CN109974317A - A kind of solar absorption system and preparation method thereof with composite absorption mechanism - Google Patents
A kind of solar absorption system and preparation method thereof with composite absorption mechanism Download PDFInfo
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- CN109974317A CN109974317A CN201910213217.3A CN201910213217A CN109974317A CN 109974317 A CN109974317 A CN 109974317A CN 201910213217 A CN201910213217 A CN 201910213217A CN 109974317 A CN109974317 A CN 109974317A
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Abstract
The solar absorption system and preparation method thereof with composite absorption mechanism that the invention discloses a kind of solves the problems, such as not realize the absorbing material of MULTIPLE COMPOSITE mechanism of absorption effectively in the prior art.The present invention includes basal layer and the SiO for being coated with graphene doping on the base layer2Colloidal sol；The basal layer is the stainless steel plate after high-temperature oxydation；The SiO of the graphene doping2The raw material composition of colloidal sol includes: esters of silicon acis, ethyl alcohol, acid, deionized water, graphene.Present invention incorporates a variety of mechanism of absorption such as Intrinsic Gettering, light trapping absorption and the absorption of amorphous phase carbon defects, have higher selective absorbing coefficient, function admirable.
Description
Technical field
The present invention relates to a kind of solar absorption systems, and in particular to a kind of solar absorption with composite absorption mechanism
System and preparation method thereof.
Background technique
Solar energy is a kind of clean renewable energy, there is huge potentiality to be exploited, in environmental pollution, resource scarcity
Today's society gets more and more people's extensive concerning.Important channel one of of the solar heat conversion technology as Solar use, has
Wider (300-2500nm), the strong applicability using spectrum, operating temperature are distributed advantages such as wide (60 DEG C -1000 DEG C).However, mesh
It is preceding since, energy consumption high by manufacturing cost are high and the restriction for the aspects such as photothermal conversion efficiency is low, develop highly selective absorptance
Material be still heavy difficult point that the research field is urgently captured.
The solar radiation intensity for the different wave length that earth surface is subject to is not uniform, and by season, latitude,
The influence of many factors such as shape and weather.By Fig. 1 solar radiation strength distribution curve, it will be seen that solar radiation
It is mainly distributed on 300-2500nm wave band, wherein high-radiation area is about in 300-800nm wave band, and working as wavelength is more than 2500nm
When, the thermal radiation loss of material itself can be than more serious, and energy loss is significant.In view of this objective phenomenon, to improve solar energy
Photothermal conversion efficiency, it is desirable that solar selectively absorbing material must the region 300-2500nm have high absorptivity α (formula
1)；And there is low emissivity ε (formula 2) in region of the wavelength greater than 2500nm.
Wherein, RλFor the reflectivity of material surface；IsλFor solar energy a certain wavelength radiation intensity, herein with AM1.5
(ISO, ASTMG179-03) is standard spectrum；IBλFor at a certain temperature, ideal black-body substance is black in the Planck of a certain wavelength
Body radiant power.
It can not realize the absorbing material of MULTIPLE COMPOSITE mechanism of absorption effectively in the prior art, selectivity factor is lower,
It cannot effectively be applied in a variety of solar energy heat utilization devices.
Summary of the invention
Present invention aim to address the absorption materials that can not realize MULTIPLE COMPOSITE mechanism of absorption effectively in the prior art
The problem of material, provides a kind of solar absorption system and preparation method thereof with composite absorption mechanism, with high selection
Property coefficient can be applied in a variety of solar energy heat utilization devices.
The present invention is achieved through the following technical solutions:
A kind of solar absorption system with composite absorption mechanism including basal layer and is coated with graphite on the base layer
The SiO of alkene doping2Colloidal sol；
The basal layer is the stainless steel plate after high-temperature oxydation；
The SiO of the graphene doping2The raw material composition of colloidal sol includes: esters of silicon acis, ethyl alcohol, acid, deionized water, graphite
Alkene.
Stainless steel surface of the present invention after high-temperature oxydation in sub-wavelength structure is coated with the SiO of graphene doping2Colloidal sol, should
The SiO of graphene doping2Colloidal sol is with SiO2As the skeleton of gel coat, sub-wavelength structure is being effectively reduced in doped graphene
While degree of roughness, and remain effect and the Fe of its " light trapping "2O3Intrinsic Gettering effect, reach while improving material
Expect the absorptivity α on surface, reduce the effect of emissivity ε, so that selectivity factor S (S=α/ε) has more significant increase, and
It is finally reached the more efficient purpose using solar heat, there is biggish application potential in solar energy thermal-power-generating field.
Present invention incorporates a variety of mechanism of absorption such as Intrinsic Gettering, light trapping absorption and the absorption of amorphous phase carbon defects, have
Higher selective absorbing coefficient, function admirable.
Further, by weight, the SiO of the graphene doping2The raw material of colloidal sol forms
Content is 80~90 parts of esters of silicon acis of 99.0%, and content is 1270-1350 part of ethyl alcohol of 99.9%, content for 36~
6~9 parts of 38% hydrochloric acid, 10~15 parts of deionized water, 1~5 part of graphene, 1~5 part of dispersing agent.
Further, by weight, the SiO of the graphene doping2The raw material of colloidal sol forms
Content is 86 parts of esters of silicon acis of 99.0%；Content is 1290 parts of ethyl alcohol of 99.9%；Content be 36.0%~
38.0% 7 parts of hydrochloric acid；2 parts of graphene；2 parts of dispersing agent of commercialization.
Further, the basal layer is in sub-wavelength structure.
A kind of preparation method of the solar absorption system with composite absorption mechanism, comprising:
(1) SiO of graphene doping is prepared respectively2Colloidal sol and basal layer；
(2) SiO for adulterating graphene2Colloidal sol is coated on the base layer；
(3) it is heat-treated under the conditions of high pure nitrogen；
The SiO of the graphene doping2The preparation process of colloidal sol are as follows: disperse ethyl alcohol simultaneously for esters of silicon acis and graphene
In, esters of silicon acis is made after hydrolytic condensation in ethanol；
The preparation process of the basal layer are as follows: stainless steel plate is handled using high temperature, is obtained after over cleaning and drying
Obtain the layer structure in sub-wavelength structure.
The reaction equation of hydrolytic condensation is as follows in the present invention:
Hydrolytic condensation: Si (OC2H5)4+4H2O→Si(OH)4+C2H5OH
Si(OH)4→SiO2+2H2O
The SiO that the present invention is adulterated in graphene2In the preparation process of colloidal sol, reaction condition is mild, to equipment and experiment item
Part requires low, energy saving, and the discharge of overall process no liquid pollutant, environmental-friendly；And in the present invention base material place
Reason, the preparation process of coating are simple, and equipment requirement is low, without providing the harsh experiment condition such as vacuum.
Further, of the invention specific the preparation method is as follows:
1, the SiO of graphene doping2The preparation of colloidal sol
A) by metering by esters of silicon acis, ethyl alcohol, hydrochloric acid, deionized water, graphene, the dispersing agent of commercialization is added to reaction flask
In, it is placed in constant temperature water bath at 25 DEG C and is aged 7 days in 30 DEG C of at a temperature of stirring 2h；
B) each component by weight of component described in colloidal sol is constituted are as follows: content is 80~90 parts of esters of silicon acis of 99.0%, is contained
Amount is 1270-1350 part of ethyl alcohol of 99.9%, and content is 6~9 parts of hydrochloric acid of 36~38%, 10~15 parts of deionized water, graphite
1~5 part of alkene (oxidation state), 1~5 part of commercialization dispersing agent with graphene homogenous quantities；As the best preferred of said components, institute
State each component composition by weight are as follows: content is 86 parts of esters of silicon acis of 99.0%；Content is 1290 parts of ethyl alcohol of 99.9%；Contain
Amount is 7 parts of 36.0%~38.0% hydrochloric acid；2 parts of graphene；2 parts of dispersing agent of commercialization.
2, the processing of stainless steel base
A) substrate selects the stainless steel plate of 4k mirror finish, with a thickness of 1mm, the models such as material selection 304,306,316L
Stainless steel；
B) the stainless steel substrates clear water washes clean mirror-finished, removes the insoluble impurities such as the dust on surface, then sets
It in the seal container for holding acetone, is ultrasonically treated in ultrasonic cleaning tank, rinses simultaneously wiped clean with ethyl alcohol after taking-up；
C) stainless steel substrates that cleaning finishes are placed in Muffle furnace, are handled, has been handled under 800-1000 DEG C of high temperature
Be down to room temperature with furnace at rear stainless steel substrate, take out to be rinsed with ethyl alcohol again and remove surface, drying be placed on it is spare in desiccator,
Most preferably as the step, treatment temperature is 900 DEG C, and the processing time is 2h.
3, the preparation of coating for selective absorption
A) SiO for being adulterated graphene using dipping-lifting coating machine2Colloidal sol is coated on the stainless steel watch after high-temperature oxydation
Face, pull rate 180-280mm/min, between plated film humidity be maintained at 30% hereinafter, temperature control at 30 DEG C or so, as this
Most preferably, pull rate is selected as 250mm/min to step；
B) coating prepared carries out the heat treatment no more than 450 DEG C in tube furnace, and intraluminal atmosphere is complete in advance
Portion is replaced into high pure nitrogen, the loss generated with preventing graphene component from aoxidizing at high temperature.
Compared with prior art, the present invention having the following advantages and benefits:
1, solar selectively absorbing material prepared by the present invention is compared with absorbing material prepared by congenic method, Qian Zhejie
A variety of mechanism of absorption such as Intrinsic Gettering, light trapping absorption and the absorption of amorphous phase carbon defects have been closed, there is higher selective absorbing
Coefficient, function admirable.
2, in preparation process of the present invention, reaction condition is mild, requires low, energy saving to equipment and experiment condition, and complete
The discharge of process no liquid pollutant, environmental-friendly, preparation process is simple, and equipment requirement is low, harsh without providing vacuum etc.
Experiment condition；
3, solar selectively absorbing material of the invention is suitable for 400 DEG C of a variety of solar heat conversion devices below.
Detailed description of the invention
Fig. 1 is AM1.5 (ISO, ASTMG179-03) solar radiation spectrogram.
Fig. 2 is the reflectance curve figure of the present invention and stainless steel base in 300-2500nm wave band.
Fig. 3 is the reflectance curve figure of the present invention and stainless steel base in 2.5-25 mu m waveband.
Fig. 4 is the surface topography map of the present invention and stainless steel base.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment, the present invention is made
Further to be described in detail, exemplary embodiment of the invention and its explanation for explaining only the invention, are not intended as to this
The restriction of invention.
Embodiment 1
A kind of preparation method of the solar absorption system with composite absorption mechanism, detailed process are as follows:
The graphene powder of phase homogenous quantities is homogeneously dispersed in 1270 parts of contents using 2 parts of commodity dispersant B YK-190
For in 99.9% ethyl alcohol, and the esters of silicon acis that 80 parts of contents are 99.0% is added, 8 part 36.0~38.0% is added after mixing
Hydrochloric acid react stand-by after 12h as catalyst, in 30 DEG C of water-baths.The 316L stainless steel substrates of mirror finish are washed with clear water and are done
Only, the insoluble impurities such as the dust on surface are removed, are subsequently placed in the seal container for holding acetone, it is ultrasonic in ultrasonic cleaning tank
30min is handled, rinses simultaneously wiped clean with ethyl alcohol after taking-up.The stainless steel substrates that cleaning finishes are placed in Muffle furnace, with 1000
DEG C high-temperature process 2h, stainless steel substrates are down to room temperature with furnace after the completion of processing, take out to be rinsed with ethyl alcohol again and remove surface, 80 DEG C of bakings
It is dry be placed on it is spare in desiccator.The silicon dioxide gel that graphene adulterates is coated on high temperature using dipping-lifting coating machine
Stainless steel surface after oxidation, pull rate 200mm/min, between plated film humidity be maintained at 30% hereinafter, temperature control 30
DEG C or so.The coating prepared carries out 400 DEG C of heat treatment in tube furnace, and intraluminal atmosphere is all replaced into height in advance
Pure nitrogen gas, the loss generated with preventing graphene component from aoxidizing at high temperature.
Embodiment 2
A kind of preparation method of the solar absorption system with composite absorption mechanism, detailed process are as follows:
The graphene powder of phase homogenous quantities is homogeneously dispersed in 1290 parts of contents using 2 parts of commodity dispersant B YK-2012
For in 99.9% ethyl alcohol, and the esters of silicon acis that 86 parts of contents are 99.0% is added, 7 part 36.0~38.0% is added after mixing
Hydrochloric acid react stand-by after 12h as catalyst, in 30 DEG C of water-baths.316 stainless steel substrates of mirror finish are washed with clear water and are done
Only, the insoluble impurities such as the dust on surface are removed, are subsequently placed in the seal container for holding acetone, it is ultrasonic in ultrasonic cleaning tank
30min is handled, rinses simultaneously wiped clean with ethyl alcohol after taking-up.The stainless steel substrates that cleaning finishes are placed in Muffle furnace, with 900 DEG C
High-temperature process 2h, stainless steel substrates are down to room temperature with furnace after the completion of processing, take out and rinse removing surface, 80 DEG C of drying with ethyl alcohol again
It is placed on spare in desiccator.The silicon dioxide gel that graphene adulterates is coated on high temperature oxygen using dipping-lifting coating machine
Stainless steel surface after change, pull rate 250mm/min, between plated film humidity be maintained at 30% hereinafter, temperature control at 30 DEG C
Left and right.The coating prepared carries out 450 DEG C of heat treatment in tube furnace, and intraluminal atmosphere has all been replaced into high-purity in advance
Nitrogen, the loss generated with preventing graphene component from aoxidizing at high temperature.
Stainless steel base after high-temperature process disclosed in absorption system, with the present embodiment made of the present embodiment is carried out
Contrasting detection, testing result is as shown in figs 2-4.
In Fig. 2, S1For reflectance curve of the stainless steel base in 300-2500nm wave band after high-temperature process, S2For this hair
Reflectance curve of the bright absorption system in 300-2500nm wave band；In Fig. 3, S1Exist for the stainless steel base after high-temperature process
The reflectance curve of 2.5-25 mu m waveband, S2For absorption system of the invention 2.5-25 mu m waveband reflectance curve.Pass through
The absorptivity that formula shown in the curve and convolution 1 and formula 2 of Fig. 2 and Fig. 3 can calculate composite absorption system may be up to
For 0.93,200 DEG C of emissivity down to 0.205, selective absorbing coefficient can reach 4.54.
In Fig. 4, a is the surface topography of the stainless steel base after high-temperature process, and b is the surface shape of absorption system of the invention
Stainless steel can be observed after high-temperature process in looks from a of Fig. 4, Surface Creation Fe2O3Crystal, the size that concave-convex surface rises and falls
It is differed from several hundred nanometers to one micron, for light of the wavelength lower than respective width, just plays the role of " trap ".It introduces
After coating, as shown in the b of Fig. 4, " light trapping " structure is still remained.Depressed section " backfill " declines roughness by coating,
Emissivity reduces.
Embodiment 3
A kind of preparation method of the solar absorption system with composite absorption mechanism, detailed process are as follows:
The graphene powder of phase homogenous quantities is homogeneously dispersed in 1330 parts of contents using 2 parts of commodity dispersant B YK-2012
For in 99.9% ethyl alcohol, and the esters of silicon acis that 90 parts of contents are 99.0% is added, 9 part 36.0~38.0% is added after mixing
Hydrochloric acid react stand-by after 12h as catalyst, in 30 DEG C of water-baths.304 stainless steel substrates of mirror finish are washed with clear water and are done
Only, the insoluble impurities such as the dust on surface are removed, are subsequently placed in the seal container for holding acetone, it is ultrasonic in ultrasonic cleaning tank
30min is handled, rinses simultaneously wiped clean with ethyl alcohol after taking-up.The stainless steel substrates that cleaning finishes are placed in Muffle furnace, with 800 DEG C
High-temperature process 2h, stainless steel substrates are down to room temperature with furnace after the completion of processing, take out and rinse removing surface, 80 DEG C of drying with ethyl alcohol again
It is placed on spare in desiccator.The silicon dioxide gel that graphene adulterates is coated on high temperature oxygen using dipping-lifting coating machine
Stainless steel surface after change, pull rate 220mm/min, between plated film humidity be maintained at 30% hereinafter, temperature control at 30 DEG C
Left and right.The coating prepared carries out 450 DEG C of heat treatment in tube furnace, and intraluminal atmosphere has all been replaced into high-purity in advance
Nitrogen, the loss generated with preventing graphene component from aoxidizing at high temperature.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of solar absorption system with composite absorption mechanism, which is characterized in that including basal layer and be coated on substrate
The SiO of graphene doping on layer2Colloidal sol；
The basal layer is the stainless steel plate after high-temperature oxydation；
The SiO of the graphene doping2The raw material composition of colloidal sol includes: esters of silicon acis, ethyl alcohol, acid, deionized water, graphene.
2. a kind of solar absorption system with composite absorption mechanism according to claim 1, which is characterized in that by weight
Measure part meter, the SiO of the graphene doping2The raw material of colloidal sol forms
Content is 80~90 parts of esters of silicon acis of 99.0%, and content is 1270-1350 parts of ethyl alcohol of 99.9%, and content is 36~38%
6~9 parts of hydrochloric acid, 10~15 parts of deionized water, 1~5 part of graphene, 1~5 part of dispersing agent.
3. a kind of solar absorption system with composite absorption mechanism according to claim 1, which is characterized in that by weight
Measure part meter, the SiO of the graphene doping2The raw material of colloidal sol forms
Content is 86 parts of esters of silicon acis of 99.0%；Content is 1290 parts of ethyl alcohol of 99.9%；Content is 36.0%~38.0% salt
7 parts of acid；2 parts of graphene；2 parts of dispersing agent of commercialization.
4. a kind of solar absorption system with composite absorption mechanism according to claim 1, which is characterized in that described
Basal layer is in sub-wavelength structure.
5. a kind of preparation method of the solar absorption system with composite absorption mechanism characterized by comprising
(1) SiO of graphene doping is prepared respectively2Colloidal sol and basal layer；
(2) SiO for adulterating graphene2Colloidal sol is coated on the base layer；
(3) it is heat-treated under the conditions of high pure nitrogen；
The SiO of the graphene doping2The preparation process of colloidal sol are as follows: disperse esters of silicon acis and graphene in ethyl alcohol simultaneously, acid is urged
Esters of silicon acis is made after hydrolytic condensation in ethanol；
The preparation process of the basal layer are as follows: stainless steel plate is handled using high temperature, is in after over cleaning and drying
The layer structure of sub-wavelength structure.
6. a kind of preparation method of solar absorption system with composite absorption mechanism according to claim 5, special
Sign is, the SiO for being adulterated graphene using dipping-lifting coating machine2Colloidal sol is coated on the stainless steel plate table after high-temperature oxydation
Face, the pull rate are 180~280mm/min, and humidity is maintained at 30% or less between plated film.
7. a kind of preparation method of solar absorption system with composite absorption mechanism according to claim 5, special
Sign is that the heat treatment temperature is lower than 450 DEG C.
8. a kind of preparation method of solar absorption system with composite absorption mechanism according to claim 5, special
Sign is that the treatment temperature of the preparation process high temperature processing of the basal layer is 800~1000 DEG C.
9. a kind of preparation method of solar absorption system with composite absorption mechanism according to claim 5, special
Sign is, the SiO of the graphene doping2The preparation process of colloidal sol are as follows:
Esters of silicon acis, ethyl alcohol, hydrochloric acid, deionized water, graphene, dispersing agent are added in reaction flask by metering, at 28~32 DEG C
At a temperature of stir 1.5~2.5h after, be placed in constant temperature water bath be aged after be made graphene adulterate SiO2Colloidal sol；
Wherein, by weight, the specific metering of said components is as follows:
Content is 80~90 parts of esters of silicon acis of 99.0%, and content is 1270-1350 parts of ethyl alcohol of 99.9%, and content is 36~38%
6~9 parts of hydrochloric acid, 10~15 parts of deionized water, 1~5 part of graphene, 1~5 part of dispersing agent.
10. a kind of preparation method of solar absorption system with composite absorption mechanism according to claim 9, special
Sign is that the graphene is oxidation state graphene.
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| CN109206017A (en) * | 2018-11-23 | 2019-01-15 | 天津市职业大学 | A kind of graphene doped-glass coating liquid and preparation method thereof |
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| KR101097175B1 (en) * | 2010-07-09 | 2011-12-22 | 아주대학교산학협력단 | Saturable absorber comprising monolayer graphene and manufacturing method of the same |
| CN102798241A (en) * | 2012-08-31 | 2012-11-28 | 山东力诺新材料有限公司 | Solar selective absorption coating and preparation technology thereof |
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