CN100486904C - Visible light responsive photocatalytic reactor using lithium battery and solar battery as power supply unit - Google Patents
Visible light responsive photocatalytic reactor using lithium battery and solar battery as power supply unit Download PDFInfo
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- CN100486904C CN100486904C CNB200610040057XA CN200610040057A CN100486904C CN 100486904 C CN100486904 C CN 100486904C CN B200610040057X A CNB200610040057X A CN B200610040057XA CN 200610040057 A CN200610040057 A CN 200610040057A CN 100486904 C CN100486904 C CN 100486904C
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 title claims description 40
- 239000000463 material Substances 0.000 claims abstract description 56
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 239000010408 film Substances 0.000 claims description 118
- 239000000758 substrate Substances 0.000 claims description 84
- 239000010409 thin film Substances 0.000 claims description 38
- 238000007146 photocatalysis Methods 0.000 claims description 27
- 239000011521 glass Substances 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004146 energy storage Methods 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 26
- 239000002184 metal Substances 0.000 abstract description 26
- 230000005611 electricity Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract 2
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- 235000020188 drinking water Nutrition 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 210000004027 cell Anatomy 0.000 description 27
- 238000004544 sputter deposition Methods 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 229910052738 indium Inorganic materials 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 14
- 238000000151 deposition Methods 0.000 description 12
- 238000005245 sintering Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000004549 pulsed laser deposition Methods 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 iron ion Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
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- 235000020679 tap water Nutrition 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
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- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
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- 229910001430 chromium ion Inorganic materials 0.000 description 1
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- 239000005357 flat glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Classifications
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a brand new light-catalytic reactor which employs visible light in sunlight as energy and works all day long. The reactor mainly comprises energy-supply device composed with lithium battery and solar batter and visible light catalytic reactor. The said solar battery is component-gradual change film membrane type, the photoelectric transformation efficiency is high, and the transformed electricity is stored in lithium battery. The light catalytic reactor employs componet gradual change film membrane embedded with metal nanometer group as light-catalytic material, which can make full use of sunlight; said reactor uses sunlight directly for light-catalytic reaction, and it will be supplied with power by energy-supply device to ensure its normal operation when there is no sunlight and when it is in the night. The reactor is suitable to be used for treatment of wastewater containing natural or artificical non-degradable organic substance or deep treamtment of drinking water.
Description
Technical field
The present invention relates to solar visible light catalyticreactor and preparation method thereof, especially a kind of photo catalysis reactor that can rely on sun power realization all weather operations fully and preparation method thereof.
Background technology
Photochemical catalytic oxidation is a kind of high-level oxidation technology that is risen the seventies in last century, have advantages such as pollutant removal is good, reaction conditions is gentle, simple to operate, applied widely, be widely used in natural hardly degraded organic substances such as containing the algae toxin, perhaps poisonous, the processing of persistent organic pollutant wastewater of dyestuff, Organohalogen compounds, sterilant or synthetic and the advanced treatment of tap water.
At present, investigators have developed polytype photo catalysis reactor, and wherein most of reactors adopt all that catalytic performance is good, chemical stability good, nontoxic no burn into cost is low and have TiO than the long life
2As photocatalyst material, light source is sunlight or ultra-violet lamp.According to TiO
2Catalyzer have form, a TiO
2Photo catalysis reactor can be divided into two kinds of suspensoid reactor and fixed-bed reactor.
TiO in the suspensoid reactor
2Exist with powdered form, the catalyzer of this form has bigger specific surface area, but exist to handle the back separation difficulty, easily causes secondary pollution and easily condenses inactivation, causes defectives such as working cost is higher; There is the investigator on the basis of suspended powder catalyzer, to do improvement, with TiO
2Catalyzer is fixed on the inert support, and carrier commonly used has the hollow bead of glass, ceramic element or magnetic ball etc., under the effect in current or magnetic field, load TiO
2The carrier of catalyzer is in suspended state in reactor, avoided TiO simultaneously in the purpose that has reached the processing pollutent
2A series of problems such as difficult separation and recycling.
In the fixed bed photocatalytic reactor, TiO
2Often be fixed on the carriers such as Stainless Steel Cloth, glass fiber mesh, activated carbon fiber net, sheet glass, glass tube walls, reactor wall, ultraviolet lamp tube wall, these carriers are fixed in the reactor, by the irradiation realization light-catalyzed reaction of sunlight or ultra-violet lamp.
But no matter be the suspension type or the TiO of fixed
2All there is the common limitation in photo catalysis reactor, and this is because TiO
2The energy band structure characteristics have determined it to be excited by the ultraviolet radiation of wavelength X＜387.5nm, and the UV-light part that is radiated ground only accounts for 4%～6% of sunlight, make solar energy utilization rate very low, when no sunlight, need to consume the works better that extra electric energy just can be kept reactor simultaneously.
In order effectively to utilize sun power, investigator to develop the photocatalyst material that the visible light in the sunlight is produced response, wherein a class visible light responsive photocatalytic material is to TiO commonly used at present
2Carry out doping vario-property or carry out the photosensitization processing.Doping vario-property material commonly used has neodymium ion, lanthanum ion, iron ion, chromium ion, ruthenium ion, vanadium ion, silver ions and gold, phosphorus, nitrogen etc., and photosensitizer has xanthene, CdS, MoS
2, WS
2, copper phthalocyanine, thionine etc.; An other class visible light responsive photocatalytic material mainly comprises Bi
12GeO
20, α-Fe
2O
3, Bi
2WO
6, RbBiNb
5O
16, RbBiNb
2O
7, CaBi
2O
4, TiP
2O
7/ C mixture, unformed micropore metal oxide compound, MIn
2O
4(M=Ca, Sr, Ba), In
2BiTaO
7, Ga
2BiTaO
7Deng, known visible light film catalytic material has ZnO film, ZnFe
2O
4Film and pucherite film etc.But visible light film light catalyticreactor is but rarely reported, utilizes the content gradually variational film type photo catalysis reactor of visible light realization round-the-clock running in the sunlight to yet there are no report simultaneously fully.
In sum, the visible light catalytic reactor that can utilize sun power to carry out all weather operations will become research focus from now on.
Summary of the invention
The objective of the invention is: at the deficiency of existing photo catalysis reactor, develop a kind of brand-new, can maximally utilise the visible light in the sunlight, thereby realize the solar energy photocatalytic reactor of all weather operations and the preparation method of critical material thereof, this reactor can be widely used in and contain natural or synthetic is poisonous, the advanced treatment of the processing of hardly degraded organic substance waste water or tap water.
The object of the present invention is achieved like this:
With lithium cell and solar cell is the visible light responsive photocatalytic reactor of power supply device, is provided with film on substrate, and the concrete component of described film catalytic material is CaIn
2O
4, BaIn
2O
4Or SrIn
2O
4The present invention contains three kinds to visible light-responded single-phase film composition, i.e. CaIn
2O
4/ BaIn
2O
4/ SrIn
2O
4And content gradually variational.The film catalytic material is embedded with metal nanometer cluster Ag or Ni.
The single-phase thin-film material of three components is bulk or strip, and geometrical dimension is: the width of the monophasic strip film of each component is 1～15cm;
Film composition replaces gradual change, and the film thickness size is 3～18 microns.
Substrate material is transparent substrate materials such as quartzy and glass.
Be provided with solar photocell and energy storage lithium ion battery simultaneously, use with the visible light catalytic combination of reactors, base material is quartz or glass rotating cylinder.
The photo catalysis reactor structure is that the quartz or the glass rotating cylinder that are provided with the film catalytic material constitute photo catalysis reactor, be provided with the lattice that flap constitutes, one of every lattice installation photochemical catalysis quartz or glass rotating cylinder, every inner xenon lamp of installing of tube, under no daylight and night situation, xenon lamp is lighted by solar cell and the power supply of energy storage lithium ion battery, and rotating cylinder drives by solar cell and energy storage lithium ion battery drive electric motor and rotates.
Solar cell adopts hull cell, and described thin film solar cell contains two or three component thin-film materials of bulk or strip splicing, and its formation is InTaO
4/ InVO
4, InNbO
4/ InVO
4Or InNbO
4/ InVO
4/ InTaO
4, and on every thin-film material adulterated al, gallium, phosphorus or arsenic atom, doping is 1～15 * 10
-6Atom; Two or three component thin-film materials are bulk or strip, and geometrical dimension is: the width of the monophasic strip film of each component is 1～15cm.
The present invention is novel visible-light response type content gradually variational film solar photocell and preparation method thereof.Photocell thin-film material component of the present invention is InTaO
4/
InNbO
4/ InVO
4Or InNbO
4/ InVO
4/ InTaO
4, utilize the photocell electricity conversion of above-mentioned film preparation to be respectively 2.13%, 2.24% and 2.61%, and by single component film InTaO
4, InNbO
4And InVO
4The photronic electricity conversion of preparation is respectively 1.09%, 1.14% and 1.62%, as can be seen by the photronic electricity conversion of content gradually variational film preparation greater than photronic electricity conversion by the single component film preparation, therefore can effectively utilize sun power more.
The present invention has the following advantages: at first, photo catalysis reactor has adopted embedding metal nanometer cluster content gradually variational film type visible light responsive photocatalytic material, this film catalytic material has avoided conventional fine catalyst to be difficult to the shortcoming of Separation and Recovery, this film is a content gradually variational type film simultaneously, can utilize the visible light in the sunlight more fully, improved utilising efficiency to sunlight, the metal nanometer cluster that is embedded at the content gradually variational single thin film simultaneously can form doped energy-band, promptly in content gradually variational single thin film forbidden band, introduced new energy level, thereby under radiation of visible light transition of electron become two the step or multistep carry out, light activated threshold value decreases; In addition, also make the less photon energy of energy excite the light induced electron and the photohole of catching on the doped energy-band, improve the utilization ratio of photon, the metal nanometer cluster that embeds can also increase the productive rate of light induced electron and photohole, prolong the life-span of light induced electron and photohole, and then inhibition light induced electron and photohole is compound, expansion content gradually variational single thin film is to the spectral response range of visible light, thus the efficient of organic pollutants such as raising content gradually variational single thin film photocatalyst material degraded water body inner dye; Second, the power supply device that adopts solar cell and lithium battery to form, overcome the shortcoming that general sunlight catalytic reactor can not move or need the consumption additional electrical energy to move when no sunlight, in energy-conservation, guaranteed the round-the-clock works better of reactor; The 3rd, the solar cell among the present invention has adopted the content gradually variational film material, has the visible light and the electricity conversion advantages of higher that can make full use of in the sunlight simultaneously.
Description of drawings
Fig. 1 is content gradually variational film synoptic diagram (left side is three component synoptic diagram, and the right side is two component synoptic diagram)
Fig. 2 is the photo catalysis reactor structural representation
A rotating cylinder catalytic unit B visible lamp C flap D content gradually variational single thin film
Fig. 3 is used mask synoptic diagram
Fig. 4 is photo catalysis reactor and solar cell combination utilization structure synoptic diagram
Embodiment
As shown in Figure 1, photocatalysis thin film and solar battery thin film structure are the component splicing, and the solar visible light catalyticreactor is provided with the film catalytic material at substrate, and its concrete component is CaIn
2O
4, BaIn
2O
4And SrIn
2O
4, contain three kinds to visible light-responded component, be specially CaIn
2O
4/ BaIn
2O
4/ SrIn
2O
4, three kinds of components are according to the said sequence gradual change.The film catalytic material is embedded with metal nanometer cluster Ag or Ni.1,2,3 respectively corresponding photocell InNbO wherein
4/ InVO
4/ InTaO
4Or the CaIn of film catalyticreactor
2O
4/ BaIn
2O
4/ SrIn
2O
4, as have only two kinds of splicings, 1 and 2 corresponding respectively InNbO
4/ InVO
4Or InTaO
4/ InVO
4Two kinds of connecting methods.
Photo catalysis reactor (see figure 2) structure is a flap type structure, by flap reactor is divided into some lattice, the base material of the used film catalytic material of catalyticreactor is quartz or glass rotating cylinder, at every lattice of reactor one of photochemical catalysis quartz or glass rotating cylinder is installed, every inner xenon lamp of installing of rotating cylinder, under no daylight and night situation, xenon lamp is lighted by solar cell and the power supply of energy storage lithium ion battery.Rotating cylinder drives by solar cell and energy storage lithium ion battery drive electric motor and rotates.
Photo catalysis reactor adopts visible-light response type content gradually variational film catalytic material, and this film is with CaIn
2O
4/ BaIn
2O
4/ SrIn
2O
4Be embedded with the film of metal nanometer cluster Ag or Ni for base.
CaIn
2O
4, BaIn
2O
4And SrIn
2O
4Adopt the preparation of solid state reaction synthetic method.Its preparation technology is: respectively with In
2O
3And CaCO
3, In
2O
3And BaCO
3, In
2O
3And SrCO
3Behind the thorough mixing, under the normal pressure in electric furnace sintering, then at 900 ℃ of following sintering 12h, through pulverizing and compression moulding, again at 1050 ℃ of following sintering 12h.
The used content gradually variational film of above-mentioned photo catalysis reactor has two kinds of preparation technologies, the one, prepare with mask technique by multi-target magnetic control sputtering: select different substrate materials, in the mixed gas of argon gas and oxygen, carry out magnetic control co-sputtering as target with pure metal In and Ca, In and Sr, In and Ba; The 2nd, adopt pulsed laser deposition deposition and mask technique preparation, work atmosphere is an argon gas, distinguishes cosputtering CaIn at the same time
2O
4, BaIn
2O
4And SrIn
2O
4Target.Then deposition is a base with the content gradually variational single thin film on substrate, adopt the vacuum magnetic-control sputtering method, with metal A g or Ni is target, embed metal nanometer cluster Ag or Ni on film catalytic material surface, with this film in nitrogen comparatively high temps (100～300 ℃) following thermal treatment for some time (0.5～3h), make it crystallization and obtain required film.
The solar battery thin film structure is the component splicing, the upper surface that is provided with electrode and solar battery thin film, solar cell on substrate is provided with electrode, described thin film solar cell contains two or three component thin-film materials of bulk or strip splicing, and its formation is InTaO
4/ InVO
4, InNbO
4/ InVO
4Or InNbO
4/ InVO
4/ InTaO
4, and on every kind of thin-film material adulterated al, gallium, phosphorus or arsenic atom, doping is 1～15 * 10
-6Atom.The present invention is provided with two or three component thin-film materials, is bulk or strip, and geometrical dimension is: the width of the strip film of each component is 1～15cm.Two or three component thin-film materials are content gradually variational films, and are visible-light response type.
This content gradually variational film gauge is 3～18 microns.
The substrate material of solar cell is selected quartz, pottery, glass, YSZ single-crystal substrate, Si base substrate or polymkeric substance etc., can grow on the substrate ITO or other electrode materialss for use.
The preparation method of solar cell adopts ion implantation or chemical diffusion method to thin-film material doping trivalent or pentavalent atom; The vacuum plating ITO or the silk screen print method printing conductive utmost point are adopted in the preparation of electrode, and it is characterized in that preparing the required target of photronic thin-film material is InTaO
4, InVO
4, InNbO
4Deng compound.Above-mentioned solar cell component film with gradually variable has two kinds of preparation technologies, the one, prepare with mask technique by multi-target magnetic control sputtering: select different substrate materials, in the mixed gas of argon gas and oxygen, carry out magnetic control co-sputtering as target with pure metal In and Ta, In and Nb, In and V; The 2nd, adopt pulsed laser deposition deposition and mask technique preparation: with InVO
4, InTaO
4And InNbO
4As target, work atmosphere is an argon gas, control laser splash deposition time, and pulsed laser power density is 5～60mJ/mm
2, deposition component gradual change single thin film on substrate.Concrete preparation method: at first target, substrate and substrate are placed in the sputtering chamber, are provided with the nib of two to three switchings on mask, a nib is opened during every kind of target material sputter, and other one to two nib is covered.When preparing three component thin-film materials, InVO
4At InNbO
4And InTaO
4The centre.
The used target InTaO of solar cell among the present invention
4, InVO
4, InNbO
4Preparation be with In
2O
3And M
2O
5(M=V, Ta, Nb) is starting material, behind thorough mixing, put into the aluminium sesquioxide crucible, in air under the normal pressure in electric furnace sintering, the compound target adopts the method preparation of solid phase synthesis, at 800～1200 ℃ of following sintering 12～24h, through pulverizing, granulation, compression moulding, again at 1100 ℃ of following sintering 24h.
Application example
The film catalytic material preparation method that content gradually variational film and photo catalysis reactor adopted that being used among the present invention prepares solar cell is multi-target magnetic control sputtering, pulsed laser deposition deposition and mask technique, prepared film is the content gradually variational single thin film, be that the single thin film different zones is made up of the single-phase of different components, this structure can make full use of the response characteristic of the single-phase film of different components to the different wave length visible light, improves the utilization ratio to visible light in the sunlight.Wherein, the content gradually variational film that can be used for preparing solar cell has three kinds, and three kinds of thin film compositions Wei InTaO
4/ InVO
4, InVO
4/ InNbO
4, InNbO
4/ InVO
4/ InTaO
4, utilize the photocell electricity conversion of above-mentioned film preparation to be respectively 2.13%, 2.24% and 2.61%, and by single component film InTaO
4, InNbO
4And InVO
4The photronic electricity conversion of preparation is respectively 1.09%, 1.14% and 1.62%, as can be seen by the photronic electricity conversion of content gradually variational film preparation greater than photronic electricity conversion by the single component film preparation, therefore can effectively utilize sun power more.The used film catalytic material of photo catalysis reactor is the content gradually variational film that is embedded with metal nanometer cluster, and its component is CaIn
2O
4/ BaIn
2O
4/ SrIn
2O
4, embedded metal nanometer cluster component is pure metal Ag or Ni.Being used to prepare novel thin film photocatalyst material that the content gradually variational film material and the photo catalysis reactor of solar cell adopted and preparation method thereof is the main points of this invention.
One, is used to prepare the synthetic method of the content gradually variational film material of solar cell
1, with the high-purity reagent In of stoichiometric ratio weighing
2O
3And M
2O
5(M=V, Ta, Nb) behind thorough mixing, puts into the aluminium sesquioxide crucible, in air under the normal pressure in electric furnace sintering, adopt the method preparation of solid phase synthesis; At 800～1200 ℃ of following sintering 12～24h,,, make required compound target InTaO again at 1100 ℃ of following sintering 24h through pulverizing, granulation, compression moulding
4, InVO
4, InNbO
4
2, adopt the multi-target magnetic control sputtering technology to prepare the content gradually variational single thin film
The mask that is adopted in this technology and the following technology is the novel mask of self-control, and as shown in Figure 3, all nibs concentrate on a slice mask, seamless closely continuous between each nib, during use, at first first nib is opened other nib sealings, carry out the sputter of first kind of component, treat after operation is finished next nib to be opened, the sputter of second kind of component is carried out in other nib sealings, the rest may be inferred, can guarantee that like this different components has associativity preferably between single-phase.
2.1 InTaO
4/ InVO
4The preparation of film
1) at first target, substrate and substrate are placed in the sputtering chamber, substrate is placed on the central authorities of substrate;
2) adopt the self-control mask, mask is placed on the substrate, and mask covers substrate fully, opens nib 1 and closes nib 2 and 3 simultaneously;
3) with screw and compressing tablet mask is pressed on the substrate; Substrate is placed on the pallet, closes sputtering chamber; Be evacuated to 1.0～2.0 * 10
-5Pa;
4) add argon gas, air pressure is 0.5Pa;
5) build-up of luminance, aerating oxygen is controlled argon gas and oxygen flow ratio and is 4:1 then, or 1:2, or 3:2, and sputter pure metal targets In and Ta, sputtering power are 20～40W, thus control target as sputter speed;
6) the beginning plated film, makes InTaO at the control plated film time
4Film;
7) opening door, close nib 1 and 3 and open nib 2 simultaneously, is that target repeats aforesaid operations with pure metal In and V, makes InVO
4Film;
8) make content gradually variational film InTaO by above-mentioned technology
4/ InVO
4
2.2 InNbO
4/ InVO
4The preparation of film
1) at first target, substrate and substrate are placed in the sputtering chamber, substrate is placed on the central authorities of substrate;
2) adopt the self-control mask, mask is placed on the substrate, and mask covers substrate fully, opens nib 1 and closes nib 2 and 3 simultaneously;
3) with screw and compressing tablet mask is pressed on the substrate; Substrate is placed on the pallet, closes sputtering chamber; Be evacuated to 1.0～2.0 * 10
-5Pa;
4) add argon gas, air pressure is 0.5Pa;
5) build-up of luminance, aerating oxygen is controlled argon gas and oxygen flow ratio and is 4:1 then, or 1:2, or 3:2, and sputter pure metal targets In and Nb, sputtering power are 20～40W, thus control target as sputter speed;
6) the beginning plated film, makes InNbO at the control plated film time
4Film;
7) opening door, close nib 1 and 3 and open nib 2 simultaneously, is that target repeats aforesaid operations with pure metal In and V, makes InVO
4Film;
8) make content gradually variational film InNbO by above-mentioned technology
4/ InVO
4
2.3InNbO
4/ InVO
4/ InTaO
4The preparation of film
1) at first target, substrate and substrate are placed in the sputtering chamber, substrate is placed on the central authorities of substrate;
2) adopt the self-control mask, mask is placed on the substrate, and mask covers substrate fully, opens nib 1 and closes nib 2 and 3 simultaneously;
3) with screw and compressing tablet mask is pressed on the substrate; Substrate is placed on the pallet, closes sputtering chamber; Be evacuated to 1.0～2.0 * 10
-5Pa;
4) add argon gas, air pressure is 0.5Pa;
5) build-up of luminance, aerating oxygen is controlled argon gas and oxygen flow ratio and is 4:1 then, or 1:2, or 3:2, and sputter pure metal targets In and Nb, sputtering power are 20～40W, thus control target as sputter speed;
6) the beginning plated film, makes InNbO at the control plated film time
4Film;
7) opening door, close nib 1 and 3 and open nib 2 simultaneously, is that target repeats aforesaid operations with pure metal In and V, makes InVO
4Film;
8) opening door, close nib 1 and 2 and open nib 3 simultaneously, is that target repeats aforesaid operations with pure metal In and Ta, makes InTaO
4Film;
9) make content gradually variational film InNbO by above-mentioned technology
4/ InVO
4/ InTaO
4
3, adopt the pulsed laser deposition deposition technique to prepare the content gradually variational single thin film
3.1 InTaO
4/ InVO
4The preparation of film
1) at first target and substrate are placed in the vacuum chamber, target InTaO
4Be placed on the target platform, substrate is placed on the substrate table, and mask is placed on the substrate, and mask covers substrate fully, opens nib 1 and closes nib 2 and 3 simultaneously;
2) with screw and compressing tablet mask is pressed on the substrate, substrate table adopts temperature program control heating by resistance wire;
3) vacuum chamber is evacuated to 10
-4～10
-5Pa, heated substrate to 500～750 ℃ then;
4) aerating oxygen, oxygen pressure is controlled at 5～20Pa;
5) adopt the pulsed laser deposition plated film, control laser splash deposition time, pulsed laser power density is 5～60mJ/mm
2, make InTaO
4Film;
6) open door, close nib 1 and 3 and open nib 2 simultaneously, with InVO
4For target repeats aforesaid operations, make InVO
4Film;
7) make content gradually variational film InTaO by above-mentioned technology
4/ InVO
4
3.2 InNbO
4/ InVO
4The preparation of film
1) at first target and substrate are placed in the vacuum chamber, target InNbO
4Be placed on the target platform, substrate is placed on the substrate table, and mask is placed on the substrate, and mask covers substrate fully, opens nib 1 and closes nib 2 and 3 simultaneously;
2) with screw and compressing tablet mask is pressed on the substrate, substrate table adopts temperature program control heating by resistance wire;
3) vacuum chamber is evacuated to 10
-4～10
-5Pa, heated substrate to 500～750 ℃ then;
4) aerating oxygen, oxygen pressure is controlled at 5～20Pa;
5) adopt the pulsed laser deposition plated film, control laser splash deposition time, pulsed laser power density is 5～60mJ/mm
2, make InNbO
4Film;
6) open door, close nib 1 and 3 and open nib 2 simultaneously, with InVO
4For target repeats aforesaid operations, make InVO
4Film;
7) make content gradually variational film InNbO by above-mentioned technology
4/ InVO
4
3.3 InNbO
4/ InVO
4/ InTaO
4The preparation of film
1) at first target and substrate are placed in the vacuum chamber, target InNbO
4Be placed on the target platform, substrate is placed on the substrate table, and mask is placed on the substrate, and mask covers substrate fully, opens nib 1 and closes nib 2 and 3 simultaneously;
2) with screw and compressing tablet mask is pressed on the substrate, substrate table adopts temperature program control heating by resistance wire;
3) vacuum chamber is evacuated to 10
-4～10
-5Pa, heated substrate to 500～750 ℃ then;
4) aerating oxygen, oxygen pressure is controlled at 5～20Pa;
5) adopt the pulsed laser deposition plated film, control laser splash deposition time, pulsed laser power density is 5～60mJ/mm
2, make InNbO
4Film;
6) open door, close nib 1 and 3 and open nib 2 simultaneously, with InVO
4For target repeats aforesaid operations, make InVO
4Film;
7) open door, close nib 1 and 2 and open nib 3 simultaneously, with InTaO
4For target repeats aforesaid operations, make InTaO
4Film;
8) make content gradually variational film InNbO by above-mentioned technology
4/ InVO
4/ InTaO
4
Two, the preparation of photo catalysis reactor content gradually variational film catalytic material
1, utilize solid state reaction synthetic method to prepare CaIn
2O
4, BaIn
2O
4And SrIn
2O
4Target.Its preparation technology is: with the high-purity reagent In of stoichiometric ratio weighing
2O
3And CaCO
3, In
2O
3And BaCO
3, In
2O
3And SrCO
3, behind thorough mixing, put into the aluminium sesquioxide crucible, in air under the normal pressure in electric furnace sintering.At 900 ℃ of following sintering 12h, through pulverizing and compression moulding, again at 1050 ℃ of following sintering 12h.
2, adopt the pulsed laser deposition deposition technique to prepare the content gradually variational single thin film
1) at first target and substrate are placed in the vacuum chamber, target CaIn
2O
4Be placed on the target platform, substrate is placed on the substrate table, and mask is placed on the substrate, and mask covers substrate fully, opens nib 1 and closes nib 2 and 3 simultaneously;
2) with screw and compressing tablet mask is pressed on the substrate, substrate table adopts temperature program control heating by resistance wire;
3) vacuum chamber is evacuated to 10
-4～10
-5Pa, heated substrate to 500～700 ℃ then;
4) aerating oxygen, oxygen pressure is controlled at 8～25Pa;
5) adopt the pulsed laser deposition plated film, control laser splash deposition time, pulsed laser power density is 10～50mJ/mm
2, make CaIn
2O
4Film;
6) open door, close nib 1 and 3 and open nib 2 simultaneously, with BaIn
2O
4For target repeats aforesaid operations, make BaIn
2O
4Film;
7) open door, close nib 1 and 2 and open nib 3 simultaneously, with SrIn
2O
4For target repeats aforesaid operations, make SrIn
2O
4Film;
8) make content gradually variational film CaIn by above-mentioned technology
2O
4/ BaIn
2O
4/ SrIn
2O
4
9) be substrate with the above-mentioned content gradually variational film that makes; with pure metal Ag or Ni is target, is protective atmosphere with the argon gas, and non-mask covers above-mentioned film; other condition is with above operation, and making with the content gradually variational film is the film that base is embedded with nanometer Ag cluster or nanometer Ni cluster.
3, adopt the multi-target magnetic control sputtering technology to prepare the content gradually variational single thin film
1) at first target, substrate and substrate are placed in the sputtering chamber, substrate is placed on the central authorities of substrate;
2) adopt the self-control mask, mask is placed on the substrate, and mask covers substrate fully, opens nib 1 and closes nib 2 and 3 simultaneously;
3) with screw and compressing tablet mask is pressed on the substrate; Substrate is placed on the pallet, closes sputtering chamber; Be evacuated to 0.5～2.0 * 10
-5Pa;
4) add argon gas, air pressure is 0.5～1Pa;
5) build-up of luminance, aerating oxygen is controlled argon gas and oxygen flow ratio and is 4:1 then, or 1:2, or 3:2, and sputter pure metal targets Ca and In, sputtering power are 10～40W, thus control target as sputter speed;
6) the beginning plated film, makes CaIn at the control plated film time
2O
4Film;
7) opening door, close nib 1 and 3 and open nib 2 simultaneously, is that target repeats aforesaid operations with pure metal Ba and In, makes BaIn
2O
4Film;
8) opening door, close nib 1 and 2 and open nib 3 simultaneously, is that target repeats aforesaid operations with pure metal Sr and In, makes SrIn
2O
4Film;
9) make content gradually variational film CaIn by above-mentioned technology
2O
4/ BaIn
2O
4/ SrIn
2O
4
10) be substrate with the above-mentioned content gradually variational film that makes; with pure metal Ag or Ni is target, is protective atmosphere with the argon gas, and non-mask covers above-mentioned film; other condition is with above operation, and making with the content gradually variational film is the film that base is embedded with nanometer Ag cluster or nanometer Ni cluster.
This reactor (see figure 4) principle of work is as described below: reactor mainly is made up of power supply device and the content gradually variational film type photo catalysis reactor two parts that solar cell and lithium battery constitute, and connects by circuit between two portions.When sunlight is arranged, photo catalysis reactor can directly utilize visible light in the sunlight to containing natural and synthetic is poisonous, the waste water of hardly degraded organic substance or tap water are handled, simultaneously solar cell is converted into electric energy with the visible light in the sunlight and stores standbyly in lithium battery, and the circuit that has photoswitch of the visible lamp power supply of power supply device this moment in photo catalysis reactor disconnects; When not having sunlight and night, photoswitch is connected the circuit between power supply device and the reactor, by the visible lamp in the lithium battery supply terminals light catalyticreactor, guarantee that reactor can works better, under two kinds of operating modes, the power supply of the rotating cylinder catalytic unit in photo catalysis reactor all the time of solar cell and lithium cell makes this device be in the normal operation that rotary state guarantees reactor all the time.By above mode can the realization response device round-the-clock running.
Claims (6)
1, be the visible light responsive photocatalytic reactor of power supply device with lithium cell and solar cell, on the photo catalysis reactor substrate, be provided with the film catalytic material, it is characterized in that the film catalytic material contains three kinds to visible light-responded single-phase film catalyst component, i.e. CaIn
2O
4, BaIn
2O
4And SrIn
2O
4And content gradually variational; Three component thin-film materials are bulk or strip, and geometrical dimension is: the width of the monophasic strip film of every component is 1～15cm.
2, visible light responsive photocatalytic reactor according to claim 1 is characterized in that the film catalytic material is embedded with Ag nanocluster or Ni nanocluster.
3, visible light responsive photocatalytic reactor according to claim 1 and 2, the thickness that it is characterized in that the film catalytic material are 3～18 microns.
4, visible light responsive photocatalytic reactor according to claim 1 and 2 is characterized in that substrate material is quartz or glass transparent substrate material.
5, visible light responsive photocatalytic reactor according to claim 1, it is characterized in that the photo catalysis reactor structure is, the quartz or the glass rotating cylinder that are provided with the film catalytic material constitute photo catalysis reactor, be provided with the lattice that flap constitutes, one of every lattice installation quartz or glass rotating cylinder photo catalysis reactor, every inner xenon lamp of installing of glass rotating cylinder, xenon lamp is lighted by solar cell and energy storage lithium battery power supply, and the glass rotating cylinder rotates by solar cell and energy storage lithium cell drive electric motor.
7, visible light responsive photocatalytic reactor according to claim 1 and 2 is characterized in that solar cell adopts hull cell, and described thin film solar cell contains the single-phase thin-film material of two or three components of bulk or strip splicing, and its formation is InTaO
4And InVO
4, InNbO
4And InVO
4Or InNbO
4, InVO
4And InTaO
4, and on every thin-film material adulterated al, gallium, phosphorus or arsenic atom, doping is 1～15 * 10
-6Atom; The single-phase thin-film material of two or three components is bulk or strip, and geometrical dimension is: the width of the monophasic strip form film of each component is 1～15cm.
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| JP5582638B2 (en) * | 2010-02-25 | 2014-09-03 | 独立行政法人産業技術総合研究所 | Solar cell |
| CN102136372B (en) * | 2011-01-22 | 2012-11-14 | 上海联孚新能源科技有限公司 | Dye sensitized solar cell treated by ion implantation and preparation method thereof |
| CN102701316B (en) * | 2012-05-09 | 2013-07-31 | 河海大学 | Photoelectric catalysis reactor taking photocatalysis fuel battery as power supply |
| CN104591263B (en) * | 2014-12-26 | 2016-08-24 | 西安理工大学 | Ba4in2o7hydrothermal preparing process and application |
| CN104528806B (en) * | 2014-12-26 | 2016-04-06 | 西安理工大学 | Ba 4in 2o 7self-propagating combustion preparation method and application |
| CN104528871B (en) * | 2015-01-04 | 2016-05-18 | 安徽理工大学 | Solar energy photocatalytic decomposition apparatus |
| CN106941202B (en) * | 2017-04-12 | 2023-05-30 | 安徽朗越能源股份有限公司 | Low-temperature protection device and low-temperature protection method for light-operated lithium battery pack |
| CN109160649B (en) * | 2018-10-17 | 2023-10-27 | 北京科技大学 | All-weather visible light catalytic emergency water purifying cup |
| CN112108157B (en) * | 2019-06-20 | 2023-05-12 | 天津城建大学 | Ag (silver) alloy 2 S quantum dot sensitized nano leaf-shaped InVO 4 Method for producing film |
| CN110681874B (en) * | 2019-11-07 | 2022-05-31 | 西南大学 | Preparation method and hydrogen evolution application of silver-nickel nanocluster |
| CN111036238B (en) * | 2019-11-20 | 2022-08-12 | 哈尔滨理工大学 | Fe 2 O 3 /WS 2 Heterojunction photocatalyst and preparation method thereof |
| CN110980966A (en) * | 2019-12-18 | 2020-04-10 | 南京公诚节能新材料研究院有限公司 | Combined artificial aquatic weed |
| CN115259504A (en) * | 2022-08-31 | 2022-11-01 | 中国石油大学(北京) | Sewage treatment method and device |
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