CN1343378A - Metal vanadium oxide particles - Google Patents
Metal vanadium oxide particles Download PDFInfo
- Publication number
- CN1343378A CN1343378A CN00804664A CN00804664A CN1343378A CN 1343378 A CN1343378 A CN 1343378A CN 00804664 A CN00804664 A CN 00804664A CN 00804664 A CN00804664 A CN 00804664A CN 1343378 A CN1343378 A CN 1343378A
- Authority
- CN
- China
- Prior art keywords
- particle
- metal
- vanadium oxide
- silver
- vanadium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002245 particle Substances 0.000 title claims abstract description 302
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 161
- 239000002184 metal Substances 0.000 title claims abstract description 160
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 80
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000376 reactant Substances 0.000 claims abstract description 138
- 239000002105 nanoparticle Substances 0.000 claims abstract description 113
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000010438 heat treatment Methods 0.000 claims abstract description 75
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 69
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 45
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 189
- 238000000034 method Methods 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 68
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 42
- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- 238000009826 distribution Methods 0.000 claims description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 20
- -1 vanadium metal compound Chemical class 0.000 claims description 20
- 239000011164 primary particle Substances 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 230000005855 radiation Effects 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 230000005611 electricity Effects 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
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- 239000010931 gold Substances 0.000 claims description 8
- 230000005672 electromagnetic field Effects 0.000 claims description 7
- SALZVZXDBQJLKA-UHFFFAOYSA-N copper barium(2+) oxygen(2-) Chemical compound [O--].[O--].[Cu++].[Ba++] SALZVZXDBQJLKA-UHFFFAOYSA-N 0.000 claims description 2
- 239000006100 radiation absorber Substances 0.000 claims description 2
- GNZKCLSXDUXHNG-UHFFFAOYSA-N Vanadium cation Chemical compound [V+] GNZKCLSXDUXHNG-UHFFFAOYSA-N 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 28
- 238000000197 pyrolysis Methods 0.000 abstract description 27
- 238000001725 laser pyrolysis Methods 0.000 abstract description 6
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- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
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- 229940076131 gold trichloride Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 210000003128 head Anatomy 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- YDHABVNRCBNRNZ-UHFFFAOYSA-M silver perchlorate Chemical compound [Ag+].[O-]Cl(=O)(=O)=O YDHABVNRCBNRNZ-UHFFFAOYSA-M 0.000 description 1
- KIIUTKAWYISOAM-UHFFFAOYSA-N silver sodium Chemical compound [Na].[Ag] KIIUTKAWYISOAM-UHFFFAOYSA-N 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
The present invention relates to metal vanadium oxide particles.The invention still further relates to the manufacture method of metal vanadium oxide powder particle, for example use the laser high-temperature decomposition.Especially, the present invention relates to a kind ofly will use laser pyrolysis manufactured nano level metal barium oxide powder particle.The invention still further relates to and nano level metal barium oxide particle, as the battery of the relevant improved properties of silver-vanadium oxide particle.
Lithium-base battery is owing to its very high energy density and at the commercial very ten-strike that obtained.The positive electrode material that lithium-base battery is suitable for should comprise that those can be inserted into lithium atom the material that goes in their lattices.Negative electrode can adopt the lithium metal, and lithium alloy or compound can reversibly insert lithium atom in its lattice because of them and to go.The battery of being made by lithium metal or lithium alloy negative electrode is called lithium battery, and the battery of being made by the anode that can insert lithium ion (negative electrode) reactive metal is called lithium ion battery.
In order to produce the battery of improvement, various materials once on probation are made negative electrode (positive electrode) active material of lithium-base battery.Various materials are arranged, and normally chalcogenide can be applicable to lithium-base battery, and for example vanadium oxide is effective material of making the lithium-base battery positive electrode under certain state of oxidation.Metal vanadium oxide is considered to have high energy density and power density always as the positive electrode of lithium-base battery the time.Silver-vanadium oxide then has the power density of very high energy as lithium-base battery the time.The silver-vanadium oxide battery has been found that its special applications in implantable heart defibrillator, and battery wherein must be had the ability in ten seconds even shorter time, heavily covers charging with quick continuation mode to electric capacity and transmits strong energy pulse.
A first aspect of the present invention is to belong to a kind of cluster of grains that comprises metal vanadium oxide, and its average diameter is less than 500 nanometers.
Another aspect of the present invention belongs to a kind of method of producing metal vanadium oxide, it is characterized in that comprising that the average diameter of barium oxide particle is less than 500 nanometers with barium oxide particle and the heating of non-vanadium metal hopcalite.
One side more of the present invention belongs to a kind of battery, it is characterized in that comprising that its barium oxide average diameter of particles is less than about 500 nanometers with containing the positive electrode of vanadium oxide active particle in binding agent.
The present invention also belongs to the method for producing metal vanadium oxide particles, it is characterized in that comprising reacting in reacting furnace containing the synthetic reactant flow of the vanadium primary particle and the second metal primary particle, and the energy that reaction absorbs in the electromagnetic field causes.
Another aspect of the present invention is to belong to a kind of battery, it is characterized in that comprising a kind of negative electrode that is formed by silver-vanadium oxide active particle and adhesive.When the energy density that this positive electrode had discharges into 1.0 volts, greater than about 340 Milliampere Hours/every gram active particle.
And the present invention also belongs to a kind of battery, it is characterized in that comprising a kind of anode with vanadium metal active particle and adhesive, and the energy density that positive electrode had is when discharging into 1.0 volts, greater than about 400 Milliampere Hours/every gram active particle.
Of the present inventionly on the one hand belong to a kind of implantable defibrillator again, it is characterized in that wherein battery has the negative electrode of a silver-vanadium oxide, its energy density is when discharging into 1.0 volts, greater than about 340 Milliampere Hours/every gram active material of cathode.
The present invention also belongs to a kind of method of producing metal element nano particle and barium oxide mixture of nanoparticles; the feature of this method is to comprise reacting in reacting furnace containing the synthetic reactant flow of the vanadium primary particle and the second metal primary particle that reaction causes by absorbing energy of electromagnetic field.
One side more of the present invention belongs to a kind of method of producing metal vanadium oxide particles, it is characterized in that comprising the vanadium primary particle and the second metal primary particle synthetic reaction logistics are reacted in reacting furnace, and reaction is caused by the energy that absorbs combustion flame.
Another aspect of the present invention belongs to a kind of single element metallic particles group that is selected from copper, silver, the golden family of containing, and the average-size of particle is less than about 500 nanometers in the cluster of grains, and in fact the diameter of any particle all is not more than four times of its average diameter.
In addition, the present invention also belongs to a kind of method of making particle, particle comprises an a kind of single element metal that is selected from copper, silver, the golden family, the feature of this method is to comprise the reaction of a kind of molecular flow in reacting furnace, this molecular flow comprises a kind of metal initial particle and radiation adsorber, and reaction wherein is to be caused by electromagnetic field radiation.
The drawing explanation of accompanying drawing of the present invention is:
Fig. 1 is the sketch of analysing and observe of an example of a laser high temperature pyrolysis device, and section is the mid-sectional from the laser emission approach.The top illustration is a vertical view of collecting nozzle; The bottom illustration is the top view that sends nozzle.
Fig. 2 is the sketch of a reactant dispensing device, and this device is used for the steam reaction thing sent in the laser high temperature pyrolysis device as Fig. 1 and goes.
Fig. 3 A is the side-looking sketch of a reactant dispensing device, and this device is used for the air supporting reactant sent in the laser high temperature pyrolysis device as Fig. 1 and goes.
Fig. 3 B is the side-looking sketch of another example of reactant dispensing device, and this device is used for the air supporting reactant sent in the laser high temperature pyrolysis device as Fig. 1 and goes.
Fig. 4 is the perspective sketch of the reacting furnace of an execution laser high temperature pyrolysis that has amplified, and wherein the assembly of reacting furnace is transparent in showing its internal structure.
Fig. 5 is a cutaway view of cutting open along the 5-5 line as the reacting furnace among Fig. 4.
Fig. 6 is the sketch of analysing and observe of a device that is used for the heat treatment nano particle, and its section is cut open by this device center.
Fig. 7 is the sketch of analysing and observe of a stove that is used for high heat effect nano particle, and section is from the stove mid-sectional.
Fig. 8 is the perspective sketch of the embodiment of a battery of the present invention.
Fig. 9 is a VO
2The X-light crystallogram of nano particle.
Figure 10 be one with VO
2The nano particle crystallization is done heat treatment and the V that produces
2O
5The X-light crystallogram of nano particle.
Figure 11 is a V
2O
5The transmission electron microscope figure of nano particle crystallization.
Figure 12 be one as the V among Figure 11
2O
5The particle size distribution figure of nano particle crystallization.
Figure 13 be one by V
2O
5Nanocrystal adds behind the silver nitrate heat treatment in oxygenation atmosphere and four kinds of X-ray diffraction patterns of the silver-vanadium oxide of output, and wherein each diffraction pattern is that different condition according to material forming draws.
Figure 14 be one by V
2O
5Nanocrystal adds behind the silver nitrate heat treatment in argon filling atmosphere and four kinds of X-ray diffraction patterns of the silver-vanadium oxide of output, and wherein each diffraction pattern is that different condition according to material forming draws.
Figure 15 is the transmission electron microscope view of a silver-vanadium oxide nano particle.
Figure 16 is a V who is used for producing as Figure 15 silver-vanadium oxide particle
2O
5The transmission electron microscope view of particulate samples.
Figure 17 is a V
2O
5After nano particle and the silver nitrate powder in oxidation the X-ray diffraction pattern of the silver-vanadium oxide of output after the heat treatment.
Figure 18 be one from having the curve chart that measures with the differential scanning calorimetry method as the sample of the X-ray diffraction pattern of Figure 17.
Figure 19 is the X-ray diffraction pattern of a mixed phase silver-vanadium oxide material of directly producing with the laser high temperature pyrolytic cracking (HTP) and getting.
Figure 20 is that direct transmission electron microscope view of using the silver-vanadium oxide material of laser high temperature pyrolytic cracking (HTP) output that obtains X-ray diffraction pattern as shown in figure 19.
Figure 21 is silver-vanadium oxide particle X-ray diffraction pattern after the heat treatment in having passed through the oxygen atmosphere with the synthetic nanoscale silver-vanadium oxide material of laser pyrolysis processes.
Figure 22 is a transmission electron microscope figure by the silver-vanadium oxide particle of heat treatment nanometer-level silver barium oxide manufacture of materials gained.
Figure 23 be one contain directly by laser pyrolysis production two of the silver-vanadium oxide nano particle X-ray diffraction patterns that under different condition slightly, obtain.
Figure 24 A be one from suitable Ying Yu such as the transmission electron microscope figure that draws the sample of a diffraction pattern above Figure 23.
Figure 24 B be one from corresponding to the transmission electron microscope figure that draws in the sample as a diffraction pattern below Figure 23.
Figure 25 is five X-ray diffraction patterns of the mixed phase material of the silver-vanadium oxide nano particle directly produced with the laser high temperature pyrolytic cracking (HTP), and wherein the material of being produced among each figure is to be drawn by different silver-colored vanadium ratios.
Figure 26 be one produce under by laser elevated temperature heat method as the specified condition of first row in the table 5 and the X-ray diffraction pattern of elemental silver nano particle.
Figure 27 be one produce under by the laser high temperature pyrolytic cracking (HTP) as the specified condition of secondary series in the table 5 and the X-ray diffraction pattern of elemental silver nano particle.
Figure 28 is a transmission electron microscope figure corresponding to the specimen material among diffraction Figure 26.
Figure 29 be a lithium battery that forms by the silver-vanadium oxide nano particle manufacturing that obtains according to heat treatment step described in the example 4 be the voltage curve of function with time.
Figure 30 be one corresponding to being the voltage curve of function with the capacitance as the voltage one time graph figure of Figure 29.
Figure 31 be one by according to as the made lithium battery of the mixed phase silver-vanadium oxide nano particle of the described laser high temperature pyrolytic cracking (HTP)s acquisitions of example 5 be the voltage curve of function with time.
Figure 32 be one corresponding to being the voltage curve of function with the capacitance as the voltage-time curve figure of Figure 31.
It is the voltage curve of function with time by the lithium battery of making according to the silver-vanadium oxide nano particle of making as example 6 described heat treatment steps that Figure 33 is one.
It is the voltage curve of function with the capacitance corresponding to voltage-time curve figure shown in Figure 33 that Figure 34 is one.
Figure 35 be one by according to as the voltage of the made lithium battery of example 7 described mixed phase silver-vanadium oxide nano particles to time plot.
Figure 36 be one corresponding to the voltage of Figure 35 curve chart to the voltage versus capacity of time plot.
The production of nano level metal barium oxide particle is directly to adopt the laser high temperature pyrolytic cracking (HTP); Also can adopt the laser high-temperature decomposition to come to accept again after the synthesis nano barium oxide particle high temperature/heat treatment and receive the material particle to make metal vanadium oxide. Therefore metal vanadium oxide is directly to be made by the laser high temperature pyrolytic cracking (HTP), and wherein laser high temperature pyrolysis reaction composition thing comprises primary particle and a kind of bimetallic primary particle of vanadium. And the barium oxide nano particle can be used for making the metal vanadium oxide nano particle, for example, and silver-vanadium oxide nano particle and do not lose the nano-grade size of its particle. Nano level metal barium oxide particle can be used for making the battery with improved performance.
Nano particle with barium oxide of various stoicheiometries and crystal structure is to make with the laser high temperature pyrolytic cracking (HTP) separately, also can add processing method again and make. Various multi-form barium oxide nano particles can be as the initial feed of making the metal vanadium oxide nano particle. Add the metallic compound of preparing to go in the importing barium oxide with the barium oxide nano particle and mix many metal nanoparticles in order to be formed in the material that two kinds of metals are arranged in the lattice. The treatment conditions that adopt suitable selection and get can be made the characteristic that combination has the particle of two kinds of metals and do not lose the nanometer scale of initial barium oxide nano particle.
Preferred metal vanadium oxide particles because of its average diameter less than 1 micron, and the decentralization of its particle diameter is very narrow. The decentralization of particle diameter even all do not have afterbody. In other words, simply just do not have the sort of particle than the large order of magnitude of average diameter, that is the particle size decentralization drops to zero rapidly. Be processed into metal vanadium oxide in order to produce barium oxide nano particle original material with further processing, can adopt separately the laser high temperature pyrolytic cracking (HTP) or combine with other processing methods again and use together. Especially, the laser high temperature pyrolytic cracking (HTP) is a kind of method of good effective production barium oxide nano particle always, and it has the decentralization of very narrow average particulate diameter. In addition, the nanoscale barium oxide particle of producing with the laser high temperature pyrolytic cracking (HTP) can be in oxygenation atmosphere or in the inert atmosphere destroy it with the soft-condition heating and receives the dimensional characteristic of material particle in order to change the stoicheiometry of its crystalline nature and/or barium oxide particle. Like this, just can produce the nano particle of various dissimilar barium oxide bases.
The basic characteristics of producing the successful Application of barium oxide nano particle with the laser high temperature pyrolytic cracking (HTP) are to be to produce a reaction composition logistics that contains the vanadium primary, a radiation absorption source and a source of oxygen, the reaction logistics is by the strong beam pyrolytic as laser beam. The laser high temperature pyrolytic cracking (HTP) provides and has been different from the phase of making material under the heat power equilibrium condition. In case reactant wander about as a refugee open the light the bundle after, the barium oxide nano particle cools off fast.
Can be made with heat treatment method by the metal vanadium oxide particles that nanoscale barium oxide particle begins, the second metal initial particle comprises a kind of transition metal of non-vanadium. Preferred the second metal initial particle comprise have copper, silver, the gold component. The second metal initial particlized compound is to mix the particle that again heating then forms two kinds of metals of combination with barium oxide nano particle group. Heat-treat under suitable flexible condition that effective real estate gets particle and the nanometer scale size of not destroying initial barium oxide particle.
As mentioned above, the essential characteristic of successful Application laser high temperature method manufacturing metal vanadium oxide nano particle is to produce a kind of reaction logistics that contains the vanadium primary; A kind of bimetallic primary; A radiation absorption source and an oxygen source. The reaction logistics is to carry out pyrolytic with strong beam. For example laser beam or other intense light sources. Open the light after the bundle in case reactant is wandered about as a refugee, the vanadium metal particle is namely produced the metal vanadium oxide nano particle with well-proportioned size dispersion degree by quick quenching.
As mentioned above, lithium ion and/or ion can be inserted in the barium oxide of various forms and the metal vanadium oxide particles and go. In order to make positive electrode, the negative electrode during as battery discharge, metal vanadium oxide nano particle for example can utilize that the such binder combination of polymer forms electrode. Preferably also in metal vanadium oxide particles, make up together with electroconductive particle with in adhesive again in the electrode. Kind electrode can be used as positive electrode in lithium battery or lithium ion battery. More taller than the theoretical maximum of estimating with corresponding reguline metal barium oxide with the energy density that the lithium-base battery that contains the nano level metal barium oxide and do negative electrode has. Especially use metal vanadium oxide, particularly silver-vanadium oxide production and energy density be greater than about 340 Milliampere Hours/every gram. The energy density that has of barium metal oxide particle can better then can reach 360 Milliampere Hours/every gram greater than 350 Milliampere Hours/every gram preferably, best can be high to about 370, even reach 405 Milliampere Hours/every gram.
When the first notice of the primary of producing metal vanadium oxide nano particle or metal vanadium oxide nano particle concentrates on application laser high temperature pyrolytic cracking (HTP); the method of transmission air supporting primary as described herein can also be applicable to other synthetic method equally; especially, primary can be applied in the flame high temperature pyrolytic cracking (HTP). The transfer approach of this primary can be useful in the various flame high temperature pyrolysis methods. In a mode of priority, the reaction logistics is to enter into oxyhydrogen flame. The energy of flame is used for high temperature pyrolysis. This flame high temperature pyrolysis method should be able to be produced the material similar to this paper laser high temperature pyrolysis technology, but generally can not obtain very narrow particle size decentralization.
Produce when including the ternary compound that two kinds of metals form when the notice of this processing concentrates on, this method has equally also disclosed to produce has the very nano particle of the IB family metallic element of high uniformity. The production of the nano particle of silver element especially, as described below is exactly an example. Copper, gold and other IB family element have similar chemical property. Therefore copper also can be with wanting similar method to produce with gold nano grain.
(1) for the production of the laser high temperature pyrolytic cracking (HTP) of nano particle
It is the effective tool of producing nanoscale barium oxide particle that the laser high temperature pyrolytic cracking (HTP) has disclosed it. In addition, the particle of being produced by the laser high temperature pyrolytic cracking (HTP) is that a kind of good material is so that expansion further produces required barium oxide particle. So, use separately the laser high temperature pyrolytic cracking (HTP) or combine to produce the various barium oxide particles that have a wide reach with the processing method that adds again. And, laser high temperature pyrolytic cracking (HTP) or the successful methods of directly producing metal vanadium oxide particles.
The quality of being produced particle by the laser high temperature pyrolytic cracking (HTP) is to depend on reaction condition, and the reaction condition of laser high temperature pyrolytic cracking (HTP) can very accurately be controlled so that obtain the particle of desirable characteristics.Be applicable to that the reaction condition of producing a certain type of particle normally depends on the design of specific device, be applicable to that in specific device the special reaction condition of producing the barium oxide particle will be described in the example below.Produce other information of barium oxide nano particle with the laser high temperature pyrolytic cracking (HTP) and can consult transfer Bi and other people U.S. Patent application to be examined, application number is 08/897,778, and exercise question is " a barium oxide nano particle ".In addition, in specific device, be used for directly producing the silver-vanadium oxide particle the laser high temperature pyrolytic cracking (HTP) specified conditions also below example described.But also made some the general observed result of the correlation between reaction condition and the gained result.
The power that increases laser causes the rising of reaction temperature of reaction zone and the quickening of quench rate.Quench rate can obtain the high energy thing phase of high-quality fast, this be when handling under the thermal equilibrium state can not obtain.Equally, increase the high energy structure that chamber pressure also can obtain.The oxygen content that particle is provided if the oxidation source reactant concentration that is provided in reactant flow raises increases.
The degree of reactant flow becomes opposite relation with the speed of reactant gas flow with the size of particle, i.e. then particle size is less in reactant flow speed increase.The growth kinetics performance of particle has very significant effects to the size of particle.That is under the same conditions, multi-form compound products is made the particles with different sizes of another kind of thing in mutually entirely.Laser power also can influence the size of particle, promptly increases laser power and will help low melting material is formed bigger particle, then forms smaller particles for materials with high melting point.
The laser high temperature pyrolytic cracking (HTP) is generally moved with vapor-phase reactant.This has just had some restrictions to the type of primary compound can only to adopt vapor-phase reactant.So just impelling technical development introduces in the laser high temperature pyrolysis chamber to the air supporting that can contain the reactant primary.The air float body sprayer can rough classification becomes with ultrasonic transmitter with the ultrasonic nebulizer that forms air float body with the energy of one or more fluids that flowing (liquid, gas or the supercritical fluid) mechanical atomizer with the formation air float body itself.Having improved the air supporting dispensing device is used in the reactant systems, and the description of laser high temperature pyrolysis device can be consulted common Gardner of transferring and other people U.S. Patent application to be examined, application number No.09/188,670, title is " reactant delivery apparatuses ".
After using air supporting method conveyer, solid primary compound is sent out after just can being dissolved in compound in the solution.Perhaps, the form that Powdered primary compound promptly can liquid/solution is used for the transmission of air float body.Liquid initial particlized compound, as long as be ready, just can be without use liquid, or the liquid/gas mixture, or the liquid mixture with mixing, or the variety of way of liquid solution etc. is sent out an air float body.The air float body reactant can be used for obtaining significant reactant output flow.If with the work of solvent, can also select and reach required dissolution characteristics.Suitable solvent comprises various organic solvents such as water, methyl alcohol and ethanol.Thereby solvent should have required purity level makes the gained particle that required purity grade also be arranged.
If the air float body primary is made with solvent, then when suffering laser beam in the reative cell, solvent just has been evaporated very soon, gas-phase reaction so just takes place, the essential characteristic of laser high temperature pyrolysis reaction can not change.But the existence of air float body but influences to some extent to reaction condition.Applicable elements with the laser pyrolysis manufactured Mn oxide that has the air supporting primary is described in the U.S. Patent application of having transferred the possession of to be examined, application number No.09/188, and 770, on November 9 1998 applying date, exercise question is " metal oxide particle ".Only for reference at this.
Produce the appropraite condition of silver-vanadium oxide particle is described with following embodiment with the laser high temperature pyrolytic cracking (HTP) that has pneumatically supported primary.
Be applicable to that the vanadium primary that air supporting is produced comprises as vanadium trichloride (VCl
3), vanadium oxytrichloride (VOCl
3), vanadic sulfate (VOSO
4.H
2O), vanadic acid amine (NH
4VO
3), the oxide of barium (that is V,
2O
5And V
2O
3, these dissolve in the moisture nitric acid), and dissolve in dichloro vanadyl (VOCl in the absolute ethyl alcohol
2).The primary of the silver that is suitable for comprises as silver sulfate (Ag
2SO
4), silver carbonate (Ag
2CO
3), silver nitrate (AgNO
3), silver chlorate (AgClO
3) and silver perchlorate (AgClO
4), the copper primary that is suitable for comprises as copper nitrate [Cu (NO
3)
2], dichloride copper (CuCl
2), stannous chloride (CuCl) and copper sulphate (CuSO
4).The primary of the gold that is suitable for comprises as, gold trichloride (AuCl
3) and golden powder.
These compounds are preferably to be dissolved in concentration greater than in 0.1 mole the solution.Usually, the bigger then reactant of the concentration of initial grain in solution is also bigger by the output flow of reative cell.But along with the increase of concentration, it is thicker that solution just becomes, so air float body will have than desirable larger-size droplet.Therefore, the selection of solution concentration will be considered the balance of each factor in preferred solution concentration is selected.
Be suitable for generally comprising the vfanadium compound with reasonable steam pressure with the vanadium primary compound that steam transmits, that is, steam pressure should be enough to obtain the required primary vapor volume in reactant flow.If desired, solid in the container or liquid vanadium primary compound can be heated to increase the steam pressure of vanadium primary.The vanadium primary that is suitable for comprises, as VCl
4, VOCl
2, V (CO)
6And VOCl
3Chlorine in these representational primary compounds can substitute with other halogens.For example, bromine, iodine and fluorine.
In order to produce metal vanadium oxide particles, suitable metal initial particle to have enough steams at pressure so that can obtain the required metal initial particle vapor volume in reactant flow.Be applicable to that the copper primary that steam is carried comprises, as, dichloride copper (CuCl
2), be applicable to that the silver-colored primary that steam is carried comprises, as, silver chlorate (AgCl).On the other hand, a kind of in vanadium primary and the metal initial particle can carry its another kind then can carry with the steam mode with the mode of air float body.Especially, the metal initial particle as silver-colored primary can transmit and vanadium primary side can be carried with the steam mode with pneumatically supported mode.
For with two or more Metal Production mixed-metal oxides, the variation of the relative quantity of various metals in reactant flow will cause the change of gained metal component relative quantity.The phasor of mixed-metal oxides than the phasor complexity of respective metal oxide many.The phase of resulting this increment metal after the metal that the amount of the another kind of metal of a kind of ratio is bigger adds, or a kind of main phase in the mixed phase product, or the phase of a kind of big relative populations of mixed phase product.
Therefore, along with the variation of the various metal relative quantities in solution or the transmission air float body, the stoicheiometry of grain products also can play change.Transmitting two or more independently during the metal first phase particle of air float body, can both obtain same result, the relative quantity of wherein various metal initial particles can change with the variation of the concentration of metal in the relative quantity of liquid or air float body.And one or more are planted the metal initial particle and can transmit under vapor state, obtain required product so the relative quantity of metal can be adjusted easily.
Comprise as the preferred reactant of oxygen source, as, O
2, CO, CO
2, O
3With and composition thereof.Compound of reaction as oxygen source.This it is important should not be in and just enters before the reaction zone earlier and the vanadium primary reacts, because will cause oarse-grained formation usually.
The laser high temperature pyrolytic cracking (HTP) can be carried out in the light beam of various frequencies.Light source comprises laser preferably, especially is operated in the laser in the infra-red electromagnetic spectral coverage.CO
2Laser is particularly preferred light source.The infrared absorber that is contained in the molecular flow comprises, as, C
2H
4, isopropyl alcohol (CH
3CHOHCH
3), NH
3, SF
6, SiH
4And O
3O
3Both can be used as infrared absorber and also can be used as oxygen source.On the other hand, a kind of when solvent transmits in the mode of air float body in liquid as isopropyl alcohol, can be from light beam absorbing light.Radiation absorber as the infrared absorber can from radiation beam, absorb energy and with energy distribution in other reactants to impel high temperature pyrolysis.
The energy that absorbs from radiation beam can be with great ratio elevated temperature, and they are mainly also big doubly a lot of than the energy that powerful exothermic reaction produced under the controlled condition.When this process included non-equilibrium condition usually, then temperature can be that the basis adds description with the heat in the uptake zone approx.Be to be different from process in the combustion reactor on the laser high temperature pyrolysis procedural nature, though also be that a kind of energy is facilitated a kind of reaction in combustion reactor, this reaction promptly is to be driven by a kind of energy that should discharge of putting back.
A kind of inert protective gas can be used to reduce the quantity of reactant, and the molecule and the reaction chamber component of generation contact, and the protective gas that is suitable for can comprise, as argon, and helium and nitrogen.Inert gas also can mix with reactant flow so that reaction is slowed down.
A suitable laser high temperature pyrolysis device generally includes a reative cell that separates with surrounding environment.A reaction inlet is connected and produces a reactant flow with the reactant feed system and passes reative cell, and a light beam intersects in reaction 5 neutralization reaction logistics.Reactant/product stream is continuing to flow to outlet again through after the reaction zone, and this reactant/product stream enters gathering system with regard to discharging reative cell then.Usually light source is arranged on the reative cell outside, and light beam enters reative cell by a suitable window.
Referring to Fig. 1, a special case 100 of a laser high temperature pyrolysis device is to comprise a reactant feed system 102, reative cell 104 gathering systems 106, light source 108 and protective gas transfer system 110.There are two kinds of interchangeable reactant feed systems can be applied in the device of Fig. 1.First kind of reactant feed system is specifically designed to and transmits vapor-phase reactant, and second kind of reactant feed system then is used to transmit one or more air float body reactants, has multiple element reaction thing feed system all can use.
Referring to Fig. 2, first embodiment 112 of reactant feed system 102 comprises a vanadium primary compound source 120, for liquid or solid vanadium primary, the carrier gas in the carrier gas source 122 can be led in the primary source 120, so that the vanadium primary is sent out with the steam form.Preferably a kind of infrared absorber of the carrier gas of from source 122, drawing or a kind of inert gas, and when the primary compound by liquid, become bubble, or be sent in the solid primary transfer system and go.Inert gas can slow down reaction condition as carrier gas.The quantity of steam of primary is the flow that roughly is proportional to carrier gas in the reaction zone.
On the other hand, carrying vapour also can directly draw from INFRARED ABSORPTION body source 124 or inert gas source 126.Add reactant as the oxygen source, supplied with by reactant source 128, it can be a gas cylinder or other appropriate containers.The gas that comes out the gas that comes out from the primary source and INFRARED ABSORPTION source 124, inert gas source 126 and the reactant source is that the mode in the synthetic pipeline 130 of these gases is mixed.These gases have enough distances just to be synthesized together leaving reative cell 104, so that gas just fully mixed before entering reative cell 104, forming gas in the pipe 130 enters in the rectangular channel 134 by a segment pipe 132, the part that this passage 134 constitutes nozzle is used for reactant is directly sprayed into reaction zone, and some position in the reactant feed system 112 can be heated to prevent that the primary compound is deposited on the limit wall of transfer system.
The metal initial particle can be supplied with by metal initial particle source 138, and it can be a liquid reactants transfer equipment, a solid reactant transfer equipment, other one or several containers that are suitable for of air bottle type.If metal initial particle source 138 is to transmit a kind of liquid or solid reactant, then can be used for the transmission of reactant by the carrier gas in carrier gas source 122 or other carrier gas source.As shown in Figure 2, the primary source 138 usefulness pipelines 130 of metal are delivered to the metal initial particle in the pipeline 132 and are gone.
The flow that comes out from each provenance 122,124,126 and 128 preferably adopts independently quality controller 136 to be controlled separately, and mass flow controller 136 preferably provides one tunnel controlled flow velocity from each source.The mass flow controller that is suitable for comprises, as, by Edwavds HighVacuum International, Wilmington, Edward's mass flow controller that MA (U.S. Ma Sheng, Wilmington, the international high vacuum of Edward company) is produced, model 825 series.
Referring to Fig. 3 A, another alternate embodiments 150 of reactant feed system 102 is to be used for supplying with air float body to go to passage 134.As mentioned above, the part of passage 134 formation nozzles is used for reactant is injected to reative cell by reactant entrance.Reactant feed system 150 comprises an air float body generator 152, carrier gas/steam supply pipe 154 and junction station 156, passage 134, air float body generator 152 and supply pipe 154 converge in the cavity 158 of junction station 156, and the direction of aiming at passage 134 for pipe 154 sends carrier gas.Air float body generator 152 is installed to such an extent that make air float body be created on the inlet of passage 134 in the inner chamber 158 and in the space between pipe 154 the outlet.
Air float body generator 152 can be worked by multiple principle.For example, the method for generation air float body can be: use ultrasonic nozzle; Use the electrostatic spray system; With baric flow sprayer or simple sprayer; With the foaming sprayer or use a kind of gas sprayer, wherein liquid is under high pressure forced to loose into droplet by an aperture and by gas shock.Be fit to the ultrasonic nozzle of thing and can comprise piezoelectric emitter.Ultrasonic nozzle with piezoelectric emitter is existing, i.e. Sono-Tek Corporation, Milton, the model 8700-120 of NY (U.S., New York, Milton, Sono.Tek company).
Suitable air float body generator also further is described in the following document: wait to examine the U.S. Patent application with people such as the common Gardner of transferring, and application number No.09/188,670, exercise question is " reactant delivery apparatuses ", for your guidance.The air float body generator that adds can be attached on the junction station 156 by other mouthful 162 again, and Fu Jia air float body can produce so that be sent in the reative cell in inner chamber 158 like this.
Carrier gas/steam supply pipe 154 links to each other with source of the gas 164.Source of the gas 164 can comprise a plurality of gas containers, liquid reactants conveyer, and/or a solid reactant conveyer, and they link to each other to transmit selected gas or gas mixture with supplying pipe 154.Carrier gas like this/steam just can transmit various required gases and/or steam in reactant flow for pipe 154, and they comprise, as, laser absorption gas, reactant, and/or inert gas.The air-flow that goes to supply pipe 154 from source of the gas 164 is that feed pipe 168 is linked on the air float body generator 152 by one or more mass flow controller 166 controls, and feed pipe 168 also links to each other with liquid source 170.
In order to produce the barium oxide particle, the liquid that comprises the vanadium primary can adorned in liquid source 170, and in order to produce metal vanadium oxide particles, the liquid that contains a kind of vanadium primary and a kind of metal initial particle is simultaneously preferably being adorned in stream source 170.Perhaps, in order to produce metal oxide particle, the liquid that contains the metal initial particle can adorned in liquid source 170, and the vanadium primary then transmits by source of the gas 164 with for steam pipe 154.As long as be ready also can allow liquid source 170 adorn a kind of liquid that contains the vanadium primary, the metal initial particle is then supplied with by source of the gas source of the gas 164 with for steam pipe 154.Also can adopt two independently air float body generators 152 in junction station 156, one of them generation has the air float body of vanadium primary, and another generation has the air float body of metal initial particle.
In the embodiments of figure 3, the momentum of the air float body that produces of air float body generator 152 is and flows quadrature almost by flow to carrier gas that passage 134 goes for pipe 154.Like this, from being about to by the air float body primary guiding admission passage 134 that produces the air float body generator 152 from managing the 154 carrier gas/steams that come out.When actual motion, carrier gas stream is about to send in the air float body introduction channel 134 in the chamber 158.Like this, the transfer rate of air float body promptly has the place of production to depend on the flow velocity of carrier gas.
In another embodiment, the air float body generator is arranged on horizontal direction and is one on the position of upper angle, make air float body forward the one-component of momentum be what to point to passage 134 corresponding to directions.In a preferred embodiment, the output stream that the air float body generator is drawn is and the positive direction that is limited by passage 134 openings promptly to be provided with by the angle at 45 that flows to for pipe 154 admission passages 134.
Referring to Fig. 3 B, be another embodiment 172 that can be used for supplying with the reactant feed system 102 of air float body to passage 134, reactant feed system 172 comprises an outer nozzle 174 and an interior nozzle 176, outer nozzle 174 has a passage that makes progress 178, it is guided one 5/8 inch * 1/4 inch rectangle outlet 180 into and arrives the top of outer nozzle 174, as the illustration among Fig. 3 B.The top of outer nozzle 174 is as the illustration among Fig. 3 B.Outer nozzle 174 comprises that a fistulae 183 is on bottom surface 184.Fistulae 183 is that the air float body that is used for gathering is discharged outside the outer nozzle.Interior nozzle 176 is fixed on the outer nozzle 174 by sleeve 185.
Interior nozzle 176 is gas ejectors that provided by " Spraying Systems (Wheatm, IL) ", and the diameter of interior nozzle is 0.5 inch, long 12 inches.The top of nozzle is to mix nozzle 186 (0.055 inch at pore, 0.005 inch in liquid hole) in the diplopore.Liquid leads to reflector by managing 187, and gas then leads to reflector and imports in the reative cell by managing 188, and the interaction of gas and liquid impels the formation of drop.
Outer nozzle and interior nozzle are coaxial being installed together.Outer nozzle 174 is pressed into a flat square-section with the air float body that interior nozzle 176 produces.Outer in addition nozzle makes also that the flow velocity of air float body is all even and is evenly distributed on the cross section.The shape of outer nozzle 174 can also be done to such an extent that be applicable to various reative cell.
Referring to Fig. 1, protective gas transfer system 110 comprises the inertia source of the gas 190 that links with an indifferent gas conduit 192, and indifferent gas conduit 192 flows to into annular channel 194, and mass flow controller 196 controls enter the flow of the inert gas of indifferent gas conduit 192.If adopt reactant transfer system 112, then inertia source of the gas 126 also can be as the inertia source of the gas of conduit 192.
The end that sprays nozzle 202 has a circular opening 204 so that there is inert protective gas to pass through, reactant entrance 206 then make reactant therefrom by and form a reactant flow and enter reative cell.Reactant entrance 206 is a seam preferably, and as shown in Figure 1, the diameter of circular opening 204 for example, is about 1.5 inches, and is about 1/8 inch to 1/16 inch along the wide of radial direction.Protective gas stream by circular opening 204 is to help to prevent by the reactant gas of reative cell 104 and scattering and disappearing of grain products.Tube portion 208,210 respectively comprises a ZnSe window, and the diameter of window 212,214 is about 1 inch.Window 212,124 is two cylindrical mirrors preferably, and its focal length equals the distance of reative cell center to minute surface, so that many belows that light beam is just in time focused on nozzle open centre point.Window 212,214 preferably has one deck anti-reflective film, and suitable ZnSe lens can be handled by " Janos Technology, Towrshend, Vermont ".The existence of tube portion 208,210 makes that window 212,214 can be far away from main reaction chamber 200, thus the less pollution that is subjected to reactant and/or product.Window 212,214 can be in from the about 3 centimetres place of main reaction chamber 200.
Window 212,214th in tube portion 208,210, is gone into reative cell 104 to prevent flow of ambient air with the seal with elastometic washer of O-type.Protective gas enters a portion 208,210 to reduce the pollution to window 212,214 by inlet tube 216,218, and inlet tube 216,218 links to each other with inertia source of the gas 138, perhaps receives on the independent inertia source of the gas.In another case, the air-flow that enters inlet tube 216,218 is preferably controlled by mass flow controller 220.
Light source 108 produces a light beam 222, retouches standard and enters window 212 and go out from window 214 again.Window 212,214 defines a light path, passes main reaction chamber 200 and in reaction zone 224 neutralization reaction logistics intersections, passes after the window 214, and light beam 222 is flushed on the power meter 226, makes the light beam unloading.Suitable power meter can be located to obtain by " Coherenf Inc., Santa Clara, CA ", and light source 108 is laser preferably, though it can be common intense light source also, such as arc lamp, lasing light emitter 108 is infrared laser preferably, especially a kind of continuous CO
2Laser, the peak power output that for example a kind of " PRCCorp., Landing, NJ " locates are 1800 watts laser.Another example is to use another kind of electromagnetic-energy, and for example microwave generator replaces light source 108.In this example, comprise a kind of radiation absorbing compound in the reactant flow, for example microwave-absorbing body.
Thereby reactant forms a reactant flow by the reactant entrance 206 that sprays in the nozzle 202.Reactant flow is passed reaction zone 224, primary wherein and add reactant compound and promptly react, and gas is heating rapidly in reaction zone 224, according to specified conditions, roughly can reach 10
5The magnitude of degree/second.Leave reaction behind the reaction zone 224 promptly by fast quench, promptly in reactant flow, promptly form particle, and the non-equilibrium character of process impels the nano particle that is generated to have distribution of sizes and structural integrity very uniformly.
Reactant/product stream footpath on the way continues to flow to collection nozzle 230 places again.Collect nozzle 230 and be and emission nozzle 230 between spacing very little and exist again and collect nozzle 230 and cause reactant and product that the pollution of reative cell 104 is reduced.Collecting nozzle 230 has a circular open 232, promptly enters gathering system 106 by this opening 232.
The constant pressure of reative cell is by the pressure gauge monitoring that is contained in the main chamber.
The preferred constant pressure of making required oxide generally at about 80 torrs between 500 torrs.
Whole device is controlled by computer.The pressure of common computer control laser and monitoring reaction chamber, computer can be used to control reactant flow and/or protection air-flow.Pump speed is by the manual needle-valve or the automatic control throttle valve control that are inserted in pump 274 and the filter 272.When constant pressure increases because of filter 272 gathers particle, can corresponding constant pressure that needle-valve or throttle valve adjustment are kept pump speed is constant.
Accumulate on the filter 272 so that pump no longer can overcome when keeping reative cell 104 in required pressure by the resistance on the filter 272 as abundant particle, reaction i.e. termination.When the pressure in the reative cell 104 can not be kept normal value, reaction stopped, and took off filter 272.In pressure one before keeping inadequately taken turns, collect 6 particle in the present embodiment and be about the 1-300 gram.Common one time of taking turns can continue about 10 hours, and with the reactant transfer system, it is relevant to produce the type of particle and the kind of filter etc.
Reaction condition can very accurately be controlled.Especially mass flow can be controlled very accurately.The power stability of laser generally is about 0.5%, and chamber pressure can be with manual needle-valve or automatic control throttle valve control in 1%.
The dosage of reactant feed system 102 and gathering system 106 can be conversely.In replacement scheme, reactant is supplied with by the top of reactor, and product particle is then collected in the reative cell bottom.Gathering system in this configuration can without bend pipe so de-entrainment filter directly be contained in reative cell below.
The another kind design of laser high temperature pyrolysis device is to be described in the U.S. Patent No. 5,958,348 that is entitled as " effectively producing particle with chemical reaction ", for consulting.This design is intended to produce a kind of a large amount of particles of the commerce usefulness that is made by the laser high temperature pyrolytic cracking (HTP).Reative cell is extending on the direction of laser beam with on the perpendicular size of reactant flow, makes the output variable of reactant and product increase.The original design of device is to introduce pure gas reactant and basis.Another is introduced air float body and then is described in people's such as the common Gardner of transferring pending U.S. Patent Application to the embodiment of the reative cell that extends, No.09/188, and 670, (1998.11.09 application) exercise question is " reactant delivery apparatuses ", and is for reference.
Usually, the high temperature pyrolysis device that is substituted comprises: one is intended to reduce locular wall and pollutes the reative cell of increase production capacity and effective use of energy sources.In order to finish these purposes, adopted a kind of reative cell that has extended, increasing the output variable of reactant and product, but dead band in the not corresponding increase reative cell.This reative cell dead band can be contaminated because of unreacted compound and/or product.
The chamber designs of having improved 300 is by Fig. 4 and shown in Figure 5.Reactant entrance 302 enters into main chamber 304, and reactant entrance 302 is for introducing the usefulness that gas and/or air float body reactant enter main chamber 304.The shape of reactant entrance 302 generally is to conform to the shape of main chamber 304.Though introducing reactant by reactant entrance 302 can be along with discussing as the laser high temperature pyrolysis device after the alternative structure that suitably adopts reactant entrance among Fig. 1 how to introduce air float body and/or the steam primary is finished with the process of producing barium oxide particle or metal vanadium oxide particles.
Letter portion 320,322nd is extended outward by main chamber 304.Tube portion 320,322 is fixedly adorning window 324,326 and is passing reative cell 300 to limit laser beam.Tube portion 320,322 can comprise that the introducing inert gas enters the inert gas entrance 330,332 of a portion 320,322.
The size of the reactant entrance 316 behind the lengthening (annotate: it is 302 mistake-annotations of translation that sic is doubted) designs by the High-efficient Production particle.As the CO that uses 1800 watts
2During laser, for the reasonable size of the reactant entrance of producing barium oxide nano particle and metal vanadium oxide nano particle usefulness is from about 5 millimeters to 1 meter.
Improved device comprises that a gathering system is used for taking out nano particle at molecular flow, gathering system can be designed to need not end to produce to collect a large amount of product particles, perhaps, preferably in gathering system, adopt the method for another particle collection case of switching to guarantee continuous production.In gathering system, can be provided with on stream and be similar to the such bending part of the bend pipe in the gathering system among Fig. 1.
The more preferably embodiment of the gathering system of a particle manufacture system that is used for continuous collection mode can be referring to people's such as the common Gavdner of transferring pending trial U.S. Patent application, No, and 09/107,729, exercise question is " particle collection device and relevant method ".A kind of batch collection system of the reaction system that is used for improveing can be referring to the pending U.S. Patent Application No.09/188 of common transfer, and 770, (applying date: 1998.11.09) exercise question is " metal oxide particle ".The configuration of reactant emitting module and gathering system can be turned around, and promptly particle can be collected at the top of device.
The character of barium oxide particle and metal vanadium oxide particles can change because of the following process method as mentioned above.Be fit to be used for heat treated parent material comprise by the laser high temperature pyrolytic cracking (HTP) produce barium oxide particle and metal vanadium oxide particles.The barium oxide material that is suitable for comprises, as, VO, VO
1.27, VO
2, V
2O
3, V
3O
5, V
4O
9, V
6O
13With non-crystal V
2O
5, same, minimum material can be the metal vanadium oxide particles by laser high temperature pyrolytic cracking (HTP) output, as silver-vanadium oxide particle and/or copper barium oxide particle.The metal vanadium oxide material that is suitable for comprises Ag
2V
4O
11Form with new silver-vanadium oxide crystal a kind of as that describe below.In addition, the particle that is used for original material also is positioned on the heat treatment step that carries out one or many under the different condition.
Original material generally can be the particle of virtually any size and shape, and certainly nano-scale particle is preferred original material, this nanometer receive particle average diameter approximately less than 1000 nanometers and preferably enough from about 5 nanometers to 500 nanometers; Be more preferably from about 5 nanometers to 150 nanometers, suitable nanoscale original material has been produced by the laser high temperature pyrolytic cracking (HTP) and has been obtained.
Barium oxide particle and metal vanadium oxide particles are preferably in the stove and heat so that be heated evenly.This is that condition is all very soft usually, and a large amount of particle sintering phenomenons of unlikely appearance.Heating-up temperature preferably will be lower than the fusing point of original material and product material.
For some target product particle, additional heating can cause the further change that particle is formed in the time of can not reaching balance on one point, and the atmosphere of heat treated can be oxidizing atmosphere or inert atmosphere.Especially under essentially identical stoicheiometry condition, be another kind of crystal structure, when perhaps changing crystal grain into, normally use inert atmosphere by a kind of noncrystal particle by a kind of crystal structure transition.The residing atmosphere of particle can be static, or passes through system and mobile gas.
The oxidizing gas that is suitable for comprises, as, O
2, O
3, CO, CO
2Combination with these gases.O
2Can from air, supply with.Oxidizing atmosphere can be optionally by as Ar, He and N
2Mix Deng inert gas, when oxidizing gas and indifferent gas mixed, the ratio of oxic gas in gaseous mixture can be from about 1% to 99%, and be more preferably from 5% to 99%, can certainly adopt the oxic gas or the pure inert gas of substantially pure separately.
Accurate condition can change the type of the barium oxide product of being produced or the type of metal vanadium oxide.For example, temperature, heating time, heating and cooling speed, gas and be exposed to condition in the gas etc. and can change.Usually, when heating in oxidizing atmosphere, heating time is long more, and then before reaching balance, it is just many more to be attached to the oxygen that goes in the material.In case reach equilibrium condition, various conditions have just determined the crystalline phase in the powder.
Various stoves all can be used for heating, and Fig. 6 is exactly equipment 400 examples finishing this processing.Equipment 400 comprises a cup 402, makes with glass or other inert material, wherein is placed with particle.The product that the existing glass reaction that is suitable for is bad to be " Ace Glass (Vineland, NJ) " produces.Cup top 402 usefulness glass covers 404 are sealed, and are lined with Teflon sealing gasket 405 between cup 402 lids 403.Lid 404 can be clamped with one or more clip.On the lid 404 a plurality of holes 406 that respectively have Teflon lining are arranged, be inserted with a leafy stainless steel blender 408 by covering 404 centre bores 406, it is by suitable driven by motor.
There is one or more pipe 410 to insert in the cup 402 to send into gas by hole 406.Pipe 410 is made by stainless steel or other inert materials, and spray gun 412 is contained in the head of pipe 410 in order to gas is sprayed in the cup 402.Around cup 402, putting a heater/stove 414.From " Glas-Col (Terre Haute, IN) " the available suitable resistance heater of company.Wherein there is a pipe to comprise a T shape connector 416, inserts a thermocouple 416 with the temperature in the measuring cup 402 by T shape connector.T shape pipe 416 also can link to each other with an exhaust outlet 418, and exhaust outlet 418 offers by the circulating ventilation gas of cup 402 and discharges.Exhaust outlet 418 preferably leads to fume hood or other ventilation equipment.
Preferably by desired gas flow through the cup 402.Pipe 410 normally links to each other with a source of oxygen and/or an inertia source of the gas, the oxygen that from suitable source of the gas, comes, and indifferent gas and combination thereof can produce required atmosphere in cup 402.Can adopt various stream to connect, flow velocity is preferably in about 1 standard cubic centimeters per minute between about 1000 standard cubic centimeters per minute (sccm), is more preferably from about 10 sccm to 500sccm.Though flow velocity and gas composition can be done system's adjustment in the course of processing, flow velocity is constant in whole heating steps usually.In addition, also can adopt gas at rest atmosphere.
In the laser high temperature pyrolysis device of foregoing description, has very dystectic material VO
2Make VO than being easier to
2Be a kind of suitable original material so that be oxidized to other forms of barium oxide.Also need some experimental adjustment to be applicable to the condition of making the material that required with generation.In addition, the lattice of the heat treatment crystal that can change and/or remove on the particle absorbed compound with the quality of improvement particle.
Be used to handle barium oxide nano particle or metal vanadium oxide nano particle, temperature range for example is from about 50 ℃ to about 500 ℃ or be more preferably from about 60 ℃ to about 400 ℃ preferably.The heating preferably be extended to about more than 5 minutes and as be about 2 hours to about 100 hours, preferably from about 2 hours to 50 hours.Also need pacify some empirical adjustment and produce the condition of producing material requested that is applicable to.Adopt flexible condition to form bigger particle size around knot to avoid intergranular.On higher slightly temperature, carry out some controlled particle sintering to produce bigger slightly average particulate diameter.
With crystallization VO
2Be transformed into orthorhombic V
2O
5With 2-D crystal V
2O
5With with noncrystal V
2O
5Be transformed into orthorhombic V
2O
5With 2-D crystal V
2O
5Condition be described in the U.S. Patent No. 5,989,514 that transfers people such as Bi, exercise question is " with hot working barium oxide particle ", and is for reference.(2) heat treatment method is made metal vanadium oxide particles
In the time can directly producing metal vanadium oxide particles with the laser high temperature pyrolytic cracking (HTP) as mentioned above, also found also can generate nano level metal barium oxide particle simultaneously with heat treatment method.Generate in the method for metal vanadium oxide particles in a kind of preferred heat, at first barium oxide nano particle and non-vanadium metal compound are in the same place, its mixture is heated in stove to form a metal vanadium oxide composition.Melts combine is advanced the heat treatment process of going in the barium oxide lattice can carry out at oxidation environment or in inert environments.In the ambiance of any form, heating steps all will cause the variation of oxygen to the vanadium ratio usually, and in addition, heat treatment can also make crystal lattice change and/or remove the compound that absorbs on the degranulation to improve the performance of particle.
Use quite gentle condition, promptly temperature must be lower than the fusing point of barium oxide particle, causes melts combine to be gone in the barium oxide particle and does not cause particle to sinter bigger particle in a large number into.The employed barium oxide particle of process preferably nanoscale barium oxide particle has been found that the metal vanadium oxide composition can be by being in+5 (pentavalents) or less than obtaining in the barium oxide in the state of oxidation of+5 (pentavalents).Especially be in+2 (two valencys) are (VO) to+5 (pentavalent) (V
2O
5) the state of oxidation in barium oxide can be used for making metal vanadium oxide particles.
Usually, the metal that is combined in the metal vanadium oxide particles is that any non-vanadium shifts metal.The metal that is combined into barium oxide comprises: as, copper, silver, gold and its composition, suitable silver compound comprises as silver nitrate (AgNO
3).The copper compound that is suitable for comprises as, copper nitrate [Cu (NO
3)
2].Perhaps, also available silver metal dust, copper metal powder end or golden metal dust are as the corresponding metal source.
The oxic gas that is suitable for comprises as, O
2(also can supply with) with air, O
3, CO, CO
2With its composition, reactant gas can be used Ar, He and N
2Deng inert gas dilution.Perhaps, gas also can only be used inert gas.The silver-vanadium oxide particle can be produced with inert atmosphere or with oxidizing atmosphere, describes as following Example.
Multiple device can be used to carry out the usefulness of the heat treatment of sample annealing.The example 400 of suitable devices can be referring to Fig. 6 of mistake described above, the heat treatment of the barium oxide that gets for use in being produced by the laser high temperature pyrolytic cracking (HTP).Another 430 in device that is used for metal group is incorporated into the barium oxide lattice is seen Fig. 7.Particle is placed on the vial 432 in the pipe 434.In the red or similar vessel.Required gas is then by pipe 434.Gas can offer sample by introducing in oxidation source gas 438 or the inertia source of the gas 436.
Pipe 434 is placed in the stove 440, and stove 440 can adopt the commodity stove as " Mini-Mite
TM1000 ℃ of Tube Fumacl " produce by " Lindberg/Blue M, Asheville, NC ".Pipe 434 relevant portion is kept its normal temperature by stove 440, and temperature can be by in addition system's adjustment of treatment step certainly.Temperature monitoring adopts a thermocouple 442.
In order in heating steps, to produce metal vanadium oxide particles, the mixture of barium oxide particle and metallic compound can be placed in batch pipe 432 boats in the pipe 434.Preferably in stove, further earlier solution of metal compound and barium oxide nano particle are mixed the back evaporate to dryness before the heating.As long as be ready, evaporation can realize to form the metal vanadium oxide composition with heating simultaneously.For example, silver nitrate and copper nitrate can be added in the barium oxide particle as aqueous solution and go.Perhaps, barium oxide sodium rice particle can with metal oxide dry powder or metal element powder, so just can avoid evaporating this step.Add sufficient amount metallic compound or metal element powder so that the metal group of production requirement is incorporated in the barium oxide lattice.This mixing that enters barium oxide is for example to use, and the x-ray diffraction instrument is checked, and is as described below.
Can select accurate condition for use, comprise the kind of oxic gas (if the work that has), the concentration of oxic gas, the flow of gas and pressure, are produced the product material of required type at temperature and processing time etc.Temperature is not high usually, promptly is significantly less than the fusing point of material, and using softer condition is to sinter large-size particle into for fear of between particle, thereby can produce the bigger slightly particle of average particulate diameter with the sintering that higher slightly temperature is controlled particle.
For metal group is incorporated in the barium oxide, the scope of temperature normally from about 50 ℃ to about 500 ℃, is preferably from 80 ℃ to about 400 ℃, is more preferably from 80 ℃ to about 325 ℃.Temperature ranges can be from about 80 ℃ to about 250 ℃, and particle preferably is heated from about 5 minutes to about 100 hours.In order to produce the condition that is suitable for making required material, also may need the adjustment of some experiences.(3) character of particle
An average diameter that includes common its primary particles of particle of metal vanadium oxide compound is less than 500 microns, is preferably from about 5 microns to about 100 microns.Be more preferably from about 5 microns to about 50 microns, best is from about 5 microns to about 25 microns.Primary particles has rough spherical appearance usually substantially.Examine, crystalline particle generally always has and the corresponding face of its crystal lattice.Yet the primary particles crystallization all shows the trend of growth because of attempt on three directions in space, be spherical appearance substantially so just form.In preferred embodiment, 95% primary particles, even the long axis length that is preferably 99% particle is to be not more than 2 approximately to the ratio of minor axis length.The measurement of the diameter of asymmetry particle is the basis that is measured as with its main shaft average length.
Because the size of these particles is very little, so primary particles can trend towards occurring loose agglomeration because of near the electromagnetic force of particle and the effect of Van der Waal power.Yet the primary nanometer scale can clearly be observed in the transmission electron microscope figure to particle.Particle has the surperficial face with the corresponding nanometer scale of particle usually, can in microscope figure, observe, and, owing to the very big surface area of the very little size of particle and its Unit Weight demonstrates its very unique characteristic.For example, the barium oxide particle has the high-energy-density that makes us very surprised in lithium battery, and referring to U.S. Patent No. 5,952,125, exercise question is " battery with electric activated nano particle ".
The size of primary particles preferably has the very high uniformity.The laser high temperature pyrolytic cracking (HTP) can obtain the very narrow particle of its diameter distribution usually.And the heat treatment of carrying out under very soft condition can't change the very narrow characteristics of its diameter distribution, when transmitting with air float body, the distribution of particle diameter is very responsive to reaction condition, certainly, if the words that reaction condition is suitably controlled, in the air float body transfer system, can obtain the very narrow particle of diameter distribution, as mentioned above.According to the observed result of transmission electron microscope, the common distribution of sizes that has of primary particles is: at least about 95%, the diameter that is preferably 99% primary particles is greater than the about 40% of average diameter, and less than about 160% of average diameter.Be preferably, the diameter of primary distributes and is: at least about 95% and better be the diameter of 99% primary particles be greater than average diameter about 60% and less than about 140% of average diameter.
And, in a preferred embodiment, not about four times primary than average diameter, perhaps be more preferably three times, even twice, in other words, not occurring an expression on the size distribution plot of particle has the afterbody that has in a small amount obvious larger-diameter particle, and this is because reaction zone is very little and particle is subjected to the cause of hurried cooling.The afterbody of size distribution plot is excised effectively, this means 10
6Its diameter diameter bigger particle more bigger than a certain specific cut value more than the average diameter can be above one in the particle of quantity.
Very narrow distribution of sizes does not have afterbody and roughly is that spherical form can be developed a lot of applications in the distribution map.
In addition, nano particle generally has very high purity.Metal vanadium oxide particles with the crystallization of said method production is expected to have higher purity than reactant, because in the process that crystallization forms the trend that impurity is excluded is arranged from lattice.And has very high degree of crystallinity by the barium oxide particle of the crystallization of laser temperature adjustment pyrolysismethod production.Equally, the metal vanadium oxide nano particle with the crystallization of heat treatment method production also has very high degree of crystallinity.Be eliminated during at the impurity of particle surface, make particle not only obtain very high degree of crystallinity but also obtain very high purity in heating.
Barium oxide has a kind of complicated phasor, because vanadium has a variety of possible states of oxidation.The existing state of oxidation of known vanadium is to arrive between the pentavalent vanadium at two valency vanadium, and the energy difference under the different states of oxidation between the oxide of vanadium is little.Therefore, just might produce the compound of chemical mixing valency.The form known of barium oxide has VO, VO
1.27, V
2O
3, V
3O
5, V
2O, V
6O
13, V
4O
9, V
3O
7, and V
2O
5, adopt the laser high temperature pyrolytic cracking (HTP) separately or again in conjunction with adding the single-phase barium oxide that heating can very successful real estate goes out to have a lot of different states of oxidation, and proved by the x-ray diffraction sky.These monophase materialses are crystalline solid normally, and some noncrystal nano particle output is no doubt also arranged.Heat treatment method is to help increasing the state of oxidation of barium oxide particle or make the barium oxide particle be transformed into more orderly phase.
The mixed phase zone is also arranged in the barium oxide phasor.Particle can be shaped as the different states of oxidation in the mixed phase district, perhaps wherein can have simultaneously to have the not variable grain of gaseous state.In other words, other parts with other particles of a kind of stoicheiometry or particle of some part of some particle or particle then have another kind of different stoicheiometry.The mixed phase nano particle is made.The non-chemical proportion material also can be made.
The crystal that barium oxide forms usually is octahedra or impaired octahedral coordination.Particularly, VO, V
2O
3, VO
2, V
6O
13And V
3O
7Can form octahedral coordination.And, V
3O
7Also can form the coordination of bipyramid trigonal system.V
2O
5The formed side of being pyramid crystalline texture, V recently
2O
5Also can generate two dimension crystal structures, show " Solid State Ionics " 79:239-244 (1995) one books referring to people such as M.Hibino.Under the condition that is fit to, the barium oxide nano particle can also be noncrystal.The crystal lattice of barium oxide can be estimated with the x-ray diffraction method of measurement.
The metal vanadium oxide compound can form various stoicheiometries, quotes people's such as Liang U.S. Patent No. 4,310,609 herein, and exercise question is " metal oxide is formed cathode material and is used for high energy density cells ", and wherein Xu Shu form has: Ag
0.7V
2O
5.5, AgV
2O
5.5And Cu
0.7V
2O
5.5Oxygen debt silver-vanadium oxide product is the U.S. Patent No. 5,389,472 that is described in people such as Takenchi, and exercise question is " with Ag (0) and V
2O
5Prepare the silver-vanadium oxide negative electrode as parent material " in chemical formula be Ag
xV
2O
y, wherein: 0.3≤X≤2.0,4.5≤Y≤6.0, contain chemical admixture V again
2O
5And AgVO
3The phasor of silver-vanadium oxide be that to be described in exercise question be in " cathode material in the non-aqueous electrochemical cells " european patent application No.0689256A one literary composition, be listed as that this is for reference.(4) battery
Referring to Fig. 8 battery 450 negative electrode 452, one positive electrodes 454 and the interlayer 456 between negative battery 452 and positive electrode 454 are arranged.A monocell can comprise a plurality of positive electrodes and/or a plurality of negative electrode, and dielectric can be supplied with by various forms, and is as described below.Battery 450 preferably includes and link respectively together flow collection sheet 458,460 of positive electrode 454 and negative electrode 452.As long as be ready, a plurality of flow collection sheets can link with each electrode.
Lithium is used in battery in the reducing/oxidizing reaction always, because it is the lightest metal and because it is the most electropositive metal.Lithium ion inserted or similar mechanism is known with the form that the topochemistry absorption process is combined to some metal oxide that goes in its structure for example, can be in the various appropriate formats of barium oxide lattice, and insert lithium ion in the lattice of metal vanadium oxide composition.In battery, be suitable for folding metal vanadium oxide nano particle can be with barium oxide nano particle and metallic compound heat treatment together output, also can directly add in addition again or methods of heating treatment output in addition not with the metal vanadium oxide nano particle by the laser high temperature pyrolytic cracking (HTP).Especially lithium is inserted in the barium oxide lattice or in the metal vanadium oxide lattice when battery discharge.Lithium leaves lattice when discharge, promptly work as and receive on the battery by adding EMF, and voltage is added on the battery.When making electric current flow to positive electrode, lithium leaves lattice.Positive electrode 454 time is that a negative electrode and negative electrode 452 are anodes during at battery discharge in discharge.Metal vanadium oxide particles can directly be used as the positive electrode of lithium-base battery, to offer the high energy density of battery.Proper metal barium oxide particle can be the active material of effective electricity of anode in lithium or the lithium ion battery.Positive electrode 454 comprises that electricity for example lives useless nano particle, the metal vanadium oxide nano particle that combines with the such adhesive of superpolymer adhesive.Usually has different shape with the nano particle in electrode 454 just, for example spherical substantially nano particle or the nano particle of elongation.Except that metal vanadium oxide particles, positive electrode 45 also comprises other electricity active nano particle, for example TiO
2Nano particle, barium oxide nano particle and manganese oxide nanoparticles.TiO
2The existing U.S. Patent No. 4,705,762 of the production of nano particle is described, and is for reference.Known barium oxide nano particle demonstrates very surprising high-energy-density, referring to U.S. Patent No. 5,952,125.Exercise question is " battery with the active nano particle of electricity ".The production of manganese oxide nanoparticles is described in people's such as the common Kumar of transferring U.S. Patent application No.09/188 to be examined, and 770, the applying date is 1998,11,09, exercise question is for reference in " metal oxide particle ".
The active material of some electricity is rational electric conductor.Positive electrode comprises also in the active nano particle of electricity that usually the electricity that adds leads particle.These add, and electricity is led particle and is entrained in the adhesive usually.The electricity that is suitable for is led particle and is comprised for example carbon black of the carbon granule that can lead, and for example silver-colored particle of metallic particles, metallic fiber be stainless steel fibre etc. for example.The high amount of inserting of particle can obtain in adhesive.More than 80% of the preferably whole positive electrode weight of the weight of particle is more preferably greater than 90%.Adhesive can be the suitable high polymer of any kind of, for example, copolymer (EPDM) and their mixture and the copolymer of poly-inclined to one side trifluoro-ethylene, polyethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylate, ethene-(propylene-diene monomers).
Lithium ion battery adopts a kind of particle that can insert the composition of lithium.This particle is to be carried secretly among negative electrode by adhesive.
The insertion compound that is suitable for comprises, for example, graphite, synthetic graphite, coke, middle charcoal element contains the charcoal (doped carbons) of additive, niobium pentoxide, ashbury metal, SnO
2With their mixture and composition.
Flow collection sheet 458,460 is used to collect the electric current that flows out from battery.Flow collection sheet 458,460th, electric conductor is generally made by metals such as nickel, copper, aluminium, iron and stainless steels, and makes metal forming or a metal gate preferably.Flow collection sheet 458,460 can be placed on their relevant electrodes, perhaps is among their related electrodes.
There are various materials to can be used for interlayer.For example, interlayer can be made of the many empty matrix of form of glass fibers.Best interlayer is by making as the high polymer that is used in the adhesive.The high polymer interlayer can be made many empty forms so that the conduction of ion.The perhaps solid dielectric that can make with the high polymer as polyethylene oxide of high polymer interlayer.Make ion needn't need liquid solution also to be conducted in conjunction with the solid dielectric that advances in the high polymer matrix in dielectric.
The dielectric that is used for lithium battery or lithium ion battery can comprise the salt of various lithiums.Lithium salts has the inertia anion and is nontoxic preferably.The lithium salts that is suitable for comprises, as, lithium hexafluoro phosphate, hexafluoroarsenate lithium, and 2-(3 methyl fluoride sulfuric acid imines) lithium, trifluoromethayl sulfonic acid lithium, 3-(the 3 methyl fluoride sulfonyl) lithium that methylates, LiBF4, lithium perchlorate, tetrachloro-lithium aluminate, lithium chloride and cross fluorine butane lithium.
If dissolve dielectric with liquid solution, solution inertia and unlikely preferably then with the active material dissolves of electricity.What be suitable for usually comprises: as, propene carbonate, dimethyl carbonic ether, diethyl carbonate, 2-methyltetrahydrofuran, dioxolane, oxolane, 1,2-dimethoxy-ethane, ethylene carbonate, a-fourth lactones, dimethyl sulfoxide (DMSO), second eyeball, formamide, dimethyl formamide, nitromethane.
The shape of battery components can be adjusted to be adapted to last required product, for example button cell, rectangle or circular batteries.Battery generally includes an involucrum, and the collector plate and/or the electrode of its suitable part and battery keep being electrically connected.If the employing liquid dielectric, then shell should prevent that dielectric from leaking.Shell should keep each unit of battery to rely closely mutually, with the resistance of the inside of reducing battery.A plurality of batteries can be placed in the shell, wherein each battery can in parallel or series connection.EXAMPLE Example 1-produces barium oxide with the laser high temperature pyrolytic cracking (HTP)
Single-phase VO
2Particle can be produced with laser pyrolysis processes.VOCl
3(MA produces for Strem Chemical Inc., Newburyport) initial steam can be by argon gas at room temperature by the VOCl in the container
3Liquid becomes bubble and brings in the reative cell.Contain VOCl
3, Ar, O
2And C
2H
4The reactant mist enter in reactant gas nozzle and the spirt reative cell, the size of reactant gas nozzle is 5/8 inch * 1/8 inch.C
2H
4Gas is as laser absorption gas.Argon is as inert gas.
Synthetic barium oxide nano particle can directly contain band in air, produce the representative reactions condition of this material referring to table 1.
Table
Wherein: the sccm=standard cubic centimeter/minute
| Phase | ????VO 2 |
| Crystal structure | Monoclinic prism |
| Pressure (torr) | ????210 |
| Argon-window (sccm) | ????700 |
| Argon-protection (slm) | ????7.0 |
| Ethene (slm) | ????1.61 |
| Carrier gas-argon (slm) | ????1.4 |
| Oxygen (slm) | ????0.47 |
| Initial grain temperature (℃) | ????40 |
| Productive rate (gm/hr) | ????35 |
| Laser power input (Watts) | ????780 |
| Laser power output (Watts) | ????640 |
Slm=standard liter/minute
The argon gas stream of argon-window=process inlet 216,218
Argon-protection=through the argon gas stream of circular passage 142.
A kind of X-ray diffraction pattern of representative nano particle is seen Fig. 9, and is high-visible therein with the corresponding diffraction class of a kind of branch prism shape structure peak.Structure of being assert in diffraction pattern and the structure in the corresponding bulk of larger particle size almost are on all four.Embodiment 2-treated forms V
2O
5The nano particle crystal
Being used for heat treated original material is the VO that is produced by the parameter of table 1 by the laser high temperature pyrolytic cracking (HTP)
2Receive the material particle.
Nano particle heat treatment in roughly as the stove among Fig. 6.It is a collection of that particle restrains about 150 grams by about 100, sends in the glass by criticizing.Oxidation is 155 cubic centimetres of/minute stainless steel tubes that pass through 1/8 inch by flow.When heat treatment, adopt constant mixing velocity 5rpm mixed-powder.Powder is earlier with 100 ℃ of heating 30 minutes, again with 200 ℃ of heating 30 minutes, at last with 230 ℃ of heating 16 hours.Firing rate is by per 4 ℃/minute sample to be heated to target temperature.The nano particle that is obtained is the V of single phase crystalline
2O
5Nano particle.The X-ray diffraction pattern of this material is seen Figure 10.The particle that can determine gained from the X-ray diffraction pattern is orthorhombic V
2O
5
Transmission electron microscope (TEM) figure can obtain under typical nano particle after heat treatment.See Figure 11.Particle diameter among manual measurement Figure 11 can obtain distribution of sizes roughly, sees Figure 12.Can get and on average be about the 10-11 nanometer.Only its size is just measured and write down to sharp-edged particle among the figure, to avoid the confusion region of electron microscope picture.This and the unlikely measured deviation that causes because electron microscope only from folk prescription to observation, then point to and can't see the picture rich in detail of all particles in the difference of crystal.Embodiment 3-is with V
2O
5Nano particle heat treatment and form silver-vanadium oxide
Present embodiment is that employing barium oxide nano particle is the silver-vanadium oxide of the production nanometer scale of original material.This silver-vanadium oxide is produced with heat treatment method.
Silver nitrate (AgNO with about 9.5 grams
3) (" EM lndustries, Hawthorne, NY " produce) be dissolved in about 15 ml deionized water.Will be by the V of resulting about 10 grams of method described in the embodiment 2
2O
5Nano particle is put into and forms mixed liquor in the liquor argenti nitratis ophthalmicus, and stir about is 30 minutes in magnetic stirrer.Solution after fully stirring is heated to 160 ℃ and removes moisture in stove.Grind the powder mixture of its gained again with mortar and pestle.From the gained abrasive flour, calculate weight in 6 about 100 milligrams to 300 milligrams duplicate samples are placed on 1 cubic centimetre boat respectively.Boat is put in the quartz ampoule that passes heating furnace again heat-treats.Heating furnace is basic as above-mentioned shown in Figure 7.Feed the oxygen in the 1.0 inch diameter quartz ampoules or the flow of argon gas and be about 20 sccm.Each sample heats in stove under following condition:
1) 250 ℃, in the argon gas 60 hours,
2) 250 ℃, in the oxygen 60 hours,
3) 325 ℃, in the argon gas 4 hours,
4) 325 ℃, in the oxygen 4 hours,
5) 400 ℃, in the argon gas 4 hours,
6) 400 ℃, in the oxygen 4 hours.
The average heating speed of sample is about 2 ℃/minute, and by about 1 ℃/minute speed cooling.Time in the above-mentioned condition does not comprise heats up and cooling time.
With the sample particle structure after the x-ray diffraction method detection heat treatment, the x-ray diffraction pattern of the sample in argon gas and oxygen after the heating is illustrated respectively among Figure 13 and Figure 14.Peak in the diffraction pattern of various heating back sample gained, expressing wherein has Ag
2V
4O
11Sample after heating on 400 ℃ shows that it lacks a large amount of V
2O
5When sample is when doing long period heat treatment with lower temperature, then should be with any residual V
2O
5Original material is removed.
The transmission electron microscope figure of silver-vanadium oxide particle sees Figure 15.As a comparison, in Figure 16, express the V that manufacturing silver-vanadium oxide sodium rice particle is used
2O
5The transmission electron microscope figure of nano particle sample.The dimension scale of two figure is identical.V among Figure 16
2O
5The scale condition of nano particle is identical with described in embodiment 1 and 2, and the average diameter of the silver-vanadium oxide particle among Figure 15 is also also slightly smaller than the barium oxide nano particle original material among Figure 16 very in surprise unexpectedly.Embodiment 4 is with VO
2Nano particle heat treatment and form silver-vanadium oxide
This embodiment has represented to utilize VO
2The barium oxide nano particle is as the example of primary production nanometer scale silver-vanadium oxide.Silver-vanadium oxide is to produce with heat treatment method.
VO
2Nano particle with embodiment 1 in produce under the condition of similarity and get.With 10 gram nanocrystal VO
2Powder to remove residual chlorine, is the 500 milliliter filtration systems of " Corming " with a trade mark through the clear condition of 500 ml deionized water, and " Nylon " (nylon) film and the side arm that have 0.2 micron are to take out its empty filtration system to clean.Nanocrystal VO after the cleaning
2Powder is between 100 ℃ to 120 ℃ with being lower than 30 inches of mercury (750) temperature under vacuum, at least 12 hours dryings.Clean and dried nanocrystal VO
2In " SPEX TM 800 " mixed grinding device, handle 15 minutes again so that aggregate is smashed.
Use the silver nitrate crystalline powder of producing by " EM lndustries (Hawthorne, NY) " (99% above purity) to be added to the nanocrystal VO after reuniting by weight proportion
2In the powder, ratio is 1 mole AgNO
3VO to 2 moles
2Again this mixed-powder is placed on the trade mark for " (Worthington OH) ground 20 minutes in " the mill FritschMortar Grinder Model P-2 for Gilson Company, Inc..And then in tube furnace, heat, as shown in Figure 7, wherein the oxygen flow of the oxygen atmosphere of Liu Donging is 190 ml/min.
Heat treatment also comprises with the time more than one hour and is heated to 180 ℃ and then change at least one hour time for balance from room temperature.Progressively be warmed up to about 400 ℃ afterwards again, this final temperature kept about 20 hours, and then with product with the time cool to room temperature more than 5 to 15 hours.
The crystalline texture of the powder of gained is that x-ray diffraction method is measured, and its X-ray diffraction pattern is seen Figure 17.Have among the figure and silver-vanadium oxide (Ag
2V
4O
11) the class peak.
The silver-vanadium oxide nano particle of gained uses differential scanning calorimeter (DSC) to measure its characteristic again.This DSC device is " the model Universal V2.3C DSC " device that is provided by " TA Instruments, Inc., New Castle, DE ", and what record is that the heat balance diagram of function is seen Figure 18 by temperature.This curve table illustrate have only two each corresponding to 558 ℃ have peritectic reaction and 545 ℃ have eutectic point etc. warm spot.Further describing of transfer phenomena in silver-vanadium oxide can be referring to document: " P.Flenry, Rev.Chim.miner., 6 (5) 819 (1969) ".
Do not observe the more decalescence point of low temperature, especially corresponding to AgVO
3463 ℃ of fusing points near decalescence point do not observe.
Like this, the DSC data have just illustrated that with respect to nanometer-level silver barium oxide material with regard to the material that had phase transfer before 1000 ℃ of DSC test limits be very pure on composition.
This dry powder blend method also can be successfully produced the silver-vanadium oxide nano particle from the mixed-powder of the silver nitrate powder of nano particle crystallization V2O5 and crystallization, so for no other reason than that nanocrystal V2O5 particle be by heat treatment do not contain chlorine and just no longer need the situation step usually.In addition, fill molecular proportion also as corresponding adjustment.Embodiment 5-directly uses laser high temperature pyrolytic cracking (HTP) synthesis nano silver-vanadium oxide material
Synthetic the finishing of the described nanoscale silver-vanadium oxide of present embodiment material with the laser high temperature pyrolytic cracking (HTP).The production of particle mainly is laser high temperature pyrolysis device and the employing reactant delivery apparatuses as shown in Figure 3A that adopts as shown in Figure 1.
The solution that transmits as air float body in the reative cell is produced and is got with the vanadium primary.In order to produce this vanadium primary solution, V (trivalent) the oxide V of earlier will " Aldrich Chemical (Milwaukee, WI) " producing
2O
3Sample 20.0 restrains in the deionized water that is suspended in 240 milliliters.Moisture nitric acid (HNO with 60 milliliters
3) (70% weight ratio) splash in the trivalent vanadium oxide and powerful stirring the in addition.Notice that this reaction that adds nitric acid is exothermic reaction and discharges the doubtful NO that is
2Brown gas.The vanadium primary solution of gained is avy blue.
Make the usefulness of air float body transmissions for producing primary solution, the silver nitrate 22.7 of will " Aldrich Chemical (Milwaukee, WI) " producing restrains to be dissolved in and is prepared into liquor argenti nitratis ophthalmicus in 200 ml deionized water.Should be added in the vanadium primary solution and constantly stirring in order to the liquor argenti nitratis ophthalmicus of the usefulness of air float body transmissions as metal mixture solution.The vanadium of this avy blue solution is about 2: 1 to the mol ratio of silver.Adopt the silver of higher rate amount to obtain much the same result.
The aqueous solution that will have vanadium and silver-colored primary is sent in the reative cell as air float body.C
2H
4Gas is that argon gas then is an inert gas as laser absorption gas.O
2, Ar and C
2H
4All send in the air supply pipe of reactant feed system.Contain barium oxide, silver nitrate, Ar, O
2, and C
2H
4Reactant mixture be admitted to the reactant nozzle to be ejected in the reative cell, the opening size of reactant nozzle is 5/8 inch * 1/4 inch.Other parameters synthetic with the laser high temperature pyrolytic cracking (HTP) that particle is relevant among the embodiment 1 see Table 2.
Table 2
| Crystalline texture | Mix phase |
| Pressure (torr) | ????450 |
| Argon-window (sccm) | ????2.00 |
| Argon-protection (slm) | ????9.81 |
| Ethene (slm) | ????0.73 |
| Argon (slm) | ????4.00 |
| Oxygen (slm) | ????0.96 |
| Laser power is failed (Watts) | ????490-510 |
| Laser power output (Watts) | ????450 |
| Vanadium/silver-colored mol ratio | ????221 |
| The primary temperature (℃) | Room temperature |
Slm=standard liter/minute,
The argon flow amount of argon-window=process inlet 216,218,
Argon-protection=through the argon flow amount of circular passage 142,
The argon=directly and the argon flow amount of air float body mixing.
In order to estimate atomic arrangement, on " Siemess D 500 " X-ray diffractometer, utilize Cu (K α) radiation to carry out the x-ray diffraction test.The x-ray diffraction pattern of the sample of being produced by table 2 condition is seen Figure 19, and the peak value on the diffraction pattern can be assert and VO
2, V
2O
3And elemental silver.Other peaks misknow with known material and are associated among the figure, and will further be discussed in embodiment 7.
Under table 2 condition, produce sample powder do further to analyze with transmission electron microscope, its transmission electron microscope (TEM) is seen Figure 20.It is to drop on the different size branch matter cloth that a collection of particle is arranged among the TEM figure.The feature of the mixed phase material that Here it is makes with the laser high temperature pyrolytic cracking (HTP), wherein each material has a very narrow particle size distribution usually.
In addition, following embodiment is described, and these nanoscale silver-vanadium oxide materials in the oxygen environment can obtain the very Ag of high yield
2V
4O
11Crystalline solid.Embodiment 6-laser high temperature pyrolytic cracking (HTP) produce nanoscale silver-vanadium oxide material hot treatment
Present embodiment represented to utilize as laser high temperature pyrolytic cracking (HTP) as described in the embodiment 5 produce nanometer-level silver barium oxide material come the silver-vanadium oxide Ag of production nano crystals as original material
2V
4O
11
To be that nano particle between 300 to 700 milligrams is placed in 1 cubic centimetre the bateau corresponding to the about weight of embodiment 5 gained sample silver-vanadium oxide powder samples, and bateau will be put in the quartz ampoule that is through in the heating furnace heat-treat.This stove is basically as above-mentioned shown in Figure 7.Oxygen feeds in the quartz ampoule of 10 inch diameters with the flow of 30sccm.
Heat treatment is to be heated to 180 ℃ with the time more than 1 hour from room temperature earlier, and then changes at least one hour as time for balance.Then, with the speed of 3 ℃ of about per minutes temperature is raised to about 360 ℃, kept 16.5 hours on this final temperature, after heating on the final temperature reached required time, product was again with the speed cool to room temperature of 1 ℃ of per minute.Above-mentioned heat treatment time does not comprise the heating and cooling time.
Grain structure after the heat treatment is measured with the x-ray diffraction method, and the x-ray diffraction pattern of sample is seen Figure 21 after the heat treatment.Powder after the heat treatment is also used transmission electron microscope (TEM) test, and the TEM figure of sample sees Figure 22.Embodiment 7-is directly with the synthetic silver-vanadium oxide nano particle of laser high temperature pyrolytic cracking (HTP)
Present embodiment has been described with the synthetic silver-vanadium oxide nano particle of laser high temperature pyrolytic cracking (HTP).The production of particle is the laser high temperature pyrolysis device that utilizes as shown in Figure 1 basically, and as mentioned above, and utilization is as the reactant delivery apparatuses of Fig. 3 A or 3B.
Must prepare two kinds of solution so that transmit in the reative cell as air float body.Two kinds of solution all are to draw with the production of much the same vanadium primary solution.In order to produce first kind of vanadium primary solution, locate to buy trivalent vanadium oxide (V from " Aldrich Chemical (Milwaukee, WI) "
2O
3) sample 10.0 gram is suspended in 120 ml deionized water.Moisture nitric acid (HNO with 30 milliliters
3) (70% weight ratio) solution splashes into V
2O
3In the suspension, the powerful stirring.Notice that its reaction that adds nitric acid is exothermic reaction, and discharge the doubtful brown gas of NO2 that is.The vanadium primary solution of gained (about 150 milliliters) is avy blue solution.
Second kind of vanadium primary solution and first kind of vanadium primary solution just the same just wherein the amount of each composition be first kind three times.
In order to produce first kind of silver-colored solution, the silver carbonate (Ag that will " Alclrich Chemieal (Milwaukee, WI) " produces
2CO
3) 9.2 grams are suspended in 100 milliliters the deionized water and form Ag
2CO
3Solution.Moisture nitric acid (70% weight ratio) with 10 ml vols splashes into wherein powerful the stirring again.After dripping off, nitric acid obtains colourless clear solution.In order to produce first kind of metal mixture solution, silver-colored solution is added in first kind of vanadium primary solution constantly stirs for the usefulness that transmits air float body.It is about 2: 1 to the mol ratio of silver that the gained avy blue first metal mixed solution has vanadium.
In order to produce second kind of silver-colored solution, silver carbonate (Ag that will " Alclrich Chemical (Milwaukee, WI) "
2CO
3) 34.0 grams dissolve in 300 milliliters the deionized water.In order to prepare second kind of metal mixture solution, liquor argenti nitratis ophthalmicus is added in second kind of vanadium primary solution constantly stirs for the usefulness that transmits air float body.It is about 2: 1 to the mol ratio of silver that second kind of avy blue metal mixed of gained solution also has vanadium.
Selected moisture vanadium and silver-colored primary solution are sent in the reative cell in the air float body mode.C
2H
4Gas is that argon gas then is an inert gas as the laser absorption body.O
2, Ar and C
2H
4All send in the air supply pipe of reactant supply systems.Contain barium oxide, silver nitrate, Ar, O
2, and C
2H
4Reactant mixture be admitted to the reactant nozzle so that spurt into reative cell, the opening size of reactant nozzle is 5/8 inch * 1/4 inch.The synthetic parameters of other that the laser high temperature pyrolytic cracking (HTP) synthetic relevant with particle is synthetic sees Table 3.The preparation of sample is the reactant transfer system that adopts as shown in Figure 3A, and the reactant transfer system shown in Fig. 3 B is then used in the preparation of sample 2.
Table 3
Wherein:
| ????1 | ????2 | |
| Crystal structure | Mix phase | Mix phase |
| Pressure (torr) | ????600 | ????600 |
| Argon-window (sccm) | ????2.00 | ????2.00 |
| Argon-protection (slm) | ????9.82 | ????9.86 |
| Ethene (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 is molten | ????1 | ????2 |
| The primary temperature (℃) | Room temperature | Room temperature |
Slm=standard liter/minute,
The argon flow amount of argon-window=process inlet 216,218,
Argon-protection=through the argon flow amount of circular passage 142,
Argon=be blended directly in argon flow amount in the air float body.
In order to estimate atomic arrangement, on " Siemess D 500 " x-ray diffraction instrument, utilize Cu (K α) radiation to carry out the x-ray diffraction test.The x-ray diffraction pattern of sample of being produced by table 3 condition 1 (following surface curve) and sample 2 (going up surface curve) is seen Figure 23, and sample has and VO
2, the corresponding peak of elemental silver, but do not have and the corresponding peak of known materials again.The peak that the main crystalline phase of these samples has on 20 equals 30-31 °, and 32,33 and 35.Once thought that this was the phase of the silver-vanadium oxide of previous the unknown mutually.This mixes the back mutually with barium oxide nano particle and silver nitrate now mutually and is heated to the not enough time cycle to produce Ag at sample
2V
4O
11Condition under the preparation and sample in observed.Specific volume after sample 1 is put in the button cell is measured and will be narrated in the back, has also supported this explanation.The sample of gained also can be observed so less peak under condition as described in example 5 above.
Under table 3 condition, produce sample powder do further to analyze with transmission electron microscope, its transmission electron microscope figure (TEM) sees Figure 24 A (first row in the table 3) and Figure 24 B (secondary series in the table 3).There is a collection of particle to drop in the different distribution of sizes among the TEM figure, the feature of the mixed phase material that Here it is makes with the laser high temperature pyrolytic cracking (HTP), wherein first kind of material has a very narrow particle size distribution usually.Oxygen flow increases, and laser power reduces and the pressure increase can make the part of silver-vanadium oxide in the mixed phase material increase.Embodiment 8-is directly with the synthetic silver-vanadium oxide nano particle of laser high temperature pyrolytic cracking (HTP)
Present embodiment has been described with the synthetic silver-vanadium oxide particle of laser high temperature pyrolytic cracking (HTP).The production of particle is the laser high temperature pyrolysis device that utilizes basically as shown in Figure 1, as mentioned above; With the reactant delivery apparatuses that utilizes shown in Fig. 3 B.
Prepare a kind of solution so that be conveyed in the reative cell as air float body.In order to produce first kind of vanadium primary solution, locate to obtain trivalent vanadium oxide (V from " Aldrich Chemical (Milwawkee, WI) "
2O
3) sample 20 gram is suspended in 240 milliliters the deionized water, with 60 milliliters moisture nitric acid (HNO
3) (70% weight ratio) solution splashes into V
2O
3The powerful stirring in the suspension.Notice that its reaction that adds nitric acid is exothermic reaction, produce and discharge the doubtful NO that is
2Brown gas, the vanadium primary solution of gained (about 300 milliliters) is avy blue solution.
Prepare five kinds of different silver-colored solution and transmit in variable silver-colored vanadium ratio as air float body so that produce a kind of solution.In order to produce silver-colored solution, silver nitrate (AgNO that will " Alarich Chewical (Milwanka, WI) "
3) dissolve in 200 milliliters the deionized water, the weight of silver nitrate is respectively in these five kinds of solution: 1) 15.9 grams, 2) 18.1 grams, 3) 20.4 grams, 4) 22.7 grams, 5) 23.8 grams.Liquor argenti nitratis ophthalmicus is added to continuous the stirring with the metal mixture solution of preparation as air float body in the vanadium primary solution.
These five kinds of solution have the mol ratio of following silver to vanadium: 1) 0.7: 2, and 2) 0.8: 2,3) 0.9: 2,4) 1.0: 2,5) 1.05: 2.
Moisturely has vanadium and silver-colored primary solution is sent in the reative cell as air float body with selected.C
2H
4Gas is that argon gas then is an inert gas as laser absorption gas.O
2, Ar and C
2H
4All send in the air supply pipe of reactant feed system.Contain barium oxide, silver nitrate, Ar, O
2, and C
2H
4Reactant mixture be admitted to the reactant nozzle to be ejected in the reative cell, the opening size of reactant nozzle is 5/8 inch * 1/4 inch.Laser high temperature pyrolytic cracking (HTP) synthetic other parameters synthetic relevant with particle see Table 4.
Table 4
| Crystalline texture | Mix phase |
| Pressure (torr) | ????600 |
| Argon-window (sccm) | ????2.0 |
| Argon-protection (slm) | ????9.86 |
| Ethene (slm) | ????0.81 |
| Argon (slm) | ????4.80 |
| Oxygen (slm) | ????1.30 |
| Laser power input (Watts) | ????390 |
| Laser power output (Watts) | ????320 |
| The primary temperature (℃) | Room temperature |
Slm=standard liter/minute,
The argon flow amount of argon-window=process inlet 216,218,
Argon-protection=through the argon flow amount of circular passage 142,
The argon=directly and the argon flow amount of air float body mixing.
In order to estimate atomic arrangement, on " Siemess D 500 " X-ray diffractometer, utilize Cu (K α) radiation to carry out the x-ray diffraction test.The x-ray diffraction pattern of the sample 1-5 that produces by condition shown in the table 4 is seen Figure 25, and sample has corresponding to VO
2, elemental silver may be V
2O
3The peak and with the corresponding peak of known materials.The peak that has on the main crystalline phase table 20 of these samples equals 30-31 °, 32,33 and 35.As above indicate, think that once this is previous not by the phase of the silver-vanadium oxide of cognition mutually.Under the condition that the ratio of silver-colored vanadium increases, just increase with the corresponding peak of barium oxide, proved that thus when the relative quantity of silver increased, what add contained vanadium, oxygen and the amorphous state composition that has silver have also increased.Embodiment 9-laser high temperature pyrolytic cracking (HTP) is produced the elemental silver nano particle
The synthetic of the described elemental silver sodium of present embodiment rice particle is to realize with the laser high temperature pyrolytic cracking (HTP).The production of particle mainly is the laser high temperature pyrolysis device of using as shown in Figure 1, as mentioned above; With the reactant delivery apparatuses that adopts as shown in Figure 3A.
The preparation that transmits 1 equimolar silver nitrate solution in the reative cell as air float body be silver nitrate 50.96 grams with " AldrichChemical, Milwaukee, WI " be dissolved in 300 milliliters the deionized water and produce settled solution.C
2H
4Gas is that argon gas then is an inert gas as laser absorption gas.O
2, Ar and C
2H
4All send in the air supply pipe of reactant feed system.Contain silver nitrate, Ar, O
2, and C
2H
4Reactant mixture be admitted to the reactant nozzle to be ejected in the reative cell, the opening size of reactant nozzle is 5/8 inch * 1/4 inch.Laser high temperature pyrolytic cracking (HTP) synthetic other parameters synthetic relevant with particle see Table 5.
Table 5
Wherein:
| ????1 | ????2 | |
| Crystal structure | The coaxial Fang Fangti of face | The coaxial Fang Fangti of face |
| Pressure (torr) | ????450 | ????450 |
| Argon-window (sccm) | ????2.00 | ????2.00 |
| Argon-protection (slm) | ????9.82 | ????9.82 |
| Ethene (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 |
| Productive rate (gv/hr) | ????1.44 | ????1.02 |
| The primary temperature (℃) | Room temperature | Room temperature |
Slm=standard liter/minute,
The argon flow amount of argon-window=process inlet 216,218,
Argon-protection=through the argon flow amount of circular passage 142,
Argon=be blended directly in argon flow amount in the air float body.
In order to estimate atomic arrangement, on " Siemess D 500 " x-ray diffraction instrument, utilize Cu (K α) radiation to carry out the x-ray diffraction test.The sample of producing by condition shown in the table 51 and the x-ray diffraction pattern of sample 2 are seen Figure 26 and 27 respectively, and sample has and the corresponding very strong peak of elemental silver.
Under the condition of table 5 first row, produce sample powder do further to analyze with transmission electron microscope.Electron microscope picture such as Figure 28, the particle size distribution in TEM figure is than wide with the synthetic particle size distribution of laser high temperature pyrolytic cracking (HTP).Particle size distribution can or be used the gas phase primary, perhaps uses more uniform air float body to transmit and narrower widely.
Exemplary particles is also analyzed with elemental microanalysis method.The typical element analysis result of these materials is about (weight ratio) silver 93.09%, carbon 2.40%, hydrogen 0.05% and nitrogen 0.35%.Oxygen can not directly be measured, and may account for the part in the surplus.Elementary analysis is to adopt " DesertAnalytics, Tucson, Arizon " to finish.
Carbon in the nano particle forms seemingly that form with coating exists, the ethene that this carbon coating can be introduced by reactant flow and forming.Usually, carbon can heat under soft oxidizing atmosphere condition and remove.This de-carbon is further described the pending trial U.S. Patent application No.09/123 that assigns common, and in 255, exercise question is that " particle of metal (silicon) oxide/carbon combination " is for reference.
Because the chemical property that other elemental copper in the IB family and gold utensil have and silver is similar is so replace silver-colored primary should obtain elemental copper or gold nano grain product under the same conditions with copper and golden primary.Embodiment 10-makes lithium battery with the silver-vanadium oxide nano particle
Present embodiment is described the possibility with the well-formedness of silver-vanadium oxide particle manufacture lithium-base battery and increase capacity.For produce insertion by one of the foregoing description produce the silver-vanadium oxide test cell,
Weigh required silver-vanadium oxide nano particle and give quantitative powdered graphite (ChuetsuGraphite Works, Co., Osaka Japan) and the black powder of calcium carbide (Catalog number 55, Cheveon Corp.) be combined into conductive diluent, product adds the Teflon disperse means of 60% (weight) as adhesive in water.This mixture comprises 70% (weight) silver-vanadium oxide nano particle, 10% (weight) graphite, black and 10% (weight) Teflon of 10% (weight) calcium carbide.The composition of gained is fully integrated the thin slice that is rolled into 1 millimeters thick, from thin slice, cut out one 2 centimetres
2The disk of area.Then with this disk dry and in the mould of 1.6 centimetres of diameters with 12,000 pounds of 45-60 second and pressurizations, to form a solid piller.Then with this piller vacuumize and weighing.
The dry disk of this compacting is used as activated cathode in 2025 button cells.Impact one 1.6 centimetres in order to make button cell
2The nickel expanded metal disk of area, with electric resistance welding be welded in 2025 button cells stainless steel casing lid (Catalog No.10769, Alfa Aesar, Inc., Ward Hill, MA) in as collector plate.Go out one 2 centimetres with the battery grade lithium paper tinsel of Hohsen Corp (Osaka Japan)
2Disk and cold welding are online at the nickel porous metals.(Charlotte NC) is placed on the lithium disk for Celgard 2400, Hoechst-Celanese with the round spacer of the porous polypropylene of appropriate size.
The dielectric of scheduled volume is added in spacer/lithium disk sub-assembly, and dielectric solution is by 1M LiPF
6Salt is formed, and the solvent of dielectric solution is the ethylene carbonate and the dimethyl carbonate of 1: 1 (volumeization).Be rushed out 1.6 centimetres with second
2The stainless steel expanded metal disk of area is welded in the stainless steel casing of 2025 button cells with electric resistance welding.The activated cathode piller is placed on the nickel porous metals to match on the net and as above-mentioned spacer/lithium wafer package.Separate with the polypropylene plastics circle between stainless steel casing and the stainless steel casing lid.Sub-assembly crimping after again this being matched is fixed into a test button cells.
With " Maccor Bottery Test Sysfem, Series 400, from Maccor, Inc., (Tulsa, OK) " battery tester of producing tests, notes its discharge figure, and obtain the discharge capacity of this active material.
When making first button cell, be adopt as described in example 4 above with nanometer VO
2The Nano Silver barium oxide 0.143 that particle and silver nitrate add thermosetting is restrained and the negative electrode piller.The open circuit voltage of measuring after the crimping is exactly 3.53 volts at once.Battery was put into thermostatic chamber (temperature is 37 ± 1 ℃) balance 4 hours.Then, there is 0.1 milliampere constant discharge current to make battery discharge by every square centimeter of active electrode interface area.When voltage reaches 1.0 volts, then allow current attenuation but allow battery keep 1.0 volts of voltages constant, reach 5 hours.Under 1.0 volts of voltages, can allow to carry out the measurement of the irrelevant battery capacity of the polarity effect that occurs when reaching last current value with discharge.The apparatus for battery capacity measurement value that draws like this is more to use the maximum that obtains when infinitely putting slowly by being bordering on.
With time is voltage pattern and Figure 29 of function, and the beginning among the figure was measured during hygral equilibrium (not comprising any battery discharge) in 4 hours.The voltage curve that with the capacitance of storage is function is seen Figure 30.Measured battery discharging capacity is 51.0 Milliampere Hours, or bulking value is about 357 Milliampere Hour/grams (active silver-vanadium oxide nano particle).This is just bigger than theoretical bulking value.
Second battery is described directly synthetic and make with silver-vanadium oxide by the foregoing description 5, and negative electrode includes 0.148 gram sodium rice silver-vanadium oxide particle.The open circuit voltage that records immediately behind the crimping is 3.3 volts.Battery put into 37 ± 1 ℃ thermostatic chamber balance 4 hours.The stable discharging electric current of battery is by 0.309 milliampere of every square centimeter of active electrode interface area.When voltage reaches 1.0 volts, allow the discharging current minimizing and keep cell voltage, 5 hours at 1.0 volts.
Voltage one time graph such as Figure 31.During hygral equilibrium, obtained in initial 4 hours among the figure, do not comprise any battery discharge.Voltage is seen Figure 32 to the capacitance of storage curve.The electric power storage discharge capacity of measuring as shown in the figure is 15.4 Milliampere Hours, or bulking value is about 104.3 Milliampere Hour/grams (active silver-vanadium oxide nano particle).The measurement of discharge capacity is obtained by voltage and the integration of the product that divides electric current to discharging current.Bulking value is obtained by the quality of discharge capacity divided by active material.
The 3rd test cell is to be made by method as mentioned above with the synthetic silver-vanadium oxide of cycle of annealing in the stove of laser high temperature pyrolytic cracking (HTP) and postorder by the foregoing description 6 is said.The activated cathode piller contains 0.157 gram silver-vanadium oxide nano particle.The open circuit voltage of testing immediately behind the crimping is 3.5 volts.Battery was placed in 37 ± 1 ℃ the thermostatic chamber balance 4 hours.The stable discharging electric current of battery is by 0.100 milliampere of every square centimeter of active electrode interface area.When voltage reaches 1.0 volts, allow the discharging current minimizing and keep cell voltage, 5 hours at 1.0 volts.
Voltage-time curve such as Figure 33.During hygral equilibrium, obtained in initial 4 hours among the figure, do not comprise any battery discharge.Voltage is seen Figure 34 to the capacitance of storage curve.The electric power storage discharge capacity of measuring as shown in the figure is 63.53 Milliampere Hours, or bulking value is about 404 Milliampere Hour/grams (active silver-vanadium oxide nano particle).
The 4th test cell is with being made as stated above with the synthetic silver-vanadium oxide of laser high temperature pyrolytic cracking (HTP) under the specified condition of the foregoing description 7 first example in table 3.The activated cathode piller contains 0.154 gram silver-vanadium oxide nano particle.The open circuit voltage that records immediately behind the crimping is 3.4 volts.Battery was placed in 37 ± 1 ℃ the thermostatic chamber balance 4 hours.The stable discharging electric current of battery is by 0.309 milliampere of every square centimeter of active electrode interface area.When voltage reaches 1.0 volts, allow the discharging current minimizing and keep cell voltage, 5 hours at 1.0 volts.
Voltage one time graph such as Figure 35.During hygral equilibrium, obtained in initial 4 hours among the figure, do not comprise any battery discharge.Voltage is seen Figure 36 to the capacitance of storage curve.Figure 35, voltage curve shown in 36 have the peculiar feature of silver-vanadium oxide, and as shown in the figure, the electric power storage discharge capacity of measuring is 35.54 Milliampere Hours, or bulking value is about 35.54 Milliampere Hour/grams (active silver-vanadium oxide nano particle).This low bulking value is considered to have in the silver-vanadium oxide particle cause of part mixed phase material.
Been reported every gram (7 gram equivalents lithiums) Ag
2V
4O
11Lithium opinion capacity be 315 Milliampere Hours, referring to " people such as Takeuchi; ' reduction of silver-vanadium oxide in lithium/silver-vanadium oxide battery ' J.Electrochem; Soc.135:2691 (Nov.1988) " and " people such as Leising, Jonrhalof Power Sources 68:730-734 (1997) ".As seen, the capacitance described in the embodiment will substantially exceed theoretical value herein.
The above embodiments just belong to want to show several but only anything but.Additional embodiments comprises in the claims.The present invention has joined with preferred embodiment and has been described, but those skilled in the art should understand that the change on any form or the details does not all depart from the scope of the present invention and spirit.
Claims (47)
1. a particle group is characterized in that comprising metal vanadium oxide, and the average diameter of described particle is not more than 500 nanometers.
2. particle as claimed in claim 1 group, the average diameter that it is characterized in that particle wherein from about 5 nanometers to 100 nanometers.
3. particle as claimed in claim 1 group, the average diameter that it is characterized in that particle wherein from about 5 nanometers to 50 nanometers.
4. a particle as claimed in claim 1 group is characterized in that metal vanadium oxide wherein comprises silver-vanadium oxide.
5. a particle as claimed in claim 1 group is characterized in that metal vanadium oxide wherein comprises Ag
2V
4O
11
6. a particle as claimed in claim 1 group is characterized in that wherein in fact not having diameter greater than the about 4 times particle of the average diameter of particle group.
7. a particle as claimed in claim 1 group is characterized in that wherein in fact not having diameter greater than the roasting about 2 times particle of average diameter of particle collection.
8. particle as claimed in claim 1 group is characterized in that the distribution of sizes of particle group wherein is greater than average about 40% with less than about 160% of average diameter at least about the diameter of 95% particle.
9. particle as claimed in claim 1 group is characterized in that the distribution of sizes of particle group wherein is greater than average about 60% with less than about 140% of average diameter at least about the diameter of 95% particle.
10. a method of producing metal vanadium oxide particles is characterized in that comprising the mixture heating with barium oxide particle and non-vanadium metal compound, and the average diameter of said barium oxide particle is less than about 500 nanometers.
11., it is characterized in that wherein the average diameter of barium oxide particle is to about 100 nanometers from about 5 nanometers as the method for claim 10.
12., it is characterized in that wherein non-vanadium metal compound comprises silver nitrate as the method for claim 10.
13., it is characterized in that barium oxide particle wherein contains the V of crystallization as the method for claim 10
2O
5
14., it is characterized in that heating condition wherein is about 200 ℃ to 330 ℃ an of maximum temperature as the method for claim 10.
15., it is characterized in that heating condition wherein is that maximum temperature is from about 200 ℃ to about 300 ℃ as the method for claim 10.
16., it is characterized in that heating condition wherein is less than about 20 hours as the method for claim 10.
17. a battery is characterized in that comprising that one has the positive electrode of active particle, described active particle comprises the metal vanadium oxide that has adhesive, and the average diameter of described active particle is less than 500 nanometers.
18. as the battery of claim 17, it is characterized in that wherein active particle and average diameter from about 5 nanometers to about 100 nanometers.
19., it is characterized in that metal vanadium oxide wherein comprises silver-vanadium oxide as the battery of claim 17.
20., it is characterized in that silver-vanadium oxide wherein contains Ag as the battery of claim 19
2V
4O
11
21., it is characterized in that metal vanadium oxide wherein comprises the copper barium oxide as the battery of claim 17.
22., it is characterized in that positive electrode wherein also comprises additional conductive particle as the battery of claim 17.
23., it is characterized in that wherein in fact not having its diameter greater than the about active particle more than 4 times of active particle group average diameter as the battery of claim 17.
24. a method of producing metal vanadium oxide is characterized in that comprising a reactant flow and one second a metal initial particle that contains the vanadium primary particles is reacted that described reaction is driven by the energy that absorbs from electromagnetic field in reative cell.
25., it is characterized in that reactant flow wherein also comprises a reactant, i.e. oxygen source as the method for claim 24.
26., it is characterized in that reactant flow wherein also comprises a radiation absorbing compound as the method for claim 24.
27., it is characterized in that wherein vanadium primary is that form with air float body exists in reactant flow as the method for claim 24.
28., it is characterized in that wherein the second metal initial particle is that form with air float body exists in reactant flow as the method for claim 24.
29., it is characterized in that wherein the vanadium primary in reactant flow and the second metal initial particle both exist with the form of air float body as the method for claim 24.
30., it is characterized in that wherein the average diameter of metal vanadium oxide particles is to 100 nanometers from 5 nanometers as the method for claim 24.
31., it is characterized in that metal vanadium oxide particles wherein comprises silver-vanadium oxide, Ag as the method for claim 24
xV
2O
y, 0.3≤X≤2.0,4.5≤Y≤6.0.
32., it is characterized in that metal vanadium oxide particles wherein comprises Ag as the method for claim 24
2V
4O
11
33., it is characterized in that wherein in fact not having the about metal vanadium oxide particles more than 4 times of its diameter particle group average diameter as the method for claim 24.
34. as the method for claim 24, it is characterized in that the particle size distribution of metal vanadium oxide wherein be at least about the diameter of 95% particle greater than average diameter about 40% and less than about 160% of average diameter.
35., it is characterized in that the second metal initial particle wherein comprises the vanadium cation as the method for claim 24.
36., it is characterized in that vanadium primary wherein comprises the vanadium cation as the method for claim 24.
37. battery, it is characterized in that comprising that one has the negative electrode of active particle, described active particle comprises the silver-vanadium oxide that has adhesive, the energy density that described positive electrode has when discharging into about 1.0 volts greater than about 340 Milliampere Hours/gram active particle.
38. as the battery of claim 37, the average diameter that it is characterized in that active particle wherein from about nanometer to 100 nanometers.
39., it is characterized in that wherein the silver-vanadium oxide particle comprises silver-vanadium oxide, Ag as the battery of claim 37
xV
2O
y, 0.3≤X≤2.0,4.5≤Y≤6.0.
40., it is characterized in that silver-vanadium oxide wherein comprises Ag as the battery of claim 39
2V
4O
11
41. the battery as claim 37 is characterized in that wherein negative electrode comprises that also additional electricity leads particle.
42. the battery as claim 37 is characterized in that energy density that negative electrode wherein has is greater than about 350 Milliampere Hours/gram active particle.
43. an implantable defibrillator, is characterized in that this cell cathode includes silver-vanadium oxide comprising a lithium-base battery and when discharging into about 1.0 volts its energy density greater than about 340 Milliampere Hours/gram active material of cathode.
44. a battery is characterized in that comprising that one has the negative electrode of active particle, described active particle comprises the metal oxide that has adhesive, and when discharging into 1.0 volts, the energy density that described positive electrode has is greater than about 400 Milliampere Hours/gram active particle.
45. method of producing metal element nano particle and barium oxide Nanoparticulate compositions, it is characterized in that this method comprises, with a reactant flow that contains the vanadium primary, react in reative cell with the second metal initial particle, described reaction is driven by inhaling the energy of drawing from electromagnetic field.
46. a method of producing metal vanadium oxide particles is characterized in that comprising a reactant flow and second a metal initial particle that contains the vanadium primary reacted that described reaction is driven by the energy that absorbs from electromagnetic field in reative cell.
47. method of producing particle, described particle comprises that a kind of choosing is by a kind of metal element that contains in gold, silver, the copper family, it is characterized in that described method comprises reacts a part stream in reative cell, described molecular flow comprises a metal initial particle and a radiation absorber, and described reaction is to be driven by electromagnetic field radiation.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/246,076 US6225007B1 (en) | 1999-02-05 | 1999-02-05 | Medal vanadium oxide particles |
| US09/246,076 | 1999-02-05 | ||
| US09/311,506 US6391494B2 (en) | 1999-05-13 | 1999-05-13 | Metal vanadium oxide particles |
| US09/311,506 | 1999-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1343378A true CN1343378A (en) | 2002-04-03 |
Family
ID=26937704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00804664A Pending CN1343378A (en) | 1999-02-05 | 2000-02-02 | Metal vanadium oxide particles |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1163703A4 (en) |
| JP (1) | JP2002536286A (en) |
| KR (1) | KR20020018997A (en) |
| CN (1) | CN1343378A (en) |
| HK (1) | HK1044631A1 (en) |
| WO (1) | WO2000046867A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102598394A (en) * | 2009-11-03 | 2012-07-18 | 诺基亚公司 | Battery cell |
| CN103123968A (en) * | 2013-01-29 | 2013-05-29 | 中国科学院过程工程研究所 | High-performance lithium iron phosphate cathode material and preparation method of lithium iron phosphate cathode material |
| CN105230659A (en) * | 2015-11-17 | 2016-01-13 | 中国科学院海洋研究所 | Ag2V4O11 nanowire photocatalysis bactericide as well as preparation method and application thereof |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6503646B1 (en) | 2000-08-28 | 2003-01-07 | Nanogram Corporation | High rate batteries |
| US20030077221A1 (en) * | 2001-10-01 | 2003-04-24 | Shivkumar Chiruvolu | Aluminum oxide powders |
| US6749648B1 (en) | 2000-06-19 | 2004-06-15 | Nanagram Corporation | Lithium metal oxides |
| US6692660B2 (en) | 2001-04-26 | 2004-02-17 | Nanogram Corporation | High luminescence phosphor particles and related particle compositions |
| US6577114B1 (en) | 2000-07-31 | 2003-06-10 | Marvell International, Ltd. | Calibration circuit |
| US7120656B1 (en) | 2000-10-04 | 2006-10-10 | Marvell International Ltd. | Movable tap finite impulse response filter |
| WO2004010520A1 (en) | 2002-07-22 | 2004-01-29 | Nanogram Corporation | High capacity and high rate batteries |
| EP2043950A4 (en) * | 2006-06-06 | 2009-09-16 | Nanoscale Corp | Synthesis of high surface area nanogrystalline materials useful in battery applications |
| WO2019006151A1 (en) * | 2017-06-28 | 2019-01-03 | The Texas A & M University System | Thermochromic fenestration films containing vanadium dioxide nanocrystals |
| EP3633042A1 (en) * | 2018-10-02 | 2020-04-08 | Nanobacterie | Method for removing impurities from nanoparticles |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07122275A (en) * | 1993-05-25 | 1995-05-12 | Wilson Greatbatch Ltd | Cathode for electrochemical battery, its manufacture and electrochemical battery |
| US5435874A (en) * | 1993-11-01 | 1995-07-25 | Wilson Greatbatch Ltd. | Process for making cathode components for use in electrochemical cells |
| US5580683A (en) * | 1993-11-01 | 1996-12-03 | Wilson Greatbatch Ltd. | high pulse power cell |
| US5549880A (en) * | 1994-03-31 | 1996-08-27 | Koksbang; Rene | Method of making lithium-vanadium-oxide active material |
| US5545497A (en) * | 1994-06-21 | 1996-08-13 | Wilson Greatbatch Ltd. | Cathode material for nonaqueous electrochemical cells |
| WO1997009454A1 (en) * | 1995-09-07 | 1997-03-13 | The Penn State Research Foundation | High production rate of nano particles by laser liquid interaction |
| IT1281338B1 (en) * | 1995-11-24 | 1998-02-18 | Cise Spa | PROCESS FOR PRODUCING NANOMETER POWDERS OF METAL OXIDES FROM METALLIC CHLORIDES |
| EP1165442A1 (en) * | 1998-11-09 | 2002-01-02 | Nanogram Corporation | Metal oxide particles |
-
2000
- 2000-02-02 EP EP00905921A patent/EP1163703A4/en not_active Withdrawn
- 2000-02-02 KR KR1020017009899A patent/KR20020018997A/en not_active Application Discontinuation
- 2000-02-02 JP JP2000597850A patent/JP2002536286A/en active Pending
- 2000-02-02 CN CN00804664A patent/CN1343378A/en active Pending
- 2000-02-02 WO PCT/US2000/002653 patent/WO2000046867A1/en not_active Application Discontinuation
-
2002
- 2002-08-21 HK HK02106124.4A patent/HK1044631A1/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102598394A (en) * | 2009-11-03 | 2012-07-18 | 诺基亚公司 | Battery cell |
| CN102598394B (en) * | 2009-11-03 | 2016-03-16 | 诺基亚技术有限公司 | There is the battery unit of the charged state that user can check |
| CN103123968A (en) * | 2013-01-29 | 2013-05-29 | 中国科学院过程工程研究所 | High-performance lithium iron phosphate cathode material and preparation method of lithium iron phosphate cathode material |
| CN103123968B (en) * | 2013-01-29 | 2015-08-19 | 中国科学院过程工程研究所 | A kind of high-performance lithium iron phosphate cathode material and preparation method thereof |
| CN105230659A (en) * | 2015-11-17 | 2016-01-13 | 中国科学院海洋研究所 | Ag2V4O11 nanowire photocatalysis bactericide as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020018997A (en) | 2002-03-09 |
| EP1163703A4 (en) | 2004-12-29 |
| HK1044631A1 (en) | 2002-10-25 |
| JP2002536286A (en) | 2002-10-29 |
| WO2000046867A1 (en) | 2000-08-10 |
| EP1163703A1 (en) | 2001-12-19 |
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