CN103752821B - A kind of conductive composite microsphere MATERIALS METHODS preparing metal fine powder covering surfaces - Google Patents
A kind of conductive composite microsphere MATERIALS METHODS preparing metal fine powder covering surfaces Download PDFInfo
- Publication number
- CN103752821B CN103752821B CN201410033800.3A CN201410033800A CN103752821B CN 103752821 B CN103752821 B CN 103752821B CN 201410033800 A CN201410033800 A CN 201410033800A CN 103752821 B CN103752821 B CN 103752821B
- Authority
- CN
- China
- Prior art keywords
- microemulsion
- powder
- composite microsphere
- described step
- porous
- 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.)
- Expired - Fee Related
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 239000000843 powder Substances 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- 239000000446 fuel Substances 0.000 claims abstract description 4
- -1 cation salt Chemical class 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- FGRJGEWVJCCOJJ-UHFFFAOYSA-N 2,2-dimethylaziridine Chemical compound CC1(C)CN1 FGRJGEWVJCCOJJ-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 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 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 5
- 238000003483 aging Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 235000013312 flour Nutrition 0.000 abstract 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010931 gold Substances 0.000 abstract 1
- 229910052737 gold Inorganic materials 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000003595 mist Substances 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 230000009514 concussion Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Inert Electrodes (AREA)
- Polymerisation Methods In General (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
Prepare a conductive composite microsphere MATERIALS METHODS for metal fine powder covering surfaces, belong to polymer composite synthetic method.The present invention is by spherical, sheet or amorphous flour gold belong to micron powder and metal cation salt, high polymer monomer, water and surfactant etc. and stir and form microemulsion, adjust ph, add polymeric initiator polymerization, ageing, filtration etc. and obtain microspheroidal composite, through heat treatment in uniform temperature, obtain conductive composite microsphere material.Composite microsphere material of the present invention has the catalysis characteristics of metal fine powder material and the sensitivity characteristic of oxide, can be used for gas sensor electrode, catalyst and the Material Field such as lithium ion cell electrode, fuel cell electrode.
Description
Technical field
The invention belongs to synthesis of polymer material and preparation method.
Background technology
Rugged environment pollutes the demand of the gas sensor caused novel high-performance low-power consumption, is quick on the draw and responds fast and stable, is the condition that gas sensor form of energy transforms and transmits.Mass transfer process in porous gas sensor and adsorption reaction speed and pore structure closely related (Li Mingchun, quiet space. pore-size distribution on the impact of porous gas sensor air-sensitive performance, sensing technology journal, VoL.25No.9,2012,1189-1193; ), as SnO
2porous coating has good sensitivity characteristic to CO gas, and (fourth accounts for; SnO2 nano particle porous membrane gas sensor to the sensitiveness of CO gas, sensing technology journal, VoL.19No.1,2006,76-87.).On the other hand, Metal Supported is formed catalyst material on oxide carrier, general preparation process is impregnating metal ion after carrier oxide material being formed certain size, sintering, reduction obtain, preparation can not remove the ion as chlorion etc. is harmful to, and have impact on induction of signal and the transmission of gas sensor.The structure of porous material, surface acidity and metallic surface characteristic will affect the characteristic of catalyst, as more easily adhered to catalytic reaction thing on catalysis material surface, accelerate (XinQinetal.Progressincatalysisinchinaduring1982-2012:the oryandtechnologicalinnovations, ChineseJournalofCatalysis34 (2013) 401-435.) such as chemical reaction rates.
High molecular polymerization, also known as pearl polymerization, be organic polymer monomer mechanical agitation or vibration and dispersant effect under, become to suspend in water by monomer dispersion spherical drop, is polymerized with initator, obtains spherical high polymer material (horse radiance through operations such as being separated, washing, be dry, Su Zhiguo writes, polymeric microball material, Chemical Industry Press, 2005).But in the polymer microsphere synthesis of routine, inorganic ion salt dispersion feed liquor can be dripped, be deposited in high molecular polymerization ball, form inorganic matter and high molecular complex microsphere; And in microballoon, add metal dust further, make it coated and be inserted into microsphere surface and inside, form metal-oxide-high molecular complex microsphere, form the composite microsphere material of the conduction adapting to the electrology characteristic of gas sensor or the porous of catalyst activation characteristic, rarely have document to record.
Summary of the invention
The object of the invention is intended to prepare complex microsphere with the micron metal powder such as spherical, sheet, amorphous by microemulsion method and high molecular polymerization technique, and in heat treatment process, remove moisture, organic solvent, part macromolecular material, obtain the composite microsphere material of the conduction of porous, this material has higher active surface sum sensitivity, can adapt to the electrology characteristic of gas sensor or/and the demand of catalyst activation characteristic.
Preparation method of the present invention comprises the following steps:
(1) particle diameter obtained using electronation or spraying or mechanical means is that the conductive metal powder of spherical, the sheet of 2 ~ 30 microns or amorphous powder is as micron metal powder;
(2) microemulsion is prepared; High polymer monomer, surfactant and water are mixed, form homogeneous latex emulsion, ultrasonic oscillation or high-speed stirred form Water-In-Oil or oil-in-water microemulsion;
Said components volume content percentage in emulsion is: high polymer monomer 20 ~ 65%, surfactant 0.1 ~ 2%, water are surplus;
(3) complex microsphere is prepared: in microemulsion, add inorganic metal ion salting liquid and micron metal powder, pH is regulated to make inorganic metal ion hydration in the emulsion droplet of microemulsion be hydroxide, drip high molecular polymerization initator simultaneously, polymerization temperature is 25 ~ 100 DEG C, preferably 40 ~ 80 DEG C, form the microballoon complex microsphere of particle diameter 10 microns ~ 3 millimeters;
Said components weight percentage composition in microemulsion is: the salting liquid 20 ~ 40% of inorganic metal ion, micron metal powder 2 ~ 20%;
Above-mentioned high molecular polymerization initator volume content percentage is 1% ~ 3% of high polymer monomer;
(4) porous of complex microsphere: in atmosphere; or with 10 DEG C/min ramp to 80 ~ 750 DEG C in the tube furnace of nitrogen protection or hydrogen shield; form porous; insulation 2 ~ 48hr; then be cooled to room temperature with 10 DEG C/min speed, namely obtain the micro-sphere material being covered with conductive submicron powder of porous.
High polymer monomer is one or more in styrene (ST) or methyl methacrylate (MMA) or vinyl acetate (VAc) in described step (2).
In described step (2), surfactant is one or more in dodecyl sodium sulfate, neopelex, hexadecyltrimethylammonium chloride (CTAB) or Span85.
In described step (3), inorganic metal ion salt is one or more salt mixtures containing cerium, aluminium, magnesium, tin, zirconium, molybdenum, tungsten, titanium, copper, iron, nickel, manganese, cobalt and zinc, its salt can be nitrate, sulfate, chloride, oxalates or organic compound.
The alkali lye regulating pH in described step (3) is concentration 10% ~ 30%NaOH solution, or concentration 10% ~ 30% sodium carbonate liquor, preferred concentration 20% sodium carbonate liquor.
High molecular polymerization initator in described step (3) is potassium peroxydisulfate, ammonium persulfate, 2,2-azo two NSC 18620 sulfate.
The purposes of the composite microsphere material of described conduction is this material as the electrode of gas sensor or the electrode of catalyst or lithium ion battery or fuel cell electrode.
In above paragraph, cinnamic chemical name english abbreviation is ST, methyl methacrylate is MMA, vinyl acetate is VAc, dodecyl sodium sulfate is SDS, hexadecyltrimethylammonium chloride is CTAB, potassium peroxydisulfate is KPS, ammonium persulfate is NPS, 2,2-azo two NSC 18620 sulfate are V-50.
Step of the present invention (2) ~ (3) complex microsphere is to prepare the presoma of the inorganic material both with sensitivity characteristic or catalysis characteristics, has again macromolecular material and is covered with the microballoon of metal micro powder, thus forms complex microsphere.High polymer monomer wherein, be not only styrene or methyl methacrylate or vinyl acetate, all can under the effect of the aqueous solution and emulsifying agent, form microemulsion particles, and the high polymer monomer of polymerization reaction take place can be used under the effect of initator, this is because high polymer monomer effect be to be formed distribution in the oxide, there is the skeleton structure of some strength, through Overheating Treatment, decomposed volatilization is removed, and leaves the complex microsphere of loose structure; And the inorganic salts reagent that in step (3), inorganic metal ion salt can be selected according to catalytic reaction, namely there is the salt of catalytic activity or the oxide to specific gas sensitivity.
The porous of step of the present invention (4) complex microsphere is removed through Overheating Treatment by the composition containing easily evaporation or thermal decomposition, as moisture, organic material and part macromolecular material, formed porous, the micro-sphere material of metal and oxide compound, make material have more sensitiveness or catalytic.
The present invention has following substantive distinguishing features and marked improvement:
The composite microsphere material of the conduction of porous prepared by the present invention, both there is metallic character, there are again sensitivity or the catalysis characteristics of oxide, show that material is porous from microstructure, larger active surface area can be provided, improve the sensitivity of sensor, make its response frequency and signal export fast and stable.Thus there is application prospect and the market value of summary in the electrode material or fuel cell electrode etc. of the sensitive electrode of gas sensor, catalyst material, lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of composition metal micro mist microballoon.
Fig. 2 is the composition metal micro mist microballoon scanning electron microscopic picture of the structure of conductive particle and oxide after partial enlargement.
Below in conjunction with example, the present invention will be further described, and example comprises but do not limit the scope of the invention.
Detailed description of the invention
Embodiment 1
Take styrene 30g, add dodecyl sodium sulfate 1g, add ultra-pure water 20mL, magnetic agitation stirs with 800rpm speed, forms microemulsion; The SnCl of preparation
420% solution 30mL, join in microemulsion gradually, and add the spherical metal Pd micro mist that 5g domain size distribution is 0.1 ~ 5 micron, the sodium hydroxide solution adding 15% adjusts pH to 9, solution turned cloudy, add initiator potassium persulfate 6g, stir, be heated to 65 DEG C, insulation polymerization 4hr, ageing 2hr, filters, and obtains pbz polymer and SnO
2the complex microsphere of hydration presoma and Metal Palladium, is placed on this filtrate with the speed of 20 DEG C/min in tube furnace, is heated to 500 degree under air ambient, obtains the Pd/SnO of porous
2complex microsphere, this material may be used for NO
x, the preparation of the gas sensing electrodes such as CO.
Embodiment 2
Take vinyl acetate 45g, add the mixture 1.5g of hexadecyltrimethylammonium chloride and Span85, add ultra-pure water 20mL, ultrasonic wave brute force concussion 20 minutes, forms microemulsion; The cerous nitrate 2mL of prepare 10% and 20% solution aluminum nitrate 30mL, join in microemulsion gradually, and add the spherical metal Ag-Cu alloy powder that 10g domain size distribution is 0.1 ~ 5 micron, the sodium carbonate liquor adding 20% adjusts PH to 9, solution turned cloudy, add initator 2-azo two NSC 18620 sulfate 4g, stir, be heated to 80 DEG C, insulation polymerization 4hr, ageing 2hr, filters, and obtains pbz polymer and CeO2 and AL
2o
3presoma and the complex microsphere of argent copper alloy powder, this filtrate to be placed in tube furnace with the speed of 20 DEG C/min with under hydrogen shield environment, to be heated to 650 DEG C, to obtain the Ag-Cu/CeO of porous
2-AL
2o
3complex microsphere, this material may be used for cyclopropane synthesis catalyst material.
Embodiment 3
Taking methyl methacrylate is MMA45g, and styrene 15g adds the mixture 2g of hexadecyltrimethylammonium chloride and Span85, adds ultra-pure water 20mL, and ultrasonic wave brute force concussion 20 minutes, forms microemulsion; The manganese nitrate 10mL of prepare 10% and 20% solution aluminum nitrate 30mL, join in microemulsion gradually, and add the spherical metal Ni micro mist that 20g domain size distribution is 0.1 ~ 5 micron, the sodium carbonate liquor adding 20% adjusts PH to 12, solution turned cloudy, add initator 2-azo two NSC 18620 sulfate 4g, stir, be heated to 90 DEG C, insulation polymerization 8hr, ageing 2hr, filters, and obtains pbz polymer and MnO
2and AL
2o
3hydrate precipitate presoma and the complex microsphere of argent copper alloy powder, this filtrate to be placed in tube furnace with the speed of 20 DEG C/min with under hydrogen shield environment, to be heated to 650 DEG C, to obtain the Ni/MnO of porous
2-AL
2o
3complex microsphere, this material may be used for the catalyst material of organic synthesis hydrogenation reaction.
Embodiment 4
Take vinyl acetate 45g, styrene 15g, add dodecyl sodium sulfate 1g, Span852g, add ultra-pure water 30mL, ultrasonic wave brute force concussion 20 minutes, forms microemulsion; The tungsten chloride ethanolic solution 10mL of prepare 10% and 20% solution S nCl430mL, joins in microemulsion gradually, and adds the spherical metal Ni micro mist that 20g domain size distribution is 0.1 ~ 5 micron, ultrasonic wave brute force concussion 20 minutes, the sodium carbonate liquor adding 20% adjusts PH to 12, and solution turned cloudy, adds initator 2-azo two NSC 18620 sulfate 4g, stir, be heated to 90 DEG C, insulation polymerization 8hr, ageing 2hr, filter, obtain pbz polymer and WO
3and SnO
2presoma and the complex microsphere of argent copper alloy powder, this filtrate to be placed in tube furnace with the speed of 20 DEG C/min under air ambient, to be heated to 700 DEG C, to obtain the Pt/WO of porous
3-SnO
2complex microsphere, this material may be used for the electrode material of lithium ion battery.
Claims (7)
1. prepare a conductive composite microsphere MATERIALS METHODS for metal fine powder covering surfaces, comprise the following steps:
(1) particle diameter obtained using electronation or spraying or mechanical means is that the conductive metal powder of spherical, the sheet of 2 ~ 30 microns or amorphous powder is as micron metal powder;
(2) microemulsion is prepared; High polymer monomer, surfactant and water are mixed, form homogeneous latex emulsion, ultrasonic oscillation or high-speed stirred form Water-In-Oil or oil-in-water microemulsion;
Said components volume content percentage in emulsion is: high polymer monomer 20 ~ 65%, surfactant 0.1 ~ 2%, water are surplus;
(3) complex microsphere is prepared: in microemulsion, add inorganic metal ion salting liquid and micron metal powder, pH is regulated to make inorganic metal ion hydration in the emulsion droplet of microemulsion be hydroxide, drip high molecular polymerization initator simultaneously, polymerization temperature is 40 ~ 80 DEG C, forms the microballoon complex microsphere of particle diameter 10 microns ~ 3 millimeters;
Said components mass content percentage in microemulsion is: the salting liquid 20 ~ 40% of inorganic metal ion, micron metal powder 2 ~ 20%;
Above-mentioned high molecular polymerization initator mass content percentage is 1% ~ 3% of high polymer monomer;
(4) porous of complex microsphere: in atmosphere; or with 10 DEG C/min ramp to 80 ~ 750 DEG C in the tube furnace of nitrogen protection or hydrogen shield; form porous; insulation 2 ~ 48hr; then be cooled to room temperature with 10 DEG C/min speed, namely obtain the micro-sphere material being covered with conductive submicron powder of porous.
2. the method for claim 1, is characterized in that high polymer monomer in described step (2) is one or more in styrene or methyl methacrylate or vinyl acetate.
3. the method for claim 1, is characterized in that surfactant in described step (2) is one or more in dodecyl sodium sulfate, neopelex, hexadecyltrimethylammonium chloride or Span85.
4. the method for claim 1, it is characterized in that in described step (3), inorganic metal ion salt is one or more salt mixtures containing cerium, aluminium, magnesium, tin, molybdenum, tungsten, titanium, copper, zirconium, iron, nickel, manganese, cobalt and zinc, its salt is nitrate, sulfate, chloride, oxalates or organic compound.
5. the method for claim 1, is characterized in that the alkali lye regulating pH in described step (3) is concentration 10% ~ 30%NaOH solution, or concentration 10% ~ 30% sodium carbonate liquor.
6. the method for claim 1, is characterized in that the high molecular polymerization initator in described step (3) is potassium peroxydisulfate, ammonium persulfate, 2,2-azo two NSC 18620 sulfate.
7. the purposes of the composite microsphere material of the conduction as described in claim 1 ~ 6, is characterized in that electrode or the fuel cell electrode of electrode using this material as gas sensor or catalyst or lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410033800.3A CN103752821B (en) | 2014-01-24 | 2014-01-24 | A kind of conductive composite microsphere MATERIALS METHODS preparing metal fine powder covering surfaces |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410033800.3A CN103752821B (en) | 2014-01-24 | 2014-01-24 | A kind of conductive composite microsphere MATERIALS METHODS preparing metal fine powder covering surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103752821A CN103752821A (en) | 2014-04-30 |
| CN103752821B true CN103752821B (en) | 2016-01-20 |
Family
ID=50520225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410033800.3A Expired - Fee Related CN103752821B (en) | 2014-01-24 | 2014-01-24 | A kind of conductive composite microsphere MATERIALS METHODS preparing metal fine powder covering surfaces |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103752821B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105521745B (en) * | 2014-10-21 | 2018-10-16 | 中国科学院深圳先进技术研究院 | The preparation method of organic polymer-based heat conduction microballoon |
| JP6304198B2 (en) * | 2015-11-04 | 2018-04-04 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery and method for producing non-aqueous electrolyte secondary battery |
| CN106229151B (en) * | 2016-07-14 | 2018-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of ultracapacitor coats silver composite material and preparation method thereof with manganese oxide/cerium oxide |
| CN110842213B (en) * | 2019-11-12 | 2022-05-27 | 广东羚光新材料股份有限公司 | High-activity silver powder and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7718262B2 (en) * | 2005-01-20 | 2010-05-18 | Luminex Corporation | Magnetic microspheres for use in fluorescence-based applications |
| JP2007224359A (en) * | 2006-02-23 | 2007-09-06 | Nissan Motor Co Ltd | Metal matrix composite powder, metal matrix composite and method for producing the same |
| DE102007044918A1 (en) * | 2007-09-19 | 2009-04-09 | Bayer Technology Services Gmbh | Hydrogen-permeable membranes of metallic composite material |
| CN101499348B (en) * | 2008-10-30 | 2011-11-16 | 同济大学 | Hollow silicon dioxide/magnetic composite microsphere and its production method |
| CN101935381B (en) * | 2010-08-19 | 2012-10-31 | 苏州大学 | A kind of preparation method of organic/inorganic nano hybrid magnetic material |
-
2014
- 2014-01-24 CN CN201410033800.3A patent/CN103752821B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103752821A (en) | 2014-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103736996B (en) | A kind of method being covered with the composite microsphere material of conductive submicron line/rod preparing porous | |
| CN103752821B (en) | A kind of conductive composite microsphere MATERIALS METHODS preparing metal fine powder covering surfaces | |
| CN101381423B (en) | A kind of preparation method of polystyrene coated silver nanoparticles | |
| Shen et al. | Morphology-controlled synthesis of palladium nanostructures by sonoelectrochemical method and their application in direct alcohol oxidation | |
| CN102974365B (en) | The preparation method of support type high dispersive many components noble metal nano particles catalyst | |
| JP5782505B2 (en) | Metal alloys with microbiological components and catalytic properties | |
| CN110201680B (en) | Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde/ketone, preparation method and catalysis method | |
| CN102911474B (en) | Polyvinylpyrrolidone hybrid graphene catalyst carrier material, preparation method and application | |
| CN102407329B (en) | Method for preparing nickel-silver coreshell structure nanoparticles | |
| CN102489314A (en) | Graphene-loaded double-metal nano particles for methanol and ethanol fuel cells, and preparation method for graphene-loaded double-metal nano particles | |
| CN106825552B (en) | The preparation method of 3D printing graphene coated alloy powder composite material | |
| CN107775014B (en) | Method for preparing noble metal/graphene composite nano material by using atmospheric pressure cold plasma | |
| CN110143843B (en) | Nano aluminum-based porous microspheres and preparation method thereof | |
| CN103157389B (en) | A kind of preparation method of asymmetric porous metal film | |
| TW201307208A (en) | Micro-scaled flake silver particles and method for producing the same | |
| CN106311223B (en) | A kind of preparation method of noble metal/graphene nanocomposite material | |
| CN105895930B (en) | A kind of preparation method of nanometer alloy catalyst | |
| Momeni et al. | Gold nanosheets synthesized with red marine alga Actinotrichia fragilis as efficient electrocatalysts toward formic acid oxidation | |
| Rajesh et al. | Preparation, characterization and Pd (II) adsorption characteristics of chitosan–AC composites from electroless plating solutions | |
| CN107008478A (en) | A kind of preparation method of magnetic nano-catalyst | |
| TWI323747B (en) | Method and apparatus for surface modification of film component by carbon dioxide supercritical fluid | |
| WO2008101602A2 (en) | Catalysts containing platinum group metal nanoparticles and process for production of dispersions of nanoparticles of platinum group metal | |
| CN109092297A (en) | Carbon quantum dot load type palladium nanocomposite and its preparation method and application | |
| CN103230794A (en) | Graphene-oxide-loaded double-metal nano-particles used in methanol and ethanol fuel cells and in catalytic reactions, and preparation method thereof | |
| CN104962774A (en) | Super-structure Pd-Cu alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20170124 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |