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
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- 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
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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.
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| 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 |
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