CN102496677B - Preparation method of poly(p-phenylene) nanoparticle composite ZnO-based thermoelectric material system - Google Patents
Preparation method of poly(p-phenylene) nanoparticle composite ZnO-based thermoelectric material system Download PDFInfo
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- CN102496677B CN102496677B CN201110379452.1A CN201110379452A CN102496677B CN 102496677 B CN102496677 B CN 102496677B CN 201110379452 A CN201110379452 A CN 201110379452A CN 102496677 B CN102496677 B CN 102496677B
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- 239000000463 material Substances 0.000 title claims abstract description 47
- -1 poly(p-phenylene) Polymers 0.000 title claims abstract description 40
- 229920000265 Polyparaphenylene Polymers 0.000 title claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000004246 zinc acetate Substances 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000011858 nanopowder Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- CHUYYOSIZBKMJD-UHFFFAOYSA-N acetic acid;gold Chemical compound [Au].CC(O)=O CHUYYOSIZBKMJD-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 2
- 239000002019 doping agent Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000005619 thermoelectricity Effects 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001803 electron scattering Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 229910052714 tellurium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of a poly(p-phenylene) nanoparticle composite ZnO-based thermoelectric material system. The preparation method comprises the following steps of: adding poly(p-phenylene) nanoparticles into sulfuric acid of which the concentration is higher than 85%, stirring, filtering, washing, drying, and carrying out ball milling on a high-energy ball mill; dissolving 0.1-10mol% of acetate of dopant ion and 2.20g of zinc acetate into 500ml of diglycol, adding 20ml of water, stirring for 10 minutes, and standing for 2 hours after a white precipitate appears, thereby obtaining ZnO sol; adding the treated poly(p-phenylene) nanoparticles into the ZnO sol, stirring, dispersing under the ultrasonic condition, heating to 160-170 DEG C, and reacting for 1 hour; and washing the product with anhydrous alcohol and deionized water many times, drying, and carrying out discharge plasma sintering to obtain the blocky poly(p-phenylene) nanoparticle composite ZnO-based thermoelectric material. The preparation method provided by the invention has the characteristics of simple and practicable method, low reaction temperature, short reaction time, low energy consumption and good chemical uniformity.
Description
Technical field
The preparation method who the present invention relates to the compound zno-based thermoelectric material of a kind of polyparaphenylene's nano particle system, belongs to novel energy technical field of material.
Background technology
Along with becoming increasingly conspicuous of the energy and environmental problem, the recycling problem of a large amount of used heat that industrial production, communications and transportation and resident living discharge receives the more and more concern of height of people.It is one of effective way that used heat utilizes more than the high temperature that vehicle exhaust and waste incineration are produced that the device that utilization is prepared based on thermoelectric material carries out thermo-electric generation.Thermoelectric power generation technology is compared with the conventional Blast Furnace Top Gas Recovery Turbine Unit (TRT) that has working medium circulation, there is the advantages such as simple in structure, movement-less part, life-span length, combined and instant, be expected to bring into play huge effect in human lives's various aspects, but, thermoelectric material conversion efficiency is low is its deadly defect, generally only have 10%～20% of Carnot efficiency, improve conversion efficiency, key is to seek high performance thermoelectric material.Material thermopower generation efficiency index generally uses dimensionless figure of merit (figure of merit) ZT value to be described, ZT value determines by Seebeck coefficient S, conductivity δ, conductive coefficient k and the absolute temperature T of thermoelectric material, and its expression formula is ZT=(S*S* δ * T)/k.ZT value is larger, represents that the conversion efficiency of thermoelectric of material is higher.Along with going deep into gradually of research, the raising of the pyroelectric material performance of unitary system becomes more and more difficult, so the research of nano composite thermoelectric materials starts to be subject to people's concern.But a large amount of active metal elements such as Pb, Bi, Sb, Te that use in traditional thermoelectric material, exist that processing preparation is difficult, expensive, resource scarcity, easily cause the easy oxidized problems such as performance degradation that cause under environmental pollution and high temperature.For most of remaining Waste Heat Recovery utilization, thermoelectric generation elements need to be worked in high temperature atmosphere environment, therefore needs element to have oxidation resistent susceptibility.And metal oxide generally also can stable existence under high temperature in atmosphere, the low and low price of toxicity, determined manufacture process cheaply, so metal oxide is expected to become extensively practical thermoelectric material.Yet oxide pyroelectric material often thermal conductivity is larger, figure of merit is difficult for promoting, and its application is restricted.
Summary of the invention
The object of the present invention is to provide the preparation method of the compound zno-based thermoelectric material of a kind of polyparaphenylene's nano particle system.By synthesis of nano structure, be not significantly increased electron scattering, do not have obviously to change under the prerequisite of material electric conductivity, significantly increase the interface scattering of phonon, be expected greatly to reduce the thermal conductivity of material; Give full play to the thermal conductivity that conducting polymer is lower, higher conductivity and the higher advantages such as Seebeck coefficient of inorganic material, improve the thermoelectricity capability of nanocomposite system, to overcome traditional thermoelectric material owing to using active metal element, cause that processing preparation is difficult, expensive, resource scarcity, easily cause the problem such as easy oxidized under environmental pollution and high temperature, and oxide pyroelectric material thermal conductivity is larger, figure of merit is difficult for promoting, and makes the drawbacks such as its application is restricted.
Technical solution of the present invention is achieved in that
The preparation method of the compound zno-based thermoelectric material of polyparaphenylene's nano particle system, is characterized in that preparing according to the following steps:
A) utilizing strong acid or high-energy mechanical ball milling to carry out early stage to polyparaphenylene's nano particle processes, improve the dispersiveness of nano particle, concrete grammar is: it is in more than 85% sulfuric acid that polyparaphenylene's nano particle is joined to concentration, at 20～50 ℃ of temperature, stir 5～10 minutes, then filter, wash, dry, by gained sample ball milling 0.5～4 hour on high energy ball mill;
B) 0.1～10% ratio is dissolved in 500ml diglycol by the acetate of ion to be adulterated and 2.20g zinc acetate in molar ratio, adds 20ml water, at 160～170 ℃ of temperature, stirs 10 minutes, after there is white precipitate standing 2 hours, makes ZnO colloidal sol;
C) by A) polyparaphenylene's nano particle after processing adds ZnO colloidal sol and stirs, and then under ultrasound condition, disperses 30 minutes, is warming up to 160～170 ℃ of reactions 1 hour;
D) by step C) products therefrom with the washing of absolute ethyl alcohol and deionized water repeatedly, finally dry at 100 ℃, obtain nano-powder material;
E) nano-powder material makes the compound zno-based thermoelectric material of block polyparaphenylene nano particle through discharge plasma sintering, and the condition of sintering is 800～1000 ℃, sintering 5～10min, and pressure is 40～60MPa.
F) acetate of described ion to be adulterated comprises any one in aluminum acetate, ferric acetate, cobalt acetate, nickel acetate, silver acetate, acetic acid gold.
G) described ion to be adulterated is any one ion in aluminium ion, iron ion, cobalt ions, nickel ion, silver ion or gold ion.
The compound zno-based thermoelectric material of method compositing conducting polymer nano granules that the present invention combines with plasma discharging by sol method, by introduce cotton-shaped conductive polymer particles in ZnO nano material, significantly increase the interface scattering of phonon, can greatly reduce the thermal conductivity of material; Utilize the thermal conductivity that conducting polymer is lower, higher conductivity and the higher advantages such as Seebeck coefficient of inorganic material, improve the thermoelectricity capability of nanocomposite system.
The present invention adopts the oxide-base nano composite thermoelectric materials of the synthetic ZnO of solution chemical method (sol method) and doping thereof, the feature such as the preparation method of this material is simple, reaction temperature is low, the reaction time is short, energy consumption is low, chemical uniformity is good, and be easily generalized to other material system.
Accompanying drawing explanation
The compound ZnO block of Fig. 1 polyparaphenylene XRD figure;
The compound ZnO powder SEM figure of Fig. 2 polyparaphenylene;
The compound Zn0.925Co0.075O block of Fig. 3 polyparaphenylene XRD figure;
The compound Zn0.925Co0.075O powder of Fig. 4 polyparaphenylene SEM figure;
The compound Zn0.95 Ag of Fig. 5 polyparaphenylene 0.05O block XRD figure;
The compound Zn0.95 Ag of Fig. 6 polyparaphenylene 0.05O powder SEM figure.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
The preparation of the compound zno-based thermoelectric material of embodiment 1. polyparaphenylene's nano particle
First, polyparaphenylene puts into the sulfuric acid of 85% concentration, at 30 ℃ of temperature, stir 8 minutes after filtration washing then dry, gained sample ball milling 3 hours on high energy ball mill, rotating speed is 210r/min; 13.23g zinc acetate is dissolved in to 3000ml diglycol, add 120ml water, at 165 ℃ of temperature, stir 10 minutes, after there is white precipitate standing 2 hours, make ZnO colloidal sol, the polyparaphenylene's particle taking after the processing of 0.0057g adds ZnO colloidal sol and stirs, then under ultrasound condition, disperse 30 minutes, be warming up to 165 ℃ of reactions and filter after 1 hour, and wash repeatedly with absolute ethyl alcohol and deionized water, finally dry at 100 ℃, obtain nano-powder material.Dusty material makes the compound zno-based thermoelectric material of block polyparaphenylene nano particle through discharge plasma sintering, and sintering condition is: 980 ℃, and sintering time 8min, pressure is 60MPa.Composite material characterizes sees Fig. 1 and Fig. 2.
The preparation of the compound Zn0.925Co0.075O base thermoelectricity material of embodiment 2. polyparaphenylene's nano particle
After polyparaphenylene stirs 10 minutes at 30 ℃ of temperature of sulfuric acid of 85% concentration, filtration washing is then dry, gained sample ball milling 3 hours on high energy ball mill, and rotating speed is 180r/min; 13.23g zinc acetate and 1.125g cobalt acetate are dissolved in to 3000ml diglycol, add 120ml water, at 160 ℃ of temperature, stir 10 minutes, after there is white precipitate standing 2 hours, make ZnO colloidal sol, the polyparaphenylene's particle taking after the processing of 0.0019g adds ZnO colloidal sol and stirs, then under ultrasound condition, disperse 30 minutes, be warming up to 160 ℃ of reactions and filter after 1 hour, and wash repeatedly with absolute ethyl alcohol and deionized water, finally dry at 100 ℃, obtain nano-powder material.Dusty material makes the compound Zn0.925Co0.075O base thermoelectricity material of block polyparaphenylene nano particle through discharge plasma sintering, and sintering condition is: 950 ℃, and sintering time 8min, pressure is 50MPa.Composite material characterizes sees Fig. 3 and Fig. 4.
The preparation of the compound Zn0.95 Ag of embodiment 3. polyparaphenylene's nano particle 0.05O base thermoelectricity material
Polyparaphenylene puts into the sulfuric acid of 85% concentration, at 30 ℃ of temperature, stir 8 minutes after filtration washing then dry, gained sample ball milling 4 hours on high energy ball mill, rotating speed is 210r/min; 13.2g zinc acetate and 0.52g silver acetate are dissolved in to 3000ml diglycol, add 120ml water, at 170 ℃ of temperature, stir 10 minutes, after there is white precipitate standing 2 hours, make ZnO colloidal sol, the polyparaphenylene's particle taking after the processing of 0.0040g adds ZnO colloidal sol and stirs, then under ultrasound condition, disperse 30 minutes, be warming up to 170 ℃ of reactions and filter after 1 hour, and wash repeatedly with absolute ethyl alcohol and deionized water, finally dry at 100 ℃, obtain nano-powder material.Dusty material makes the compound Zn0.925Co0.075O base thermoelectricity material of block polyparaphenylene nano particle through discharge plasma sintering, and sintering condition is: 850 ℃, and sintering time 8min, pressure is 40MPa.Composite material characterizes sees Fig. 5 and Fig. 6.
Claims (1)
1. the preparation method of the compound zno-based thermoelectric material of polyparaphenylene's nano particle system, is characterized in that preparing according to the following steps:
A) utilizing strong acid or high-energy mechanical ball milling to carry out early stage to polyparaphenylene's nano particle processes, improve the dispersiveness of nano particle, concrete grammar is: it is in more than 85% sulfuric acid that polyparaphenylene's nano particle is joined to concentration, at 20～50 ℃ of temperature, stir 5～10 minutes, then filter, wash, dry, by gained sample ball milling 0.5～4 hour on high energy ball mill;
B) 0.1～10% ratio is dissolved in 500ml diglycol by the acetate of ion to be adulterated and 2.20g zinc acetate in molar ratio, adds 20ml water, at 160～170 ℃ of temperature, stirs 10 minutes, after there is white precipitate standing 2 hours, makes ZnO colloidal sol;
C) by A) polyparaphenylene's nano particle after processing adds ZnO colloidal sol and stirs, and then under ultrasound condition, disperses 30 minutes, is warming up to 160～170 ℃ of reactions 1 hour;
D) by step C) products therefrom with the washing of absolute ethyl alcohol and deionized water repeatedly, finally dry at 100 ℃, obtain nano-powder material;
E) nano-powder material makes the compound zno-based thermoelectric material of block polyparaphenylene nano particle through discharge plasma sintering, and the condition of sintering is 800～1000 ℃, sintering 5～10min, and pressure is 40～60MPa;
F) acetate of described ion to be adulterated comprises any one in aluminum acetate, ferric acetate, cobalt acetate, nickel acetate, silver acetate, acetic acid gold;
G) described ion to be adulterated is any one ion in aluminium ion, iron ion, cobalt ions, nickel ion, silver ion or gold ion.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050595A (en) * | 2007-05-22 | 2007-10-10 | 北京科技大学 | Nano inorganic powder coated high molecular fiber and its preparing method |
| US7309830B2 (en) * | 2005-05-03 | 2007-12-18 | Toyota Motor Engineering & Manufacturing North America, Inc. | Nanostructured bulk thermoelectric material |
| CN101276743A (en) * | 2007-03-26 | 2008-10-01 | 株式会社半导体能源研究所 | Method for manufacturing semiconductor device |
| CN101436640A (en) * | 2008-12-26 | 2009-05-20 | 哈尔滨工业大学 | ZnO/beta-FeSi2 composite material and preparation method |
| CN101931043A (en) * | 2009-06-19 | 2010-12-29 | 清华大学 | Thermoelectric conversion material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7309830B2 (en) * | 2005-05-03 | 2007-12-18 | Toyota Motor Engineering & Manufacturing North America, Inc. | Nanostructured bulk thermoelectric material |
| CN101276743A (en) * | 2007-03-26 | 2008-10-01 | 株式会社半导体能源研究所 | Method for manufacturing semiconductor device |
| CN101050595A (en) * | 2007-05-22 | 2007-10-10 | 北京科技大学 | Nano inorganic powder coated high molecular fiber and its preparing method |
| CN101436640A (en) * | 2008-12-26 | 2009-05-20 | 哈尔滨工业大学 | ZnO/beta-FeSi2 composite material and preparation method |
| CN101931043A (en) * | 2009-06-19 | 2010-12-29 | 清华大学 | Thermoelectric conversion material |
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