CN102001835B - Method for preparing modified glass microspheres - Google Patents
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- CN102001835B CN102001835B CN 201010294898 CN201010294898A CN102001835B CN 102001835 B CN102001835 B CN 102001835B CN 201010294898 CN201010294898 CN 201010294898 CN 201010294898 A CN201010294898 A CN 201010294898A CN 102001835 B CN102001835 B CN 102001835B
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- glass microballon
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- titanium dioxide
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- 239000011521 glass Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title abstract description 5
- 239000004005 microsphere Substances 0.000 title abstract 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000010936 titanium Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 16
- 230000008313 sensitization Effects 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 11
- 238000007669 thermal treatment Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000002978 peroxides Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- 238000001935 peptisation Methods 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 10
- 238000000149 argon plasma sintering Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000005337 ground glass Substances 0.000 abstract 1
- 230000001788 irregular Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a method for preparing modified glass microspheres, which comprises the steps of: firstly, coprecipitating a titanium source and a basic hydrolysis reaction solution in water, reacting to obtain a white titanium hydroxide deposit; obtaining a titanium dioxide sol precursor after carrying out washing, peptizing and aging; then carrying out hydro-thermal treatment to obtain anatase phase titanium dioxide sol; mixing the anatase phase titanium dioxide sol with glass microspheres; mill-grinding, and cooling after thermal treatment to obtain the titanium dioxide modified glass microspheres for light scattering of a dye sensitization solar battery. The finished glass microsphere product prepared by using the method for preparing the modified glass microsphere is wrapped with well-crystallized anatase phase titanium dioxide particles on the surface; and the mill-ground glass microspheres have irregular shapes, and have maximum particle diameter of about 400nm and minimum particle diameter of about 200nm, which ensures the compactness of the glass microspheres subjected to film formation.
Description
Technical field
The invention belongs to technical field of solar batteries, relate to a kind of dye sensitization solar battery scattering of light and use the modified glass microballon, especially a kind of dye sensitization solar battery scattering of light is with the preparation method of modified glass microballon.
Background technology
Titanium oxide is as a kind of important semiconductor material; In dye sensitization solar battery and photochemical catalysis association area extensive application; Improve the photoelectric properties of dye sensitization solar battery, raising light anode is one of a kind of valid approach [1] [Kuang, D. to the utilization ratio of sunshine; Wang, P.; Ito, S.; Zakeeruddin, S.M.; Gratzel, M.J.Am.Chem.Soc., 2006,128:7732-7745].Study [2,3] [2] [Barb é C.J., Arendse F. both at home and abroad; Comte P., Jirousek M., Lenzmann F.; ShkloverV.;
M., J.Am.Ceram.Soc.1997,80; 3157-3171]; [3] [
M.Chem.Lett, 2005,34 (1): 8-13] show that big particle diameter titanium oxide light scattering layer can effectively improve the photoelectric properties of battery.But it is less that each seminar prepares the research of aspect, and what high-caliber research was mainly used is the titanium dioxide powder of the 400nm of Japanese RiHui catalyst synthesis Co., Ltd.The related application of the glass microballon that uses in conjunction with present light reflecting material, the combination light reflecting material of this paper novelty and big particle diameter scattering layer have proposed a kind of preparation method of modified glass microballon of brand-new suitable used by dye sensitization solar battery with titanium dioxide powder.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art; A kind of preparation method of modified glass microballon is provided; This method is carried out ball milling through preparation TiO 2 sol and the glass microballon of choosing special requirement; The titania modified glass microballon surface that obtains is at last attached by well-crystallized's anatase phase titanium dioxide particle bag, guarantee the compactness after its film forming.
The objective of the invention is to solve through following technical scheme:
The preparation method of this modified glass microballon is characterized in that, may further comprise the steps:
1) with titanium source and the co-precipitation of basic hydrolysis liquid in water, reaction obtains white titanium hydroxide deposition, washing is deposited in the white titanium hydroxide that obtains under 30～80 ℃ then, presses Ti
4+: organic acid: the mol ratio of ydrogen peroxide 50 is 1: (2～10): peptization is carried out in (2～10), obtains the TiO 2 sol presoma behind still aging 10～16h;
2) the TiO 2 sol presoma that obtains is being obtained the xanchromatic anatase titanic oxide sol behind hydrothermal treatment consists 4～24h under 70～250 ℃ of conditions;
3) will sieve the back particle diameter between the glass microballon of 300～700nm according to 1～10g/ml and step 2) TiO 2 sol mix; Place agate jar then; Take out naturally cooling behind 240～260 ℃ of thermal treatment 1～3h behind ball milling 20～24h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
Above-mentioned steps 1) in, described titanium source is one or more mixing in titanyl sulfate, titanium sulfate and the titanium tetrachloride; Described basic hydrolysis liquid is NaOH, KOH, NaHCO
3, ammoniacal liquor or NH
4HCO
3Described organic acid is oxalic acid, Hydrocerol A, tartrate, phenylformic acid, hexanodioic acid or acetic acid.
Above-mentioned steps 3) in, the specific refractory power of said glass microballon is 1.8～2.6.
The present invention has following beneficial effect:
Utilize its surface of glass microballon finished product of the preparation method preparation of modified glass microballon of the present invention to attach by well-crystallized's anatase phase titanium dioxide particle bag; And the glass microballon out-of-shape behind the ball milling; Particle is maximum is about 400nm; Little can arrive about 200nm, and this has guaranteed the compactness after its film forming.
Description of drawings
Fig. 1 is the TEM collection of illustrative plates of glass microballon after the modification that obtains;
Fig. 2 is the high power TEM collection of illustrative plates of glass microballon after the modification that obtains.
Embodiment
Below in conjunction with embodiment the present invention is done and to describe in further detail:
Embodiment 1
1) at first after the mixed that under 15-20 ℃ by titanium ion concentration is 2mol/L, leaves standstill clarification in 12 hours with 0.1mol titanyl sulfate and water; The ammoniacal liquor co-precipitation titration of filtering back and 1mol/L is to the 200ml deionized water; When the pH value equals till 7; The white precipitate that obtains, centrifuge washing is extremely with Ba (NO
3)
2Solution detects the SO less than remnants
4 2-Till the ion, under 60 ℃, press Ti then
4+: oxalic acid: the mol ratio of ydrogen peroxide 50 is to dissolve at 1: 5: 5, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 12 hours and promptly obtains the TiO 2 sol presoma;
2) then the TiO 2 sol presoma is obtained the xanchromatic anatase titanic oxide sol in water heating kettle behind 90 ℃ of following hydrothermal treatment consists 20h;
3) be that the glass microballon of 350nm is according to 1g/ml and step 2 with median size at last) anatase titanic oxide sol mix; Wherein the specific refractory power of glass microballon is 1.8～2.6; Place agate jar then; Take out naturally cooling behind 250 ℃ of thermal treatment 2h behind the ball milling 24h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
Embodiment 2
1) at first with the TiCl of 0.1mol
4NaHCO with the 1mol/L of 400ml
3The white precipitate that obtains in the co-precipitation titration 100ml deionized water, centrifuge washing 3 times under 50 ℃, is pressed Ti then
4+:, Hydrocerol A: the mol ratio of ydrogen peroxide 50 is to dissolve at 1: 5: 6, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 12 hours and promptly obtains the TiO 2 sol presoma;
2) then the TiO 2 sol presoma is obtained the xanchromatic anatase titanic oxide sol in water heating kettle behind 250 ℃ of following hydrothermal treatment consists 4h;
3) be that the glass microballon of 350nm mixes with anatase titanic oxide sol according to 10g/ml with median size at last; Place agate jar then; Take out naturally cooling behind 250 ℃ of thermal treatment 2h behind the ball milling 24h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
Embodiment 3
1) white precipitate that at first obtains in the NaOH co-precipitation titration 200ml deionized water with the lmol/L of the titanium sulfate of 0.1mol and 400ml, centrifuge washing 3 times under 80 ℃, is pressed Ti then
4+:, tartrate: the mol ratio of ydrogen peroxide 50 is to dissolve at 1: 10: 10, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 12 hours and promptly obtains the TiO 2 sol presoma;
2) then the TiO 2 sol presoma is obtained the xanchromatic anatase titanic oxide sol in water heating kettle behind 160 ℃ of following hydrothermal treatment consists 6h;
3) at last the glass microballon of particle diameter between 300～700nm mixed with anatase titanic oxide sol according to 5g/ml; Place agate jar then; Take out naturally cooling behind 250 ℃ of thermal treatment 2h behind the ball milling 24h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
Embodiment 4:
1) at first with the titanium sulfate of 0.1mol and the NH of 200ml
4HCO
3The white precipitate that obtains in the shallow lake titration 100ml deionized water; Centrifuge washing 3 times; Then under 50 ℃; By Ti4+:, phenylformic acid: the mol ratio of ydrogen peroxide 50 is to dissolve at 1: 5: 6, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 12 hours and promptly obtains the TiO 2 sol presoma;
2) then the TiO 2 sol presoma is obtained the xanchromatic anatase titanic oxide sol in water heating kettle behind 70 ℃ of following hydrothermal treatment consists 24h;
3) at last the glass microballon of particle diameter between 300～700nm mixed with anatase titanic oxide sol according to 7g/ml; Place agate jar then; Take out naturally cooling behind 250 ℃ of thermal treatment 2h behind the ball milling 24h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
Embodiment 5:
1) white precipitate that at first obtains in the KOH shallow lake titration 100ml deionized water with the titanyl sulfate of 0.1mol and 200ml, centrifuge washing 3 times under 50 ℃, is pressed Ti then
4+:, hexanodioic acid: the mol ratio of ydrogen peroxide 50 is to dissolve at 1: 2: 2, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 12 hours and promptly obtains the TiO 2 sol presoma;
2) then the TiO 2 sol presoma is obtained the xanchromatic anatase titanic oxide sol in water heating kettle behind 120 ℃ of following hydrothermal treatment consists 8h;
3) will sieve at last the back particle diameter between 300～700nm glass microballon mix with anatase titanic oxide sol according to 4g/ml; Place agate jar then; Take out naturally cooling behind 250 ℃ of thermal treatment 2h behind the ball milling 24h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
Embodiment 6:
1) white precipitate that at first obtains in KOH titration to the 100ml deionized water with the titanium tetrachloride of 0.1mol and 200ml, centrifuge washing 3 times under 50 ℃, is pressed Ti then
4+:, acetic acid: the mol ratio of ydrogen peroxide 50 is to dissolve at 1: 4: 6, with ammoniacal liquor the pH value of this solution is adjusted to 7-8 then, leaves standstill after 16 hours and promptly obtains the TiO 2 sol presoma;
2) then the TiO 2 sol presoma is obtained the xanchromatic anatase titanic oxide sol in water heating kettle behind 120 ℃ of following hydrothermal treatment consists 8h;
3) the back median size of will sieving at last is that the glass microballon of 350nm mixes with anatase titanic oxide sol according to 2g/ml; Place agate jar then; Take out naturally cooling behind 250 ℃ of thermal treatment 2h behind the ball milling 24h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
Embodiment 7
1) with titanium source and the co-precipitation of basic hydrolysis liquid in water, reaction obtains white titanium hydroxide deposition, washing is deposited in the white titanium hydroxide that obtains under 30 ℃ then, presses Ti
4+: organic acid: the mol ratio of ydrogen peroxide 50 is to carry out peptization at 1: 5: 5, obtains the TiO 2 sol presoma behind the still aging 10h; Wherein titanyl sulfate is selected in the titanium source, and basic hydrolysis liquid is selected NaOH, and organic acid is selected oxalic acid;
2) the TiO 2 sol presoma that obtains is being obtained the xanchromatic anatase titanic oxide sol behind the hydrothermal treatment consists 24h under 100 ℃ of conditions;
3) will sieve the back particle diameter between the glass microballon of 300～700nm according to 5g/ml and step 2) anatase titanic oxide sol mix, wherein the specific refractory power of glass microballon is 1.8～2.6.Place agate jar then, take out naturally cooling behind 240 ℃ of thermal treatment 3h behind the ball milling 20h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
Embodiment 8
1) with titanium source and the co-precipitation of basic hydrolysis liquid in water, reaction obtains white titanium hydroxide deposition, washing is deposited in the white titanium hydroxide that obtains under 30 ℃ then, presses Ti
4+: organic acid: the mol ratio of ydrogen peroxide 50 is to carry out peptization at 1: 5: 5, obtains the TiO 2 sol presoma behind the still aging 10h; Wherein titanyl sulfate is selected in the titanium source, and basic hydrolysis liquid is selected NaOH, and organic acid is selected oxalic acid;
2) the TiO 2 sol presoma that obtains is being obtained the xanchromatic anatase titanic oxide sol behind the hydrothermal treatment consists 24h under 100 ℃ of conditions;
3) will sieve the back particle diameter between the glass microballon of 300～700nm according to 5g/ml and step 2) anatase titanic oxide sol mix, wherein the specific refractory power of glass microballon is 1.8～2.6.Place agate jar then, take out naturally cooling behind 260 ℃ of thermal treatment 1h behind the ball milling 20h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
The TEM collection of illustrative plates of glass microballon is as shown in Figure 1 after the modification that obtains of the present invention, and by seeing among the figure behind the ball milling that the microballon shape is not a rule very, particle is maximum is about 400nm, and little can arrive about 200nm, and this has also guaranteed the compactness after its film forming.Utilize after the modification that method of the present invention obtains the high power TEM collection of illustrative plates of glass microballon as shown in Figure 2, attach by the anatase phase titanium dioxide particle bag of the visible powder surface of figure by the well-crystallized.
Claims (3)
1. the preparation method of a modified glass microballon is characterized in that, may further comprise the steps:
1) with titanium source and the co-precipitation of basic hydrolysis liquid in water, reaction obtains white titanium hydroxide deposition, washing is deposited in the white titanium hydroxide that obtains under 30～80 ℃ then, presses Ti
4+: organic acid: the mol ratio of ydrogen peroxide 50 is 1: (2～10): peptization is carried out in (2～10), obtains the TiO 2 sol presoma behind still aging 10～16h;
2) the TiO 2 sol presoma that obtains is being obtained the xanchromatic anatase titanic oxide sol behind hydrothermal treatment consists 4～24h under 70～250 ℃ of conditions;
3) will sieve the back particle diameter between the glass microballon of 300～700nm according to 1～10g/ml and step 2) anatase titanic oxide sol mix; Place agate jar then; Take out naturally cooling behind 240～260 ℃ of thermal treatment 1～3h behind ball milling 20～24h, promptly obtain being suitable for the titania modified glass microballon that the dye sensitization solar battery scattering of light is used.
2. the preparation method of modified glass microballon according to claim 1 is characterized in that, in the step 1), described titanium source is one or more mixing in titanyl sulfate, titanium sulfate and the titanium tetrachloride; Described basic hydrolysis liquid is NaOH, KOH, NaHCO
3, ammoniacal liquor or NH
4HCO
3Described organic acid is oxalic acid, Hydrocerol A, tartrate, phenylformic acid, hexanodioic acid or acetic acid.
3. the preparation method of modified glass microballon according to claim 1 is characterized in that, in the step 3), the specific refractory power of said glass microballon is 1.8～2.6.
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| CN103915260B (en) * | 2012-12-26 | 2018-07-20 | 凯惠科技发展(上海)有限公司 | Flexible titanium radical dye sensitization solar battery module, production method and power supply |
| CN103566977B (en) * | 2013-10-30 | 2015-09-30 | 西安工程大学 | A kind of dye-sensitized nano ferric oxide coated hollow glass micropearl method |
| CN106128771B (en) * | 2016-06-29 | 2018-09-25 | 深圳市深大南方实业发展有限公司 | It is a kind of based on the building lighting equipment for realizing continuous work round the clock |
| CN106195884B (en) * | 2016-06-29 | 2019-01-22 | 海盐金隆照明科技有限公司 | A kind of solar illumination apparatus |
| CN105931850B (en) * | 2016-06-29 | 2018-08-21 | 陕西华逸东方展览装饰设计工程有限公司 | A kind of energy-saving luminous construction wall |
| CN106195885B (en) * | 2016-06-29 | 2019-02-05 | 成都光无界科技股份有限公司 | A kind of Solar lamp |
| CN105914042B (en) * | 2016-06-29 | 2018-11-09 | 深圳供电局有限公司 | Electrical cabinet with temperature adjusting function |
| CN106128770B (en) * | 2016-06-29 | 2018-09-25 | 泰州神威新材料科技有限公司 | A kind of parking lot generating equipment based on solar energy equipment |
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| CN101062800A (en) * | 2007-04-19 | 2007-10-31 | 浙江大学 | Photocatalysis sewage treatment equipment |
| CN201033747Y (en) * | 2007-04-19 | 2008-03-12 | 浙江大学 | Photocatalytic sewage treatment device |
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| JP3896580B2 (en) * | 1998-06-26 | 2007-03-22 | 日本電気硝子株式会社 | Glass beads for retroreflector |
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|---|---|---|---|---|
| CN101062800A (en) * | 2007-04-19 | 2007-10-31 | 浙江大学 | Photocatalysis sewage treatment equipment |
| CN201033747Y (en) * | 2007-04-19 | 2008-03-12 | 浙江大学 | Photocatalytic sewage treatment device |
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