WO2007015670A1 - Nickel-alumina coated solar absorbers - Google Patents
Nickel-alumina coated solar absorbers Download PDFInfo
- Publication number
- WO2007015670A1 WO2007015670A1 PCT/SE2006/050119 SE2006050119W WO2007015670A1 WO 2007015670 A1 WO2007015670 A1 WO 2007015670A1 SE 2006050119 W SE2006050119 W SE 2006050119W WO 2007015670 A1 WO2007015670 A1 WO 2007015670A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- solar
- nickel
- solar absorber
- alumina
- Prior art date
Links
- 239000006096 absorbing agent Substances 0.000 title claims abstract description 67
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 77
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 238000001228 spectrum Methods 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 59
- 230000005855 radiation Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 aluminum ions Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/10—Details of absorbing elements characterised by the absorbing material
- F24S70/12—Details of absorbing elements characterised by the absorbing material made of metallic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
- F24S70/25—Coatings made of metallic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
- F24S70/225—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption for spectrally selective absorption
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Definitions
- the present invention relation in general to thermal solar collector systems and in particular to spectrally selective coated solar absorbers.
- solar energy systems have been become more and more commercially interesting.
- the huge amount of solar radiation that is potentially available on the earth constitutes a practically unlimited source of energy.
- One alternative to make use of the solar energy is to use thermal solar collector systems.
- One very important component of a solar collector system is typically the solar thermal collector.
- Two collector types are dominating the market today, flat-plate types and vacuum tube types.
- the most important part of both constructions is the absorber, which converts solar radiation into heat using photo-thermal conversion. Absorbed heat is typically transferred to a liquid or gaseous medium, which flows through a tube connected to the absorber. Losses are caused by convection, radiation and conduction. Convection and conduction are reduced by covering the absorbers with transparent glazing and insulating the collector box, respectively. Radiation losses can be reduced by manipulating the absorber surface.
- absorbers are constructed as fin absorbers and consist of a metal plate that has a good heat conductivity and high infrared reflectance such as aluminum or copper.
- the plate is preferably coated with a thin surface layer that is spectrally selectively absorbing.
- An ideal absorber should absorb all solar radiation but avoid losing the absorbed energy as infrared radiation, i.e. heat.
- an absorber having a substrate covered by a two thin layers is investigated.
- the first layer covering the substrate consists of nickel nano- particles embedded in a dielectric matrix of alumina.
- the optimal coating had a solution nickel content of 65 volume percent, a thickness of 0.1 ⁇ m and a particle size of around 10 nm.
- the outermost layer is an anti-reflection layer.
- the bare first layer provided a normal solar absorptance of 0.83 and a normal thermal emittance of 0.03.
- the solar absorptance could be increased to a maximum of 0.92.
- the optimum anti-reflection layer was found to be an alumina layer, while silica and hybrid silica anti-reflection layers provided absorptances of 0.90-
- alumina can not withstand necessary accelerated ageing tests and can therefore not be used in a commercial product.
- a general problem with prior art solar absorbers is that they still exhibit undesired high radiation losses.
- a further problem with prior art solar absorbers is that production costs are too high.
- Yet a further problem is that the manufacturing process of leading commercially available solar thermal absorbers utilizes vacuum techniques which are complicated and costly.
- a general object of the present invention is therefore to provide improved solar absorbers, in particular concerning absorptance.
- a further object of the present invention is to provide such improved solar absorbers allowing for cost efficient and environmentally friendly manufacturing.
- Yet a further object is to provide solar absorbers which allow manufacturing avoiding vacuum techniques.
- a solar absorber has a substrate covered with at least three thin layers.
- the outermost layer is preferably an anti-reflection layer.
- the most inner layer is composed by nickel nano-particles embedded in a dielectric matrix of alumina, with an aluminum to nickel atomic ratio between 0.15-0.25, and preferably between 0.18-0.23.
- the second layer consists of nano-particles embedded in a dielectric matrix of alumina, here with an aluminum to nickel atomic ratio between 0.8-1.2.
- the innermost layer has in preferred embodiments a thickness of 68-98 nm, while the second layer has a thickness of 50-80 nm.
- the nickel particles have a preferred average diameter of 5-10 nm.
- the anti- reflection layer has in preferred embodiments a refractive index in the solar spectrum wavelength interval of 1.38-1.46, e.g. silica or hybrid silica, with a thickness of 48-78 nm.
- One advantage with the present invention is that a solar absorber with an unexpectedly high absorptance is achieved, where the loss in absorbed incoming solar radiation limited to 3%, i.e. about one third compared to previous similar systems and considerably lower than what was expected to be possible to achieve. Furthermore, the manufacturing can be performed in a cost efficient and environmentally friendly manner in ambient pressure.
- FIG. 1 is a schematic drawing of a typical thermal solar system
- FIG. 2 is a schematic drawing of a cross-section of a typical flat plate solar collector
- FIG. 3 is a diagram illustrating the solar intensity distribution and blackbody emission
- FIG. 4 is a schematic drawing of a cross section of an embodiment of a solar absorber according to the present invention
- FIG. 5 is a diagram illustrating reflectance measurement results for an absorber according to the present invention and for an absorber according to prior art.
- Fig. 1 illustrates a typical thermal solar system 50, in which a solar collector 20 according to the present invention can be utilised.
- the sun 41 emits solar radiation 40, which falls onto the solar collector 20.
- a liquid or gaseous medium is pumped by a pump 30 through an inlet pipe 31 to the solar collector 20, where heat generated by the solar radiation 40 heats the liquid or gaseous medium.
- the heated liquid or gaseous medium is transferred by an outlet pipe 32 to a heat exchanger tank 33.
- a heat exchanger 34 a part of the heat content of the liquid or gaseous medium is transferred to a liquid or gaseous medium of the tank 33, before the liquid or gaseous medium is returned to the solar collector 20.
- a second heat exchanger 35 uses the heat content of the liquid or gaseous medium in the exchanger tank 33 to heat water input by an inlet pipe 37.
- the heated water is provided in an outlet pipe 36 to be used for any purpose.
- Fig. 2 illustrates an embodiment of a flat plate solar collector 20, in which an absorber according to the present invention advantageously can be used.
- the solar collector 20 comprises a housing 22 comprising a number of solar absorbers 1.
- the solar absorbers 1 are in conductive contact with tubes 25 for the heat medium.
- the solar absorbers 1 are typically insulated thermally from the housing 22 by insulation material 23. Convection from the solar absorbers 1 is prevented by the provision of a transparent glazing 21 above the solar absorbers 1 , creating an air gap 24 of essentially non-flowing air.
- Fig. 3 depicts a diagram illustrating the solar intensity distribution as a curve 100. In order to utilise the available energy in an optimal manner, the absorptance of a solar absorber surface should be high within an interval 104.
- a surface coating having a high reflectance in a wavelength interval 105 can thereby minimize the emitted thermal radiation.
- Blackbody emittance distributions corresponding to 100 0 C, 200 0 C and 300°C are represented by curves 101, 102 and 103, respectively.
- a spectrally selective solar absorber therefore ideally has a high absorptance in the interval 104 and a high reflectance in the interval 105.
- Fig. 4 illustrates a presently preferred embodiment of a solar absorber 1 according to the present invention.
- a substrate 2 is covered by a first 11 , a second 12 and a third 13 layer.
- the first 11 and second 12 layers are main absorption layers, while the third layer 13 acts as an anti-reflection and protection layer.
- the substrate 2 is in this embodiment made of aluminium, but other substrates having good heat conductivity and high infrared reflectance may also be used, e.g. copper or stainless steel.
- the first layer 11 comprises nickel nano-particles embedded in a dielectric matrix of alumina.
- the performance of the solar absorber 1 is relatively sensitive to the aluminum to nickel atomic ratio.
- a preferred aluminum to nickel atomic ratio is 0.2.
- the thickness Dl of the first layer 11 is within the interval 68 to 98 nm with a most preferable thickness of around 82 nm.
- Most nickel particles are in the size of 5-10 nm, whereby an average diameter of the nickel particles is in the interval of 5-10 nm.
- the particles are preferably essentially spherical.
- the second layer 12 also comprises nickel nano-particles embedded in a dielectric matrix of alumina.
- the performance of the solar absorber 1 is also in this layer relatively sensitive to the nickel content.
- a preferred aluminum to nickel atomic ratio is 0.95. In the interval 0.8-1.2 of the aluminum to nickel atomic ratio, the performance is estimated to be better than expected from prior art predictions.
- the thickness D2 of the second layer 12 is within the interval 50 to 80 nm with a most preferable thickness of 65 nm.
- most nickel particles are of the size of 5-10 nm, whereby at least an average diameter of the nickel particles is in the interval of 5-10 nm.
- the particles are preferably essentially spherical.
- the third layer 13 is an anti-reflection layer.
- anti-reflection layer Experiments have proven that pure silica and hybrid silica, described more in detail below, are useful indeed. However, also other anti-reflection materials, having the real part of the refractive index in the interval of 1.38 to 1.46, in the solar spectrum wavelength interval would operate well.
- An optimum thickness of the anti- reflection layer in the present embodiment has been found to be around 62 nm, and at least preferably within the interval of 48-78 nm.
- a three-layer structure is utilised.
- absorbers having more layers may be possible, e.g. three absorbing layers covered by an anti-reflection layer. It is then, according to the present invention, useful to have an innermost layer having the above discussed composition.
- the outermost layer in a three-layer configuration may be used also for absorption purposes. Either, the configuration operates without any anti-reflection layer, or the outermost layer could be a layer that simultaneously acts as an anti-reflection layer with regards to the underlying layers and as an absorbing layer as such.
- the two inner layers of the presented embodiments of the present invention are based mainly on the dielectric matrix of alumina with embedded nickel particles. However, this dielectric matrix may be modified or altered by adding or changing to other elements or compounds. The dielectric matrix may for example be composed of silica or titania instead of alumina or any combination of these matrix materials. Likewise, it is also possible to tune the properties by adding or changing to particles of other elements or compounds. Possible particle elements are C, Al, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag or Sn or combinations of these elements. In particular, having an alumina matrix,
- Mg, Ca, Ti, Mn, Ni, Zn, or Sn or combinations of these elements could be useful and also C could be a possible particle candidate.
- silica matrices Al, Mg, Ca, Ti, Mn, Fe, Co, Zn, Ag or Sn or combinations of these elements could be useful.
- the aluminum to nickel atomic ratio in the first layer should be kept within the interval of 0.15-0.25.
- other intervals are applicable, which have to be determined from combination to combination.
- the absorber of the embodiment of Fig. 4 was produced in three steps. First, the substrate was coated with a solution containing nickel and aluminum ions. First, an aluminum precursor solution and a nickel precursor solution were prepared, which subsequently were mixed in the requested ratio. The mixed solution was spin-coated onto the substrate. The coated substrate was then subjected to a heat treatment, forming the first absorbing layer. The heat treatment was performed in an oxygen-free atmosphere in order to reduce the nickel ions into metallic nickel. In the heat treatments for the performed test absorbers, nitrogen gas was flowing over the surface during the heat treatment. The temperature was gradually increased up to a maximum temperature of 450- 580 0 C, in order to remove residual organic groups completely.
- the first two absorbing nickel-alumina layers may though be heated differently. In order to save energy, time and money it could be sufficient to heat them to a lower temperature and do the final high temperature heat treatment when the last anti-reflection layer is added. Alternatively the first two absorbing nickel-alumina layers could simply be cured with UV-light before a final high temperature heat treatment is done with the anti- reflection layer.
- a second layer was deposited on top of the first layer as a solution of a different concentration of nickel and aluminum ions, followed by a heat treatment, in analogy with the fabrication of the first layer.
- silica or hybrid silica anti-reflection layer selected for the test absorbers is based on a sol-gel approach, known as such in prior art. There are a number of different solution based procedures to create silica or hybrid silica but the employed method for the test absorbers was the following.
- TEOS Tertraethoxysilane
- MTES methyltrietoxysilane
- T. Bostr ⁇ m et al. "Solution-chemical derived nickel-alumina coatings for thermal solar absorbers", Solar energy 74 (2003) pp. 497-503.
- T. Bostr ⁇ m et al. "Anti reflection coatings for solution-chemically derived nickel-alumina solar absorbers", Solar energy materials and solar cells, vol. 84, Issues 1-4, October 2004, pp. 183-191.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2006800286055A CN101273238B (en) | 2005-08-02 | 2006-05-12 | Nickel-alumina coated solar absorbers |
CA002617667A CA2617667A1 (en) | 2005-08-02 | 2006-05-12 | Nickel-alumina coated solar absorbers |
US11/997,777 US20080210219A1 (en) | 2005-08-02 | 2006-05-12 | Nickel-Alumina Coated Solar Absorbers |
EP06733489.6A EP1920199B1 (en) | 2005-08-02 | 2006-05-12 | Method for producing nickel-alumina coated solar absorbers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE0501773A SE530464C2 (en) | 2005-08-02 | 2005-08-02 | Nickel alumina coated solar absorber |
SE0501773-6 | 2005-08-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007015670A1 true WO2007015670A1 (en) | 2007-02-08 |
Family
ID=37708914
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/SE2006/050119 WO2007015670A1 (en) | 2005-08-02 | 2006-05-12 | Nickel-alumina coated solar absorbers |
Country Status (6)
Country | Link |
---|---|
US (1) | US20080210219A1 (en) |
EP (1) | EP1920199B1 (en) |
CN (1) | CN101273238B (en) |
CA (1) | CA2617667A1 (en) |
SE (1) | SE530464C2 (en) |
WO (1) | WO2007015670A1 (en) |
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EP2098805A2 (en) * | 2008-03-07 | 2009-09-09 | Tsing Hua University | Solar collector and solar heating system using same |
JP2009216376A (en) * | 2008-03-07 | 2009-09-24 | Qinghua Univ | Solar heat collector and solar heat collecting system using the same |
JP2009257749A (en) * | 2008-04-11 | 2009-11-05 | Qinghua Univ | Solar collector and solar heating system using same |
CN101922816A (en) * | 2010-07-14 | 2010-12-22 | 北京航空航天大学 | Solar selective absorbing coating and preparation method thereof |
CN101666557B (en) * | 2008-09-01 | 2011-12-14 | 北京有色金属研究总院 | Non-vacuum solar spectrum selective absorption film and preparation method thereof |
US8561603B2 (en) | 2008-04-18 | 2013-10-22 | Tsinghua University | Solar collector and solar heating system using same |
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Also Published As
Publication number | Publication date |
---|---|
CN101273238B (en) | 2010-04-07 |
CA2617667A1 (en) | 2007-02-08 |
US20080210219A1 (en) | 2008-09-04 |
SE0501773L (en) | 2007-02-03 |
CN101273238A (en) | 2008-09-24 |
EP1920199B1 (en) | 2015-01-14 |
SE530464C2 (en) | 2008-06-17 |
EP1920199A4 (en) | 2012-10-03 |
EP1920199A1 (en) | 2008-05-14 |
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