WO2012097687A1 - 一种掺杂二氧化钒粉体、分散液及其制备方法和应用 - Google Patents
一种掺杂二氧化钒粉体、分散液及其制备方法和应用 Download PDFInfo
- Publication number
- WO2012097687A1 WO2012097687A1 PCT/CN2012/070025 CN2012070025W WO2012097687A1 WO 2012097687 A1 WO2012097687 A1 WO 2012097687A1 CN 2012070025 W CN2012070025 W CN 2012070025W WO 2012097687 A1 WO2012097687 A1 WO 2012097687A1
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- WO
- WIPO (PCT)
- Prior art keywords
- vanadium dioxide
- dioxide powder
- vanadium
- doped
- tetravalent
- Prior art date
Links
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 204
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 239000000843 powder Substances 0.000 title claims abstract description 148
- 239000006185 dispersion Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 51
- 239000000126 substance Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 59
- 239000007864 aqueous solution Substances 0.000 claims description 39
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 33
- 229910052720 vanadium Inorganic materials 0.000 claims description 33
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 230000007704 transition Effects 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052718 tin Inorganic materials 0.000 claims description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- 229910052787 antimony Inorganic materials 0.000 claims description 17
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 14
- 230000000737 periodic effect Effects 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 150000003681 vanadium Chemical class 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 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 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 42
- 239000011521 glass Substances 0.000 description 24
- 239000010408 film Substances 0.000 description 21
- 239000011135 tin Substances 0.000 description 21
- 230000027311 M phase Effects 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- 239000011858 nanopowder Substances 0.000 description 12
- 238000004448 titration Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- 238000004627 transmission electron microscopy Methods 0.000 description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 241000533950 Leucojum Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000009420 retrofitting Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- 229940041260 vanadyl sulfate Drugs 0.000 description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ASRYXPOBJNMFNB-UHFFFAOYSA-N [O-2].[O-2].[V+5].[W+4] Chemical compound [O-2].[O-2].[V+5].[W+4] ASRYXPOBJNMFNB-UHFFFAOYSA-N 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/127—Silica-free oxide glass compositions containing TiO2 as glass former
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2204/00—Glasses, glazes or enamels with special properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the invention relates to the preparation of vanadium dioxide powder in the field of chemical industry and materials, in particular to the doping of vanadium dioxide powder, and a preparation method and application thereof.
- Low-emission glass for energy-saving glass currently on the market Mainly based on glass, it has high transmission of visible light and high reflection of medium and far infrared rays, which can greatly reduce the indoor heat transfer caused by radiation compared with ordinary glass and traditional architectural coated glass. . however Low-E glass is not only expensive but not 'smart', so it is urgent to develop a next-generation smart energy-saving glass with independent intellectual property rights.
- rutile phase vanadium dioxide is a metal oxide having phase transition properties, which occurs at 68 ° C from a low temperature monoclinic phase (M Phase) to high temperature rutile phase (R Phase) reversible metal-semiconductor phase transition.
- M Phase low temperature monoclinic phase
- R Phase high temperature rutile phase
- the physical properties such as electrical conductivity, magnetic susceptibility, and light transmittance have changed drastically, making it more useful on intelligent temperature-controlled glass.
- the commonly used methods include reactive sputtering, reactive vapor deposition, chemical vapor deposition, sol-gel method, pulsed laser ablation, etc., but these methods are expensive, complicated in process parameter control, and poor in process stability. Or the deposition rate is low, the film formation area is small, and it is not suitable for mass production and other limitations.
- the replacement of the existing glass into energy-saving glass is too expensive, it is preferred to carry out energy-saving retrofit on the basis of the existing ordinary glass, that is, the vanadium dioxide powder having the smart energy-saving effect is coated on the existing ordinary glass. .
- the vanadium oxide is a complex system of multivalent and polycrystalline phases.
- the crystal structure of vanadium dioxide is more than 10 kinds, mainly including phase A and phase B. More than 10 crystal phases such as phase C, phase M, phase R and hydrate. Among them, the preparation of M/R phase vanadium dioxide has become a technical difficulty in the preparation of energy-saving glass.
- the existing M/R phase vanadium dioxide powder is mostly sintered by high temperature, Chinese patent CN 10164900A
- a method for preparing doped tungsten vanadium dioxide is disclosed: firstly preparing phase B vanadium dioxide powder, and then heat-treating at a high temperature of 350 to 800 ° C to obtain a phase R vanadium dioxide powder.
- Existing M/R The phase vanadium dioxide powder also has a spray pyrolysis method (U.S. Patent No. 5,247,763), a pyrolysis method (Chinese Patent CN 1321067C), and a sol-gel method (US Patent US6682596) And the inverse microemulsion method (WO 2008/011198 A2) and the like.
- the prior Chinese patent application CN 101391814A also discloses a one-step hydrothermal preparation of M/R. A method of phase vanadium dioxide powder.
- vanadium dioxide powder and vanadium dioxide powder and other materials to prepare a film, the method is simple, easy to operate on a large scale, not only can be used for energy-saving transformation of the original glass window, and can be coated on different substrates, Expand the applicability of vanadium dioxide.
- the preparation of the vanadium dioxide film and the coating have special requirements on the morphology and particle size of the vanadium dioxide powder, and the vanadium dioxide powder is required to have excellent dispersibility.
- the vanadium dioxide powder prepared by adding the doping element disclosed in the above prior art has a large size (mostly larger than 100 nm). ), often columnar (longitudinal to diameter ratio is mostly greater than 10:1), the doping element does not regulate the crystal phase, and the prepared doped vanadium dioxide powder has poor dispersibility, which is not suitable for preparing vanadium dioxide film. And coating.
- CN 10164900A mentions the addition of tungsten to prepare a particle size of ⁇ 50n
- the doped vanadium dioxide powder but it does not involve the microscopic morphology of the powder, that is, its doped tungsten element does not involve controlling the aspect ratio of the vanadium dioxide powder.
- this patent document uses a high temperature sintering method from B. Preparation of phase R vanadium dioxide powder with phase vanadium dioxide powder, the crystal phase of which is difficult to control.
- Chinese patent application before the applicant CN 101391814A Although it is mentioned that the prepared vanadium dioxide powder may be in the form of particles, it does not disclose the size of the particles, nor does it disclose the aspect ratio of the particles, and it can be seen from Fig. 2 that the crystal grains are columnar rather than granular. .
- the doped vanadium dioxide powder disclosed in the above prior art is mostly used to control the phase transition temperature of vanadium dioxide by doping other metal elements, and the doping elements used are mostly tungsten and molybdenum, which are not concerned. Up to its grain size and morphology, it is even less thought to control the size, morphology and size of vanadium dioxide powder by doping specific elements. / or crystal form.
- Japanese Patent Laid-Open 2009-102373 discloses a small size (particle diameter ⁇ 200nm) M phase VO 2, however, the process is induced into the M-phase second surface Ti02 VO 2, to obtain the VO 2 / TiO 2 composite particles Rather than doping vanadium dioxide with a single chemical composition.
- One aspect of the present invention provides a doped vanadium dioxide powder having a chemical composition of V 1-x M x O 2 , wherein 0 ⁇ x ⁇ 0.5, preferably 0.03 ⁇ x ⁇ 0.3, more preferably, 0.03 ⁇ x ⁇ 0.1, further, 0.005 ⁇ x ⁇ 0.025 is also preferable, M is a doping element, and the doping element can control the size and morphology of the doped vanadium dioxide powder.
- the size and morphology of the vanadium dioxide powder can be controlled by doping the predetermined doping element, and the prepared vanadium dioxide powder has a small grain size, uniform particle size, and the doping dioxide
- the vanadium powder is stable in crystal form, and has good dispersibility in water, a dispersing agent (for example, polyvinylpyrrolidone), and is easily coated on a substrate such as glass, and is suitable for preparing a film and a coating of vanadium dioxide powder.
- the doping element M specified in the present invention may be 21 ⁇ 30 near the vanadium in the periodic table.
- the transition elements include tantalum, titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, and the tin and its nearby elements include indium, antimony, tin, gallium, antimony, lead, and antimony.
- Preferred doping elements are bismuth, tin, iron, zinc and titanium.
- the size and morphology of the doped vanadium dioxide powder can be controlled, which is substantially different from the prior art in which the doping element only changes the phase transition temperature.
- the doping elements used can also modulate the phase transition temperature of vanadium dioxide.
- the doped vanadium dioxide powder is preferably in the form of particles, and the aspect ratio of the particles is from 1:1 to 10:1, preferably 1:1. 5:1, more preferably 1:1 to 2:1.
- the particle size is no more than 1 ⁇ m in at least one dimension, preferably no more than 100 nm in at least one dimension, more preferably no greater than three dimensions 100 nm, most preferably no more than 70 nm in all three dimensions.
- the granules may be, for example, a nearly spherical shape, an elliptical shape, a snowflake shape, a cuboid shape, a sheet shape, or the like.
- the vanadium dioxide powder having the above size and morphology has better dispersibility.
- the doped vanadium dioxide powder comprises rutile phase vanadium dioxide, and the rutile phase vanadium dioxide can account for up to 80%. It can even reach 100%.
- the doped vanadium dioxide powder of the present invention not only has a controllable size and morphology, but also has a semiconductor-metal phase transition property, and the phase transition temperature of the doped vanadium dioxide powder of the present invention is -30 Continuously adjustable between ⁇ 90 °C.
- the invention also provides a doped vanadium dioxide powder, wherein the chemical composition of the doped vanadium dioxide powder is V 1-x M x O 2 , wherein 0 ⁇ x ⁇ 0.5, M is a doping element,
- the doping element M may be one or any combination of 21 to 30 transition elements in the vicinity of vanadium in the periodic table, tin and its adjacent elements.
- 21 ⁇ 30 transition elements near vanadium in the periodic table include tantalum, titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc.
- the tin and its adjacent elements include indium, antimony, tin, gallium, antimony, lead, and antimony.
- Preferred doping elements are bismuth, tin, iron, zinc and titanium.
- the invention also provides a doped vanadium dioxide powder, wherein the chemical composition of the doped vanadium dioxide powder is V 1-x M x O 2 , wherein 0 ⁇ x ⁇ 0.5, M is a doping element,
- the doped vanadium dioxide powder is in the form of particles, and the aspect ratio of the particles is from 1:1 to 10:1, preferably from 1:1 to 5:1, more preferably from 1:1 to 2:1. It is also possible that the particle size is no more than 1 ⁇ m in at least one dimension, preferably no more than 100 nm in at least one dimension, more preferably no more than 100 nm in three dimensions, most preferably no greater than three dimensions. 70nm.
- the granules may be, for example, a nearly spherical shape, an elliptical shape, a snowflake shape, a cuboid shape, a sheet shape, or the like.
- the present invention also provides a method for preparing a doped vanadium dioxide powder, which comprises treating a precursor solution of a suspension with an aqueous solution of a tetravalent vanadium ion using an alkaline reagent.
- the chemical composition of the doped vanadium dioxide powder prepared by the method is V 1-x M x O 2 , wherein 0 ⁇ x ⁇ 0.5, preferably 0.03 ⁇ x ⁇ 0.3, more preferably 0.03 ⁇ x ⁇ 0.1 , Further, 0.005 ⁇ x ⁇ 0.025 is also preferable.
- M is a doping element, and the doping element can control the size and morphology of the doped vanadium dioxide powder.
- the doping element M in the chemical composition V 1-x M x O 2 of the doped vanadium dioxide powder prepared by the method may be a 21 ⁇ 30 transition element near the vanadium in the periodic table, tin and its vicinity.
- 21 ⁇ 30 transition elements near vanadium in the periodic table include tantalum, titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc.
- the tin and its adjacent elements include indium, antimony, tin, gallium, antimony, lead, and antimony.
- Preferred doping elements are bismuth, tin, iron, zinc and titanium.
- the doped vanadium dioxide powder prepared by the method is granular, and the aspect ratio of the particles is 1:1 to 10:1, preferably 1:1 to 5:1, more preferably 1:1. 2:1. It is also possible that the particle size is no more than 1 ⁇ m in at least one dimension, preferably no more than 100 nm in at least one dimension, more preferably no more than 100 nm in three dimensions, most preferably no greater than three dimensions. 70nm.
- the granules may be, for example, a nearly spherical shape, an elliptical shape, a snowflake shape, a cuboid shape, a sheet shape, or the like.
- the method of the present invention processes the precursor (tetravalent vanadium ion aqueous solution) with an alkaline reagent before doping the predetermined doping element, and can obtain a vanadium dioxide powder size with controllable size and morphology (in at least one dimension) Greater than 1 ⁇ m And morphology (granular, aspect ratio no greater than 10:1)
- the prepared vanadium dioxide powder has a small crystal grain size, uniform particle size, and stable crystal form, and has good dispersibility in water and a dispersant (for example, polyvinylpyrrolidone), and is easily coated on a substrate such as glass.
- a dispersant for example, polyvinylpyrrolidone
- the preparation method of the invention is simple in operation, low in cost, easy to control, and has good crystallinity and high yield for scale production.
- the reaction precursor Before the hydrothermal reaction, the reaction precursor is treated with a base, which can make the subsequent hydrothermal reaction easier, the hydrothermal reaction temperature is low, and the yield is higher, which is suitable for scale production.
- the molar ratio of the alkaline agent to the tetravalent vanadium ion aqueous solution used is 1:50 to 10:1, preferably 1:10 to 5:1, more preferably 1:5 to 2:1.
- the precursor treatment step may be a titration method in which an aqueous solution of tetravalent vanadium ions is titrated with an alkaline reagent until a suspension is formed, and the pH of the end point of the titration is 2 to 12, preferably 5 to 10. .
- the method is easy to operate and control and requires no special equipment.
- the concentration of the aqueous solution of tetravalent vanadium ions used in the present invention may be from 0.005 to 0.5 mol/L, and usually 0.01 mol/L may be selected. It can be prepared by dissolving a soluble vanadium material in water.
- the commonly used soluble vanadium raw material may be a trivalent, tetravalent or pentavalent vanadium salt and/or a hydrate thereof, preferably a tetravalent soluble vanadium salt and a hydrate thereof, such as vanadyl sulfate (VOSO 4 ) or vanadium oxychloride (VOCl).
- vanadyl oxalate anhydrate VOC 2 O 4 .5H 2 O
- VOC 2 O 4 .5H 2 O vanadyl oxalate anhydrate
- the insoluble vanadium raw material can also be used to prepare an aqueous solution of tetravalent vanadium ions, that is, the insoluble vanadium raw material is solubilized by pretreatment such as oxidation, reduction or dissolution.
- the insoluble vanadium feedstock can be a metal vanadium, a vanadium oxide, or a combination thereof.
- the alkaline reagent used in the present invention may be ammonia water, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, sodium hydrogencarbonate aqueous solution, potassium carbonate aqueous solution, potassium hydrogencarbonate aqueous solution or the like or any combination thereof; preferably ammonia water or hydroxide
- a sodium aqueous solution or an aqueous potassium hydroxide solution is more preferably an aqueous sodium hydroxide solution.
- the concentration of the alkaline reagent used may be 0.5 to 5 mol/L, preferably 0.5 to 2 mol/L.
- the above-mentioned alkali-treated suspension can then be mixed with a prescribed dopant, and the desired doped vanadium dioxide powder can be obtained by hydrothermal reaction.
- the molar ratio of the doping element in the dopant to the aqueous solution of tetravalent vanadium ions may be 1:1000 ⁇ 1:1, preferably 3:97 to 3:7, more preferably 3:97 to 1:9; in addition, 1:199 to 1:39 are also preferable.
- Hydrothermal reaction temperature can be 200 ⁇ 400 °C, preferably 200 to 350, more preferably 250 to 300 °C.
- the hydrothermal reaction time is from 1 to 240 hours, preferably from 2 to 120 hours, more preferably from 4 to 60 Hours.
- the hydrothermal reaction filling ratio may be from 20 to 90%, preferably from 30 to 80%, more preferably from 50 to 80%.
- the element doped in vanadium dioxide may be a metal such as molybdenum or tungsten which is commonly used to regulate the phase transition temperature of vanadium dioxide, or may be in the vicinity of vanadium in the periodic table.
- 21 ⁇ 30 Transition element one or any combination of tin and its nearby elements. Among them, 21 ⁇ 30 near vanadium in the periodic table
- the transition elements include tantalum, titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, and the tin and its nearby elements include indium, antimony, tin, gallium, antimony, lead, and antimony, with preferred doping.
- the elements are antimony, tin, iron, zinc and titanium; with these doping elements, the size and morphology of the doped vanadium dioxide powder can be controlled, which is fundamentally different from the prior art in which the doping element only changes the phase transition temperature. .
- the doping elements used can also modulate the phase transition temperature of vanadium dioxide.
- the precursor of the hydrothermal reaction is pretreated with a base, and the reaction temperature of the subsequent hydrothermal reaction is low, and the reaction can be completed in one step, and the yield is high. Moreover, the size and morphology of the obtained doped vanadium dioxide particles can be controlled within a prescribed range. Moreover, the preparation method of the present invention is simple in operation, low in cost, easy to control, and has good crystallinity of the product.
- the present invention also provides a vanadium dioxide dispersion containing the above vanadium dioxide powder.
- the amount of vanadium dioxide powder may be 0.1 ⁇ 100g/L. It is preferably 1 to 50 g/L, more preferably 5 to 30 g/L.
- the above vanadium dioxide dispersion can be applied to a suitable substrate, and can be applied to thermochromic films, energy-saving coatings, energy-saving paints, smart energy-saving glass curtain walls, temperature control devices (such as solar temperature control devices), and energy-saving coatings.
- thermochromic films energy-saving coatings
- energy-saving paints energy-saving paints
- smart energy-saving glass curtain walls temperature control devices (such as solar temperature control devices)
- energy-saving coatings for example, it is suitable for directly manufacturing energy-saving glass, and can also be used for retrofitting existing ordinary glass, and can also be applied to energy-saving renovation of existing buildings, vehicles and ships.
- the vanadium dioxide powder of the present invention can also be applied to energy information equipment, including miniature photoelectric switching devices, thermistors, battery materials, and optical information storage devices.
- the energy-saving film prepared by using the doped vanadium dioxide powder of the invention has the advantages of simple process, low cost, wide application, and spectral characteristics comparable or better than other methods such as sputtering method and electroless plating method.
- Figure 1 is an X-ray diffraction diagram of a vanadium dioxide powder corresponding to a comparative example
- Figure 3 is an X-ray diffraction diagram of the vanadium dioxide powder corresponding to Example 1;
- Example 4 is a transmission electron micrograph of the vanadium dioxide powder corresponding to Example 1;
- Figure 5 is an X-ray diffraction diagram of the vanadium dioxide powder corresponding to Example 2.
- Example 6 is a transmission electron micrograph of the vanadium dioxide powder corresponding to Example 2.
- Figure 7 is an X-ray diffraction diagram of the vanadium dioxide powder corresponding to Example 8.
- Figure 8 is a transmission electron micrograph of the vanadium dioxide powder corresponding to Example 8.
- Figure 9 is an X-ray diffraction diagram of the vanadium dioxide powder corresponding to Example 12.
- Figure 10 is a transmission electron micrograph of the vanadium dioxide powder corresponding to Example 12;
- FIG. 11 is a spectral graph of a phase change of a film prepared by the vanadium dioxide nanopowder of the present invention.
- Figure 13 is a graph showing the X-ray diffraction pattern of the solid in the suspension of the intermediate product in the method for producing vanadium dioxide powder of the present invention.
- the present embodiment will be described by taking a hydrothermal method for preparing a vanadium dioxide powder.
- a rutile phase doped vanadium dioxide powder and a dispersion thereof by hydrothermal method will be described as an example.
- the process of the present invention can also be used to prepare undoped vanadium dioxide powder, as well as other crystalline phases of vanadium dioxide powder, for example A phase vanadium dioxide powder.
- the vanadium dioxide powder of the present invention can be prepared by using a tetravalent vanadium ion aqueous solution as a reaction precursor, and treating the reaction precursor with an alkaline reagent.
- the configuration of the aqueous solution of tetravalent vanadium ions can be prepared by a method commonly used in the art: the tetravalent soluble vanadium raw material is dissolved in an appropriate amount of water, preferably deionized water, and the suitable concentration can be 0.005 to 0.5 mol/L, and usually 0.01 can be selected. Mol/LL.
- the tetravalent soluble vanadium salt can be a commonly used vanadium salt which is inexpensive and readily available, such as vanadyl sulfate (VOSO 4 ) and vanadium oxychloride (VOCl 2 ).
- vanadium salts such as vanadyl oxalate pentahydrate (VOC 2 O 4 .5H 2 O ).
- VOC 2 O 4 .5H 2 O vanadyl oxalate pentahydrate
- the configuration of the tetravalent vanadium ion solution is usually carried out at room temperature, but it is also understood that it may be slightly heated to promote dissolution or assisted by ultrasonic or the like.
- the vanadium raw material as an aqueous solution of tetravalent vanadium ions may also include other soluble or insoluble vanadium raw materials, for example, trivalent or pentavalent soluble vanadium salts and / Or its hydrate is used as a vanadium raw material, which is dissolved in water and oxidized or reduced to an aqueous tetravalent vanadium ion solution. It should be understood that if insoluble matter is precipitated during the redox process, an appropriate amount of water may be added to dissolve it, or it may be slightly heated to dissolve.
- An insoluble vanadium material can also be used to prepare an aqueous solution of tetravalent vanadium ions: an insoluble vanadium material, such as a metal vanadium, a vanadium oxide or a combination thereof, which is solubilized by oxidation, reduction or dissolution, and then dissolved in water. The desired aqueous solution of tetravalent vanadium ions is obtained.
- aqueous solution of tetravalent vanadium ions was titrated with an alkaline reagent until a suspension was formed.
- an alkaline reagent for titration ammonia water, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, sodium hydrogencarbonate aqueous solution, potassium carbonate aqueous solution, potassium hydrogencarbonate aqueous solution, or the like, or any combination thereof may be used; preferably, ammonia water or hydroxide
- a sodium aqueous solution or an aqueous potassium hydroxide solution is more preferably an aqueous sodium hydroxide solution.
- the inventors have found through repeated experiments that controlling the concentration of the aqueous solution of tetravalent vanadium ions and the alkaline reagent used is advantageous for the formation of the suspension to determine the end point of the titration, wherein An alkaline reagent of 0.5 to 2 mol/L is advantageous.
- the pH of the suspension is usually 2 to 12
- the molar ratio of the alkaline reagent to the tetravalent vanadium ion aqueous solution is usually 1:50 to 10:1, the amount of alkaline reagent used should be at least the minimum amount that can form a suspension.
- a molar ratio of the alkaline agent to the tetravalent vanadium ion aqueous solution of more than 1:10 is preferable, and more preferably 1:5 ⁇ 2:1.
- the alkaline reagent should not be excessively large, and the molar ratio of the alkaline reagent to the tetravalent vanadium ion aqueous solution should preferably not exceed 5:1.
- Titration takes the presence of a suspension as the endpoint of the titration, making it easy to observe and control, without the need for additional equipment.
- the solid obtained by filtering the above-mentioned suspension obtained by alkali treatment was dried, and the X-ray diffraction pattern thereof was measured, as shown in Fig. 13, and it was found that the chemical composition of the suspension intermediate obtained by the alkali treatment of the method of the present invention was V 4 . H 6 O 10 .
- the suspension obtained by the above alkali treatment is transferred to a hydrothermal reaction vessel, and the vanadium dioxide powder which can be obtained by hydrothermal reaction and drying is separated.
- the aqueous solution of vanadium ions may also be hydrothermally reacted with a dopant to prepare a doped vanadium dioxide powder, and the prescribed dopant may be an oxide of a predetermined doping element M as a doping element.
- M may be 21 ⁇ 30 transition elements near vanadium in the periodic table, such as tantalum, titanium, chromium, manganese, iron, cobalt, nickel, copper; or zinc tin and its nearby elements, such as indium, antimony, tin, gallium, ⁇ , lead, and ⁇ .
- Doping element M It can be a single element or any combination of the above elements.
- the oxide may contain a single oxide of a single doping element, an oxide containing two or more doping elements, or a mixture of oxides of different doping elements.
- the doping element can control the size and morphology of the resulting doped vanadium dioxide powder.
- the molar ratio of the doping element in the dopant to the aqueous solution of tetravalent vanadium ions can be determined according to the doping amount of the doping element, and can be selected in the present invention. 1:1000 to 1:1, preferably 3:97 to 3:7, more preferably 3:97 to 1:9; and 1:199 to 1:39 are also preferable.
- the hydrothermal reaction temperature may be from 200 to 400 ° C, preferably from 200 to 350, more preferably from 250 to 300 °C. In these temperature ranges, the higher the temperature, the more favorable the formation of rutile vanadium dioxide.
- the hydrothermal reaction time can be from 1 to 240 hours, and can be adjusted according to the reaction temperature, preferably from 2 to 120. The hour is more preferably 4 to 60 hours. Those skilled in the art can understand that a suitable reaction kettle can be selected according to the amount of feed.
- the hydrothermal reaction filling ratio can be 20 to 90%, and the filling ratio of the hydrothermal reaction can be 20 to 90%. Preferably, it is 30 to 80%, more preferably 50 to 80%.
- the hydrothermal reaction product can be separated and dried by centrifugal drying, but it should be understood that other methods of drying the powder such as freeze drying can also be employed.
- the doped vanadium dioxide powder produced by the present invention has a single chemical composition, which is represented herein as V 1-x M x O 2 , wherein x satisfies 0 ⁇ x ⁇ 0.5, preferably 0.03 ⁇ x ⁇ 0.3 More preferably, 0.03 ⁇ x ⁇ 0.1, further, 0.005 ⁇ x ⁇ 0.025 is also preferable, and M is a doping element as described above.
- the shape and particle diameter of the obtained vanadium dioxide powder prepared by the present embodiment are observed by transmission electron microscopy (TEM).
- the doped vanadium dioxide powder prepared in this embodiment is granular, and the size is mainly concentrated between 10 and 100 nm. .
- the TEM is model JEM2010 JEOL manufactured by Tokyo Corporation of Japan.
- the process of the invention can also produce undoped vanadium dioxide powder, or it can have a single chemical composition VO 2 .
- FIG. 3 an X-ray diffraction pattern of an undoped vanadium dioxide powder prepared according to an embodiment of the present invention (the abscissa is an angle of 2 ⁇ , and the ordinate represents a diffraction peak intensity), which is a phase A VO. 2 .
- Figure 4 the transmission electron micrograph of the above undoped vanadium dioxide powder
- the vanadium dioxide powder is a long rod shape, and each vanadium dioxide long rod is a single crystal, and its length is reached. Hundreds of nm to tens of ⁇ m and a width of several hundred nm.
- the energy-saving film prepared by the doped vanadium dioxide powder has spectral characteristics comparable to those of other methods such as sputtering and electroless plating.
- Fig. 3 there is shown an X-ray diffraction pattern of undoped vanadium dioxide powder (the abscissa is an angle of 2 ⁇ and the ordinate is a diffraction peak intensity) which is phase A VO 2 .
- Figure 4 the transmission electron micrograph of the above undoped vanadium dioxide powder
- the vanadium dioxide powder is a long rod shape, and each vanadium dioxide long rod is a single crystal, and its length is reached.
- the doped vanadium dioxide of the present invention is M phase VO 2 having a particle shape of about 50 nm, an aspect ratio of less than 2:1, and a uniform particle diameter.
- the present invention can control the size and morphology of the vanadium dioxide powder by doping the predetermined doping element, and the prepared vanadium dioxide powder has a small grain size and a particle size. Uniform and stable crystalline form.
- the doped vanadium dioxide powder of the invention has good dispersibility in water, a dispersant (for example, polyvinylpyrrolidone), 0.1 to 100 g/L, and is easily coated on a substrate such as glass, and is suitable for preparing vanadium dioxide. Powder film and coating.
- the doped vanadium dioxide powder is ground and dispersed in water, and a dispersing agent such as polyvinylpyrrolidone is added during stirring, and the mixture is stirred and ultrasonic for 30 min to 2 h to obtain a vanadium dioxide dispersion.
- the doped vanadium dioxide powder of the present invention exhibits very good dispersibility in both water and a dispersant.
- the prepared dispersion is applied to a substrate, such as a glass substrate, and dried to obtain a vanadium dioxide film. Referring to Figure 12, there is shown a vanadium dioxide film of the present invention having a uniform thickness. It should be understood that the dispersion may also be applied to other suitable substrates to prepare films, and suitable substrates include plastic substrates, silicon substrates, and metal substrates. This can be used for energy-saving retrofitting of existing buildings, vehicles and ships.
- UV-visible near-infrared spectrophotometer (model U-4100, Japan Hitachi) The company obtained the film obtained by heating and cooling the temperature control unit, and measured the spectral curves at 30 °C and 90 °C respectively to obtain the spectral curves before and after the phase change of vanadium dioxide. See Figure 11
- the doped vanadium dioxide has a significant change in light transmittance before and after the phase change. For example, for a light wave of about 2000 nm, the transmittance before and after the phase change is 40.6%.
- Figure 12 for the produced film. 2000nm
- the curve of light wave transmittance with temperature shows that the prepared doped vanadium dioxide has phase transition property, and the transmittance of infrared light wave is significantly reduced after phase change.
- the results show that the energy-saving film prepared by using the vanadium dioxide powder of the present invention has spectral characteristics comparable to those of other methods such as sputtering and electroless plating.
- V 2 O 5 powder 0.225 g was dissolved in 50 ml of 0.15 mol/L oxalic acid solution, stirred for 10 minutes, added to a hydrothermal kettle, 26 mg of tungstic acid was added, and hydrothermally reacted at 240 ° C for 7 days, and dried by centrifugation.
- the vanadium dioxide powder has a chemical formula of V 0.96 W 0.04 O 2 and a yield of 75%.
- the crystal phase is M phase.
- the vanadium dioxide powder obtained is also long rod-shaped.
- VOSO 4 powder Dissolve 1 g of VOSO 4 powder in 50 ml of deionized water, titrate with 1 mol/L NaOH solution, and stir constantly. After the titration is complete, the suspension is placed in a 50 ml hydrothermal kettle containing 45 ml of deionized water. Hydrothermal reaction at 250 °C for 12 hours, centrifugal drying to obtain vanadium dioxide powder, the chemical formula is VO 2 , the yield is 90%. As shown in the XRD spectrum of Fig. 3, the crystal phase is phase A. As shown in the TEM photograph of Fig. 4, the vanadium dioxide powder obtained is a long rod shape, and each vanadium dioxide vane is a single crystal, and its length is reached. Hundreds of nm to tens of ⁇ m and a width of several hundred nm.
- the experiment of 2 was repeated with 1 g of VOSO 4 and 7.5 mg of Bi 2 O 3 to prepare a vanadium dioxide nanopowder having a chemical formula of V 0.995 Bi 0.005 O 2 in a yield of 85%.
- the crystal phase is also M phase, and each vanadium dioxide particle is a single crystal particle, and its grain size is mainly concentrated between 40-70 nm, and the aspect ratio is 1:1 to 3:1.
- the experiment of repeating 2 was carried out by replacing the Bi 2 O 3 with SnO to obtain a vanadium dioxide nano powder having a chemical formula of V 0.962 Sn 0.038 O 2 and a yield of 95%.
- the crystal phase is also M phase, and each vanadium dioxide particle is a single crystal particle, and its grain size is mainly concentrated between 30-40 nm, and the aspect ratio is 1:1 to 1.5:1.
- the experiment of repeating 2 was carried out by replacing 25 mg of Bi 2 O 3 with 21 mg of SnO to obtain a vanadium dioxide nano powder having a chemical formula of V 0.975 Sn 0.025 O 2 in a yield of 90%.
- the crystal phase is also M phase, and each vanadium dioxide particle is a single crystal particle, and its grain size is mainly concentrated between 40-50 nm, and the aspect ratio is 1:1 to 2:1.
- the experiment of repeating 2 was carried out by replacing Bi 2 O 3 with Fe 2 O 3 to obtain a vanadium dioxide nano powder having a chemical formula of V 0.953 Fe 0.047 O 2 in a yield of 90%.
- the crystal phase is also M phase, and each vanadium dioxide particle is a single crystal particle, and its grain size is mainly concentrated between 40-60 nm, and the aspect ratio is 1:1 to 3:1.
- the experiment of performing 2 was repeated with 55 mg of Fe 2 O 3 instead of 25 mg of Bi 2 O 3 to obtain a vanadium dioxide nano powder having a chemical formula of V 0.9 Fe 0.1 O 2 in a yield of 80%.
- the crystal phase is also M phase, and each vanadium dioxide particle is a single crystal particle, and its grain size is mainly concentrated between 30-40 nm, and the aspect ratio is 1:1 to 1.5:1.
- each vanadium dioxide particle is a single crystal particle, and its grain size is mainly concentrated between 80 and 100 nm, and the aspect ratio is 1:1 to 3:1.
- the experiment of repeating 8 was carried out by replacing 260 ° C with 300 ° C, and the finally obtained vanadium dioxide nano powder had a chemical formula of V 0.97 Zn 0.03 O 2 , and the yield was 95%.
- the crystal phase is still pure M phase, and each vanadium dioxide particle is a single crystal particle, and its grain size is mainly concentrated between 80 and 100 nm, and the aspect ratio is concentrated at 1:1 to 2:1.
- each vanadium dioxide particle is a single crystal particle with a grain size of about 50 nm and a length to diameter ratio of 1:1 to 3:1.
- the experiment of 12 was repeated by replacing 50 mg of Ti 2 O 3 with 50 mg of molybdic acid, and the finally obtained vanadium dioxide nano powder having a chemical formula of V 0.93 Mo 0.07 O 2 was obtained in a yield of 85%.
- the crystal phase is still pure M phase
- the prepared vanadium dioxide powder is long rod shape
- each vanadium dioxide long rod is a single crystal, and its length reaches several hundred nm, and the aspect ratio is more than 10:1.
- the dispersibility of the prepared vanadium dioxide powder was examined, and the dispersion of the vanadium dioxide powder of the comparative example and the example 1 was poor, and Examples 2 to 13 of the present invention were obtained.
- the vanadium dioxide powders all showed good dispersibility, and the vanadium dioxide powders of Examples 2, 4, 5, 7, 8, 11, and 13 were particularly excellent in dispersibility.
- the above examples illustrate that the doping of the doping element plays an important role in the regulation of the size, morphology and crystal form of the vanadium dioxide powder.
- the vanadium dioxide powder is composed of the first undoped phase A micron rod structure. Converted to doped M The phase is nano-grained and the size can be well controlled at the nanoscale.
- Bi, Sn, Fe, Zn, Ti, Mo are given. Specific examples of such elements, but should understand 21 ⁇ 30 near vanadium in the periodic table
- Elements which are not specifically listed in the transition element and elements in the vicinity of tin are also suitable, and it is also understood that the method of the present invention can also prepare other doping elements such as doped tungsten.
- Example 7 0.1 g of the vanadium dioxide powder prepared in Example 7 was ground and placed in a small beaker containing 5 ml of water, and continuously stirred and added. 0.25 g of polyvinylpyrrolidone K-30 was stirred for 30 min and then ultrasonicated for 60 min to obtain a dispersion.
- the obtained dispersion liquid is applied onto a glass substrate by a spin coating method, and then dried at room temperature or in an oven to obtain a vanadium dioxide film.
- the energy-saving film prepared by the vanadium dioxide powder of the invention has spectral characteristics comparable to those of other methods (such as sputtering method and electroless plating method), and in particular, infrared control performance is superior.
- the vanadium dioxide powder and dispersion of the present invention can be widely applied to energy saving and emission reduction equipment, such as energy saving film, energy saving coating, solar temperature control device, or energy information equipment, for example, micro photoelectric switch device, thermal Resistors, battery materials, and optical information storage devices.
- energy saving and emission reduction equipment such as energy saving film, energy saving coating, solar temperature control device, or energy information equipment, for example, micro photoelectric switch device, thermal Resistors, battery materials, and optical information storage devices.
- the method for preparing vanadium dioxide powder of the invention has the advantages of simple process, low cost and high yield, and is suitable for scale production.
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Abstract
Description
Claims (35)
- 一种掺杂二氧化钒粉体,所述掺杂二氧化钒粉体的化学组成为 V1-xMxO2 , 0<x ≤ 0.5 ,其中 M 为掺杂元素,所述掺杂元素 M 是元素周期表中钒附近的 21~30 过渡元素、锡及其附近的元素中的一个或者任意组合,且所述掺杂元素 M 用于控制所述掺杂二氧化钒粉体的颗粒尺寸和形貌。
- 根据权利要求 1 所述的掺杂二氧化钒粉体,其特征在于,元素周期表中钒附近的 21~30 过渡元素包括钪、钛、铬、锰、铁、钴、镍、铜、和锌,所述锡及其附近的元素包括铟、锑、锡、镓、锗、铅、和铋。
- 根据权利要求 1 所述的掺杂二氧化钒粉体,其特征在于, 0.03<x ≤ 0.3 。
- 根据权利要求 3 所述的掺杂二氧化钒粉体,其特征在于, 0.03<x ≤ 0.1 。
- 根据权利要求 1 所述的掺杂二氧化钒粉体,其特征在于, 0.005 ≤ x ≤ 0.025 。
- 根据权利要求 1 ~ 5 中任一项所述的掺杂二氧化钒粉体,其特征在于,所述掺杂二氧化钒粉体为颗粒状,且颗粒的长径比为 1:1 ~ 10:1 。
- 根据权利要求 6 所述的掺杂二氧化钒粉体,其特征在于,所述掺杂二氧化钒粉体的颗粒尺寸在至少一个维度上不大于 1 μ m 。
- 根据权利要求 7 所述的掺杂二氧化钒粉体,其特征在于,所述掺杂二氧化钒粉体的颗粒尺寸在至少一个维度上不大于 100nm 。
- 根据权利要求 8 所述的掺杂二氧化钒粉体,其特征在于,所述掺杂二氧化钒粉体的颗粒尺寸在三个维度上均不大于 100nm 。
- 根据权利要求 9 所述的掺杂二氧化钒粉体,其特征在于,所述掺杂二氧化钒粉体的颗粒尺寸在三个维度上均不大于 70nm 。
- 根据权利要求 1 ~ 5 或 6~10 中任一项所述的掺杂二氧化钒粉体,其特征在于,所述掺杂二氧化钒粉体包括金红石相二氧化钒。
- 一种水热法制备权利要求 1 所述的掺杂二氧化钒粉体的方法,包括采用碱性试剂处理四价钒离子水溶液得到悬浊液的前驱体处理工序。
- 根据权利要求 12 所述的方法,其特征在于,所述前驱体处理工序包括采用碱性试剂滴定所述四价钒离子水溶液直至生成悬浊液。
- 根据权利要求 12 或 13 所述的方法,其特征在于,所述碱性试剂和所述四价钒离子水溶液的摩尔比为 1:50 ~ 10:1 。
- 根据权利要求 14 所述的方法,其特征在于,所述碱性试剂和所述四价钒离子水溶液的摩尔比为 1:5 ~ 2:1 。
- 根据权利要求 12 所述的方法,其特征在于,所述方法还包括掺杂掺杂元素的掺杂工序,所制备的二氧化钒粉体为掺杂二氧化钒粉体。
- 根据权利要求 16 所述的方法,其特征在于,所述方法还包括掺杂能够调节二氧化钒相变温度的元素、和 / 或能够调节二氧化钒尺寸和相貌的掺杂元素的掺杂工序。
- 根据权利要求 16 所述的方法,其特征在于,所述掺杂元素为元素周期表中钒附近的 21~30 过渡元素、锡及其附近的元素中的一个或者任意组合。
- 根据权利要求 16 或 17 所述的方法,其特征在于,所述掺杂元素与四价钒离子水溶液的摩尔比为 1:1000 ~ 1:1 。
- 根据权利要求 18 所述的方法,其特征在于,所述掺杂元素与四价钒离子水溶液的摩尔比为 3:97 ~ 3:7 。
- 根据权利要求 18 所述的方法,其特征在于,所述掺杂元素与四价钒离子水溶液的摩尔比为 1:199 ~ 1:39 。
- 根据权利要求 12 、 13 或 16 所述的方法,其特征在于,还包括从钒原料制备四价钒离子水溶液的工序。
- 根据权利要求 22 所述的方法,其特征在于,包括将可溶性钒原料溶于水中,所述可溶性钒原料包括三价、四价或五价的钒盐。
- 根据权利要求 22 所述的方法,其特征在于,包括对不可溶性钒原料进行氧化、还原或溶解预处理,所述不可溶性钒原料包括金属钒、钒氧化物或其混合物。
- 根据权利要求 12 、 13 或 16 所述的方法,其特征在于,所述碱性试剂为氨水、氢氧化钠水溶液、氢氧化钾水溶液或其混合溶液。
- 根据权利要求 12 ~ 25 中任一项所述的方法,其特征在于,还包括将经碱试剂处理的四价钒离子的水溶液加入水热釜中进行水热反应,水热反应过程中水热釜的填充比为 20 ~ 90% ;升温并控制水热反应温度为 200 ~ 400 ℃,水热反应保温时间为 1 ~ 240 小时。
- 根据权利要求 26 所述的方法,其特征在于,所述水热反应温度为 200 ~ 350 ℃。
- 根据权利要求 27 所述的方法,其特征在于,所述水热反应温度为 250 ~ 300 ℃。
- 根据权利要求 26 所述的方法,其特征在于,所述填充比为 30 ~ 80% 。
- 根据权利要求 29 所述的方法,其特征在于,所述填充比为 50 ~ 80% 。
- 根据权利要求 26 所述的方法,其特征在于,所述水热反应保温时间为 2 ~ 120 小时。
- 根据权利要求 31 所述的方法,其特征在于,所述水热反应保温时间为 4 ~ 60 小时。
- 一种二氧化钒分散液,包含权利要求 1 ~ 11 中任一项所述的掺杂二氧化钒粉体。
- 根据权利要求 33 所述的二氧化钒分散液,所述掺杂二氧化钒粉体的含量为 0.1 ~ 100g/L 。
- 一种如权利要求 1 ~ 11 中任一项所述的二氧化钒粉体在制备节能减排设备或能源信息设备中的应用。
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US13/980,862 US20130344335A1 (en) | 2011-01-21 | 2012-01-04 | Application and synthesis of doped vanadium dioxide powder and dispersing agent |
JP2013548725A JP2014505651A (ja) | 2011-01-21 | 2012-01-04 | ドーピング二酸化バナジウム粉体、分散液及びそれらの製造方法と応用 |
EP12736117.8A EP2666754B1 (en) | 2011-01-21 | 2012-01-04 | Preparation of a doped vo2 powder |
US14/697,481 US10167223B2 (en) | 2011-01-21 | 2015-04-27 | Preparation method of doped vanadium dioxide powder |
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CN2011100242295A CN102120615B (zh) | 2011-01-21 | 2011-01-21 | 一种掺杂二氧化钒粉体、分散液及其制备方法和应用 |
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-
2012
- 2012-01-04 US US13/980,862 patent/US20130344335A1/en not_active Abandoned
- 2012-01-04 EP EP12736117.8A patent/EP2666754B1/en active Active
- 2012-01-04 WO PCT/CN2012/070025 patent/WO2012097687A1/zh active Application Filing
- 2012-01-04 JP JP2013548725A patent/JP2014505651A/ja active Pending
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2015
- 2015-04-27 US US14/697,481 patent/US10167223B2/en active Active
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US10167223B2 (en) | 2019-01-01 |
JP2014505651A (ja) | 2014-03-06 |
US20130344335A1 (en) | 2013-12-26 |
EP2666754A1 (en) | 2013-11-27 |
EP2666754B1 (en) | 2018-03-07 |
US20150251948A1 (en) | 2015-09-10 |
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