stoichiometric mixed valence compounds. Known forms of vanadium oxide include VO, VO 1.27 , V 2 O 3 , V 3 O 5 , VO 2 , V 6 O 13 , V 4 O 9 , V 3 O 7 , and V 2 O 5 . Laser pyrolysis alone or with additional heating can successfully yield single phase vanadium oxide in many different oxidation states, as evidenced by x-ray diffraction studies. These single phase materials are generally crystalline, although some amorphous nanoparticles have been produced. The heat treatment approaches are useful for increasing the oxidation state of vanadium oxide particles or for converting vanadium oxide particles to more ordered phases. 
     There are also mixed phase regions of the vanadium oxide phase diagram. In the mixed phase regions, particles can be formed that have domains with different oxidation states, or different particles can be simultaneously formed with vanadium in different oxidation states. In other words, certain particles or portions of particles have one stoichiometry while other particles or portions of particles have a different stoichiometry. Mixed phase nanoparticles have been formed. Non-stoichiometric materials also can be formed. 
     The vanadium oxides generally form crystals with octahedral or distorted octahedral coordination. Specifically, VO, V 2 O 3 , VO 2 , V 6 O 13  and V 3 O 7  can form crystals with octahedral coordination. In addition, V 3 O 7  can form crystals with trigonal bipyramidal coordination. V 2 O 5  forms crystals with square pyramidal crystal structure. V 2 O 5  recently also has been produced in a two dimensional crystal structure. See, M. Hibino, et al., Solid State Ionics 79:239-244 (1995), incorporated herein by reference. When produced under appropriate conditions, the vanadium oxide nanoparticles can be amorphous. The crystalline lattice of the vanadium oxide can be evaluated using x-ray diffraction measurements. 
     Metal vanadium oxide compounds can be formed with various stoichiometries. U.S. Pat. No. 4,310,609 to Liang et al., entitled “Metal Oxide Composite Cathode Material for High Energy Density Batteries,” incorporated herein by reference, describes the formation of Ag 0.7 V 2 O 5.5 , AgV 2 O 5.5 , and Cu 0.7 V 2 O 5.5 . The production of oxygen deficient silver vanadium oxide, Ag 0.7 V 2 O 5 , is described in U.S. Pat. No. 5,389,472 to Takeuchi et al., entitled “Preparation of Silver Vanadium Oxide Cathodes Using Ag(O) and V 2 O 5  as Starting Materials,” incorporated herein by reference. The phase diagram of silver vanadium oxides of the formula Ag x V 2 O y  are described in published European Patent Application 0 689 256A, entitled “Cathode material for nonaqueous electrochemical cells,” incorporated herein by reference. 
     D. Batteries 
     Referring to  FIG. 8 , battery  450  has an negative electrode  452 , a positive electrode  454  and separator  456  between negative electrode  452  and positive electrode  454 . A single battery can include multiple positive electrodes and/or multiple negative electrodes. Electrolyte can be supplied in a variety of ways as described further below. Battery  450  preferably includes current collectors  458 ,  460  associated with negative electrode  452  and positive electrode  454 , respectively. Multiple current collectors can be associated with each electrode if desired. 
     Lithium has been used in reduction/oxidation reactions in batteries because it is the lightest metal and because it is the most electropositive metal. Certain forms of metal oxides are known to incorporate lithium ions into its structure through intercalation or similar mechanisms such as topochemical absorption. Intercalation of lithium ions can take place also into suitable forms of a vanadium oxide lattice as well as the lattice of the metal vanadium oxide composition. 
     In particular, lithium intercalates into the vanadium oxide lattice or metal vanadium oxide lattice during discharge of the battery. The lithium leaves the lattice upon recharging, i.e., when a voltage is applied to the cell such that electric current flows into the positive electrode due to the application of an external EMF to the battery. Positive electrode  454  acts as a cathode during discharge, and negative electrode  452  acts as an anode during discharge of the cell. Metal vanadium oxide particles can be used directly in a positive electrode for a lithium based battery to provide a cell with a high energy density. Appropriate metal vanadium oxide particles can be an effective electroactive material for a positive electrode in either a lithium or lithium ion battery. 
     Positive electrode  454  includes electroactive nanoparticles such as metal vanadium oxide nanoparticles held together with a binder such as a polymeric binder. Nanoparticles for use in positive electrode  454  generally can have any shape, e.g., roughly spherical nanoparticles or elongated nanoparticles. In addition to metal vanadium oxide particles, positive electrode  454  can include other electroactive nanoparticles such as TiO 2  nanoparticles, vanadium oxide nanoparticles and manganese oxide nanoparticles. The production of TiO 2  nanoparticles has been described, see U.S. Pat. No. 4,705,762, incorporated herein by reference. Vanadium oxide nanoparticles are know to exhibit surprisingly high energy densities, as described in copending and commonly assigned U.S. patent application Ser. No. 08/897,776 now U.S. Pat. No. 5,952,125, entitled “Batteries With Electroactive Nanoparticles,” incorporated herein by reference. The production of manganese oxide nanoparticles is described in copending and commonly assigned U.S. patent application Ser. No. 09/188,770 to Kumar et al. filed on Nov. 9, 1998, now U.S. Pat. No. 6,506,493, entitled “Metal Oxide Particles,” incorporated herein by reference. 
     While some electroactive materials are reasonable electrical conductors, a positive electrode generally includes electrically conductive particles in addition to the electroactive nanoparticles. These supplementary, electrically conductive particles generally are also held by the binder. Suitable electrically conductive particles include conductive carbon particles such as carbon black, metal particles such as silver particles, metal fibers such as stainless steel fibers, and the like. 
     High loadings of particles can be achieved in the binder. Particles preferably make up greater than about 80 percent by weight of the positive electrode, and more preferably greater than about 90 percent by weight. The binder can be any of various suitable polymers such as polyvinylidene fluoride, polyethylene oxide, polyethylene, polypropylene, polytetrafluoro ethylene, polyacrylates, ethylene-(propylene-diene monomer) copolymer (EPDM) and mixtures and copolymers thereof. 
     Negative electrode  452  can be constructed from a variety of materials that are suitable for use with lithium ion electrolytes. In the case of lithium batteries, the negative electrode can include lithium metal or lithium alloy metal either in the form of a foil, grid or metal particles in a binder. 
     Lithium ion batteries use particles of an composition that can intercalate lithium. The particles are held with a binder in the negative electrode. Suitable intercalation compounds include, for example, graphite, synthetic graphite, coke, mesocarbons, doped carbons, fullerenes, niobium pentoxide, tin alloys, SnO 2  and mixtures and composites thereof. 
     Current collectors  458 ,  460  facilitate flow of electricity from battery  450 . Current collectors  458 ,  460  are electrically conductive and generally made of metal such as nickel, iron, stainless steel, aluminum and copper and can be metal foil or preferably a metal grid. Current collector  458 ,  460  can be on the surface of their associated electrode or embedded within their associated electrode. 
     The separator element  456  is electrically insulating and provides for passage of at least some types of ions. Ionic transmission through the separator provides for electrical neutrality in the different sections of the cell. The separator generally prevents electroactive compounds in the positive electrode from contacting electroactive compounds in the negative electrode. 
     A variety of materials can be used for the separator. For example, the separator can be formed from glass fibers that form a porous matrix. Preferred separators are formed from polymers such as those suitable for use as binders. Polymer separators can be porous to provide for ionic conduction. Alternatively, polymer separators can be solid electrolytes formed from polymers such as polyethylene oxide. Solid electrolytes incorporate electrolyte into the polymer matrix to provide for ionic conduction without the need for liquid solvent. 
     Electrolytes for lithium batteries or lithium ion batteries can include any of a variety of lithium salts. Preferred lithium salts have inert anions and are nontoxic. Suitable lithium salts include, for example, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithiumbis(trifluoromethyl sulfonyl imide), lithium trifluoromethane sulfonate, lithium tris(trifluoromethyl sulfonyl) methide, lithium tetrafluoroborate, lithium perchlorate, lithium tetrachloroaluminate, lithium chloride and lithium perfluorobutane. 
     If a liquid solvent is used to dissolve the electrolyte, the solvent preferably is inert and does not dissolve the electroactive materials. Generally appropriate solvents include, for example, propylene carbonate, dimethyl carbonate, diethyl carbonate, 2-methyl tetrahydrofuran, dioxolane, tetrahydrofuran, 1,2-dimethoxyethane, ethylene carbonate, γ-butyrolactone, dimethyl sulfoxide, acetonitrile, formamide, dimethyl formamide and nitromethane. 
     The shape of the battery components can be adjusted to be suitable for the desired final product, for example, a coin battery, a rectangular construction or a cylindrical battery. The battery generally includes a casing with appropriate portions in electrical contact with current collectors and/or electrodes of the battery. If a liquid electrolyte is used, the casing should prevent the leakage of the electrolyte. The casing can help to maintain the battery elements in close proximity to each other to reduce resistance within the battery. A plurality of battery cells can be placed in a single case with the cells connected either in series or in parallel. 
     EXAMPLES 
     Example 1 
     Production of Vanadium Oxide by Laser Pyrolysis 
     Single phase VO 2  particles were produced by laser pyrolysis. The VOCl 3  (Strem Chemical, Inc., Newburyport, Mass.) precursor vapor was carried into the reaction chamber by bubbling Ar gas through the VOCl 3  liquid stored in a container at room temperature. The reactant gas mixture containing VOCl 3 , Ar, O 2  and C 2 H 4  was introduced into the reactant gas nozzle for injection into the reactant chamber. The reactant gas nozzle had dimensions ⅝ in×⅛ in. C 2 H 4  gas was used as a laser absorbing gas. Argon was used as an inert gas. 
     The synthesized vanadium oxide nanoscale particles can be directly handled in the air. Representative reaction conditions for the production of this material are described in Table 1. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Phase 
                 VO 2   
               
               
                   
                   
               
             
            
               
                   
                 Crystal 
                 Monoclinic 
               
               
                   
                 Structure 
               
               
                   
                 Pressure 
                 210 
               
               
                   
                 (Torr) 
               
               
                   
                 Argon-Win 
                 700 
               
               
                   
                 (sccm) 
               
               
                   
                 Argon-Sld. 
                 7.0 
               
               
                   
                 (slm) 
               
               
                   
                 Ethylene (slm) 
                 1.61 
               
               
                   
                 Carrier Gas- 
                 1.4 
               
               
                   
                 Argon (slm) 
               
               
                   
                 Oxygen (slm) 
                 0.47 
               
               
                   
                 Precursor 
                 40 
               
               
                   
                 Temp. (° C.) 
               
               
                   
                 Production 
                 35 
               
               
                   
                 Rate (gm/hr) 
               
               
                   
                 Laser Power- 
                 780 
               
               
                   
                 Input (watts) 
               
               
                   
                 Laser Power- 
                 640 
               
               
                   
                 Output (watts) 
               
               
                   
                   
               
               
                   
                 sccm = standard cubic centimeters per minute 
               
               
                   
                 slm = standard liters per minute 
               
               
                   
                 Argon-Win. = argon flow through inlets 216, 218 
               
               
                   
                 Argon-Sld. = argon flow through annular channel 142 
               
            
           
         
       
     
     An x-ray diffractogram of representative product nanoparticles is shown in  FIG. 9 . Clear diffraction peaks corresponding to a monoclinic crystalline structure are visible. The identified structure from the diffractogram is almost identical to that of the corresponding bulk material, which has larger particle sizes. 
     Example 2 
     Heat Treatment to Form Crystalline V 2 O 5  Nanoparticles 
     The starting materials for the heat treatment were VO 2  nanoparticles produced by laser pyrolysis according to the parameters in Table 1. 
     The nanoparticles were heat treated at in an oven roughly as shown in  FIG. 6 . The particles were fed in batches of between about 100 grams to about 150 grams into the glass jar. Oxygen is fed through a ⅛″ stainless steel tube at an oxygen flow rate of 155 cc/min. A mixing speed of 5 rpm was used to constantly mix the powders during the heat treatment. The powders were heated for 30 minutes at 100° C., then for 30 minutes at 200° C. and finally at 230° C. for 16 hours. A heating rate of 4° C./minute was used to heat the samples to the target temperatures. The resulting nanoparticles were single phase crystalline V 2 O 5  nanoparticles. The x-ray diffractogram of this material is shown in  FIG. 10 . From the x-ray diffractogram, it could be determined that the resulting particles were orthorhombic V 2 O 5 . 
     TEM photographs were obtained of representative nanoparticles following heat treatment. The TEM photograph is shown in  FIG. 11 . An approximate size distribution was determined by manually measuring diameters of the particles shown in  FIG. 11 . The particle size distribution is shown in  FIG. 12 . An average particle size of about 10-11 nm was obtained. Only those particles showing clear particle boundaries were measured and recorded to avoid regions distorted in the micrograph. This should not bias the measurements obtained since the single view of the micrograph may not show a clear view of all particles because of the orientation of the crystals. 
     Example 3 
     Heat Processing to Form Silver Vanadium Oxide 
     This example demonstrates the production of nanoscale silver vanadium oxide using a vanadium oxide nanoparticle starting material. The silver vanadium oxide is produced by a heat processing. 
     About 9.5 g of silver nitrate (AgNO 3 ) was dissolved into about 15 ml of deionized water. Then, about 10 g of V 2 O 5  nanoparticles produced as described in Examples 2 were added to the silver nitrate solution to form a mixture. The resulting mixture was stirred on a magnetic stirrer for about 30 minutes. After the stirring was completed the solution was heated to about 160° C. in an oven to drive off the water. The dried powder mixture was ground with a mortar and pestle. 
     Six samples from the resulting ground powder weighing between about 100 and about 300 mg of nanoparticles were placed separately into an open 1 cc boat. The boat was placed within the quartz tube projecting through an oven to perform the heat processing. The oven was essentially as described above with respect to  FIG. 7 . Oxygen gas or argon gas was flowed through a 1.0 in diameter quartz tube at a flow rate of about 20 sccm. The samples were heated in the oven under the following conditions:
         1) 250° C., 60 hrs in argon   2) 250° C., 60 hrs in oxygen   3) 325° C., 4 hrs in argon   4) 325° C., 4 hrs in oxygen   5) 400° C., 4 hrs in argon   6) 400° C., 4 hrs in oxygen.
 
The samples were heated at approximately the rate of 2° C./min. and cooled at the rate of approximately 1° C./min. The times given above did not include the heating and cooling time.
       

     The structure of the particles following heating was examined by x-ray diffraction. The x-ray diffractograms for the samples heated in oxygen and in argon are shown in  FIGS. 13 and 14 , respectively. All of the heated samples produces diffractograms with peaks indicating the presence of Ag 2 V 4 O 11 . The samples heated at 400° C. appear to lack significant amounts of V 2 O 5 . Heating the samples for somewhat longer times at the lower temperatures should eliminate any remaining portions of the V 2 O 5  starting material. 
     A transmission electron micrograph of the silver vanadium oxide particles is shown in  FIG. 15 . For comparison, a transmission electron micrograph of the V 2 O 5  nanoparticle sample used to form the silver vanadium oxide nanoparticles is shown in  FIG. 16 , at the same scale as  FIG. 15 . The V 2 O 5  nanoparticles in  FIG. 16  were produced under conditions similar to the conditions described in Examples 1 and 2. The silver vanadium oxide particles in  FIG. 15  surprisingly have a slightly smaller average diameter than the vanadium oxide nanoparticle starting material in  FIG. 16 . 
     The embodiments described above are intended to be illustrative and not limiting. Additional embodiments are within the claims below. Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.