CN102080227A - Preparation method of low-cost selective coating for solar thermal collector - Google Patents
Preparation method of low-cost selective coating for solar thermal collector Download PDFInfo
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- CN102080227A CN102080227A CN2010105899699A CN201010589969A CN102080227A CN 102080227 A CN102080227 A CN 102080227A CN 2010105899699 A CN2010105899699 A CN 2010105899699A CN 201010589969 A CN201010589969 A CN 201010589969A CN 102080227 A CN102080227 A CN 102080227A
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Abstract
The invention aims to provide a preparation method of a low-cost selective coating for a solar thermal collector, comprising the following steps: (1) adding alkali and oxidant into deionized water at a molar ratio of (1-5):1, fully stirring to obtain a first evenly-mixed solution, and putting into a constant-temperature water bath of 20-100 DEG C; (2) mixing ammonium persulphate, ammonium chloride, deionized water and pyridine at a molar ratio of 1:(1-10):(10-100):(0-0.1), and fully stirring to obtain a second evenly-mixed solution; (3) slicing a copper sheet into proper size, and putting the sliced copper sheets into the solution obtained in the step (2) to react for 10-30 minutes; putting into the solution obtained in the step (1) to react for 5-60 minutes; and taking out after the reaction, washing with deionized water, and drying in air at 50-100 DEG C to obtain the selective coating for a solar thermal collector. The method has low cost and is easy to widely popularize. Meanwhile, the prepared coating not only has good solar absorbability, but also has lower emission characteristics in the infrared radiation wave band.
Description
Technical field
The invention belongs to sun power and utilize the material field, particularly a kind of solar energy collector of the cheapness preparation method and application aspect solar energy heating of selective coating.
Technical background
Sun power is as inexhaustible green energy resource, and wide the sending out that is subjected to people paid close attention to.The utilization of sun power comprises photo-thermal, photoelectricity, photochemistry etc., and wherein solar thermal utilization is sun power utilization tradition and an one of efficient manner the most.Solar energy collector is exactly one of key element of solar energy thermal utilization, make solar energy collector reach the purpose of efficient thermal utilization, one of part can just be absolutely necessary with the solar selective coat that the solar spectrum coupling has a less emittance at the thermal radiation wave band simultaneously.At present, the preparation selective coating can be used kinds of processes methods such as plating, spraying, physical vapor deposition and chemical vapour deposition.Diverse ways depends on and obtains optionally mechanism difference, conclusion gets up to have substantially following several: (1) intrinsic absorbing film, the spectral distribution on the radiation characteristic of some material and ideal selectivity surface is comparatively approaching, this material mainly contains two classes, the one, the compound of transition metal, comprise oxide compound, sulfide, carbide and nitride, the 2nd, semiconductor material.By the external coating semiconductor material or add the particulate that some can produce the scattering-in effect, threshold wavelength is moved to infrared region.But, also there are many problems with it as selective material at present, all bigger as semi-conductive specific refractory power, influence the specific absorption of visible part, must reduce the reflectivity of visible part by extra antireflection layer; The selective coating of brushing is usually because binding agent exists the inherent absorption band to cause emittance more high at infrared region; (2) optical interference coating, utilize interference of light principle, in the multilayered structure of forming by transparent dielectric film, absorbing film and metal substrate, control the optical thickness of every tunic by strictness, make solar radiation be absorbed by the multiple reflection mode in film system, long wave then is reflected.Such film generally prepares by the physical gas-phase deposite method that can strictly control film thickness, as magnetron sputtering, and thermal evaporation etc.(3) multilayer graded films, this film are meant that from the top layer to the bottom rete is made of the film system that optical constant increases gradually, and the concentration or the content of the chemical ingredients of film system present graded, and it is to utilize successively absorbing of beam incident optical reached the high purpose that absorbs.Common multilayer graded films, as gradual change Al-N/Al, multilayer gradual change stainless steel-C/Cu, metal ceramics thin film etc.; (4) optical trap film, pattern and structure by the control film surface make that they are uneven surfaces to shortwave, can fully absorb, and long wave is presented minute surface, reflectivity is very high.At present, Shang Yong solar selective coat is mainly black chromium, black nickel coating and Cr-Al
2O
3Metal ceramics thin film etc., they mainly adopt the method preparation of electrochemical method and physical vapor deposition, because the waste liquid that electrochemical method produces causes second environmental pollution easily, there is the inferior position of poor high temperature stability in the coating of electrochemical production simultaneously, the feasible physical vapor deposition of environmental protection more becomes the selective coating technology of preparing of main flow gradually, but processes of physical vapor deposition all need carry out under certain vacuum tightness, sedimentation effect is lower, and there are reasons such as system operation cost height, make selective coating become in the solar energy collector cost than higher part, and to reduce the cost of heat collector, large-area popularization and use solar energy collector just must be found the solar selective coat that a kind of cheapness also can large-area preparation.
Cu
2O is the vacant P-type semiconductor of a kind of typical metal, and its energy gap is 2eV, and visible light is had higher uptake factor.Under irradiation of sunlight, Cu
2The O particle can break water into hydrogen and oxygen, has good visible light catalytic performance, and its theoretical transformation efficient as solar cell is 12% simultaneously.Therefore, Cu
2O is with a wide range of applications at the aspects such as conversion of photo-thermal coating, photochemical catalysis, photovoltaic cell, lithium ion battery, hull-bottom antifouling, magnetic storage, air-sensitive sensing and CO.At present, the method for preparing Red copper oxide is a lot, industrial sintering process, electrolytic process, the glucose reduction methods etc. of mainly containing, sintering process are earlier cupric oxide and copper powder mixing back to be carried out solid-solid reaction about 1000 ℃, generate Red copper oxide, under inert atmosphere, use levigate equipment that sintered product is levigate again after the cooling, this method energy consumption is big, and the purity of Red copper oxide is lower, and is powder, when carrying out the coating preparation in later stage, find binding agent relatively more difficult with better infrared low emission characteristic.Though adopt the copper electrode electrolytic process can reasonable Red copper oxide powder of output quality and film, power consumption be big, and production efficiency is lower, and electrolytic waste liquid can produce bigger pollution etc. to environment simultaneously.The glucose reduction method needs the expensive raw material of consumption rate, and production cost is than higher.Many researchers is improved the preparation method of preparation Red copper oxide, Li Yadong seminar of Tsing-Hua University provides a kind of low temperature method of synthetic accurate monodispersed Nano balls of cuprous oxide fast in Chinese patent (CN1759965A), but need to use some volatile organic solvents in this method, and will prepare the certain thickness film comparison difficulty that seems with this method.People such as Han (Thin Solid Films 517 (2008) 1195-1199) by magnetron sputtering is prepared the Cu film then earlier under air atmosphere 500 ℃ heat-treat and prepare the CuO film, then the CuO film at N
2Carry out the Cu that microwave plasma sintering is prepared pure phase under the atmosphere
2The film of O, the preparation process of this method are not only complicated and need high temperature, are not suitable for big area and prepare Cu cheaply
2The O film.People such as Yang (Thin Solid Films 517 (2008) 967) are with Cu
2O is a target, has prepared the Cu of pure phase by rf magnetron sputtering
2The O film, but because the efficient of radio-frequency sputtering itself is lower, and Cu
2The making of O target itself has difficulties, and makes this method also have cost and large-area problem.
Summary of the invention
The purpose of this invention is to provide the preparation method of a kind of solar energy collector of cheapness with selective coating.This method not only cost is low, and very easily carries out large-area popularization, and Zhi Bei coating not only has good absorptive character to sunlight simultaneously, has lower emission characteristic at the ir radiation wave band simultaneously.
Utilization of the present invention has flexible and copper that itself have than low-launch-rate is substrate, by the cryochemistry caustic solution, directly obtains Cu in the copper substrate
2The film of O has the advantage of the low and easy big areaization of cost.
Purpose of the present invention is achieved through the following technical solutions, and a kind of solar energy collector of cheapness selective coating preparation method comprises the steps:
(1) with the mineral alkali of water-soluble or contain the solubility organic bases of amido and the saline oxidizing agent of water-soluble according to mol ratio 1～5: 1 joins in the deionized water, after fully stirring, homogeneous mixture solotion, put into 20～100 ℃ water bath with thermostatic control;
(2) with ammonium persulphate, ammonium chloride, deionized water and pyridine mix according to mol ratio 1: 1～10: 10～100: 0～0.1, after fully stirring, get homogeneous mixture solotion;
(3) copper sheet is cut into suitable size and puts into solution reaction that step (2) obtains after 10 seconds～30 minutes, putting into the solution that step (1) obtains reacted 5～60 minutes, take out earlier behind deionized water rinsing the reflection back, 50～100 ℃ of oven dry in air then promptly obtain the solar energy collector selective coating.
In order better to realize the present invention, can further improve as follows to the present invention:
In the step (1), described alkali is selected from the mineral alkali such as the sodium hydroxide of water-soluble, potassium hydroxide, hydrated barta, lithium hydroxide, calcium hydroxide etc. contain the organic bases such as the ammoniacal liquor of amido, thanomin, diethanolamine, trolamine, one of in the 4-Dimethylamino pyridine etc. or two kinds and more than.The saline oxidizing agent of described water-soluble is one or both in clorox, the Textone.
In the step (3), described copper is brass, one or both in the red copper;
Cu of the present invention
2The O film can be used as sun power and selects coating or photocatalyst, has wide environment protection application potential.
The present invention compares with prior art, has following advantage and beneficial effect:
The Cu that the present invention is prepared
2The O selective coating passes through single stage method, under cold condition, energy consumption mode with minimum directly is created in the copper substrate with thermal conductive resin and low-launch-rate, it is low to have cost, simple to operate, but the advantage of big areaization, simultaneously because the copper substrate has good flexibility, so this selective coating can be applied to multiple compromise face.The Cu of the present invention's preparation
2The O selective coating has reached 0.9 to the specific absorption of sunlight, only is 0.086 100 ℃ emittance simultaneously, and the ratio of specific absorption and emittance can compare favourably with the absorptivity-emissivity ratio of commercial selective coating greater than 10.The Cu of the present invention's preparation
2The O selective coating through 200 degree heating 24 hours after, its specific absorption to sunlight is 0.75, emittance is 0.12, the ratio of specific absorption and emittance has still shown good spectral selectivity feature greater than 6.The Cu of the present invention's preparation
2The best use temperature of O selective coating satisfies the service requirements of low-temperature solar energy heat collector fully below 150 ℃.
Description of drawings
Fig. 1 is embodiment of the invention Cu
2The X ray diffracting spectrum of O selective coating;
Fig. 2 is embodiment of the invention Cu
2The field emission scanning electron microscope figure (SEM) of O selective coating;
Fig. 3 is embodiment of the invention Cu
2The reflectogram of O selective coating.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
The used water-bath of following enforcement is thermostat water bath (HH-2), and baking is digital display air dry oven (GZX-9070MBE) with baking oven, and thermal cycling program used for test temperature control retort furnace, chemical reagent do not have to specify to be that commercially available chemical analysis is pure.
Embodiment 1
(1) sodium hydroxide and clorox are joined in the deionized water according to mol ratio at 3: 1, after fully stirring, get homogeneous mixture solotion, put into 80 ℃ water bath with thermostatic control;
(2) with ammonium persulphate, ammonium chloride, deionized water mixes according to mol ratio at 1: 2: 66, after fully stirring, gets homogeneous mixture solotion;
(3) copper sheet is cut into suitable size and puts into the solution reaction of step (2) after 1 minute, after the solution of putting into step (1) after 100 ℃ of oven dry reacts 5 minutes, take out earlier after deionized water washes repeatedly, 100 ℃ of oven dry in air promptly obtain the solar energy collector selective coating among the present invention.
The performance of the selective coating of gained is as follows:
1.XRD collection of illustrative plates
Cu to gained
2The O selective coating has carried out XRD analysis, and the collection of illustrative plates result as shown in Figure 1.The prepared selective coating of the present invention is in 2 θ=29.52 ° as seen from the figure, and 36.36 °, 42.24 °, 61.3 ° corresponding diffraction peak occurred, find and Cu through contrast (JCPDS No.05-0667)
2The characteristic peak of O is consistent, this means successfully to prepare Cu
2The selective coating of O can predict that this coating has good selectivity absorption characteristic.
2.SEM figure
Fig. 2 has provided Cu
2The field emission scanning electron microscope figure of O selective coating, as can be seen from the figure, coatings prepared of the present invention is a kind of porous structure, this helps this coating to have good absorptive character.
3. reflectogram
Fig. 3 is Cu
2The reflected light spectrogram of O selective coating, as can be seen from the figure, selective coating is very low at the reflectivity of solar spectrum wave band, this means that this coating has good specific absorption at wave band, simultaneously have very high reflectivity, mean that this coating has lower emittance at the ir radiation wave band at the ir radiation wave band.By the above result Cu of the present invention preparation as can be seen
2The O coating is a kind of solar selective coat of Cheap highly effective, has application potential widely.
The Cu for preparing according to following examples
2The XRD figure spectrum and the SEM collection of illustrative plates of O selective coating are similar to Example 1, have good spectrum-selectivity characteristic equally.
(1) potassium hydroxide and clorox are joined in the deionized water according to mol ratio at 1: 1, after fully stirring, get homogeneous mixture solotion, put into 60 ℃ water-bath;
(2) with ammonium persulphate, ammonium chloride, deionized water mixes according to mol ratio at 1: 5: 40, after fully stirring, gets homogeneous mixture solotion;
(3) copper sheet is cut into suitable size and puts into the solution reaction of step (2) after 10 seconds, 50 ℃ of oven dry in air, the solution reaction of putting into step (1) is after 30 minutes, take out earlier after deionized water washes repeatedly, 80 ℃ of oven dry promptly obtain the solar energy collector selective coating in air.
Embodiment 3
(1) sodium hydroxide and Textone are joined in the deionized water according to mol ratio at 5: 1, after fully stirring, get homogeneous mixture solotion, put into 20 ℃ water-bath;
(2) with ammonium persulphate, ammonium chloride, deionized water and pyridine were according to mol ratio 1: 2: 100: 0.1 mixes, after fully stirring, homogeneous mixture solotion;
(3) copper sheet is cut into suitable size and puts into the solution reaction of step (2) after 30 minutes, 70 ℃ of oven dry in air, the solution reaction of putting into step (1) is after 10 minutes, take out earlier after deionized water washes repeatedly, 50 ℃ of oven dry promptly obtain the solar energy collector selective coating in air.
Embodiment 4
(1) 4-Dimethylamino pyridine (DMAP) and clorox are joined in the deionized water according to mol ratio at 4: 1, after fully stirring, get homogeneous mixture solotion, put into 40 ℃ water-bath;
(2) with ammonium persulphate, ammonium chloride, deionized water and pyridine mix according to mol ratio at 1: 1: 10, after fully stirring, get homogeneous mixture solotion;
(3) copper sheet is cut into suitable size and puts into the solution reaction of step (2) after 30 seconds, 100 ℃ of oven dry in air, the solution reaction of putting into step (1) is after 15 minutes, take out earlier after deionized water washes repeatedly, 100 ℃ of oven dry promptly obtain the solar energy collector selective coating in air.
Embodiment 5
(1) calcium hydroxide and Textone are joined in the deionized water according to mol ratio at 5: 1, after fully stirring, get homogeneous mixture solotion, put into 100 ℃ water-bath;
(2) with ammonium persulphate, ammonium chloride, deionized water and pyridine were according to mol ratio 1: 7: 50: 0.05 mixes, after fully stirring, homogeneous mixture solotion;
(3) copper sheet is cut into suitable size and puts into the solution reaction of step (2) after 30 seconds, 100 ℃ of oven dry in air, the solution reaction of putting into step (1) is after 20 minutes, take out earlier after deionized water washes repeatedly, 50 ℃ of oven dry promptly obtain the solar energy collector selective coating in air.
Embodiment 6
(1) sodium hydroxide, hydrated barta and Textone are joined in the deionized water according to mol ratio at 1: 1: 1, after fully stirring, get homogeneous mixture solotion, put into 20 ℃ water-bath;
(2) with ammonium persulphate, ammonium chloride, deionized water and pyridine were according to mol ratio 1: 10: 80: 0.01 mixes, after fully stirring, homogeneous mixture solotion;
(3) copper sheet is cut into suitable size and puts into the solution reaction of step (2) after 1 minute, 50 ℃ of oven dry in air, the solution reaction of putting into step (1) is after 60 minutes, take out earlier after deionized water washes repeatedly, 50 ℃ of oven dry promptly obtain the solar energy collector selective coating in air.
Embodiment 7
(1) sodium hydroxide, clorox and Textone are joined in the deionized water according to mol ratio at 5: 0.8: 0.2, after fully stirring, get homogeneous mixture solotion, put into 20 ℃ water-bath;
(2) with ammonium persulphate, ammonium chloride, deionized water and pyridine were according to mol ratio 1: 10: 100: 0.02 mixes, after fully stirring, homogeneous mixture solotion;
(3) copper sheet is cut into suitable size and puts into the solution reaction of step (2) after 1 minute, 50 ℃ of oven dry in air, the solution reaction of putting into step (1) is after 60 minutes, take out earlier after deionized water washes repeatedly, 50 ℃ of oven dry promptly obtain the solar energy collector selective coating in air.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification made under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (4)
1. the solar energy collector of a cheapness is characterized in that may further comprise the steps with the preparation method of selective coating:
(1) with the inorganic base of water-soluble or contain the solubility organic bases of amido and the saline oxidizing agent of water-soluble according to mol ratio 1～5: 1 joins in the deionized water, after fully stirring, homogeneous mixture solotion, the waters bath with thermostatic control of putting into 20～100 degree;
(2) with ammonium persulphate, ammonium chloride, deionized water, pyridine mixes according to mol ratio 1: 1～10: 10～100: 0～0.1, after fully stirring, gets homogeneous mixture solotion;
(3) copper sheet is cut into suitable size and puts into solution reaction that step (2) obtains after 10 seconds～30 minutes, through 50～100 degree oven dry, putting into the solution that step (1) obtains immediately reacted 5～60 minutes, reaction back is taken out earlier through deionization repeatedly after the water flushing, 50～100 degree oven dry promptly obtain this selective coating in air.
2. the solar energy collector of a kind of cheapness according to claim 1 selective coating preparation method, it is characterized in that: in the step (1), the mineral alkali of described water-soluble is selected from sodium hydroxide, potassium hydroxide, hydrated barta, lithium hydroxide, calcium hydroxide etc., the described organic bases that contains amido is selected from ammoniacal liquor, thanomin, diethanolamine, trolamine, one of in the 4-Dimethylamino pyridine etc. or two kinds and more than.
3. the solar energy collector of a kind of cheapness according to claim 1 selective coating preparation method, it is characterized in that: in the step (1), the saline oxidizing agent of described water-soluble is selected from clorox, one or both in the Textone.
4. the solar energy collector of a kind of cheapness according to claim 1 selective coating preparation method, it is characterized in that: in the step (3), described copper sheet is a brass, one or both in the red copper.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103226989A (en) * | 2012-01-30 | 2013-07-31 | 比亚迪股份有限公司 | Corrosive carrier, preparation method thereof, crystalline silicon solar battery front/back side silver conductive paste and preparation method thereof |
| CN103772727A (en) * | 2013-11-08 | 2014-05-07 | 长兴化学工业股份有限公司 | Passivation composition and application thereof |
| CN106835110A (en) * | 2017-01-23 | 2017-06-13 | 海南省环境科学研究院 | A kind of environment-friendly type antiradar reflectivity membrane material and preparation method thereof |
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2010
- 2010-12-15 CN CN2010105899699A patent/CN102080227A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103226989A (en) * | 2012-01-30 | 2013-07-31 | 比亚迪股份有限公司 | Corrosive carrier, preparation method thereof, crystalline silicon solar battery front/back side silver conductive paste and preparation method thereof |
| CN103226989B (en) * | 2012-01-30 | 2016-01-06 | 比亚迪股份有限公司 | Corrosivity carrier and preparation method, crystal silicon solar energy battery just/back silver electrocondution slurry and preparation method |
| CN103772727A (en) * | 2013-11-08 | 2014-05-07 | 长兴化学工业股份有限公司 | Passivation composition and application thereof |
| CN103772727B (en) * | 2013-11-08 | 2016-10-05 | 长兴材料工业股份有限公司 | Passivation composition and application thereof |
| CN106125414A (en) * | 2013-11-08 | 2016-11-16 | 长兴材料工业股份有限公司 | Passivation composition and application thereof |
| CN106835110A (en) * | 2017-01-23 | 2017-06-13 | 海南省环境科学研究院 | A kind of environment-friendly type antiradar reflectivity membrane material and preparation method thereof |
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