CN103752821A - Method for preparing conductive composite microsphere material with surface covered by metal micro powder - Google Patents
Method for preparing conductive composite microsphere material with surface covered by metal micro powder Download PDFInfo
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- CN103752821A CN103752821A CN201410033800.3A CN201410033800A CN103752821A CN 103752821 A CN103752821 A CN 103752821A CN 201410033800 A CN201410033800 A CN 201410033800A CN 103752821 A CN103752821 A CN 103752821A
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Abstract
The invention provides a method for preparing a conductive composite microsphere material with the surface covered by metal micro powder, and belongs to synthetic methods of polymer composites. The method comprises the steps that spherical, flake-shaped or amorphous metal micron powder, metal ionic salt, polymer monomer, water, a surface active agent and the like are mixed and stirred to form a micro-emulsion, the pH value is adjusted, a macromolecular initiator is added for causing polymerization, seasoning, filtering and the like to obtain a microsphere composite material, thermal treatment is conducted on the microphere composite material at a certain temperature, and the conductive composite microsphere material is acquired. The composite microphere material has the catalytic characteristic of metal micro powder materials and the sensitive characteristic of oxides, and can be applied to the field of gas sensor electrodes, catalysts, lithium ion battery electrodes, fuel battery electrodes and the like.
Description
Technical field
The invention belongs to synthesis of polymer material and preparation method.
Background technology
Rugged environment pollutes and causes the demand to the gas sensor of 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. the impact of pore-size distribution on porous gas sensor air-sensitive performance, sensing technology journal, VoL.25 No.9,2012,1189-1193; ), as SnO
2porous coating has good sensitivity characteristic to CO gas, and (fourth accounts for and comes etc.; The sensitiveness of SnO2 nano particle porous membrane gas sensor to CO gas, sensing technology journal, VoL.19 No.1,2006,76-87.).On the other hand, Metal Supported is formed on oxide carrier to catalyst material, general preparation process is that oxide material is formed to impregnating metal ion after the carrier of certain size, sintering, reduction obtain, preparation can not be removed as harmful ions such as chlorions, has affected 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 (Xin Qin et al. Progress in catalysis in china during 1982-2012:theory and technological innovations, Chinese Journal of Catalysis 34 (2013) 401-435.) such as chemical reaction rates.
High molecular polymerization, claim again pearl polymerization, be organic polymer monomer under the effect of mechanical agitation or vibration and dispersant, monomer is dispersed into the spherical drop that suspends in water, with initator, carries out polymerization, through separated, washing, the operation such as dry, obtain spherical high polymer material (horse radiance, Su Zhiguo writes, polymeric microball material, Chemical Industry Press, 2005).But can in conventional polymer microsphere is synthetic, disperse feed liquor to drip inorganic ion salt, be deposited in high molecular polymerization ball, form inorganic matter and high molecular complex microsphere; And further in microballoon, add metal dust, make it be coated and be inserted into microsphere surface and inside, form metal-oxide-high molecular complex microsphere, form the composite microsphere material of the conduction that adapts 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 by microemulsion method and high molecular polymerization technique, prepare complex microsphere with micron metal powder such as spherical, sheet, amorphous, 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 area and 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) spherical, the sheet of usining that particle diameter that electronation or spraying or mechanical means obtain is 2 ~ 30 microns or the conductive metal powder of amorphous powder are as micron metal powder;
(2) prepare microemulsion; 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) prepare complex microsphere: the salting liquid and the micron metal powder that in microemulsion, add inorganic metal ion, regulating pH to make inorganic metal ion hydration in the emulsion droplet of microemulsion is hydroxide, drip high molecular polymerization initator simultaneously, polymerization temperature is 25～100 ℃, preferably 40～80 ℃, the microballoon complex microsphere that formation particle diameter is 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 high polymer monomer 1%～3%;
(4) porous of complex microsphere: in air; or with 10 ℃/min speed, be warming up to 80～750 ℃ in the tube furnace of nitrogen protection or hydrogen shield; form porous; insulation 2～48hr; then with 10 ℃/min speed, be cooled to room temperature, obtain the micro-sphere material that is covered with conductive submicron powder of porous.
In described step (2), high polymer monomer is one or more in styrene (ST) or methyl methacrylate (MMA) or vinyl acetate (VAc).
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.
In described step (3), regulating the alkali lye of pH 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 that this material is as the electrode of gas sensor or electrode or the fuel cell electrode of catalyst or lithium ion battery.
In above paragraph, cinnamic chemical name english abbreviation is that ST, methyl methacrylate are that MMA, vinyl acetate are that VAc, dodecyl sodium sulfate are that SDS, hexadecyltrimethylammonium chloride are that CTAB, potassium peroxydisulfate are that KPS, ammonium persulfate are NPS, 2, and 2-azo two NSC 18620 sulfate are V-50.
Step of the present invention (2) ~ (3) complex microsphere is that preparation had both had the presoma of the inorganic material of sensitivity characteristic or catalysis characteristics, the microballoon that there is again macromolecular material and be covered with metal powder and micron, thus form complex microsphere.High polymer monomer wherein, be not only styrene or methyl methacrylate or vinyl acetate, all can be under the effect of the aqueous solution and emulsifying agent, form micro emulsion particle, 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 is to form the skeleton structure be distributed in oxide, have some strength, through Overheating Treatment and decomposed volatilization is removed, leaves the complex microsphere of loose structure; And the inorganic salts reagent that can select according to catalytic reaction of inorganic metal ion salt in step (3) has salt or the oxide to specific gas sensitivity of catalytic activity.
The porous of step of the present invention (4) complex microsphere is that the composition that contains easy evaporation or thermal decomposition is removed through Overheating Treatment, as moisture, organic material and part macromolecular material, form porous, metal and the compound micro-sphere material of oxide, 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, the sensitivity or the catalysis characteristics that have again oxide, from microstructure, show that material is porous, larger active surface area can be provided, improve the sensitivity of sensor, make its response frequency and signal output fast and stable.Thereby application prospect and the market value at aspects such as the electrode material of the sensitive electrode of gas sensor, catalyst material, lithium ion battery or fuel cell electrodes with summary.
Accompanying drawing explanation
Fig. 1 is the ESEM picture of composition metal micro mist microballoon.
Fig. 2 is the local composition metal micro mist microballoon ESEM picture that amplifies the structure of rear conductive particle and oxide.
Below in conjunction with example, the present invention will be further described, and example comprises but do not limit the scope of the invention.
The specific embodiment
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 5g particle diameter to be distributed as the spherical metal Pd micro mist of 0.1～5 micron, add 15% sodium hydroxide solution tune pH to 9, it is muddy that solution becomes, add initiator potassium persulfate 6g, stir, be heated to 65 ℃, insulation polymerization 4hr, ageing 2hr, filters, and obtains pbz polymer and SnO
2the complex microsphere of hydration presoma and Metal Palladium, is placed in tube furnace this filtrate with the speed of 20 ℃/min, is heated to 500 degree under air ambient, obtains the Pd/SnO of porous
2complex microsphere, this material can be 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, the powerful concussion of ultrasonic wave 20 minutes, forms microemulsion; 10% cerous nitrate 2mL and 20% solution aluminum nitrate 30mL of preparation, join in microemulsion gradually, and add 10g particle diameter to be distributed as the spherical metal Ag-Cu alloy powder of 0.1～5 micron, add 20% sodium carbonate liquor tune PH to 9, it is muddy that solution becomes, add initator 2-azo two NSC 18620 sulfate 4g, stir, be heated to 80 ℃, 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 is placed in tube furnace to speed with 20 ℃/min with under hydrogen shield environment, be heated to 650 ℃, obtain the Ag-Cu/CeO of porous
2-AL
2o
3complex microsphere, this material can be for the synthetic catalyst material of cyclopropane.
Embodiment 3
Taking methyl methacrylate is MMA 45g, and styrene 15g adds the mixture 2g of hexadecyltrimethylammonium chloride and Span85, adds ultra-pure water 20mL, and the powerful concussion of ultrasonic wave 20 minutes, forms microemulsion; 10% manganese nitrate 10mL and 20% solution aluminum nitrate 30mL of preparation, join in microemulsion gradually, and add 20g particle diameter to be distributed as the spherical metal Ni micro mist of 0.1～5 micron, add 20% sodium carbonate liquor tune PH to 12, it is muddy that solution becomes, add initator 2-azo two NSC 18620 sulfate 4g, stir, be heated to 90 ℃, 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 is placed in tube furnace to speed with 20 ℃/min with under hydrogen shield environment, be heated to 650 ℃, obtain the Ni/MnO of porous
2-AL
2o
3complex microsphere, this material can be for the catalyst material of organic synthesis hydrogenation reaction.
Embodiment 4
Take vinyl acetate 45g, styrene 15g, adds dodecyl sodium sulfate 1g, and Span85 2g adds ultra-pure water 30mL, and the powerful concussion of ultrasonic wave 20 minutes, forms microemulsion; 10% tungsten chloride ethanolic solution 10mL and 20% solution S nCl430mL of preparation, join in microemulsion gradually, and add 20g particle diameter to be distributed as the spherical metal Ni micro mist of 0.1～5 micron, the powerful concussion of ultrasonic wave 20 minutes, add 20% sodium carbonate liquor to adjust PH to 12, it is muddy that solution becomes, and adds initator 2-azo two NSC 18620 sulfate 4g, stir, be heated to 90 ℃, 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 is placed in tube furnace to speed with 20 ℃/min under air ambient, be heated to 700 ℃, obtain the Pt/WO of porous
3-SnO
2complex microsphere, this material can be for the electrode material of lithium ion battery.
Claims (7)
1. a conduction composite microsphere material method of preparing metal fine powder covering surfaces, comprises the following steps:
(1) spherical, the sheet of usining that particle diameter that electronation or spraying or mechanical means obtain is 2 ~ 30 microns or the conductive metal powder of amorphous powder are as micron metal powder;
(2) prepare microemulsion; 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) prepare complex microsphere: the salting liquid and the micron metal powder that in microemulsion, add inorganic metal ion, regulating pH to make inorganic metal ion hydration in the emulsion droplet of microemulsion is hydroxide, drip high molecular polymerization initator simultaneously, polymerization temperature is 25～100 ℃, preferably 40～80 ℃, the microballoon complex microsphere that formation particle diameter is 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 high polymer monomer 1%～3%;
(4) porous of complex microsphere: in air; or with 10 ℃/min speed, be warming up to 80～750 ℃ in the tube furnace of nitrogen protection or hydrogen shield; form porous; insulation 2～48hr; then with 10 ℃/min speed, be cooled to room temperature, obtain the micro-sphere material that is covered with conductive submicron powder of porous.
2. the method for claim 1, is characterized in that in described step (2), high polymer monomer is one or more in styrene or methyl methacrylate or vinyl acetate.
3. the method for claim 1, is characterized in that in described step (2), surfactant 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 can be nitrate, sulfate, chloride, oxalates or organic compound.
5. the method for claim 1, is characterized in that in described step (3), regulating the alkali lye of pH is concentration 10% ~ 30% NaOH solution, or concentration 10% ~ 30% sodium carbonate liquor, preferred concentration 20% 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. a kind of purposes of the composite microsphere material of the conduction as described in claim 1 ~ 6, is characterized in that usining that this material is as the electrode of gas sensor or electrode or the fuel cell electrode of catalyst or lithium ion battery.
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Cited By (4)
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| CN105521745A (en) * | 2014-10-21 | 2016-04-27 | 中国科学院深圳先进技术研究院 | Method for preparing organic polymer-based heat-conduction microsphere |
| CN106229151A (en) * | 2016-07-14 | 2016-12-14 | 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 manganese oxide/cerium oxide coated with silver composite and preparation method thereof |
| CN106654168A (en) * | 2015-11-04 | 2017-05-10 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery and method for manufacturing same, and conductive additive for nonaqueous electrolyte secondary battery and method for manufacturing same |
| CN110842213A (en) * | 2019-11-12 | 2020-02-28 | 广东羚光新材料股份有限公司 | High-activity silver powder and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105521745A (en) * | 2014-10-21 | 2016-04-27 | 中国科学院深圳先进技术研究院 | Method for preparing organic polymer-based heat-conduction microsphere |
| 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 |
| CN106654168A (en) * | 2015-11-04 | 2017-05-10 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery and method for manufacturing same, and conductive additive for nonaqueous electrolyte secondary battery and method for manufacturing same |
| CN106229151A (en) * | 2016-07-14 | 2016-12-14 | 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 manganese oxide/cerium oxide coated with silver composite and preparation method thereof |
| 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 |
| CN110842213A (en) * | 2019-11-12 | 2020-02-28 | 广东羚光新材料股份有限公司 | High-activity silver powder and preparation method and application thereof |
| 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 |
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