CN102496677B - Preparation method of poly(p-phenylene) nanoparticle composite ZnO-based thermoelectric material system - Google Patents

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

The preparation method of the compound zno-based thermoelectric material of polyparaphenylene's nano particle system

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.