CN1343378A - Metal vanadium oxide particles - Google Patents

Abstract

Metal vanadium oxide particles have been produced with an average diameter less than about 500 nm. The metal vanadium oxide particles have very uniform properties. In some embodiments, silver vanadium oxide particles are formed by the heat treatment of a mixture of nanoscale vanadium oxide and a silver compound. Laser pyrolysis is used to produce directly metal vanadium oxide composite nanoparticles. To perform the pyrolysis a reactant stream is formed including a vanadium precursor and a second metal precursor. The pyrolysis is driven by energy absorbed from a light beam. Metal vanadium oxide nanoparticles can be incorporated into a cathode of a lithium based battery to obtain increased energy densities. Implantable defibrillators can be constructed with lithium based batteries having increased energy densities.

Description

Metal vanadium oxide particles

The present invention relates to metal vanadium oxide particles. The invention also relates to a method for the manufacture of metal vanadium oxide powder particles, for example by laser pyrolysis. In particular, the present invention relates to a method for producing nanoscale metal vanadium oxide powder particles by laser pyrolysis. The present invention also relates to batteries with improved performance associated with nanoscale metal vanadium oxide particles, such as silver vanadium oxide particles.

Lithium-based batteries have achieved great commercial success due to their high energy density. Suitable positive electrode materials for lithium-based batteries include those capable of inserting lithium atoms into their crystal lattices. The negative electrode can use lithium metal, lithium alloy or compound, because they can reversibly insert lithium atoms into their crystal lattice. A battery made of a lithium metal or lithium alloy negative electrode is called a lithium battery, while a battery made of an anode (negative electrode) active metal that can insert lithium ions is called a lithium ion battery.

In order to produce improved batteries, various materials have been tried as cathode (positive electrode) active materials for lithium-based batteries. There are various materials, usually chalcogenides, that can be used in lithium-based batteries, for example vanadium oxide in certain oxidation states is an effective material for making positive electrodes of lithium-based batteries. Metallic vanadium oxides have long been considered to have high energy and power densities when used as positive electrodes in lithium-based batteries. Silver vanadium oxide has a very high energy power density when used as a lithium-based battery. Silver vanadium oxide batteries have found particular application in implantable cardiac defibrillators, where the battery must be capable of recharging capacitors in rapid succession to deliver strong energy pulse.

A first aspect of the invention pertains to a cluster of particles comprising metal vanadium oxide, the average particle diameter of which is less than 500 nanometers.

Another aspect of the invention pertains to a method of producing metal vanadium oxide, characterized by comprising heating a mixture of vanadium oxide particles and non-vanadium metal oxide, the vanadium oxide particles having an average diameter of less than 500 nanometers.

Yet another aspect of the invention is a battery characterized by comprising a positive electrode comprising active particles comprising vanadium oxide in a binder, the vanadium oxide particles having an average diameter of less than about 500 nanometers.

The present invention also belongs to a method for producing metal vanadium oxide particles, which is characterized in that it comprises reacting in a reactor a stream of reactants synthesized by vanadium-containing primary particles and second metal primary particles, the reaction being caused by the absorption of energy in an electromagnetic field.

Yet another aspect of the invention is a battery characterized by comprising a cathode comprising active particles of silver vanadium oxide and a binder. The positive electrode has an energy density of greater than about 340 milliampere hours per gram of active particle when discharged to 1.0 volts.

Furthermore, the invention pertains to a battery characterized by comprising an anode having metallic vanadium active particles and a binder, the positive electrode having an energy density of greater than about 400 milliampere hours per hour when discharged to 1.0 volts grams of active particles.

Yet another aspect of the invention is an implantable defibrillator wherein the battery has a silver vanadium oxide cathode having an energy density of greater than about 340 mAh/h when discharged to 1.0 volts per gram of cathode active material.

The invention also pertains to a method for producing a mixture of elemental metal nanoparticles and vanadium oxide nanoparticles, the method being characterized in that it comprises reacting a reactant stream for the synthesis of vanadium-containing primary particles and second metal primary particles in a reaction furnace, the reaction It is caused by the absorption of electromagnetic field energy.

Still another aspect of the present invention pertains to a method for producing metal vanadium oxide particles, characterized in that it comprises reacting a vanadium primary particle and a second metal primary particle synthetic reactant stream in a reaction furnace, the reaction is formed by absorbing the energy of a combustion flame caused.

Yet another aspect of the present invention pertains to a cluster comprising a single element metal selected from the group consisting of copper, silver, and gold, the average size of the particles in the cluster being less than about 500 nanometers, and virtually any particle having a diameter no greater than four times its average diameter.

Furthermore, the present invention also pertains to a method for producing particles comprising a single elemental metal selected from the group copper, silver and gold, the method is characterized in that it involves the reaction of a molecular flow in a reaction furnace, the Molecular flow consists of a metallic precursor and a radiation absorber, where the reaction is induced by electromagnetic field radiation.

The drawing description of the accompanying drawings of the present invention is:

Fig. 1 is a schematic sectional view of an example of a laser pyrolysis device, the section being cut from the middle of the path of laser radiation. The upper inset is a top view of the collecting nozzle; the lower inset is a top view of the sending nozzle.

FIG. 2 is a sketch of a reactant sending device for sending vapor reactants to a laser pyrolysis device as in FIG. 1 .

FIG. 3A is a schematic side view of a reactant delivery device for delivering airborne reactants to a laser pyrolysis device as in FIG. 1 .

3B is a schematic side view of another example of a reactant delivery device for delivery of airborne reactants to the laser pyrolysis device of FIG. 1 .

Fig. 4 is an enlarged perspective sketch of a reactor for performing laser pyrolysis, wherein components of the reactor are transparent to show its internal structure.

Fig. 5 is a cross-sectional view of the reactor shown in Fig. 4 taken along line 5-5.

Figure 6 is a schematic cross-sectional view of an apparatus for thermally treating nanoparticles, the section being taken through the center of the apparatus.

Figure 7 is a schematic cut-away view of a furnace for high heat-affected nanoparticles, the section being cut through the middle of the furnace.

Figure 8 is a perspective sketch of an embodiment of a battery of the present invention.

Fig. 9 is an X-ray crystallographic diffraction pattern of VO ₂ nanoparticles.

FIG. 10 is an X-ray crystallographic diffraction pattern of V ₂ O ₅ nanoparticles produced by thermally treating VO ₂ nanoparticle crystallization.

Fig. 11 is a transmission electron microscope image of V ₂ O ₅ nanoparticle crystallization.

FIG. 12 is a particle size distribution graph of V ₂ O ₅ nanoparticle crystals as in FIG. 11 .

Figure 13 is a four X-ray diffraction patterns of silver vanadium oxide produced by V ₂ O ₅ nanocrystals plus silver nitrate after heat treatment in an oxygen-filled atmosphere, where each diffraction pattern is based on different conditions of material forming and derived.

Figure 14 is a four X-ray diffraction patterns of silver vanadium oxide produced by V ₂ O ₅ nanocrystals plus silver nitrate after heat treatment in an argon-filled atmosphere, where each diffraction pattern is based on different conditions of material forming and derived.

Figure 15 is a transmission electron microscope view of a silver vanadium oxide nanoparticle.

FIG. 16 is a transmission electron microscope view of a sample of V ₂ O ₅ particles used to produce the silver vanadium oxide particles of FIG. 15 .

Fig. 17 is an X-ray diffraction pattern of silver vanadium oxide produced after mixing V ₂ O ₅ nanoparticles and silver nitrate powder and heat treatment in oxidation.

FIG. 18 is a graph obtained by differential scanning calorimetry from a sample having an X-ray diffraction pattern as in FIG. 17. FIG.

Figure 19 is an X-ray diffraction pattern of a miscible silver-vanadium oxide material produced directly by laser pyrolysis.

FIG. 20 is a transmission electron microscope view of the silver-vanadium oxide material directly produced by laser pyrolysis to obtain the X-ray diffraction pattern shown in FIG. 19 .

Fig. 21 is an X-ray diffraction pattern of a silver vanadium oxide particle after heat treatment in an oxygen atmosphere of a nanoscale silver-vanadium oxide material synthesized by laser pyrolysis.

Figure 22 is a transmission electron microscope image of silver vanadium oxide particles produced by heat-treating nanoscale silver vanadium oxide material.

Figure 23 is an X-ray diffraction pattern of two samples obtained under slightly different conditions containing silver vanadium oxide nanoparticles produced directly by laser pyrolysis.

Figure 24A is a transmission electron micrograph obtained from a sample corresponding to the upper diffraction pattern of Figure 23.

FIG. 24B is a transmission electron micrograph obtained from a sample corresponding to the lower diffraction pattern in FIG. 23 .

Fig. 25 is five X-ray diffraction patterns of mixed-phase materials of silver vanadium oxide nanoparticles directly produced by laser pyrolysis, wherein the materials produced in each figure are derived from different silver vanadium ratios.

26 is an X-ray diffraction pattern of elemental silver nanoparticles produced by laser pyrothermal method under the conditions specified in the first column of Table 5. FIG.

Figure 27 is an X-ray diffraction pattern of elemental silver nanoparticles produced by laser pyrolysis under the conditions specified in the second column of Table 5.

FIG. 28 is a transmission electron micrograph of the sample material corresponding to diffraction pattern 26. FIG.

29 is a graph of voltage as a function of time for a lithium battery fabricated from silver vanadium oxide nanoparticles obtained according to the heat treatment procedure described in Example 4. FIG.

FIG. 30 is a graph of voltage as a function of capacitance corresponding to the voltage-time graph of FIG. 29. FIG.

31 is a graph of voltage as a function of time for a lithium battery made from miscible silver vanadium oxide nanoparticles obtained according to laser pyrolysis as described in Example 5. FIG.

FIG. 32 is a graph of voltage as a function of capacitance corresponding to the voltage-time graph of FIG. 31. FIG.

33 is a graph of voltage as a function of time for a lithium battery made from silver vanadium oxide nanoparticles made according to the heat treatment procedure described in Example 6. FIG.

FIG. 34 is a graph of voltage as a function of capacitance corresponding to the voltage-time graph shown in FIG. 33. FIG.

35 is a graph of voltage versus time for a lithium battery made from miscible silver vanadium oxide nanoparticles according to Example 7. FIG.

FIG. 36 is a graph of voltage versus capacitance corresponding to the voltage versus time graph of FIG. 35. FIG.

The production of nano-scale metal vanadium oxide particles can directly adopt laser pyrolysis method; laser pyrolysis method can also be used to synthesize nano-scale vanadium oxide particles and then undergo high temperature/heat treatment to make metal vanadium oxide nanomaterial particles . Therefore, metal vanadium oxides can be directly produced by laser pyrolysis, wherein the laser pyrolysis reaction composition includes primary particles of vanadium and primary particles of a second metal. Furthermore, vanadium oxide nanoparticles can be used to make metal vanadium oxide nanoparticles, eg, silver vanadium oxide nanoparticles, without losing the nanoscale size of the particles. Nanoscale metal vanadium oxide particles can be used to create batteries with improved performance.

Nanoparticles of vanadium oxides with various stoichiometric ratios and crystal structures can be produced by laser high-temperature pyrolysis alone or by additional treatment. Various forms of vanadium oxide nanoparticles can be used as starting materials for the manufacture of metal vanadium oxide nanoparticles. Multimetallic nanoparticles are made by mixing vanadium oxide nanoparticles with metal compounds to be introduced into the vanadium oxide to make materials with two metals in the crystal lattice. Using properly selected processing conditions, particles combining the two metals can be produced without losing the nanoscale properties of the original vanadium oxide nanoparticles.

Preferred metal vanadium oxide particles have an average diameter of less than 1 micron and a narrow dispersion of particle diameters. The dispersion of particle diameters doesn't even have a tail. In other words, there are simply no particles that are an order of magnitude larger than the mean diameter, ie the particle size dispersion drops rapidly to zero. In order to produce vanadium oxide nanoparticle starting materials for further processing into metal vanadium oxides, laser pyrolysis can be used alone or in combination with other processing methods. In particular, laser pyrolysis has been an excellent method for efficiently producing vanadium oxide nanoparticles with a narrow dispersion of average particle diameters. In addition, nanoscale vanadium oxide particles produced by laser pyrolysis can be heated under soft conditions in an oxygen-filled atmosphere or in an inert atmosphere in order to change their crystal properties and/or stoichiometry of the vanadium oxide particles without destroying The size characteristics of its nanomaterial particles. In this way, various types of vanadium oxide-based nanoparticles can be produced.

The basic features of the successful application of laser pyrolysis for the production of vanadium oxide nanoparticles are the generation of a reactant stream containing vanadium precursors, a source of radiation absorption and a source of oxygen, which is subjected to an intense laser beam-like reaction stream. Beam pyrolysis. Laser pyrolysis provides a different phase than the material produced under thermodynamic equilibrium conditions. Once the reactant stream exits the beam, the vanadium oxide nanoparticles cool rapidly.

Metallic vanadium oxide particles starting from nanoscale vanadium oxide particles can be produced by heat treatment, the second metallic precursor particles comprising a transition metal other than vanadium. Preferred second metal primary particles include components having copper, silver, and gold. The second metal primary particle compound is mixed with the vanadium oxide nanoparticle group and heated to form particles combining the two metals. Heat treatment under suitable flexible conditions can effectively produce particles without destroying the nanoscale size of the original vanadium oxide particles.

As mentioned above, the essential features of the successful application of laser pyromethods to fabricate metal vanadium oxide nanoparticles are the production of a reactant stream containing vanadium precursor particles; a precursor particle of a second metal; a radiation absorbing source and an oxygen source. The reactant stream is pyrolyzed with an intense beam of light. Examples include laser beams or other strong light sources. Once the reactant stream exits the beam, the metal vanadium particles are rapidly quenched to produce metal vanadium oxide nanoparticles with a very uniform size dispersion.

As noted above, lithium ions and/or ions can be intercalated into various morphologies of vanadium oxide and metal vanadium oxide particles. To create a positive electrode, used as the cathode when the battery is discharging, the metal vanadium oxide nanoparticles can be combined with a binder such as a polymer to form the electrode. In the electrode, it is preferable to combine the conductive particles and the binder in the metal vanadium oxide particles. Such electrodes can be used as positive electrodes in lithium batteries or lithium-ion batteries. Lithium-based batteries containing nanoscale metal vanadium oxides as cathodes have energy densities higher than the theoretical maximum estimated for the corresponding bulk metal vanadium oxides. In particular, metal vanadium oxides, especially silver vanadium oxides, produce energy densities greater than about 340 mAh/g. The energy density of better barium oxide particles can be greater than 350 mAh/g, better up to 360 mAh/g, and the best can be as high as about 370, or even 405 mAh. Ah/gram.

While the first focus on the production of metal vanadium oxide nanoparticles or precursors for metal vanadium oxide nanoparticles was the application of laser pyrolysis, the method of delivery of air-floated precursors described here can also be applied to Other synthetic methods, in particular, primary particles can be applied in flame pyrolysis. The delivery method of primary particles can be applied in various flame pyrolysis methods. In a preferred method, the reactant stream is passed into an oxyhydrogen flame. The energy of the flame is used for high temperature pyrolysis. This flame pyrolysis method should produce materials similar to the laser pyrolysis technique described here, but generally cannot obtain very narrow particle size dispersions.

While the focus of this process is on the production of ternary compounds consisting of two metals, this method also reveals that nanoparticles of Group IB metals can be produced with very high homogeneity. In particular, the production of nanoparticles of silver element as described below is an example. Copper, gold, and other group IB elements have similar chemical properties. Copper and gold nanoparticles can therefore also be produced in a similar way.

(1) Laser pyrolysis for the production of nanoparticles

Laser pyrolysis has been revealed to be an effective tool for the production of nanoscale vanadium oxide particles. In addition, the particles produced by laser pyrolysis are an excellent material for extended further processing to produce the desired vanadium oxide particles. Thus, laser pyrolysis alone or in combination with additional treatments can produce a wide variety of vanadium oxide particles. Moreover, laser pyrolysis is also a successful method for the direct production of metal vanadium oxide particles.

The quality of particles produced by laser pyrolysis depends on the reaction conditions, which can be precisely controlled to obtain particles with desired characteristics. The reaction conditions suitable for the production of a particular type of particle are generally dependent on the design of the particular apparatus, and the specific reaction conditions suitable for the production of vanadium oxide particles in a particular apparatus are described in the Examples below. Additional information on the production of vanadium oxide nanoparticles by laser pyrolysis can be found in co-pending US patent application Ser. No. 08/897,778 entitled "Vanadium Oxide Nanoparticles" by assigned Bi and others. In addition, the specific conditions of the laser pyrolysis process for the direct production of silver vanadium oxide particles in a specific setup are also described in the Examples below. Furthermore, some general observations are made about the interrelationship between reaction conditions and the results obtained.

Increasing the power of the laser results in an increase in the reaction temperature in the reaction zone and an increase in the quenching rate. The fast quenching rate can obtain high-quality high-energy phases, which cannot be obtained when processing near thermal equilibrium. Similarly, increasing the reaction chamber pressure can also lead to good high-energy structures. The oxygen content of the particles produced increases if the concentration of the oxidation source reactant provided in the reactant stream is increased.

The degree of reactant flow and the velocity of the reactant gas flow are inversely related to particle size, ie, the particle size is smaller as the reactant gas flow velocity is increased. The growth kinetics of particles has a great influence on particle size. That is, under the same conditions, different forms of compound products are all made into particles of different sizes in another phase. Laser power can also affect particle size, i.e. increasing laser power will favor the formation of larger particles for low melting point materials and smaller particles for high melting point materials.

Laser pyrolysis generally operates with gas phase reactants. The fact that only gas-phase reactants can be used places some restrictions on the type of precursor compound. This has prompted the development of technology to introduce the gas flotation containing the primary particles of reactants into the laser pyrolysis chamber. Aerosol nebulizers can be roughly classified into ultrasonic nebulizers that use ultrasonic emitters to form aerosols, and mechanical nebulizers that use the energy of one or more flowing fluids (liquid, gas or supercritical fluid) to form aerosols. Improved air flotation delivery devices for use in reactant systems, as well as laser pyrolysis devices, are described in co-pending U.S. Patent Application No. 09/188,670, commonly assigned to Gardner et al., entitled "Reaction object delivery device".

After applying the air flotation delivery device, the solid primary particle compound can be delivered by dissolving the compound in the solution. Alternatively, powdered primary particle compounds can be used in liquid/solution form for aerosol delivery. The liquid primary particle compound, as long as it is desired, can be transported into an aerosol in various ways such as liquid, or liquid/gas mixture, or liquid mixture, or liquid solution, etc. without doping. Airborne reactants can be used to obtain significant reactant output flows. If a solvent is used, it can also be selected to achieve the desired solubility characteristics. Suitable solvents include various organic solvents such as water, methanol, and ethanol. The solvent should be of the desired degree of purity so that the resulting particles are also of the desired degree of purity.

If the initial particles of the aerosol are made of solvent, the solvent will be evaporated quickly when it is exposed to the laser beam in the reaction chamber, so that a gas phase reaction will occur, and the basic characteristics of the laser pyrolysis reaction will not change . However, the presence of aerosols has some influence on the reaction conditions. Conditions applicable to the manufacture of manganese oxides by laser pyrolysis with airborne primary particles are described in pending assigned U.S. Patent Application No. 09/188,770, filed November 9, 1998, entitled are "metal oxide particles". This is for informational purposes only.

Suitable conditions for the production of silver vanadium oxide particles by laser pyrolysis with air-floated precursors are described in the following examples.

Vanadium primary particles suitable for air flotation production include vanadium trichloride (VCl ₃ ), vanadium oxychloride (VOCl ₃ ), vanadyl sulfate (VOSO ₄ .H ₂ O), ammonium vanadate (NH ₄ VO ₃ ) , barium oxides (ie, V ₂ O ₅ and V ₂ O ₃ , which are soluble in aqueous nitric acid), and vanadyl dichloride (VOCl ₂ ), which is soluble in absolute ethanol. Suitable silver primary particles include, for example, silver sulfate (Ag ₂ SO ₄ ), silver carbonate (Ag ₂ CO ₃ ), silver nitrate (AgNO ₃ ), silver chlorate (AgClO ₃ ) and silver perchlorate (AgClO ₄ ), Suitable copper precursors include, for example, copper nitrate [Cu(NO ₃ ) ₂ ], copper dichloride (CuCl ₂ ), cuprous chloride (CuCl) and copper sulfate (CuSO ₄ ). Suitable gold primary particles include, for example, gold trichloride (AuCl ₃ ) and gold powder.

These compounds are preferably dissolved in solutions at concentrations greater than 0.1 molar. In general, the greater the concentration of primary particles in the solution, the greater the output flow of reactants through the reaction chamber. But as the concentration increases, the solution becomes thicker and the aerosols have larger droplets than desired. Therefore, the choice of solution concentration will take into account the balance of various factors in the preferred solution concentration selection.

Vanadium precursor compounds suitable for vapor delivery generally include vanadium compounds having reasonable vapor pressures, ie, vapor pressures sufficient to obtain the desired amount of precursor vapor in the reactant stream. If desired, the solid or liquid vanadium precursor compound in the vessel can be heated to increase the vapor pressure of the vanadium precursor. Suitable vanadium precursors include, for example, VCl ₄ , VOCl ₂ , V(CO) ₆ and VOCl ₃ . Chlorine in these representative primary particle compounds can be replaced by other halogens. For example, bromine, iodine and fluorine.

For the production of metal vanadium oxide particles, suitable metal precursors have sufficient vapor pressure to obtain the desired amount of metal precursor vapor in the reactant stream. Copper precursors suitable for vapor delivery include, for example, copper dichloride (CuCl ₂ ), and silver precursors suitable for vapor delivery include, for example, silver chloride (AgCl). On the other hand, one of the vanadium primary particles and the metal primary particles can be transported in the form of an aerosol and the other can be transported in the form of vapor. In particular, metal primary particles such as silver primary particles can be transported by air flotation while the vanadium primary particle side can be transported by vapor.

To produce mixed metal oxides from two or more metals, changes in the relative amounts of the individual metals in the reactant streams result in changes in the relative amounts of the resulting metal components. The phase diagrams of mixed metal oxides are much more complex than those of the corresponding metal oxides. The phase of the added metal obtained by adding a greater amount of one metal than the other, either as a major phase in a miscible product, or as a phase of a relatively large relative amount in a miscible product .

Thus, as the relative amounts of the various metals in the solution or transport aerosol vary, the stoichiometry of the particulate product will also vary. The same result can be obtained when transmitting two or more metal primary particles of independent aerosols, wherein the relative amount of various metal primary particles can vary with the concentration of the metal in the liquid or the relative amount of the aerosol. change with change. Furthermore, one or more metal precursors can be delivered in a vapor state, so that the relative amounts of metals can be easily adjusted to obtain the desired product.

Preferred reactants for use as oxygen sources include, for example, _O2 , CO, _CO2 , _O3 , and mixtures thereof. Reactive compounds used as oxygen sources. It is important not to react with the vanadium precursors before entering the reaction zone, as this usually leads to the formation of large particles.

Laser pyrolysis can be performed in beams of various frequencies. Preferred light sources include lasers, especially lasers operating in the infrared electromagnetic spectrum. A _CO2 laser is a particularly preferred light source. Infrared absorbers included in the molecular flow include, for example, _C2H4 , isopropanol ( _{CH3CHOHCH3 )} , _NH3 , _SF6 , _{SiH4 ,} and _O3 . _O3 can act as both an infrared absorber and an oxygen source. On the other hand, one such as isopropanol can absorb light from the beam when the solvent is transported as an aerosol in the liquid. Radiation absorbers, like infrared absorbers, can absorb energy from a radiation beam and distribute the energy to other reactants to promote high temperature pyrolysis.

The energy absorbed from the radiation beam increases the temperature at an enormous rate, mainly many times greater than that produced by a strongly exothermic reaction under controlled conditions. When the process usually involves non-equilibrium conditions, the temperature can be approximately described on the basis of the heat in the absorption zone. The nature of the laser pyrolysis process is different from the process in the combustion reactor. Although an energy source promotes a reaction in the combustion reactor, the reaction is driven by the energy released by an exothermic reaction. of.

An inert shielding gas can be used to reduce the amount of reactant, generated molecules that come into contact with the chamber components. Suitable shielding gases can include, for example, argon, helium and nitrogen. Inert gases may also be mixed with the reactant streams to slow down the reaction.

A suitable laser pyrolysis device typically includes a reaction chamber that is isolated from the surrounding environment. A reaction inlet is connected to the reactant supply system and produces a reactant flow through the reaction chamber, and a light beam intersects the reactant flow in the reaction chamber. The reactant/product stream passes through the reaction zone and continues to the outlet, whereupon the reactant/product stream exits the reaction chamber and enters the collection system. Usually the light source is arranged outside the reaction chamber, and the light beam enters the reaction chamber through a suitable window.

Referring to FIG. 1 , a specific example of a laser pyrolysis apparatus 100 includes a reactant supply system 102 , reaction chamber 104 collection system 106 , light source 108 , and shielding gas delivery system 110 . There are two alternative reactant supply systems that can be used in the apparatus of FIG. 1 . The first reactant supply system is dedicated to the delivery of gaseous reactants, while the second reactant supply system is used to deliver one or more aerosol reactants, a variety of elemental reactant supply systems are available .

Referring to FIG. 2, a first embodiment 112 of the reactant supply system 102 includes a vanadium precursor compound source 120, and for liquid or solid vanadium precursors, a carrier gas in a carrier gas source 122 can be passed to the precursor source 120 In order to transport the vanadium primary particles in the form of vapor. The carrier gas drawn from source 122 is preferably an infrared absorber or an inert gas and bubbles through a liquid precursor compound or is delivered to a solid precursor delivery system. Inert gases are used as carrier gases to moderate reaction conditions. The amount of primary particle vapor in the reaction zone is approximately proportional to the flow rate of the carrier gas.

On the other hand, the carrier gas can also be drawn directly from the infrared absorber source 124 or the inert gas source 126 . Additional reactants, such as a source of oxygen, are supplied by reactant source 128, which may be a gas cylinder or other suitable container. The gas from the primary particle source is mixed with the gases from the infrared absorbing source 124 , the inert gas source 126 and the reactant source by combining these gases in a line 130 . These gases have just synthesized together at enough distance away from reaction chamber 104, so that gas just fully mixes before entering reaction chamber 104, and the synthesis gas in pipe 130 enters in a rectangular channel 134 through a section of pipeline 132, The channel 134 forms part of a nozzle for injecting the reactants directly into the reaction zone. Certain locations in the reactant supply system 112 may be heated to prevent deposition of the precursor compound on the side walls of the delivery system.

The metal primary particles can be supplied by the metal primary particle source 138, which can be a liquid reactant delivery device, a solid reactant delivery device, a gas cylinder or other suitable containers or containers. If metal precursor source 138 is delivering a liquid or solid reactant, carrier gas from carrier gas source 122 or another carrier gas source may be used for reactant delivery. As shown in FIG. 2 , the metal primary particle source 138 uses the pipeline 130 to send the metal primary particles to the pipeline 132 .

The flows from the various sources 122, 124, 126 and 128 are preferably each controlled by a separate mass flow controller 136 which preferably provides a controlled flow rate from each source. Suitable mass flow controllers include, for example, Edwards mass flow controllers, Model 825 series, manufactured by Edwavds High Vacuum International, Wilmington, MA.

Referring to FIG. 3A , an alternative embodiment 150 of reactant supply system 102 is used to supply aerosols into channel 134 . As mentioned above, passage 134 forms part of a nozzle for injecting reactants into the reaction chamber through the reactant inlet. The reactant supply system 150 includes an aerosol generator 152, a carrier gas/vapor supply pipe 154 and a confluence 156, a channel 134, the aerosol generator 152 and the supply pipe 154 converging in a cavity 158 of the confluence 156, and the supply pipe 154 The carrier gas is sent in the direction of the channel 134 . The aerosol generator 152 is installed so that the aerosol is generated in the space between the inlet of the channel 134 and the outlet of the supply pipe 154 in the inner cavity 158 .

The aerosol generator 152 can operate on a variety of principles. For example, methods of producing aerosols can be: with an ultrasonic nozzle; with an electrostatic spray system; with a pressurized spray or a simple spray; with a bubble spray or with a gas spray in which the liquid is forced through a small orifice under high pressure And it is broken into small droplets by the impact of airflow. Suitable ultrasonic nozzles may include piezoelectric emitters. An ultrasonic nozzle with piezoelectric emitters is available as model 8700-120 from Sono-Tek Corporation, Milton, NY (Sono.Tek, Milton, NY, USA).

Suitable aerosol generators are further described in copending and commonly assigned US Patent Application No. 09/188,670, entitled "Reactant Delivery Apparatus," to Gardner et al., which is incorporated by reference. Additional aerosol generators can then be attached to manifold 156 through additional ports 162 so that additional aerosols can be generated in inner chamber 158 for delivery to the reaction chamber.

The manifold 156 includes an opening 162 from outside the manifold 156 into the lumen 158 . Thus, the channel 134, the aerosol generator 152 and the supply pipe 154 can be properly installed. In one embodiment, the manifold 156 is a cube with six openings 162 , one cylindrical opening 162 mounted on each face of the manifold 156 . The manifold 156 can be fabricated from stainless steel or other durable, corrosion-resistant material. Also seal a window 161 on an opening 162 so that the inner cavity 158 can be observed, and the opening 162 of the manifold 156 at the bottom preferably also includes a leak opening 163, so that the air floats that are accumulated and sent out from the manifold are discharged from the manifold. Released in 156.

The carrier gas/vapor supply line 154 is connected to a gas source 164 . Gas source 164 may include multiple gas containers, liquid reactant delivery means, and/or a solid reactant delivery means connected to supply line 154 for delivery of the selected gas or gas mixture. Carrier gas/vapor supply line 154 can thus deliver various desired gases and/or vapors to the reactant stream, including, for example, laser absorbing gases, reactants, and/or inert gases. The gas flow from the gas source 164 to the supply pipe 154 is controlled by one or more mass flow controllers 166, the liquid supply pipe 168 is connected to the aerosol generator 152, and the liquid supply pipe 168 is also connected to the liquid source 170.

For producing vanadium oxide particles, fluid source 170 may contain a liquid containing vanadium precursors, and for producing metal vanadium oxide particles, fluid source 170 preferably contains a liquid containing both a vanadium precursor and a metal precursor. Alternatively, to produce metal oxide particles, liquid source 170 may contain a liquid containing metal precursors, while vanadium precursors are delivered by gas source 164 and vapor supply line 154 . If desired, the liquid source 170 can also be filled with a liquid containing vanadium primary particles, while the metal primary particles are supplied through the gas source 164 and the steam supply pipe 154 . Two independent aerosol generators 152 can also be used in the manifold 156, one of which generates aerosols with vanadium precursors and the other generates aerosols with metal precursors.

In the embodiment of FIG. 3 , the momentum of the aerosol generated by the aerosol generator 152 is nearly orthogonal to the carrier gas flow flowing from the supply tube 154 to the channel 134 . In this way, the carrier gas/vapor coming out of the tube 154 is about to guide the aerosol primary particles generated in the aerosol generator 152 into the channel 134 . During actual operation, the carrier gas flow is about to be sent into the aerosol introduction channel 134 in the chamber 158 . In this way, the conveying speed of the aerosol effectively depends on the flow rate of the carrier gas.

In another embodiment, the air buoyancy generator is positioned at an upward angle to the horizontal such that a component of the forward momentum of the air buoyancy is directed in a direction consistent with the channel 134 . In a preferred example, the output flow from the air aerosol generator is set at an angle of 45° to the positive direction defined by the opening of the channel 134 , that is, the flow direction of the supply pipe 154 entering the channel 134 .

Referring to Fig. 3 B, it is another embodiment 172 of the reactant supply system 102 that can be used to supply the aerosol to the channel 134, the reactant supply system 172 includes an outer nozzle 174 and an inner nozzle 176, and the outer nozzle 174 has a Upward passage 178 leads to a 5/8 inch by 1/4 inch rectangular outlet 180 to the tip of outer nozzle 174, as inset in Figure 3B. The tip of the outer nozzle 174, as inset in Figure 3B. The outer nozzle 174 includes a drain tube 183 on a bottom surface 184 . The drain pipe 183 is used to discharge the accumulated aerosol out of the outer nozzle. The inner nozzle 176 is fixed on the outer nozzle 174 by the sleeve 185 .

Inner nozzle 176 is a gas sparger supplied by "Spraying Systems (Wheatm, IL)". The inner nozzle is 0.5 inches in diameter and 12 inches long. The top of the nozzle is a dual hole internal mixing nozzle 186 (air hole 0.055 inch, liquid hole 0.005 inch). The liquid is passed to the emitter through tube 187, while the gas is passed to the emitter through tube 188 and introduced into the reaction chamber, the interaction of the gas and liquid promotes the formation of droplets.

The outer nozzle and the inner nozzle are coaxially installed together. The outer nozzle 174 compresses the aerosol produced by the inner nozzle 176 into a flat rectangular section. In addition, the outer nozzle also makes the flow velocity of the air floating body uniform and distributes uniformly on the cross section. The shape of the outer nozzle 174 can also be made to be suitable for various reaction chambers.

Referring to Fig. 1, the shielding gas delivery system 110 includes an inert gas source 190 connected with an inert gas conduit 192, the inert gas conduit 192 flows into the annular channel 194, and the mass flow controller 196 controls the flow rate of the inert gas entering the inert gas conduit 192 flow. If reactant delivery system 112 is employed, inert gas source 126 may also be used as a source of inert gas for conduit 192 .

Reaction chamber 104 includes a main chamber 200 to which reactant supply system 102 is connected at emission nozzle 202. Reaction chamber 104 may be heated to maintain the precursor compound in a vapor state. Likewise, it is best to heat the argon shielding gas as well. The main chamber can be monitored for concentration to ensure that primary particles are not deposited therein.

Injection nozzle 202 has an annular opening 204 at the end for passage of inert shielding gas, and reactant inlet 206 for passing reactant and forming a reactant flow into the reaction chamber. The reactant inlet 206 is preferably a slot, as shown in FIG. 1, the diameter of the annular opening 204 is, for example, about 1.5 inches and the radial width is about 1/8 inch to 1/16 inch. The shielding gas flow through the annular opening 204 is helpful in preventing loss of reactant gases and particulate products passing through the reaction chamber 104 . Barrels 208, 210 each contain a ZnSe window, and windows 212, 214 are about 1 inch in diameter. The windows 212, 124 are preferably two cylindrical mirrors with a focal length equal to the distance from the center of the reaction chamber to the mirrors, so as to focus the light beam just below the center point of the nozzle opening. The windows 212, 214 preferably have an anti-reflection coating, and suitable ZnSe lenses are available from "Janos Technology, Towrshend, Vermont". The presence of the barrels 208, 210 allows the windows 212, 214 to be located further away from the main reaction chamber 200 so that they are less contaminated by reactants and/or products. The windows 212, 214 may be located approximately 3 cm from the main reaction chamber 200.

The windows 212, 214 are sealed to the barrels 208, 210 with O-rings to prevent ambient air from flowing into the reaction chamber 104. Shielding gas enters the barrels 208, 210 to reduce contamination of the windows 212, 214 through inlet tubes 216, 218, which are connected to the inert gas source 138, or to a separate source of inert gas. In another instance, the gas flow into the inlet tubes 216, 218 is preferably controlled by a mass flow controller 220.

Light source 108 produces a beam of light 222 that is aimed at and enters window 212 and exits through window 214 . Windows 212, 214 define a light path through main reaction chamber 200 and intersect the reactant stream in reaction zone 224. After passing through window 214, beam 222 impinges on power meter 226, unloading the beam. A suitable power meter is available from "Coherenf Inc., Santa Clara, CA." The light source 108 is preferably a laser, although it could also be a common intense light source, such as an arc lamp. The laser source 108 is preferably an infrared laser, especially A continuous _CO2 laser, such as one available from "PRC Corp., Landing, NJ" with a maximum output power of 1800 watts. Another example is to replace the light source 108 with another electromagnetic energy source, such as a microwave generator. In this example, the reactant stream includes a radiation absorbing compound, such as a microwave absorber.

The reactants pass through reactant inlet 206 in injection nozzle 202 to form a reactant stream. The reactant flow passes through the reaction zone 224, where the initial particles react with the added reactant compound, and the gas is heated rapidly in the reaction zone 224, which can reach the order of 10 ⁵ degrees per second according to specific conditions. The reaction exiting reaction zone 224 is rapidly quenched, ie, particles are formed in the reactant stream, and the non-equilibrium nature of the process results in nanoparticles having a very uniform size distribution and structural consistency.

The reactant/product stream continues along the path to collection nozzle 230 . The distance between the collection nozzle 230 and the emission nozzle 230 is very small and the presence of the collection nozzle 230 reduces the contamination of the reaction chamber 104 by reactants and products. Collection nozzle 230 has a circular opening 232 through which it enters collection system 106 .

The chamber pressure in the reaction chamber is monitored by a pressure gauge mounted on the main chamber.

The preferred chamber pressure for producing the desired oxide is generally between about 80 Torr and 500 Torr.

The reaction chamber 104 also has two additional barrel sections not shown. One of the external cylindrical parts faces the plane of the cross section in FIG. 1 , while the other external cylindrical part faces away from the plane of the cross section in FIG. 1 . In this way, when viewed from above, the four cylindrical portions are almost symmetrically distributed around the reaction chamber. These additional barrels have windows for viewing the inside of the reaction chamber. In the configuration of this device, the two additional barrels are not used for the production of granules.

Collection system 106 preferably includes an elbow 270 extending from collection nozzle 230 . Because of the small size of the particles, the granular product follows the curve of the airflow. Collection system 106 includes a filter 272 to collect product particles in the gas stream. Due to the elbow 270 the filter 272 is not supported directly above the reaction chamber. A variety of materials can be used as a filter, such as PTFE, fiberglass, etc., as long as the material is inert and has a mesh small enough to trap particles. Preferred materials for the filters are fiberglass filters produced by "ACE Glass Inc., Vineland, NJ" and "Nomex®" brand fiber filters in cartridge form by "AF Equipment Co., Sunyvale, CA" .

Pump 274 is used to maintain collection system 106 at a selected pressure. A variety of different pumps can be used. Suitable products for pump 272 include, for example, the Busch Model B0024 pump, approximately 25 cubic feet per minute (cfm) capacity, manufactured by "Busch, Inc., Virginia Beach, VA" and "Leybold Vacuum Products, Export, PA" Produced Ley bold Model SV 300 pump with a capacity of 195cfm. Preferably the exhaust stream from the pump is passed through a scrubber 276 to wash off residual reaction chemicals before being vented to the atmosphere. The entire apparatus 100 should be placed in a fume hood to provide good ventilation and meet safety conditions. Usually the laser is placed outside the fume hood due to its large size.

The whole device is controlled by computer. Typically a computer controls the laser and monitors the pressure of the reaction chamber, and the computer can be used to control the flow of reactants and/or the shielding gas flow. The pump speed is controlled by a manually controlled needle valve or self-controlled throttle valve inserted in the pump 274 and filter 272 . When the chamber pressure increases due to the accumulation of particles in the filter 272, the needle valve or throttle valve can be adjusted accordingly to maintain the pump speed.

The reaction is terminated when enough particles have accumulated on the filter 272 that the pump can no longer maintain the desired pressure in the reaction chamber 104 against the resistance across the filter 272. When the pressure in the reaction chamber 104 cannot maintain a normal value, the reaction stops and the filter 272 is removed. In this embodiment, the particles collected in the round before the pressure was not enough to maintain 6 were about 1-300 grams. Typical round times can last about 10 hours, depending on the reactant delivery system, the type of particles being produced, and the type of filter.

The reaction conditions can be controlled with great precision. Especially mass flow can be controlled very precisely. The power stability of the laser is generally about 0.5%, and the pressure in the reaction chamber can be controlled within 1% by a manual needle valve or an automatic throttle valve.

The dosing of reactant supply system 102 and collection system 106 may be reversed. In an alternative, reactants are fed from the top of the reactor, while product particles are collected at the bottom of the reaction chamber. The collection system in this configuration can be used without elbows so the collection filter is installed directly below the reaction chamber.

Another design of a laser pyrolysis device is described in US Patent No. 5,958,348, entitled "Efficient Production of Particles Using Chemical Reaction," incorporated herein by reference. This design scheme is aimed at producing a commercially useful large quantity of particles produced by laser pyrolysis. The reaction chamber is elongated in the dimension perpendicular to the flow of reactants along the direction of the laser beam, resulting in increased output of reactants and products. The original design of the device was based on the introduction of pure gaseous reactants. Another embodiment of introducing an aerosol into an elongated reaction chamber is described in co-pending U.S. patent application commonly assigned to Gardner et al., No. 09/188,670, (1998.11.09 application) titled "Reactant Delivery Device", for reference.

Typically, the replaced pyrolysis unit consists of a reaction chamber designed to reduce chamber wall contamination, increase production capacity, and use energy efficiently. To accomplish these objectives, an elongated reaction chamber is employed to increase the output of reactants and products without a corresponding increase in the dead space in the reaction chamber. Such reaction chamber dead space can become contaminated with unreacted compounds and/or reaction products.

An improved reaction chamber design 300 is shown in FIGS. 4 and 5 . The reactant inlet 302 enters into the main chamber 304 , and the reactant inlet 302 is used for introducing gas and/or aerosol reactants into the main chamber 304 . The shape of the reactant inlet 302 generally matches the shape of the main chamber 304 . Although the process of introducing reactants through the reactant inlet 302 to produce vanadium oxide particles or metal vanadium oxide particles can be introduced along with the laser pyrolysis device after appropriately adopting the alternative structure of the reactant inlet as in Fig. 1 Air aerosols and/or vapor primary particles are accomplished.

The main reaction chamber 304 includes an outlet 306 along the reactant/product flow for removal of product, unreacted gases and inert gases. The shielding gas inlet 310 is located on both sides of the reactant inlet 302 . The shielding gas inlet is used to create an inert gas boundary layer on both sides of the reactant flow to prevent the reactants and products from contacting the chamber walls.

The simple parts 320 , 322 extend outward from the main chamber 304 . Barrels 320 , 322 are secured with windows 324 , 326 to confine the passage of the laser beam through reaction chamber 300 . The barrel portion 320, 322 may include an inert gas inlet 330, 332 for introducing an inert gas into the barrel portion 320, 322.

The size of the reactant inlet 316 (note: the original text is suspected to be the error of 302-annotation of 302) after the lengthening is designed by efficient particle production. Reasonable sizes of reactant inlets for the production of vanadium oxide nanoparticles and metal vanadium oxide nanoparticles are from about 5 mm to 1 meter when using an 1800 watt _CO2 laser.

The modified plant includes a collection system for removing nanoparticles in the molecular stream, the collection system can be designed to collect a large number of product particles without stopping production, or, preferably, switch to another particle collection box in the collection system method to ensure continuous production. In the collecting system, a curved part similar to the curved pipe in the collecting system in FIG. 1 can be provided in the process.

A more preferred embodiment of a collection system for use in a continuous collection mode particle production system can be found in co-pending U.S. Patent Application No. 09/107,729, commonly assigned to Gavdner et al., entitled "Particle Collection Apparatus and Related method". A bulk collection system for use in the improved reaction system can be found in commonly assigned co-pending US Patent Application No. 09/188,770, (Filing Date: 1998.11.09) entitled "Metal Oxide Particles". The configuration of the reactant emission assembly and collection system can be reversed, ie particles can be collected at the top of the unit.

The properties of the vanadium oxide particles and metal vanadium oxide particles may vary due to subsequent processing methods as described above. Suitable starting materials for heat treatment include vanadium oxide particles and metal vanadium oxide particles produced by laser pyrolysis. Suitable vanadium oxide materials include, for example, VO, VO _1.27 , VO ₂ , V ₂ O ₃ , V ₃ O ₅ , V ₄ O ₉ , V ₆ O ₁₃ and amorphous V ₂ O ₅ . Likewise, the minimum material It may be metal vanadium oxide particles produced by laser pyrolysis, such as silver vanadium oxide particles and/or copper vanadium oxide particles. Suitable metal vanadium oxide materials include Ag ₂ V ₄ O ₁₁ and a new silver vanadium oxide crystal formation as described below. In addition, the pellets used for the starting material are subjected to one or more heat treatment steps under different conditions.

Starting material generally can be the particle of any size and shape, certainly nano-scale particle is preferred starting material, and the average diameter of this nano-nano particle is about less than 1000 nanometers and preferably fully from about 5 nanometers to 500 nanometers; Better From about 5 nm to 150 nm, suitable nanoscale starting materials have been produced by laser pyrolysis.

The vanadium oxide particles and metal vanadium oxide particles are preferably heated in a furnace for uniform heating. Such conditions are usually mild enough to avoid substantial particle sintering. The heating temperature is preferably lower than the melting point of the starting material and the product material.

For some target product particles, additional heating will cause further changes in particle composition when the equilibrium cannot be reached at one point, and the atmosphere for heat treatment can be an oxidizing atmosphere or an inert atmosphere. Especially when changing from one crystalline structure to another crystalline structure, or changing from an amorphous particle to a crystalline particle under substantially the same stoichiometric conditions, an inert atmosphere is usually used. The atmosphere in which the particles reside can be static or a gas flowing through the system.

Suitable oxidizing gases include, for example, _O2 , _O3 , CO, _CO2 and combinations of these gases. _O2 can be supplied from air. The oxidizing atmosphere can be selectively mixed with inert gases such as Ar, He and _N2 . When there is a mixture of oxidizing gas and inert gas, the proportion of oxidizing gas in the mixed gas can be from about 1% to 99%, and better It is from 5% to 99%. Of course, basically pure oxidizing gas or pure inert gas can also be used alone.

The precise conditions can alter the type of vanadium oxide product or the type of metal vanadium oxide produced. For example, temperature, heating time, heating and cooling rates, gas, and conditions of exposure to gas can all be varied. In general, when heating in an oxidizing atmosphere, the longer the heating time, the more oxygen will be incorporated into the material before equilibrium is reached. Once equilibrium conditions are reached, various conditions determine the crystalline phase in the powder.

Various furnaces can be used for heating, and Figure 6 is an example of an apparatus 400 for accomplishing this. Apparatus 400 includes a cup 402, made of glass or other inert material, into which particles are placed. Existing suitable glass reactive glass is the product produced by "Ace Glass (Vineland, NJ)". The cup top 402 is sealed with a glass cover 404, and a Teflon® sealing gasket 405 is placed between the cover 403 of the cup 402. Cover 404 may be held on by one or more clips. Cover 404 has a plurality of holes 406 each with a Teflon(R) liner, and through center hole 406 of cover 404 is inserted a multi-blade stainless steel stirrer 408 driven by a suitable motor.

One or more tubes 410 are inserted into cup 402 through holes 406 to deliver gas. The tube 410 is made of stainless steel or other inert material, and the diffuser 412 is mounted on the head of the tube 410 to spray gas into the cup 402 . Surrounding the cup 402 is a heater/furnace 414. Suitable resistance heaters are available from the company "Glas-Col (Terre Haute, IN)". One of the tubes includes a T-connector 416 through which a thermocouple 416 is inserted to measure the temperature in the cup 402 . The tee 416 is also connected to an exhaust port 418 which provides exhaust for the circulating ventilation air passing through the cup 402 . Exhaust port 418 preferably leads to a fume hood or other ventilation.

Preferably the desired gas flows through the cup 402 . Tube 410 is typically connected to a source of oxygen and/or an inert gas source from a suitable source of oxygen, inert gas and combinations thereof to create the desired atmosphere in cup 402 . Various flow streams can be used, preferably at a flow rate of from about 1 sccm to about 1000 sccm, more preferably from about 10 sccm to 500 sccm. Flow rates are generally constant throughout the heating step, although flow rates and gas compositions can be systematically adjusted during processing. Alternatively, a static gas atmosphere may also be used.

In the laser pyrolysis apparatus described above, the material _VO2 with a very high melting point is relatively easy to make, and _VO2 is a suitable starting material for oxidation to other forms of vanadium oxides. Some empirical adjustment is also required to generate conditions suitable for making the desired material. In addition, heat treatment can alter the lattice of the crystals and/or remove absorbed compounds from the particles to improve the quality of the particles.

For treating vanadium oxide nanoparticles or metal vanadium oxide nanoparticles, a preferred temperature range is, for example, from about 50°C to about 500°C or more preferably from about 60°C to about 400°C. Heating is preferably continued for more than about 5 minutes, and generally for about 2 hours to about 100 hours, preferably from about 2 hours to 50 hours. Some empirical adjustments are also required to generate conditions suitable for producing the desired material. Soft conditions are used to avoid entanglement between particles to form larger particle sizes. Some controlled sintering of the particles is performed at a slightly higher temperature to produce a slightly larger average particle diameter.

Transform crystalline _VO2 to _{orthorhombic V2O5} and ₂ -D crystalline _V2O5 ; and transform _{amorphous V2O5} to _{orthorhombic V2O5} and 2-D crystalline _V2O The condition of ₅ is described in US Patent No. 5,989,514, entitled "Thermal Processing of Vanadium Oxide Particles," assigned to Bi et al., incorporated by reference. (2) Heat treatment method to manufacture metal vanadium oxide particles

While metal vanadium oxide particles can be produced directly by laser pyrolysis as described above, it has also been found that nanoscale metal vanadium oxide particles can also be produced by heat treatment. In a preferred method of thermally forming metal vanadium oxide particles, vanadium oxide nanoparticles and non-vanadium metal compounds are first mixed together and the mixture is heated in a furnace to form a metal vanadium oxide composition. The heat treatment process to incorporate the metal into the vanadium oxide lattice can be performed in an oxidizing environment or in an inert environment. In either form of ambient atmosphere, the heating step will generally cause a change in the ratio of oxygen to vanadium. In addition, heat treatment can modify the crystalline lattice and/or remove adsorbed compounds from the particles to improve the properties of the particles.

Relatively mild conditions are used, ie, the temperature must be below the melting point of the vanadium oxide particles, resulting in incorporation of the metal into the vanadium oxide particles without causing substantial sintering of the particles into larger particles. The vanadium oxide particles used in the process are preferably nanoscale vanadium oxide particles. It has been found that metal vanadium oxide compositions can be formed from vanadium in an oxidation state of +5 (penta) or less. obtained from oxides. Especially vanadium oxides in the oxidation state +2 (two valence) (VO) to +5 (penta valence) (V ₂ O ₅ ) can be used to produce metal vanadium oxide particles.

Typically, the metal incorporated into the metal vanadium oxide particles is any non-vanadium transition metal. Metals incorporated into vanadium oxides include, for example, copper, silver, gold and combinations thereof. Suitable silver compounds include, for example, silver nitrate ( _AgNO3 ). Suitable copper compounds include, for example, copper nitrate [Cu(NO ₃ ) ₂ ]. Alternatively, silver metal powder, copper metal powder or gold metal powder can also be used as the corresponding metal source.

Suitable oxidizing gases include, for example, O ₂ (air can also be used), 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, only an inert gas may be used as the gas. Silver vanadium oxide particles have been produced either with an inert atmosphere or with an oxidizing atmosphere, as described in the examples below.

A variety of devices are available for heat treatment of sample annealing. An example 400 of a suitable apparatus can be seen in Figure 6 already described above for the heat treatment of vanadium oxides produced by laser pyrolysis. Another apparatus 430 for incorporating metals into the vanadium oxide lattice is shown in FIG. 7 . The particles are placed in vial 432 in tube 434 . Dan or similar vessel. The required gases pass through tube 434 . Gas can be introduced to the sample from the oxidizing gas source 438 or the inert gas source 436 .

The tube 434 is placed in a furnace 440 manufactured by "Lindberg/Blue M, Asheville, NC" using a commercial furnace such as the "Mini-Mite ^™ 1000°C Tube Fumacl". The relevant portion of the tube 434 is maintained at its normal temperature by the furnace 440, although the temperature can of course be systematically adjusted through the processing steps. Temperature monitoring uses a thermocouple 442 .

To produce metal vanadium oxide particles during the heating step, a mixture of vanadium oxide particles and metal compound may be placed in a boat in batch tube 432 in tube 434 . Preferably, the solution of the metal compound and the vanadium oxide nanoparticles are mixed and evaporated to dryness before further heating in the furnace. Evaporation can be accomplished simultaneously with heat, if desired, to form the metal vanadium oxide composition. For example, silver nitrate and copper nitrate can be added to the vanadium oxide particles as an aqueous solution. Alternatively, vanadium oxide nanoparticles can be mixed with metal oxide dry powders or elemental metal powders, thus avoiding the evaporation step. A sufficient amount of metal compound or elemental metal powder is added to produce the desired amount of metal incorporated into the vanadium oxide lattice. This incorporation into the vanadium oxide can be examined, for example, by X-ray diffractometer, as described below.

Precise conditions can be selected, including the type of oxidizing gas (if any), concentration of oxidizing gas, gas flow and pressure, temperature and processing time, etc., to produce the desired type of product material. The temperature is usually not high, that is, it is much lower than the melting point of the material. The application of softer conditions is to avoid sintering of particles into large-sized particles. A slightly higher temperature can be used to control the sintering of particles to produce slightly larger average particle diameters. particle.

To incorporate the metal into the vanadium oxide, the temperature generally ranges from about 50°C to about 500°C, preferably from 80°C to about 400°C, more preferably from 80°C to about 325°C. Treatment temperatures may range from about 80°C to about 250°C, and the particles are preferably heated for from about 5 minutes to about 100 hours. Some empirical adjustments may also be required in order to generate conditions suitable for the material required for fabrication. (3) The nature of the particles

A mass of particles comprising a metal vanadium oxide compound generally has an average primary particle diameter of less than 500 microns, preferably from about 5 microns to about 100 microns. More preferably from about 5 microns to about 50 microns, most preferably from about 5 microns to about 25 microns. Primary particles generally generally have a roughly spherical appearance. On closer inspection, crystalline particles generally always have faces corresponding to their crystalline lattice. However, the primary particle crystallization tends to show growth in three directions in space, so it forms a roughly spherical appearance. In a preferred embodiment, 95% of the primary particles, even more preferably 99% of the particles, have a ratio of major axis length to minor axis length of about 2 or less. The measurement of the diameter of an asymmetrically shaped particle is based on the measurement of the average length of its major axis.

Because of the very small size of these particles, the primary particles tend to loosely agglomerate due to the electromagnetic and Van der Waal forces of nearby particles. However, the nanometer size of the primary particles can be clearly observed in the transmission electron microscopy images of the particles. Particles usually have nanometer-scale surface surfaces corresponding to particles, which can be observed in microscopic images, and show unique characteristics due to their small size and large surface area per unit weight. For example, vanadium oxide particles have a surprisingly high energy density in lithium batteries, see US Patent No. 5,952,125 entitled "Battery with Electroactive Nanoparticles".

The primary particle size is preferably highly uniform. Laser pyrolysis usually yields particles with narrow diameter distributions. Moreover, the heat treatment carried out under very gentle conditions will not change the characteristics of its narrow diameter distribution range. When transported by aerosols, the distribution of particle diameters is very sensitive to the reaction conditions. Of course, if the reaction conditions are properly controlled, Particles with narrow diameter distributions can be obtained in aerosol delivery systems, as described above. According to the observation result of transmission electron microscope, primary particle generally has the size distribution that at least about 95%, preferably 99% of primary particles have a diameter greater than about 40% of the mean diameter and less than about 160% of the mean diameter. %. Preferably, the diameter distribution of the primary particles is such that at least about 95% and preferably 99% of the primary particles have a diameter greater than about 60% of the mean diameter and less than about 140% of the mean diameter.

Moreover, in a preferred embodiment, there are no primary particles approximately four times larger than the average diameter, or better yet three times, or even two times larger, in other words, no one appears on the size distribution diagram of the particles indicating that there are small amounts of The tail of larger diameter particles due to the small reaction zone and the quenching of the particles. The tails of the size distribution plot are effectively cut off, meaning that in a population of ¹⁰⁶ there will be no more than one particle with a diameter slightly larger than a certain cutoff value above the mean diameter.

The very narrow size distribution, the absence of tails in the distribution, and the roughly spherical morphology can open up many fields of application.

Furthermore, nanoparticles are generally of very high purity. The crystalline metal vanadium oxide particles produced by the method described above are expected to be of higher purity than the reactants because of the tendency of impurities to be excluded from the crystal lattice during crystal formation. Moreover, the crystallized vanadium oxide particles produced by the laser thermolysis pyrolysis method have a high degree of crystallinity. Likewise, crystalline metal vanadium oxide nanoparticles produced by heat treatment also have a high degree of crystallinity. Impurities on the surface of the particles are removed during heating, so that the particles not only have high crystallinity but also high purity.

Vanadium oxides have an intricate phase diagram due to the many possible oxidation states of vanadium. The known oxidation state of vanadium is between divalent vanadium and pentavalent vanadium, and the energy difference between the oxides of vanadium in different oxidation states is not large. Thus, it is possible to produce compounds with chemically mixed valences. Known forms of vanadium oxides are VO, VO _1.27 , V ₂ O ₃ , V ₃ O ₅ , V ₂ O, V ₆ O ₁₃ , V ₄ O ₉ , V ₃ O ₇ , and V ₂ O ₅ , taken individually Laser pyrolysis or combined with external heating can very successfully produce single-phase vanadium oxides in many different oxidation states, as demonstrated by X-ray diffraction sky. These single-phase materials are usually crystalline, although some amorphous nanoparticles are also produced. The heat treatment method is beneficial to increase the oxidation state of the vanadium oxide particles or transform the vanadium oxide particles into a more ordered phase.

There are also miscible regions in the vanadium oxide phase diagram. The particles in the miscible region can form into different oxidation states, or there can be different particles in the non-gas state at the same time. In other words, some particles or parts of particles have one stoichiometry and other particles or parts of particles have a different stoichiometry. Miscible nanoparticles have been fabricated. Non-stoichiometric materials can also be made.

Vanadium oxides usually form crystals that are octahedral or with impaired octahedral coordination. In particular, VO, V ₂ O ₃ , VO ₂ , V ₆ O ₁₃ and V ₃ O ₇ can form octahedral coordination. Moreover, V ₃ O ₇ can also form bipyramidal trigonal coordination. What V ₂ O ₅ forms is a square pyramid crystal structure. Recently, V ₂ O ₅ can also generate a two-dimensional crystal structure. See "Solid State Ionics" 79: 239-244 (1995) by M. Hibino et al. Book. Under suitable conditions, the vanadium oxide nanoparticles can also be amorphous. The crystalline lattice of vanadium oxides can be evaluated by X-ray diffraction measurements.

Metal vanadium oxide compounds can be formed in various stoichiometric ratios. U.S. Patent No. 4,310,609 of Liang et al. is cited here, titled "Metal Oxide Composition of Cathode Materials for High Energy Density Batteries", in which the forms described are: Ag _0.7 V ₂ O _5.5 , AgV ₂ O _5.5 and Cu _0.7 V ₂ O _5.5 . Oxygen-deficient silver vanadium oxide products are described in U.S. Patent No. 5,389,472 by Takenchi et al., entitled "Preparation of silver vanadium oxide cathodes using Ag(0) and V ₂ O ₅ as starting materials" with the chemical formula Ag _x V ₂ O _y , where: 0.3 ≤ X ≤ 2.0, 4.5 ≤ Y ≤ 6.0, and then the phase diagram of silver vanadium oxide containing chemical blends V ₂ O ₅ and AgVO ₃ is described in a paper titled “In nonaqueous electrochemical cells Cathode materials for "European Patent Application No. 0689256A, which is hereby incorporated by reference. (4) Battery

Referring to FIG. 8 , battery 450 has a negative electrode 452 , a positive electrode 454 and a separator 456 between negative battery 452 and positive electrode 454 . A single cell can contain multiple positive electrodes and/or multiple negative electrodes, and the dielectric can be supplied in various forms, as described below. Battery 450 preferably includes current collector tabs 458, 460 associated with positive electrode 454, and negative electrode 452, respectively. Multiple current collectors may be associated with each electrode if desired.

Lithium has been used in batteries for reduction/oxidation reactions because it is the lightest metal, and because it is the most electropositive metal. Forms of certain metal oxides incorporating lithium ion intercalation or similar mechanisms such as localized chemisorption into their structure are known and can be found in various suitable forms in vanadium oxide lattices, as well as metal Lithium ions are inserted into the crystal lattice of the vanadium oxide composition. Applicable metal vanadium oxide nanoparticles in batteries can be produced by heat treatment of vanadium oxide nanoparticles and metal compounds, or metal vanadium oxide nanoparticles can be directly added or not added by laser pyrolysis Heat treatment method output. In particular, lithium is inserted into the vanadium oxide lattice or into the metal vanadium oxide lattice when the battery is discharged. Lithium leaves the lattice during discharge, that is, when an external EMF is connected to the battery, a voltage is applied to the battery. Lithium leaves the lattice when current flows to the positive electrode. Positive electrode 454 is a cathode when discharging and negative electrode 452 is an anode when the battery is discharging. Metal vanadium oxide particles can be directly used as the positive electrode of lithium-based batteries to provide high energy density to the batteries. Suitable metal vanadium oxide particles can be effective electroactive materials for anodes in lithium or lithium-ion batteries. Positive electrode 454 includes electroactive nanoparticles such as metal vanadium oxide nanoparticles bound together with a binder such as a polymeric binder. The nanoparticles being used in electrode 454 typically have various shapes, such as generally spherical nanoparticles or elongated nanoparticles. In addition to metal vanadium oxide particles, the positive electrode 45 also includes other electroactive nanoparticles, such as TiO ₂ nanoparticles, vanadium oxide nanoparticles, and manganese oxide nanoparticles. The production of _TiO2 nanoparticles is described in US Patent No. 4,705,762, incorporated herein by reference. Vanadium oxide nanoparticles are known to exhibit quite surprisingly high energy densities, see US Patent No. 5,952,125. The title is "Batteries with Electroactive Nanoparticles." The production of manganese oxide nanoparticles is described in co-pending US Patent Application No. 09/188,770, filed Nov. 9, 1998, entitled "Metal Oxide Particles," commonly assigned to Kumar et al.

Certain electrically active materials are reasonable conductors of electricity. Positive electrodes typically also include additional conductive particles among the electroactive nanoparticles. These additional, electrically conductive particles are usually entrapped in 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. A high loading of particles can be obtained in the binder. The weight of the particles is preferably more than 80%, more preferably more than 90%, of the weight of the entire positive electrode. The binder can be any kind of suitable polymer, for example, polyvinylidene fluoride, polyethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylate, ethylene-(propylene-diene mono Body) copolymer (EPDM) and their mixtures and copolymers.

Negative electrode 452 can be constructed from a variety of materials suitable for use with lithium-ion electrolytes. In lithium batteries, the negative electrode may comprise lithium metal or lithium alloy metal, whether in the form of foil, grid or metal particles in a binder.

Lithium-ion batteries use particles of a composition that can intercalate lithium. Such particles are entrained in the negative electrode by the binder.

Suitable intercalation compounds include, for example, graphite, synthetic graphite, coke, mesocarbons, doped carbons, niobium pentoxide, tin alloys, _SnO2, and mixtures and combinations thereof.

Current collector tabs 458, 460 are used to collect current flowing from the battery. The current collectors 458, 460 are electrical conductors, typically made of metals such as nickel, copper, aluminum, iron and stainless steel, and formed as metal foil or preferably a metal grid. Current collector tabs 458, 460 may be placed on or within their associated electrodes.

Barrier 456 is an electrical insulator and provides access to at least some forms of ions. Ion migration through the separator keeps the various parts of the battery electrically neutral. Typically, the separator prevents the electroactive compound in the positive electrode from contacting the electroactive compound in the negative electrode.

There are various materials available for the compartments. For example, the interlayer may consist of a porous matrix in the form of glass fibers. The best barriers are made of polymers such as those used in adhesives. The polymer interlayer can be made into a porous form for ion conduction. Alternatively, the polymer interlayer can use a solid dielectric made of a polymer such as polyethylene oxide. Solid dielectrics incorporating dielectrics into polymer matrices allow ions to conduct without liquid solutions.

Electrolytes used in lithium or lithium ion batteries may include various salts of lithium. Preferred lithium salts have inert negative ions and are nontoxic. Suitable lithium salts include, for example, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium 2-(3fluoromethylimidosulfate), lithium trifluoromethanesulfonate, lithium 3-(3fluoromethylsulfonyl)methyl , lithium tetrafluoroborate, lithium perchlorate, lithium tetrachloroaluminate, lithium chloride, and lithium perfluorobutane.

If a liquid solution is used to dissolve the dielectric, the solution is preferably inert and does not dissolve the electroactive material. Commonly suitable ones include, for example, propylene carbonate, dimethyl carbonate, diethyl carbonate, 2-methyltetrahydrofuran, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, ethylene carbonate , a-butyrolactone, dimethyl sulfoxide, acetonitrile, formamide, dimethylformamide, nitromethane.

The shape of the battery components can be adjusted to suit the final desired product, eg button cells, rectangular or round cells. Batteries generally include a can, appropriate portions of which are electrically connected to the battery's current collectors and/or electrodes. If a liquid dielectric is used, the enclosure shall prevent leakage of the dielectric. The case should keep the cells of the battery close to each other to reduce the internal resistance of the battery. Multiple batteries can be placed in one housing, where individual batteries can be connected in parallel or in series. Embodiment Example 1-production of vanadium oxide by laser high temperature pyrolysis

Single- _phase VO particles can be produced by laser pyrolysis. _VOCl3 (manufactured by Strem Chemical Inc., Newburyport, MA) initial vapor can be bubbled into the reaction chamber by argon gas passing through the _VOCl3 liquid in the container at room temperature. The reactant gas mixture containing VOCl ₃ , Ar, O ₂ and C ₂ H ₄ enters the reactant gas nozzle and is sprayed into the reaction chamber. The size of the reactant gas nozzle is 5/8 inch x 1/8 inch. C ₂ H ₄ gas is used as laser absorbing gas. Argon is used as the inert gas.

The synthesized vanadium oxide nanoparticles can be directly contained in air, and the representative reaction conditions for the production of this material are shown in Table 1.

surface Mutually VO ₂ Crystal structure monoclinic prism Pressure (Torr) 210 Argon-window (sccm) 700 Argon-shielded (slm) 7.0 vinyl (slm) 1.61 Carrier Gas - Argon (slm) 1.4 Oxygen (slm) 0.47 Primary particle temperature (℃) 40 Productivity (gm/hr) 35 Laser power input (Watts) 780 Laser power output (Watts) 640 Where: sccm = standard cubic centimeter per minute

slm=standard liter/minute

Argon-Window = Argon flow through inlets 216, 218

Argon-shield = flow of argon through annular channel 142.

The X-ray diffraction pattern of a representative nanoparticle is shown in Figure 9, and the diffraction peaks corresponding to a single prism-like structure are clearly visible in it. The structure identified in the diffractogram is almost identical to that in the corresponding bulk of the larger particle size. Example 2 - Heat Treatment Form V ₂ O ₅ Nanoparticle Crystals

The starting material for heat treatment was _VO nanoparticle produced by laser pyrolysis according to the parameters in Table 1.

The nanoparticles are heat treated in a furnace approximately as in FIG. 6 . The granules are delivered to the glass in batches of about 100 grams to about 150 grams. The oxidation was passed through a 1/8 inch stainless steel tube at a flow rate of 155 cc/min. The powder was mixed with a constant mixing speed of 5 rpm during heat treatment. The powder was first heated at 100°C for 30 minutes, then at 200°C for 30 minutes, and finally at 230°C for 16 hours. The heating rate is to heat the sample to the target temperature every 4°C/min. _The obtained nanoparticles are single-phase crystalline _V2O5 nanoparticles. The X-ray diffraction pattern of this material is shown in Figure 10. From the X-ray diffraction pattern, it can be confirmed that the obtained particles are orthorhombic V ₂ O ₅ .

Transmission electron microscopy (TEM) images can be obtained from typical nanoparticles after heat treatment. See Figure 11. Manual measurement of the particle diameters in Figure 11 gives an approximate size distribution, see Figure 12. An average of about 10-11 nm can be obtained. Sizes were measured and recorded only for particles with sharp edges in the image to avoid blurred areas in the electron micrograph. This will not cause measurement deviation, because the electron microscope only observes from one direction, and cannot see a clear image of all the particles due to different orientations of the crystal. Example 3 - _Thermal treatment of _V2O5 nanoparticles to form silver vanadium oxide

This embodiment uses vanadium oxide nanoparticles as the initial material to produce nanoscale silver vanadium oxide. The silver vanadium oxide is produced by heat treatment.

About 9.5 grams of silver nitrate ( _AgNO3 ) (manufactured by "EM Industries, Hawthorne, NY") was dissolved in about 15 milliliters of deionized water. About 10 grams of V ₂ O ₅ nanoparticles obtained by the method described in Example 2 were put into the silver nitrate solution to form a mixed solution, and stirred in a magnetic stirrer for about 30 minutes. The well-stirred solution was heated in an oven to 160°C to remove water. The resulting dry powder mixture is then ground with a mortar and pestle. Six samples weighing approximately 100 mg to 300 mg calculated from the resulting ground powder were placed in 1 cm3 boats. The boat is then placed in a quartz tube that passes through a furnace for heat treatment. The heating furnace is basically as shown in Fig. 7 above. The flow rate of oxygen or argon gas into the 1.0 inch diameter quartz tube is about 20 sccm. Each sample was heated in a furnace under the following conditions:

1) 250°C, 60 hours in argon,

2) 250℃, 60 hours in oxygen,

3) 325°C, 4 hours in argon,

4) 325°C, 4 hours in oxygen,

5) 400°C, 4 hours in argon,

6) 400°C, 4 hours in oxygen.

The sample was heated at an average rate of about 2°C/minute and cooled at a rate of about 1°C/minute. The time in the above conditions does not include the heating and cooling time.

The particle structure of the heat-treated sample was detected by X-ray diffraction method, and the X-ray diffraction patterns of the sample heated in argon and oxygen are shown in Fig. 13 and Fig. 14 respectively. The peaks in the diffractograms obtained for the various heated samples show that there is Ag ₂ V ₄ O ₁₁ in them. The samples heated at 400°C show a lack of significant amounts of V ₂ O ₅ . When the samples were annealed at lower temperatures for longer periods of time, any residual V ₂ O ₅ starting material should be removed.

The transmission electron microscope image of the silver vanadium oxide particles is shown in FIG. 15 . For comparison, a transmission electron microscope image of a sample of V ₂ O ₅ nanoparticles used to manufacture silver vanadium oxide nanoparticles is shown in FIG. 16 . The scale of the two figures is the same. The weighing conditions of the V ₂ O ₅ nanoparticles in Figure 16 were the same as those described in Examples 1 and 2, and the average diameter of the silver vanadium oxide particles in Figure 15 was surprisingly larger than that of the vanadium oxide particles in Figure 16 The nanoparticle starting material is also slightly smaller. Example 4 Heat Treatment of VO _{Nanoparticles} to Form Silver Vanadium Oxide

This example shows an example of the production of nanoscale silver vanadium oxide using _VO2 vanadium oxide nanoparticles as initial particles. Silver vanadium oxide is produced by heat treatment.

VO ₂ nanoparticles were produced under similar conditions as in Example 1. 10 grams of nanocrystalline VO _powder was washed through 500 milliliters of deionized water to remove residual chlorine, using a 500 milliliter filtration system of the brand "Corming®" with a 0.2 micron "Nylon®" (nylon) membrane and The sidearm is evacuated to clean the filter system. The washed nanocrystalline _VO2 powder was dried under vacuum at a temperature below 30 inches Hg (750) at a temperature between 100°C and 120°C for at least 12 hours. The washed and dried nanocrystalline _VO2 was then processed in a "SPEX™ 800" mixer mill for 15 minutes to break up agglomerates.

Silver nitrate crystalline powder (more than 99% purity) produced by "EM Industries (Hawthorne, NY)" was added to the deagglomerated nanocrystalline _VO powder in a weight ratio, and the ratio was 1 mole of AgNO ₃ to 2 moles of AgNO _VO2 . The mixed powder was then ground for 20 minutes in a "Fritsch Mortar Grinder Model P-2 (Gilson Company, Inc., Worthington, OH)" grinder. Then it was heated in a tube furnace, as shown in Fig. 7, wherein the oxygen flow rate of the flowing oxygen atmosphere was 190 ml/min.

Heat treatment also includes heating from room temperature to 180°C over a period of one hour or more followed by an equalization time of at least one hour. The temperature is then increased gradually to about 400°C, and this final temperature is maintained for about 20 hours, after which the product is allowed to cool to room temperature over a period of 5 to 15 hours.

The crystal structure of the obtained powder was measured by X-ray diffraction method, and the X-ray diffraction pattern is shown in FIG. 17 . In the figure, there are similar peaks with silver vanadium oxide (Ag ₂ V ₄ O ₁₁ ).

The properties of the obtained silver vanadium oxide nanoparticles were measured by differential scanning calorimeter (DSC). The DSC device is a "model Universal V2.3C DSC" device provided by "TA Instruments, Inc., New Castle, DE". The measured heat flow diagram as a function of temperature is shown in Figure 18. The curve shows only two isothermal points each corresponding to a transition reaction at 558°C and a eutectic point at 545°C. A further description of the transfer phenomenon in silver vanadium oxide can be found in the literature: "P. Flenry, Rev. Chim. miner., 6(5) 819 (1969)".

The endothermic point at lower temperature was not observed, especially the endothermic point corresponding to the melting point of _AgVO3 around 463 °C was not observed.

Thus, the DSC data demonstrate that the nanoscale silver vanadium oxide material is compositionally very pure relative to the material having a phase transition before the DSC test limit of 1000°C.

This dry powder mixing method can also successfully produce silver vanadium oxide nanoparticles from a mixed powder of nanoparticle crystalline V2O5 and crystalline silver nitrate powder, only because the nanocrystalline V2O5 particles are obtained by heat treatment and do not contain chlorine. Usually the case step is no longer needed. In addition, the full sub-ratio is also adjusted accordingly. Embodiment 5-directly synthesize nanoscale silver vanadium oxide material by laser high temperature pyrolysis

The synthesis of the nanoscale silver-vanadium oxide material described in this example is accomplished by laser pyrolysis. Particles are produced mainly by using a laser pyrolysis device as shown in Figure 1, and by using a reactant delivery device as shown in Figure 3A.

The solution delivered as aerosol in the reaction chamber is produced from vanadium precursors. In order to produce this vanadium primary particle solution, 20.0 g of a V (trivalent) oxide V ₂ O ₃ sample produced by “Aldrich Chemical (Milwaukee, WI)” was first suspended in 240 ml of deionized water. 60 ml of aqueous nitric acid (HNO ₃ ) (70% by weight) was dropped into the trivalent vanadium oxide and stirred vigorously. Note that this addition of nitric acid is exothermic and releases a brown gas suspected to be _NO2 . The resulting vanadium precursor solution was dark blue.

In order to produce the primary particle solution for delivery of the aerosol, 22.7 g of silver nitrate produced by "Aldrich Chemical (Milwaukee, WI)" was dissolved in 200 ml of deionized water to prepare a silver nitrate solution. The silver nitrate solution, which is used as the metal mixture solution for the delivery of the air float, is added to the vanadium primary particle solution and stirred continuously. This dark blue solution has a molar ratio of vanadium to silver of about 2:1. Similar results were obtained with higher ratio amounts of silver.

The aqueous solution with vanadium and silver precursors is fed into the reaction chamber as an aerosol. C ₂ H ₄ gas is used as a laser absorbing gas, and argon is an inert gas. O ₂ , Ar and C ₂ H ₄ are all fed into the gas supply pipe of the reactant supply system. The reaction mixture containing vanadium oxide, silver nitrate, Ar, O ₂ , and C ₂ H ₄ is fed into the reactant nozzle to be sprayed into the reaction chamber. The opening size of the reactant nozzle is 5/8 inch x 1/ 4 inches. Other parameters related to the laser pyrolysis synthesis of the particles in Example 1 are shown in Table 2.

Table 2 crystal structure mixed phase Pressure (Torr) 450 Argon-window (sccm) 2.00 Argon-shielded (slm) 9.81 vinyl (slm) 0.73 Argon (slm) 4.00 Oxygen (slm) 0.96 Laser power output (Watts) 490-510 Laser power output (Watts) 450 Vanadium/Silver Molar Ratio 221 Primary particle temperature (°C) room temperature

slm = standard liters per minute,

Argon-Window = Argon flow through inlets 216, 218,

Argon-shield = flow of argon gas through annular channel 142,

Argon = flow rate of argon mixed directly with the aerosol.

In order to evaluate the atomic arrangement, an X-ray diffraction test was performed on a "Siemess D 500" X-ray diffractometer using Cu(Kα) radiation. The X-ray diffraction patterns of the samples produced according to the conditions in Table 2 are shown in Figure 19, and the peaks on the diffraction patterns can be identified as VO ₂ , V ₂ O ₃ and elemental silver. Other peaks in the graph could not be identified to be associated with known materials and are discussed further in Example 7.

The sample powder produced under the conditions in Table 2 was further analyzed by transmission electron microscope, and its transmission electron microscope (TEM) is shown in FIG. 20 . In the TEM images, a batch of particles fall on different size distributions. This is characteristic of mixed-phase materials produced by laser pyrolysis, where each material usually has a narrow particle size distribution.

In addition, as described in the following examples, these nanoscale silver-vanadium oxide materials in an oxygen environment can obtain Ag ₂ V ₄ O ₁₁ crystals with a high yield. The heat treatment of the nanoscale silver-vanadium oxide material produced by embodiment 6-laser high temperature pyrolysis

This example shows the production of nanoscale crystallized silver vanadium oxide Ag ₂ V ₄ O ₁₁ using the nanoscale silver vanadium oxide material produced by the laser pyrolysis method as described in Example 5 as the starting material.

The nano-particles corresponding to the sample silver vanadium oxide powder sample obtained in Example 5 whose weight is about 300 to 700 mg are placed in a small boat of 1 cubic centimeter, and the small boat is put into a quartz tube worn in a heating furnace for heat treatment . The furnace is substantially as shown in Figure 7 above. Oxygen was passed through a 10 inch diameter quartz tube at a flow rate of 30 sccm.

The heat treatment is to heat from room temperature to 180°C for more than 1 hour, and then use at least one hour as the equilibrium time. Then, the temperature is raised to about 360°C at a rate of about 3°C per minute, and maintained at this final temperature for 16.5 hours. After heating at the final temperature for the required time, the product is cooled to room temperature at a rate of 1°C per minute. . The above heat treatment time does not include heating and cooling time.

The particle structure after heat treatment is measured by X-ray diffraction method, and the X-ray diffraction pattern of the sample after heat treatment is shown in FIG. 21 . The heat-treated powder was also tested with a transmission electron microscope (TEM), and the TEM image of the sample is shown in Figure 22. Embodiment 7-directly synthesize silver vanadium oxide nanoparticles by laser high temperature pyrolysis

This example describes the synthesis of silver vanadium oxide nanoparticles by laser pyrolysis. Particles are produced essentially using a laser pyrolysis device as shown in Figure 1, as described above, and using a reactant delivery device as shown in Figure 3A or 3B.

Two solutions must be prepared for delivery as aerosols in the reaction chamber. Both solutions were produced using similar vanadium precursor solutions. To produce the first vanadium precursor solution, 10.0 g of a sample of trivalent vanadium oxide (V ₂ O ₃ ) purchased from "Aldrich Chemical (Milwaukee, WI)" was suspended in 120 ml of deionized water. 30 ml of aqueous nitric acid (HNO ₃ ) (70% by weight) solution was dropped into the V ₂ O ₃ suspension and stirred vigorously. Note that the reaction of adding nitric acid is an exothermic reaction, and releases a brown gas suspected to be NO2. The resulting vanadium precursor solution (about 150 ml) was a dark blue solution.

The second vanadium primary particle solution is exactly the same as the first vanadium primary particle solution except that the amount of each component is three times that of the first one.

To produce the first silver solution, 9.2 grams of silver carbonate (Ag ₂ CO ₃ ) from "Alclrich Chemieal (Milwaukee, WI)" was suspended in 100 ml of deionized water to form an Ag ₂ CO ₃ solution. Then 10 ml of aqueous nitric acid (70% by weight) was dropped into it and stirred vigorously. After the nitric acid was dropped, a clear and colorless solution was obtained. To produce the first metal mixture solution for transporting the aerosol, the silver solution is added to the first vanadium precursor solution with constant stirring. The resulting dark blue first metal mixed solution had a molar ratio of vanadium to silver of about 2:1.

To produce _the second silver solution, 34.0 grams of silver carbonate ( _Ag2CO3 ) from "Alclrich Chemical (Milwaukee, WI)" was dissolved in 300 milliliters of deionized water. To prepare the second metal mixture solution for delivery of the aerosol, the silver nitrate solution is added to the second vanadium precursor solution with constant stirring. The resulting second dark blue metal mixed solution also had a molar ratio of vanadium to silver of about 2:1.

The selected aqueous solution of vanadium and silver precursors is fed into the reaction chamber as an aerosol. C ₂ H ₄ gas is used as a laser absorber, and argon is an inert gas. O ₂ , Ar and C ₂ H ₄ are all fed into the gas supply pipe of the reactant supply system. The reaction mixture containing vanadium oxide, silver nitrate, Ar, O ₂ , and C ₂ H ₄ is fed into the reactant nozzle for injection into the reaction chamber. The opening size of the reactant nozzle is 5/8 inch x 1/4 inch. Other synthesis parameters of laser pyrolysis synthesis related to particle synthesis are shown in Table 3. Samples were prepared using the reactant delivery system shown in Figure 3A, while sample 2 was prepared using the reactant delivery system shown in Figure 3B.

table 3 1 2 Crystal structure mixed phase mixed phase Pressure (Torr) 600 600 Argon-window (sccm) 2.00 2.00 Argon-shielded (slm) 9.82 9.86 vinyl (slm) 0.74 0.81 Argon (slm) 4.00 4.80 Oxygen (slm) 0.96 1.30 Laser power input (Watts) 490-531 390 Laser power output (Watts) 445 320 primary particle solution 1 2 Primary particle temperature (°C) room temperature room temperature in:

slm = standard liters per minute,

Argon-Window = Argon flow through inlets 216, 218,

Argon-shield = flow of argon gas through annular channel 142,

Argon = Argon flow directly mixed in the aerosol.

In order to evaluate the atomic arrangement, an X-ray diffraction test was performed on a "Siemess D 500" X-ray diffractometer using Cu(Kα) radiation. The X-ray diffraction patterns of sample 1 (lower curve) and sample 2 (upper curve) produced according to the conditions in Table 3 are shown in Figure 23. The sample has peaks corresponding to VO ₂ and elemental silver, but no corresponding peaks to known materials. peak. The main crystalline phase of these samples has peaks at 20 equal to 30–31°, 32, 33 and 35. This phase was thought to be that of a previously unknown silver vanadium oxide. This phase was now observed in samples prepared by mixing vanadium oxide nanoparticles and silver nitrate _phases after heating the samples for a period of time insufficient to generate _{Ag2V4O11 .} Specific volume measurements of sample 1 placed in a coin cell, which will be described later, also support this interpretation. Such smaller peaks were also observed for samples obtained under the conditions described in Example 5.

The sample powder produced under the conditions in Table 3 was further analyzed by transmission electron microscope, and its transmission electron microscope images (TEM) are shown in Figure 24A (the first column in Table 3) and Figure 24B (the second column in Table 3). In the TEM image, there are a number of particles falling in different size distributions, which is characteristic of the mixed-phase materials produced by laser pyrolysis, where the first material usually has a very narrow particle size distribution. Increased oxygen flow, decreased laser power, and increased pressure can all increase the fraction of silver vanadium oxide in the miscible material. Example 8 - direct synthesis of silver vanadium oxide nanoparticles by laser high temperature pyrolysis

This example describes the synthesis of silver vanadium oxide particles by laser pyrolysis. Particles were produced essentially using a laser pyrolysis device as shown in Figure 1, as described above; and using a reactant delivery device as shown in Figure 3B.

A solution is prepared for delivery into the reaction chamber as an aerosol. To produce the first vanadium precursor solution, 20 g of a sample of trivalent vanadium oxide (V ₂ O ₃ ) obtained from “Aldrich Chemical (Milwawkee, WI)” was suspended in 240 ml of deionized water, and 60 ml of aqueous Nitric acid (HNO ₃ ) (70% by weight) solution was dropped into the V ₂ O ₃ suspension and stirred vigorously. Note that the reaction of adding nitric acid is an exothermic reaction, and the product releases a brown gas suspected of being _NO , and the resulting vanadium primary particle solution (about 300 milliliters) is a dark blue solution.

Five different silver solutions were prepared in order to create one solution for delivery as an aerosol with variable ratios of silver to vanadium. To produce silver solutions, silver nitrate (AgNO ₃ ) from “Alarich Chewical (Milwanka, WI)” was dissolved in 200 ml of deionized water. The weights of silver nitrate in these five solutions were: 1) 15.9 g, 2) 18.1 grams, 3) 20.4 grams, 4) 22.7 grams, 5) 23.8 grams. Add the silver nitrate solution to the vanadium primary particle solution and keep stirring to prepare the metal mixture solution used as the air float.

The five solutions had the following molar ratios of silver to vanadium: 1) 0.7:2, 2) 0.8:2, 3) 0.9:2, 4) 1.0:2, 5) 1.05:2.

The selected aqueous solution with vanadium and silver precursors is fed into the reaction chamber as an aerosol. C ₂ H ₄ gas is used as a laser absorbing gas, and argon is an inert gas. O ₂ , Ar and C ₂ H ₄ are all fed into the gas supply pipe of the reactant supply system. The reaction mixture containing vanadium oxide, silver nitrate, Ar, O ₂ , and C ₂ H ₄ is fed into the reactant nozzle to be sprayed into the reaction chamber. The opening size of the reactant nozzle is 5/8 inch x 1/ 4 inches. Additional parameters for laser pyrolysis synthesis relevant to particle synthesis are listed in Table 4.

Table 4 crystal structure mixed phase Pressure (Torr) 600 Argon-window (sccm) 2.0 Argon-shielded (slm) 9.86 ethylene (slm) 0.81 Argon (slm) 4.80 oxygen (slm) 1.30 Laser power input (Watts) 390 Laser power output (Watts) 320 Primary particle temperature (°C) room temperature

slm = standard liters per minute,

Argon-Window = Argon flow through inlets 216, 218,

Argon-shield = flow of argon gas through annular channel 142,

Argon = flow rate of argon mixed directly with the aerosol.

In order to evaluate the atomic arrangement, an X-ray diffraction test was performed on a "Siemess D 500" X-ray diffractometer using Cu(Kα) radiation. The X-ray diffraction patterns of samples 1-5 produced under the conditions shown in Table 4 are shown in Figure 25. The samples have peaks corresponding to VO ₂ , elemental silver, possibly V ₂ O ₃ , and peaks not corresponding to known materials . The main crystalline phases of these samples on Table 20 have peaks equal to 30-31°, 32, 33 and 35. As indicated above, this phase was thought to be that of a previously unrecognized silver vanadium oxide. When the ratio of silver to vanadium increases, the peak corresponding to vanadium oxide increases, which proves that when the relative amount of silver increases, the additional amorphous components containing vanadium, oxygen and possibly silver also increase up. Example 9 - Production of Elemental Silver Nanoparticles by Laser Pyrolysis

The synthesis of elemental silver nanoparticles described in this example is achieved by laser pyrolysis. Particles were produced primarily using a laser pyrolysis apparatus as shown in Figure 1, as described above; and using a reactant delivery apparatus as shown in Figure 3A.

A 1 molar solution of silver nitrate used as an aerosol for delivery into the reaction chamber was prepared by dissolving 50.96 grams of silver nitrate from "Aldrich Chemical, Milwaukee, WI" in 300 ml of deionized water to produce a clear solution. C ₂ H ₄ gas is used as a laser absorbing gas, while argon is an inert gas. O ₂ , Ar and C ₂ H ₄ are all fed into the gas supply pipe of the reactant supply system. The reaction mixture containing silver nitrate, Ar, O ₂ , and C ₂ H ₄ was fed into a reactant nozzle for injection into the reaction chamber. The reactant nozzle had opening dimensions of 5/8 inch by 1/4 inch. Other parameters of laser pyrolysis synthesis related to particle synthesis are listed in Table 5.

table 5 1 2 Crystal structure face-coaxial cuboid face-coaxial cuboid Pressure (Torr) 450 450 Argon-window (sccm) 2.00 2.00 Argon-shielded (slm) 9.82 9.82 ethylene (slm) 1.342 0.734 Argon (slm) 5.64 3.99 oxygen (slm) 1.41 0.96 Laser power input (Watts) 970 490 Laser power output (Watts) 800 450 Productivity (gv/hr) 1.44 1.02 Primary particle temperature (°C) room temperature room temperature in:

slm = standard liters per minute,

Argon-Window = Argon flow through inlets 216, 218,

Argon-shield = flow of argon gas through annular channel 142,

Argon = Argon flow directly mixed in the aerosol.

In order to evaluate the atomic arrangement, an X-ray diffraction experiment was performed on a "Siemess D 500" X-ray diffractometer using Cu(Kα) radiation. The X-ray diffraction patterns of samples 1 and 2 produced under the conditions shown in Table 5 are shown in Figures 26 and 27, respectively, and the samples have strong peaks corresponding to elemental silver.

The sample powders produced under the conditions in the first column of Table 5 were further analyzed by transmission electron microscopy. The electron microscope picture is shown in Figure 28. The particle size distribution in the TEM picture is wider than that of the particle size distribution synthesized by laser pyrolysis. The particle size distribution can be substantially narrower using either gas phase primary particles or more uniform aerosol delivery.

Typical particles were also analyzed by elemental analysis. Typical elemental analysis results for these materials are approximately (by weight) 93.09% silver, 2.40% carbon, 0.05% hydrogen, and 0.35% nitrogen. Oxygen is not directly measurable and may account for some of the remainder. Elemental analysis was done using "DesertAnalytics, Tucson, Arizona".

The carbon composition in the nanoparticles appears to be in the form of a coating that can be formed from ethylene introduced by the reactant stream. Generally, carbon can be removed by heating under mild oxidizing atmosphere conditions. Such carbon removal is further described in commonly assigned co-pending US Patent Application No. 09/123,255, entitled "Particles of Metal (Silicon) Oxide/Carbon Combinations," incorporated by reference.

Since copper and gold, other elements in group IB, have similar chemical properties to silver, copper and gold primary particles should be used to replace silver primary particles under the same conditions to obtain elemental copper or gold nanoparticle products. Example 10 - Manufacture of Lithium Batteries with Silver Vanadium Oxide Nanoparticles

This example describes the suitability of using silver vanadium oxide particles to produce lithium-based batteries and the potential for increased capacity. To produce the silver vanadium oxide test cell inserted from one of the above examples,

Weigh the required silver vanadium oxide nanoparticles and predetermined amount of graphite powder (ChuetsuGraphite Works, Co., Osaka Japan) and calcium carbide black powder (Catalog number 55, Cheveon Corp.) to be combined into a conductive diluent, producing A 60% by weight Teflon(R) dispersant was added to the water as a binder. The mixture comprised 70% by weight of silver vanadium oxide nanoparticles, 10% by weight of graphite, 10% by weight of carbide black and 10% by weight of Teflon(R). The resulting composition was well kneaded and rolled into a 1 mm thick sheet, from which a disc with an area of ² cm2 was cut. The disc was then dried and placed in a 1.6 cm diameter mold with 12,000 lbs of pressure for 45-60 seconds to form a solid pellet. The pellets were then vacuum dried and weighed.

This pressed dry disc was used as the active cathode in a 2025 coin cell. To fabricate the coin cell shock a 1.6 cm ^square disc of nickel expanded metal was resistance welded inside the stainless steel case cover of a 2025 coin cell (Catalog No. 10769, Alfa Aesar, Inc., Ward Hill, MA) As a collector sheet. A 2 ^cm2 disc was punched out of battery grade lithium foil from Hohsen Corp (Osaka Japan) and cold welded to nickel expanded metal. An appropriately sized porous polypropylene separator disc (Celgard(R) 2400, Hoechst-Celanese, Charlotte, NC) was placed on top of the lithium disc.

A predetermined amount of dielectric was added to the separator/lithium disc assembly. The dielectric solution consisted of 1M LiPF ₆ salt. The solvent of the dielectric solution was 1:1 (volume) ethylene carbonate and dimethyl carbonate. The second stainless steel expanded metal disc punched out with an area of 1.6 ^cm2 was welded in the stainless steel casing of the 2025 button cell by resistance welding. Active cathode pellets were placed on nickel expanded metal and mated as above for the separator/lithium disc assembly. The stainless steel shell and the stainless steel shell cover are separated by a polypropylene plastic ring. The mated assembly was then crimped to form a test button cell.

Test with a battery testing device produced by "Maccor Battery Test Sysfem, Series 400, from Maccor, Inc., (Tulsa, OK)", record its discharge pattern, and obtain the discharge capacity of the active material.

When making the first button battery, the nano-silver vanadium oxide 0.143 formed by heating nano _-VO particles and silver nitrate as described in Example 4 was used to make cathode pellets. The open circuit voltage measured immediately after crimping was 3.53 volts. Put the battery into a constant temperature room (at a temperature of 37±1°C) to balance for 4 hours. The cell was then discharged at a constant discharge current of 0.1 milliamperes per square centimeter of active electrode interface area. When the voltage reached 1.0 volts, the current was allowed to decay but the battery was kept at 1.0 volts for 5 hours. A voltage of 1.0 volts allows measurement of battery capacity independent of polarization effects that occur when discharged to the final current value. This gives a battery capacity measurement that is closer to the maximum value obtained with infinite slow playback.

Graph of voltage as a function of time and Figure 29, the first 4 hours in the graph were measured during temperature equilibration (which did not include any battery discharge). The voltage curve as a function of storage capacity is shown in Figure 30. The measured battery discharge capacity was 51.0 mAh, or a specific capacitance value of about 357 mAh/g (active silver vanadium oxide nanoparticles). This is greater than the theoretical specific capacity.

A second cell was fabricated using direct synthesis of silver vanadium oxide as described in Example 5 above, and the cathode contained 0.148 grams of nanometer silver vanadium oxide particles. The open circuit voltage measured immediately after crimping was 3.3 volts. Put the battery in a constant temperature room at 37±1°C for 4 hours to balance. The stable discharge current of the battery is 0.309 mA per square centimeter of active electrode interface area. When the voltage reaches 1.0 volts, allow the discharge current to decrease and keep the battery voltage at 1.0 volts for 5 hours.

The voltage-time curve is shown in Figure 31. The initial 4 hours in the graph are taken during temperature equilibration and do not include any battery discharge. The curve of voltage versus storage capacity is shown in Figure 32. As shown in the figure, the measured storage and discharge capacity is 15.4 mAh, or the specific capacity value is about 104.3 mAh/g (active silver vanadium oxide nanoparticles). The measurement of the discharge capacity is obtained by integrating the product of the voltage and the partial current to the discharge current. The specific capacitance value is obtained by dividing the discharge capacity by the mass of the active material.

The third test cell was made of silver vanadium oxide synthesized by laser pyrolysis and subsequent furnace annealing procedures as described in Example 6 above. The active cathode pellet contained 0.157 grams of silver vanadium oxide nanoparticles. The open circuit voltage tested immediately after crimping was 3.5 volts. The battery is placed in a constant temperature room at 37±1°C for 4 hours to balance. The stable discharge current of the battery is 0.100 mA per square centimeter of active electrode interface area. When the voltage reaches 1.0 volts, allow the discharge current to decrease and keep the battery voltage at 1.0 volts for 5 hours.

The voltage-time curve is shown in Figure 33. The initial 4 hours in the graph are taken during temperature equilibration and do not include any battery discharge. The curve of voltage versus storage capacity is shown in Figure 34. As shown in the figure, the measured storage and discharge capacity is 63.53 mAh, or the specific capacity value is about 404 mAh/g (active silver vanadium oxide nanoparticles).

The fourth test battery was made by the above-mentioned method using the silver vanadium oxide synthesized by laser pyrolysis method under the conditions specified in the first example in Table 3 in the above-mentioned embodiment 7. The active cathode pellet contained 0.154 grams of silver vanadium oxide nanoparticles. The open circuit voltage measured immediately after crimping was 3.4 volts. The battery is placed in a constant temperature room at 37±1°C for 4 hours to balance. The stable discharge current of the battery is 0.309 mA per square centimeter of active electrode interface area. When the voltage reaches 1.0 volts, allow the discharge current to decrease and keep the battery voltage at 1.0 volts for 5 hours.

The voltage-time curve is shown in Figure 35. The initial 4 hours in the graph are taken during temperature equilibration and do not include any battery discharge. The curve of voltage versus storage capacity is shown in Figure 36. The voltage curve shown in Figures 35 and 36 has the unique characteristics of silver vanadium oxide. As shown in the figure, the measured storage and discharge capacity is 35.54 milliampere hours, or the specific capacitance value is about 35.54 milliampere hours/gram ( active silver vanadium oxide nanoparticles). This low specific volume value is believed to be due to some miscible material in the silver vanadium oxide particles.

A lithium theoretical capacity of 315 mAh per gram (7 gram equivalents of lithium) of Ag ₂ V ₄ O ₁₁ has been reported, see "Takeuchi et al., 'Reduction of silver vanadium oxide in lithium/silver vanadium oxide cells' J. Electrochem, Soc. 135:2691 (Nov. 1988)" and "Leising et al., Jonrhalof Power Sources 68:730-734 (1997)". It can be seen that the capacitance value described in the embodiment here greatly exceeds the theoretical value.

The above-described embodiments are intended to be illustrative but by no means exclusive. Additional embodiments are contained in the claims. The present invention has been described with reference to preferred embodiments, but those skilled in the art should understand that any changes in form or details would not depart from the scope and spirit of the invention.

Claims (47)

CLAIMS 1. A group of particles characterized by comprising metal vanadium oxide, said particles having an average diameter not greater than 500 nanometers. 2. A population of particles as claimed in claim 1, wherein the average diameter of the particles is from about 5 nm to 100 nm. 3. A population of particles as claimed in claim 1, wherein the average diameter of the particles is from about 5 nm to 50 nm. 4. A collection of particles according to claim 1, wherein the metal vanadium oxide comprises silver vanadium oxide. 5. A collection of particles as claimed _in claim 1, wherein _the metal vanadium oxide comprises _Ag2V4O11 . 6. A population of particles as claimed in claim 1, wherein there are substantially no particles having a diameter greater than about 4 times the average diameter of the population of particles. 7. A collection of particles as claimed in claim 1, wherein there are substantially no particles having a diameter greater than about 2 times the average diameter of the collection of particles. 8. A population of particles according to claim 1, wherein the population of particles has a size distribution such that at least about 95% of the particles have a diameter greater than about 40% of the mean diameter and less than about 160% of the mean diameter. 9. A population of particles according to claim 1, wherein the population of particles has a size distribution such that at least about 95% of the particles have a diameter greater than about 60% of the average and less than about 140% of the average diameter. 10. A method of producing metal vanadium oxide particles comprising heating a mixture of vanadium oxide particles and a non-vanadium metal compound, said vanadium oxide particles having an average diameter of less than about 500 nanometers. 11. The method of claim 10, wherein the average diameter of the vanadium oxide particles is from about 5 nanometers to about 100 nanometers. 12. The method of claim 10, wherein the non-vanadium metal compound comprises silver nitrate. _13. The method of claim 10, wherein the vanadium oxide particles comprise crystalline _V2O5 . 14. The method of claim 10, wherein the heating condition is a maximum temperature of about 200°C to 330°C. 15. The method of claim 10, wherein the heating conditions are a maximum temperature of from about 200°C to about 300°C. 16. The method of claim 10, wherein the heating condition is less than about 20 hours. 17. A battery comprising a positive electrode having active particles comprising metal vanadium oxide with a binder, said active particles having an average diameter of less than 500 nanometers. 18. The battery of claim 17, wherein the active particles have an average diameter of from about 5 nanometers to about 100 nanometers. 19. The battery of claim 17, wherein the metal vanadium oxide comprises silver vanadium oxide. 20. The _battery of claim 19, wherein the silver vanadium oxide comprises _{Ag2V4O11 .} 21. The battery of claim 17, wherein the metal vanadium oxide comprises copper vanadium oxide. 22. The battery of claim 17, wherein the positive electrode further comprises additional conductive particles. 23. The battery of claim 17, wherein there are substantially no active particles having a diameter greater than about 4 times the average diameter of the population of active particles. 24. A method for producing metal vanadium oxides, characterized in that it comprises reacting a reactant stream containing vanadium primary particles and a second metal primary particle in a reaction chamber, the reaction being induced by energy absorbed from an electromagnetic field driven by. 25. The method of claim 24, wherein the reactant stream further comprises a reactant, a source of oxygen. 26. The method of claim 24, wherein the reactant stream further comprises a radiation absorbing compound. 27. The method of claim 24, wherein the vanadium precursors are present in the form of aerosols in the reactant stream. 28. The method of claim 24, wherein the second metal precursors are in the form of aerosols in the reactant stream. 29. The method of claim 24, wherein both the vanadium precursors and the second metal precursors in the reactant stream are present in the form of aerosols. 30. The method of claim 24, wherein the average diameter of the metal vanadium oxide particles is from 5 nanometers to 100 nanometers. 31. The method of claim 24, wherein the metal vanadium oxide particles comprise silver vanadium oxide, _AgxV2Oy , _{0.3≤X≤2.0} , _{4.5≤Y≤6.0} . _32. The method of claim 24, wherein the _metal vanadium oxide particles comprise _Ag2V4O11 . 33. The method of claim 24, wherein there are substantially no metal vanadium oxide particles having a diameter greater than about 4 times the average diameter of the group of particles. 34. The method of claim 24, wherein the particle size distribution of the metal vanadium oxide is such that at least about 95% of the particles have a diameter greater than about 40% of the mean diameter and less than about 160% of the mean diameter. 35. The method of claim 24, wherein the second metal precursors comprise vanadium cations. 36. The method of claim 24, wherein the vanadium precursors comprise vanadium cations. 37. A battery comprising a cathode having active particles comprising silver vanadium oxide with a binder, said positive electrode having an energy density when discharged to about 1.0 volts Greater than about 340 mAh/g active particles. 38. The battery of claim 37, wherein the active particles have an average diameter of from about nanometers to about 100 nanometers. 39. The battery of claim 37, wherein the silver vanadium oxide particles comprise silver vanadium oxide, Ag _x V ₂ O _y , 0.3≤X≤2.0, 4.5≤Y≤6.0. _40. The _battery of claim 39, wherein the silver vanadium oxide comprises _Ag2V4O11 . 41. A battery as claimed in claim 37, wherein the cathode further comprises additional electrically conductive particles. 42. A battery according to claim 37, wherein the cathode has an energy density greater than about 350 milliampere hours per gram of active particles. 43. An implantable defibrillator comprising a lithium-based battery characterized in that the battery cathode comprises silver vanadium oxide and has an energy density of greater than about 340 milliampere hours/gram when discharged to about 1.0 volts cathode active material. 44. A battery comprising a cathode having active particles comprising a metal oxide with a binder, said positive electrode having an energy density greater than about 400 mAh/g of active particles. 45. A method for the production of elemental metal nanoparticles and vanadium oxide nanoparticle compositions, characterized in that the method comprises reacting a reactant stream containing vanadium precursors and second metal precursors in a reaction chamber, The reactions described are driven by energy absorbed from electromagnetic fields. 46. A method of producing metal vanadium oxide particles, characterized in that it comprises reacting a reactant stream containing vanadium precursors and second metal precursors in a reaction chamber, said reaction being induced by absorption from an electromagnetic field powered by energy. 47. A method of producing particles comprising an elemental metal selected from the group consisting of gold, silver and copper, characterized in that the method comprises reacting a molecular stream in a reaction chamber, the The molecular flow includes a metallic primary particle and a radiation absorber, and the reaction is driven by electromagnetic field radiation.

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