CN102732230A - Preparation method for ionic liquid nanometer fluid for high temperature heat utilization in solar energy - Google Patents
Preparation method for ionic liquid nanometer fluid for high temperature heat utilization in solar energy Download PDFInfo
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- CN102732230A CN102732230A CN2012102187140A CN201210218714A CN102732230A CN 102732230 A CN102732230 A CN 102732230A CN 2012102187140 A CN2012102187140 A CN 2012102187140A CN 201210218714 A CN201210218714 A CN 201210218714A CN 102732230 A CN102732230 A CN 102732230A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012530 fluid Substances 0.000 title description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 54
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 19
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 2
- -1 [BMIM] + Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- 239000004094 surface-active agent Substances 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000013529 heat transfer fluid Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种用于太阳能中高温热利用的离子液体纳米流体的制备方法，包括以下步骤：按一定质量分数将石墨烯加入咪唑类离子液体中，进行多次超声分散，形成均匀稳定的悬浮液即得到离子液体纳米流体。通过本发明的方法制备的石墨烯/离子液体纳米流体具有导热系数高、集热性能好、稳定性好等优点，并且石墨烯添加量少、不添加表面活性剂，具有环境友好性，其制备工艺简单、成本低廉，可以用于100℃以上太阳能中高温热利用领域。The invention discloses a preparation method of an ionic liquid nanofluid used for high-temperature heat utilization in solar energy, which comprises the following steps: adding graphene into an imidazole-based ionic liquid according to a certain mass fraction, performing ultrasonic dispersion several times, and forming a uniform and stable The suspension is the ionic liquid nanofluid. The graphene/ionic liquid nanofluid prepared by the method of the present invention has the advantages of high thermal conductivity, good heat collection performance, good stability, etc., and the amount of graphene added is small, no surfactant is added, and it is environmentally friendly. Its preparation The process is simple and the cost is low, and it can be used in the field of medium and high temperature heat utilization of solar energy above 100°C.
Description
Technical field
The invention belongs to the solar energy heat-transferring technical field, relate to a kind of preparation method of Graphene ionic liquid nano-fluid, be specifically related to a kind of preparation method who is used for the ionic liquid nano-fluid of sun power elevated temperature heat utilization.
Background technology
The thermal utilization of sun power is as the important component part of solar energy resources development and use, but become the important component part of countries in the world energy sustainable development strategy.It mainly is divided into low-temperature heat utilization and the medium and high temperature thermal utilization more than 100 ℃ below 100 ℃.Middle high temperature solar thermal utilization system mainly comprises subsystems such as thermal-arrest, heat accumulation, heat exchange, power, generating.
At present, thermal-arrest, heat-transfer fluid mainly are to adopt thermal oil and melting salt.The shortcoming of thermal oil is to have temperature instability, and it is low to be prone to decomposition carbonization and thermal conductivity; And the zero pour of melting salt is higher, generally greater than 120 ℃, is prone to blocking pipe in the use, needs extra increase by to overlap the heated protective system and melts process to realize the change that starts with salt, has increased the complicacy and the cost of system, and has brought defectives such as difficult in maintenance.
Ionic liquid be one type by specific organic cation and inorganic or organic anion constitutes under room temperature or nearly room temperature, presents liquid molten salt system.Compare with above-mentioned heat-transfer fluid, ionic liquid has not only that fusing point is low, the liquid journey is wide, volatilization hardly, thermostability and good chemical stability, also has the structure designability, can regulate and control performance through changing the zwitterion structure according to needs.And; Because ionic liquid has advantages such as density height, thermal capacitance and energy storage density are big, is the heat-transfer fluid of excellent property, its maximum operation (service) temperature can reach 500 ℃; Particularly elevated temperature heat utilizes the field to have broad prospect of application in sun power; But the basic ion liquid thermal conductivity of traditional method preparation is lower, and heat transfer coefficient is little, has limited its further application.
Through nano level metallics such as gold ion, cupric oxide, aluminum oxide and carbon nanotube are added in the ionic liquid, the suspension-s nano-fluid of formation, its thermal conductivity ratio basis ionic liquid fluid is significantly improved.In the existing ionic liquid nano-fluid, need usually to add the dispersing property that tensio-active agent improves nanoparticle, also seldom relate to high temperature Application for Field in sun power.
Summary of the invention
The objective of the invention is to defective, a kind of preparation method who is used for the ionic liquid nano-fluid of sun power elevated temperature heat utilization is provided to above-mentioned prior art.
The present invention directly adds Graphene in the ionic liquid to and is uniformly dispersed; Because Graphene has two-dimensional nanostructure; Have unique physical properties and excellent electricity, calorifics and optical property, its thermal conductivity is up to 5300W/mK, not only far above CuO, Al under the room temperature condition
2O
3Deng metal and metal oxide materials; Also be higher than the carbon nanotube that the axial thermal conductivity coefficient reaches 3000W/mK, therefore in ionic liquid, add the black liquor that Graphene constitutes, its solar collecting performance significantly improves; Thermal conductivity also is significantly improved simultaneously, thereby reaches the purpose of intensifying heat transfer.
In order to achieve the above object, the present invention has adopted following technical scheme:
Be used for the preparation method of the ionic liquid nano-fluid of sun power elevated temperature heat utilization, may further comprise the steps: Graphene is added in the ionic liquid, carry out ultra-sonic dispersion, form uniform and stable suspension-s and promptly obtain the ionic liquid nano-fluid.
The massfraction of Graphene according to the invention in the ionic liquid nano-fluid is 0.001～0.1%.
The process of ultra-sonic dispersion according to the invention is: earlier with 200～300W power ultrasonic, 3～4h, use 20～40W power ultrasonic, 2～4s again, leave standstill 2～6min; The number of times of said ultra-sonic dispersion is 90 ~ 130 times.
Ion liquid positively charged ion according to the invention is an imidazoles, comprises [BMIM]
+, [C
nMIM]
+, [C
nBIM]
+Or [C
nHIM], 2≤<n≤10, negatively charged ion are [BF
4]
-, [PF
6]
-, [NTf
2]
-Or [CF
3SO
3]
-
The present invention compared with prior art has the following advantages and beneficial effect:
(1) the Graphene addition of the ionic liquid nano-fluid of the present invention's preparation is few, thermal conductivity is high, solar collecting performance good, good stability;
(2) do not add tensio-active agent in the ionic liquid nano-fluid of the present invention's preparation, have environment friendly;
(3) preparing method's technology of the present invention is simple, with low cost, can be used for more than 100 ℃ the sun power elevated temperature heat and utilize the field.
Embodiment
Below in conjunction with embodiment the present invention is described further, but the protection domain that the present invention requires is not limited in this.
Embodiment 1
By Graphene massfraction in the ionic liquid nano-fluid is 0.001% requirement, and Graphene is added ionic liquid [C
2MIM] CF
3SO
3In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 3h with the 200W power ultrasonic earlier, and then disperse 2s with the 20W power ultrasonic, leave standstill 2min, repeat 90 times, form uniform and stable suspension-s and be Graphene/[C
2MIM] CF
3SO
3The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than one month.In the time of 100 ℃, its thermal conductivity ratio [C
2MIM] CF
3SO
3Ion liquid thermal conductivity improves 5.1%.
Embodiment 2
By Graphene massfraction in the ionic liquid nano-fluid is 0.001% requirement, and Graphene is added ionic liquid [C
4MIM] CF
3SO
3In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 3h with the 200W power ultrasonic earlier, and then disperse 2s with the 20W power ultrasonic, leave standstill 3min, repeat 100 times, form uniform and stable suspension-s and be Graphene/[C
4MIM] CF
3SO
3The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than one month.In the time of 120 ℃, its thermal conductivity ratio [C
4MIM] CF
3SO
3Ion liquid thermal conductivity improves 5.8%.
Embodiment 3
By Graphene massfraction in the ionic liquid nano-fluid is 0.004% requirement, and Graphene is added ionic liquid [C
8MIM] CF
3SO
3In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 4h with the 300W power ultrasonic earlier, and then disperse 4s with the 40W power ultrasonic, leave standstill 4min, repeat 110 times, form uniform and stable suspension-s and be Graphene/[C
8MIM] CF
3SO
3The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than one month.In the time of 140 ℃, its thermal conductivity ratio [C
8MIM] CF
3SO
3Ion liquid thermal conductivity improves 6.9%.
Embodiment 4
By Graphene massfraction in the ionic liquid nano-fluid is 0.004% requirement, and Graphene is added ionic liquid [C
3BIM] NTf
2In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 4h with the 200W power ultrasonic earlier, and then disperse 2s with the 30W power ultrasonic, leave standstill 2min, repeat 90 times, form uniform and stable suspension-s and be Graphene/[C
3BIM] NTf
2The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than one month.In the time of 160 ℃, its thermal conductivity ratio [C
3BIM] NTf
2Ion liquid thermal conductivity improves 7.3%.
Embodiment 5
By Graphene massfraction in the ionic liquid nano-fluid is 0.007% requirement, and Graphene is added ionic liquid [C
3HIM] NTf
2In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 3h with the 300W power ultrasonic earlier, and then disperse 2s with the 40W power ultrasonic, leave standstill 3min, repeat 100 times, form uniform and stable suspension-s and be Graphene/[C
3HIM] NTf
2The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 20 days.In the time of 180 ℃, its thermal conductivity ratio [C
3HIM] NTf
2Ion liquid thermal conductivity improves 8.8%.
Embodiment 6
By Graphene massfraction in the ionic liquid nano-fluid is 0.007% requirement, and Graphene is added ionic liquid [C
3MIM] NTf
2In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 4h with the 200W power ultrasonic earlier, and then disperse 3s with the 30W power ultrasonic, leave standstill 4min, repeat 110 times, form uniform and stable suspension-s and be Graphene/[C
3MIM] NTf
2The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 20 days.In the time of 200 ℃, its thermal conductivity ratio [C
3MIM] NTf
2Ion liquid thermal conductivity improves 9.1%.
Embodiment 7
By Graphene massfraction in the ionic liquid nano-fluid is 0.01% requirement, and Graphene is added ionic liquid [C
4MIM] PF
6In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 4h with the 200W power ultrasonic earlier, and then disperse 4s with the 20W power ultrasonic, leave standstill 3min, repeat 90 times, form uniform and stable suspension-s and be Graphene/[C
4MIM] PF
6The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 20 days.In the time of 220 ℃, its thermal conductivity ratio [C
4MIM] PF
6Ion liquid thermal conductivity improves 11.2%.
Embodiment 8
By Graphene massfraction in the ionic liquid nano-fluid is 0.01% requirement, and Graphene is added ionic liquid [C
6MIM] PF
6In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 4h with the 300W power ultrasonic earlier, and then disperse 2s with the 40W power ultrasonic, leave standstill 3min, repeat 90 times, form uniform and stable suspension-s and be Graphene/[C
6MIM] PF
6The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 1 month.In the time of 240 ℃, its thermal conductivity ratio [C
6MIM] PF
6Ion liquid thermal conductivity improves 10.8%.
Embodiment 9
By Graphene massfraction in the ionic liquid nano-fluid is 0.04% requirement, and Graphene is added ionic liquid [C
8MIM] PF
6In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 3h with the 300W power ultrasonic earlier, and then disperse 3s with the 20W power ultrasonic, leave standstill 4min, repeat 120 times, form uniform and stable suspension-s and be Graphene/[C
8MIM] PF
6The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 1 month.In the time of 260 ℃, its thermal conductivity ratio [C
8MIM] PF
6Ion liquid thermal conductivity improves 13.8%.
Embodiment 10
By Graphene massfraction in the ionic liquid nano-fluid is 0.04% requirement, and Graphene is added ionic liquid [C
10MIM] PF
6In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 3.5h with the 200W power ultrasonic earlier, and then disperse 2s with the 20W power ultrasonic, leave standstill 5min, repeat 100 times, form uniform and stable suspension-s and be Graphene/[C
10MIM] PF
6The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 1 month.In the time of 280 ℃, its thermal conductivity ratio [C
10MIM] PF
6Ion liquid thermal conductivity improves 15.3%.
Embodiment 11
By Graphene massfraction in the ionic liquid nano-fluid is 0.07% requirement, and Graphene is added ionic liquid [C
4MIM] BF
4In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 3h with the 300W power ultrasonic earlier, and then disperse 3s with the 20W power ultrasonic, leave standstill 4min, repeat 130 times, form uniform and stable suspension-s and be Graphene/[C
4MIM] BF
4The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 20 days.In the time of 300 ℃, its thermal conductivity ratio [C
4MIM] BF
4Ion liquid thermal conductivity improves 17.9%.
Embodiment 12
By Graphene massfraction in the ionic liquid nano-fluid is 0.07% requirement, and Graphene is added ionic liquid [C
6MIM] BF
4In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 4h with the 200W power ultrasonic earlier, and then disperse 2s with the 30W power ultrasonic, leave standstill 6min, repeat 120 times, form uniform and stable suspension-s and be Graphene/[C
6MIM] BF
4The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 20 days.In the time of 320 ℃, its thermal conductivity ratio [C
6MIM] BF
4Ion liquid thermal conductivity improves 18.5%.
Embodiment 13
By Graphene massfraction in the ionic liquid nano-fluid is 0.1% requirement, and Graphene is added ionic liquid [C
8MIM] BF
4In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 3h with the 250W power ultrasonic earlier, and then disperse 2s with the 20W power ultrasonic, leave standstill 2min, repeat 110 times, form uniform and stable suspension-s and be Graphene/[C
8MIM] BF
4The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 20 days.In the time of 340 ℃, its thermal conductivity ratio [C
8MIM] BF
4Ion liquid thermal conductivity improves 23.3%.
Embodiment 14
By Graphene massfraction in the ionic liquid nano-fluid is 0.1% requirement, and Graphene is added ionic liquid [C
10MIM] BF
4In, carry out ultra-sonic dispersion, the process of ultra-sonic dispersion is: disperse 4h with the 250W power ultrasonic earlier, and then disperse 2s with the 25W power ultrasonic, leave standstill 2min, repeat 120 times, form uniform and stable suspension-s and be Graphene/[C
10MIM] BF
4The ionic liquid nano-fluid.
Through measuring, this ionic liquid nano-fluid at room temperature can stable existence more than 20 days.In the time of 360 ℃, its thermal conductivity ratio [C
10MIM] BF
4Ion liquid thermal conductivity improves 25.1%.
Claims (4)
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Cited By (11)
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| CN103489645A (en) * | 2013-09-02 | 2014-01-01 | 常州大学 | Gel electrolyte for DSSC and preparation method of gel electrolyte |
| CN104388646A (en) * | 2014-12-11 | 2015-03-04 | 山东大学 | Graphene type liquid quenching cooling medium as well as preparation method and application thereof |
| CN104479644A (en) * | 2014-12-11 | 2015-04-01 | 山东大学 | Graphene-type cooling medium as well as preparation method and application thereof |
| CN105084348A (en) * | 2014-05-20 | 2015-11-25 | 中国科学院大连化学物理研究所 | Method for preparing water-phase dispersible conductive graphene dispersion slurry or solid |
| CN106928907A (en) * | 2017-02-23 | 2017-07-07 | 华南理工大学 | A kind of nano-fluid black liquor of high-temperature stable and preparation method and application |
| CN107163917A (en) * | 2017-06-20 | 2017-09-15 | 大连理工大学 | Ionic liquid solution base nano-fluid directly absorbs solar airconditioning/heat pump method and apparatus |
| CN108394892A (en) * | 2018-05-11 | 2018-08-14 | 西安交通大学 | A kind of graphene dispersion liquid and preparation method thereof that directly graphene is modified |
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| CN103489645B (en) * | 2013-09-02 | 2016-08-17 | 常州大学 | A kind of used by dye sensitization solar battery gel electrolyte and preparation method thereof |
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| CN105084348B (en) * | 2014-05-20 | 2017-06-06 | 中国科学院大连化学物理研究所 | Method for preparing water-phase dispersible conductive graphene dispersion slurry or solid |
| CN104388646A (en) * | 2014-12-11 | 2015-03-04 | 山东大学 | Graphene type liquid quenching cooling medium as well as preparation method and application thereof |
| CN104479644A (en) * | 2014-12-11 | 2015-04-01 | 山东大学 | Graphene-type cooling medium as well as preparation method and application thereof |
| CN106928907A (en) * | 2017-02-23 | 2017-07-07 | 华南理工大学 | A kind of nano-fluid black liquor of high-temperature stable and preparation method and application |
| CN106928907B (en) * | 2017-02-23 | 2020-06-19 | 华南理工大学 | High-temperature stable nanofluid black liquor and preparation method and application thereof |
| CN107163917A (en) * | 2017-06-20 | 2017-09-15 | 大连理工大学 | Ionic liquid solution base nano-fluid directly absorbs solar airconditioning/heat pump method and apparatus |
| CN109962397A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A cooling liquid for immersion liquid-cooled solid-state lasers |
| CN108394892A (en) * | 2018-05-11 | 2018-08-14 | 西安交通大学 | A kind of graphene dispersion liquid and preparation method thereof that directly graphene is modified |
| WO2020052293A1 (en) * | 2018-09-12 | 2020-03-19 | 北京科技大学 | Preparation method for perfluorotriethylamine group-based highly thermally conductive and lubricating nanofluid |
| CN113072916A (en) * | 2021-03-05 | 2021-07-06 | 西安交通大学 | Modified graphene-based heat conduction enhanced ionic liquid composite phase change heat storage material and preparation method thereof |
| CN114752362A (en) * | 2022-04-29 | 2022-07-15 | 四川大学 | Nano-fluid type wide-temperature-zone heat conduction oil based on ionic liquid and preparation method |
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