CN102509625A - In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film - Google Patents

In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film Download PDF

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CN102509625A
CN102509625A CN2011103588488A CN201110358848A CN102509625A CN 102509625 A CN102509625 A CN 102509625A CN 2011103588488 A CN2011103588488 A CN 2011103588488A CN 201110358848 A CN201110358848 A CN 201110358848A CN 102509625 A CN102509625 A CN 102509625A
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nano
tio2
tungsten
silicon
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孙明轩
崔晓莉
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Fudan University
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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

Abstract

The invention belongs to the photoelectric and chemical technical field of nano titanium dioxides, in particular to an in-situ preparation method for a silicon-tungsten and TiO2 codoped nanotube film. The invention comprises the following steps: a pretreated metal Ti piece serves as an anode, a graphite piece serves as a cathode, and an HF solution serves as an electrolyte; silicotungstic acid is added in the electrolyte; the anode of a DC stabilized voltage supply is subjected to oxidation; and heat treatment is performed in a pipe furnace, thereby, obtaining the silicon-tungsten and TiO2 codoped nanotube film; the visible light photocurrent of the electrode of the Si-W-TiO2 nanotube thin film electrode is proved to be about 2.6 times of that of the TiO2 nanotube thin film electrode through experiment; and the energy conversion efficiency of a dye sensitized solar cell assembled by the thin film electrode is higher than that of the dye sensitized solar cell made of pure TiO2 nanotube.

Description

A kind of in-situ preparing silicon tungsten codope TiO 2The method of nano-tube film light anode
Technical field
The invention belongs to nano titanium oxide Optical Electro-Chemistry technical field, be specifically related to a kind of preparation method with visible light activity silicon tungsten codoped nanaotitania film.
Background technology
Since Gratzel in 1991 teaches [[i]] TiO with dye sensitization 2Nanocrystalline porous film is as the light anode, obtained electricity conversion and is since the solar cell of electricity conversion of 7.1%-7.9%, and nano titanium oxide becomes and has development prospect and by the semi-conducting material of broad research.TiO 2Owing to have advantages such as nontoxic, active height, cheapness, good stability, all be with a wide range of applications at aspects such as photocatalysis hydrogen production, light degradation and DSSCs.But TiO 2Energy gap big (Detitanium-ore-type 3.2eV, rutile-type 3.0eV), poor to absorption of visible light, limited its range of application greatly.In order to improve the utilance of sunlight, to TiO 2Improve its visible light activity with expansion photoelectric respone scope thereby mix to modify, become present TiO 2The Optical Electro-Chemistry field is one of active subject very.
The structure solar cell is a kind of approach that solar energy utilizes.DSSC is by the light anode, electrolyte and a kind of " sandwich " structure that electrode is formed, TiO 2The light anode directly affects the efficient of DSSC as the important component part of DSSC.
TiO 2Doping be to TiO 2The important method of light anode modification modification can be divided into nonmetal doping (Si [[ii]], C [[iii]]; N [[iv]] etc.), metal-doped (Fe [[v]], W [[vi]] etc.), nonmetal codope (B-N [[vii]], Si-N [[viii]]; C-N [[ix]]; P-N [[x]], etc.) and metal and nonmetal codope (N-W [[xi]], Si-W [[xii]] etc.Existing result of study shows that codope is because the cooperative effect of foreign atom can further improve TiO 2Visible light activity.Shi etc. [8] propose Si-N codope TiO 2Visible light photocatalysis active to strengthen mainly be because energy gap narrows down and reduce in the complex centre.Lin etc. [10] have also prepared the TiO of P-N codope with sol-gel process 2, discover that the photocatalytic activity of codope is compared single TiO that mixes 2Sample has further raising.Long etc. [11] have reported N-W codope TiO 2Visible light photocatalysis active to be higher than the TiO of single nitrating or tungsten 2, at N doped Ti O 2In further mix W, resulting N-W mixes TiO altogether 2Energy gap 0.5 eV that narrowed down.You Xiujuan etc. [12] utilize the sol-gel self-propagating combustion to prepare silicon tungsten codope TiO 2, can significantly improve TiO through the doped silicon wolframic acid 2Photocatalysis efficiency, but related process is comparatively complicated.And Si-W codope TiO 2Nanotube is not also seen relevant report.
Summary of the invention
The objective of the invention is to propose the simple preparation of a kind of technology and have the method for the Si-W coblended nano TiO 2 nano-tube film of visible light activity.
The preparation that the present invention proposes has the method for the Si-W coblended nano TiO 2 nano-tube film of visible light activity; Main raw material(s) adopts Titanium; 0.5%HF solution and silico-tungstic acid, capital equipment adopts D.C. regulated power supply (anodic oxidation), tube furnace (heat treatment).
Concrete steps are: as anode, graphite flake as electrolyte, adds 0.1-0.8 M silico-tungstic acid H with 0.5%HF solution as negative electrode in electrolyte with pretreated Ti sheet 4[SiO 4(W 3O 9) 4], D.C. regulated power supply control voltage is 18-20V, anodic oxidation 35-45 min under the magnetic agitation; In tube furnace, be warming up to 400 at last oC-600 oC behind the heat treatment 2 h-3 h, can obtain silicon tungsten doped Ti O 2Nano-tube film.The preparation process is as shown in Figure 1.
Wherein, the doping of silicon and tungsten can realize through the consumption of control silico-tungstic acid.When the silico-tungstic acid consumption was 0.2M, in the doped samples, Si/Ti and W/Ti atomic ratio were 0.8.When the silico-tungstic acid consumption was 0.4M, in the doped samples, Si/Ti and W/Ti atomic ratio were respectively 0.10 and 0.09.
With the Si-W codope TiO that obtains 2Nano-tube film is made into electrode, tests its photoelectric activity under visible light.Light source is the xenon lamp of 500W during experiment, at first filters infrared light through the quartz glass tank and obtains ultraviolet-visible, and the ultraviolet light below filter elimination 420nm obtains visible light then, and optical power density is 100 mW/cm during experiment 2
Experiment shows that Si and W codope titanium dioxide nanotube thin film that the new technology that is proposed by the present invention prepares have good visible light activity.
Under radiation of visible light, the Si and the W codope TiO of the prepared that proposes with the present invention 2Nano-tube film shows tangible photocurrent response (Fig. 9 and Figure 10).Fig. 9 is TiO 2Nanotube and Si-W codope TiO 2The photoelectric current curve of nano-tube film electrode under radiation of visible light.Figure 10 is that the consumption of silico-tungstic acid is to Si and W codope TiO 2The photoelectric current curve of nano-tube film electrode under radiation of visible light.
The present invention adds silico-tungstic acid in anodic oxidation electrolyte, the one-step method in-situ preparing silicon tungsten codope TiO of visible light-responded enhancing 2Nanotube.Through the consumption of control silico-tungstic acid, can realize control to Si-W content in the sample.The thinking that the present invention proposes not only can be used for preparing the TiO that Si-W mixes 2Nanotube also is the TiO of other ion doping 2The preparation of nanotube provides new thinking.Experimental result shows, Si-W-TiO 2The visible light photoelectric current of nano-tube film electrode is TiO 22.6 times at nano-tube film electrode.The energy conversion efficiency of the DSSC that the doped samples of utilizing the present invention to obtain is simultaneously assembled also is higher than utilizes pure TiO 2The photoelectric conversion efficiency of the DSSC that nanotube is made.
The photoelectric current test result shows Si and the W codope TiO by this new technology preparation 2Have significantly visible light-respondedly, be expected to be applied at aspects such as visible light photocatalysis, the hydrogen manufacturing of photolysis water, solar cells.
Description of drawings
Fig. 1 prepares silicon tungsten codope TiO for anode oxidation method 2The experimentation diagram of nano-tube film.
The TiO that Fig. 2 obtains for anodic oxidation 2The front of nanotube and the SEM of side figure.Wherein, (A) TiO 2, (B) Si-W-TiO 2
Fig. 3 is TiO 2With Si-W codope TiO 2The XRD figure of nanotube.The influence of reflection annealing temperature: the silico-tungstic acid consumption is 0.2 M, annealing time 2.5h; (a) 400 oC; (b) 450 oC; (c) 550 oC; (d) 600 oC;
Fig. 4 is TiO 2With Si-W codope TiO 2The XRD figure of nanotube.The influence of reflection silico-tungstic acid amount: heat treatment temperature 450 oC, time 2.5h; (a) 0 M; (b) 0.2 M; (c) 0.8 M; A: anatase TiO 2, R: rutile TiO 2, T: titanium sheet.
Fig. 5 is the Si-W codope TiO of the present invention's preparation 2The XPS spectrum figure Si2p of nano-tube film sample.
Fig. 6 is the Si-W codope TiO of the present invention's preparation 2The XPS spectrum figure W4f of nano-tube film sample.
Fig. 7 is the TiO of Si and W codope 2Nano-tube film and doped Ti O not 2The ultraviolet-visible of the nano-tube film spectrogram that diffuses.
Fig. 8 is the TiO of Si and W codope 2Nano-tube film and doped Ti O not 2(the α hv) of the electronics indirect transition of nano-tube film 0.5～hv relation.
Fig. 9 is TiO 2The nano-tube film electrode under radiation of visible light photoelectric current with the irradiation (light on)/be in the light (light off) the electric current change curve.（a）Ti/Si-W TiO 2，(b)Ti/TiO 2 。
Figure 10 is TiO 2The nano-tube film electrode under radiation of visible light photoelectric current with the irradiation (light on)/be in the light (light off) the electric current change curve.Ti/Si-W TiO 2(silico-tungstic acid consumption: (a) 0.2 M; (b) 0.4 M, (c) 0.04 M).
Figure 11 is based on TiO 2And Si-W-TiO 2The DSSC dye sensitization current-voltage curve of nano-tube film light anode.
Table 1Based on TiO 2And Si-W-TiO 2The DSSC photoelectric properties of nano-tube film light anode.
Embodiment
Embodiment 1:With the Ti sheet with V (deionized water): V (HNO 3): the solution of V (HF)=5:4:1 carries out preliminary treatment, with deionized water the Ti sheet is cleaned up back flowing down at air again and dries up.With pretreated Ti sheet as anode; Graphite flake is as negative electrode; In 0.5%HF solution, add 0.2 M silico-tungstic acid as electrolyte, utilize D.C. regulated power supply control 20V voltage, anodic oxidation 40 min under the magnetic agitation; Rinse well repeatedly with deionized water at last, and dry up with air stream and to obtain silicon tungsten codope TiO 2Nano-tube film (seeing Fig. 2 B SEM figure).Ti sheet after the anodic oxidation is placed porcelain boat, be put into then in the Muffle furnace, be warming up to 450 oC, heat treatment time are 2.5 hours.Ti sheet after the heat treatment is clean with the deionized water ultrasonic cleaning, and air flow down dry up subsequent use.
As anode, graphite flake is as negative electrode with pretreated Ti sheet, with 0.5%HF solution as electrolyte; Utilize D.C. regulated power supply control 20V voltage; Anodic oxidation 40 min rinse well with deionized water at last repeatedly under the magnetic agitation, and dry up with air stream and to obtain TiO 2Nano-tube film (seeing Fig. 2 A SEM figure).
Doped samples is carried out the XPS analysis (see Fig. 5, Fig. 6 XPS figure) of surface composition, and the binding energy of Si 2p is 101.6 eV, W (VI) 4f7/2:35.4; W (VI) 4f5/2:37.8 eV; Ti 3p:37.0 eV, can confirmatory sample in the existence of Si element and W element, Si/Ti and W/Ti atomic ratio are 0.08.
Ultraviolet-visible diffuse reflection spectrum (Fig. 7, Fig. 8) by sample can be found out, Si and W codope TiO 2The purer TiO of the energy of absorption edge of nano-tube film 2The nano-tube array red shift, visible absorption strengthens.Unadulterated TiO 2The energy gap of nanotube is 3.0eV, and by the TiO of the silicon tungsten codope of the present invention preparation 2The energy gap of nano-tube film sample is 2.1 eV, and TiO is described 2Nano-tube film has improved the absorption of sample in the visible region after Si and W doping modification.
Adopt three-electrode system to carry out the test of film electrode photoelectric chemical property, with TiO 2The nano-tube film electrode is a work electrode, and platinized platinum is to electrode, and the Ag/AgCl electrode is a reference electrode, and the electrolysis tank of select tape quartz window, electrolyte are 0.5 mol .L -1Na 2SO 4Solution.The CHI660A electrochemical workstation that adopts Shanghai occasion China instrument company to produce.The simulated solar light source adopts Beijing freely to open up the xenon short-act lamp of the 500W of Science and Technology Ltd.'s production, and incident light filters infrared light through quartzy tank and obtains ultraviolet-visible light, and the ultraviolet light below filter elimination 420nm obtains visible light, and light intensity is 100 mW .Cm -2Fig. 9 illustrates Si and W codope TiO 2The photoelectric current numerical value of nano-tube film electrode under visible light is 0.97 μ A/cm 2, TiO 2The photoelectric current numerical value of nano-tube film electrode under visible light is 0.38 μ A/cm 2, the visible light photoelectricity flow valuve of visible doped samples is higher than the not photoelectric current numerical value of doped samples.
Embodiment 2:The preprocessing process of metal titanium sheet is with embodiment 1.With pretreated Ti sheet as anode; Graphite flake is as negative electrode; In 0.5%HF solution, add 0.04 M silico-tungstic acid as electrolyte, utilize D.C. regulated power supply control 20V voltage, anodic oxidation 40 min under the magnetic agitation; Rinse well repeatedly with deionized water at last, and dry up with air stream and to obtain TiO 2Nano-tube film.The test process of last handling process and photoelectric current is with embodiment 1.Figure 10 illustrates Si and W codope TiO 2The photoelectric current numerical value of nano-tube film electrode under visible light is 0.51 μ A/cm 2
Embodiment 3:The preprocessing process of metal titanium sheet is with embodiment 1.With the Ti sheet with V (deionized water): V (HNO 3): the solution of V (HF)=5:4:1 carries out preliminary treatment, with deionized water the Ti sheet is cleaned up back flowing down at air again and dries up.With pretreated Ti sheet as anode; Graphite flake is as negative electrode; In 0.5%HF solution, add 0.4 M silico-tungstic acid as electrolyte, utilize D.C. regulated power supply control 20V voltage, anodic oxidation 40 min under the magnetic agitation; Rinse well repeatedly with deionized water at last, and dry up with air stream and to obtain TiO 2Nano-tube film.The test process of last handling process and photoelectric current is with embodiment 1.Doped samples is carried out the XPS analysis of surface composition, can confirmatory sample in the existence of Si element and W element, the Si/Ti atomic ratio is 0.10, the W/Ti atomic ratio is 0.09.Figure 10 illustrates Si-W-TiO 2The photoelectric current numerical value of nano-tube film electrode under visible light is 0.74 μ A/cm 2
Embodiment 4:The preprocessing process of metal titanium sheet is with embodiment 1.With the Ti sheet with V (deionized water): V (HNO 3): the solution of V (HF)=5:4:1 carries out preliminary treatment, with deionized water the Ti sheet is cleaned up back flowing down at air again and dries up.With pretreated Ti sheet as anode; Graphite flake is as negative electrode; In 0.5%HF solution, add 0.2 M silico-tungstic acid as electrolyte, utilize D.C. regulated power supply control 20V voltage, anodic oxidation 40 min under the magnetic agitation; Rinse well repeatedly with deionized water at last, and dry up with air stream and to obtain TiO 2Nano-tube film.Ti sheet after the anodic oxidation is placed porcelain boat, be put into then in the Muffle furnace, be warming up to 400,500,550 and 600 respectively oC, heat treatment time are 2.5 hours.Ti sheet after the heat treatment is clean with the deionized water ultrasonic cleaning, and air flow down dry up subsequent use.Bright and sharp titanium ore of XRD table with test results and rutile-type silicon tungsten codope TiO 2Generation (seeing Fig. 3, Fig. 4 XRD figure).
Compare Si and W codope TiO with unadulterated sample 2The TiO of codope 2The transient state photoelectric current of nanotube significantly improves, and when the silico-tungstic acid consumption is 0.2 M, reaches maximum, has proved that silicon and tungsten codope have improved TiO 2The photoelectric respone of nanotube under radiation of visible light.
Embodiment 5:TiO 2Nano-tube film and Si-W-TiO 2The preparation of nano-tube film is as implementing case 1.With N719 dyestuff, I 3 -/ I -Electrolyte and Pt assemble DSSC to electrode.I-V curve test result shows (like Figure 11 and table 1), based on TiO 2And Si-W-TiO 2The electricity conversion of the DSSC of nano-tube film light anode is respectively 0.12% and 0.23%, need to prove, the cell photoelectric efficient of assembling is on the low side, can improve through improving manufacture craft.With Si-W-TiO 2The efficient of the battery of nano-tube film light anode assembling is higher than with TiO 2The efficient of the battery of nano-tube film light anode assembling shows that the Si-W codope can improve the electricity conversion of DSSC.
Table 1
Sample Short circuit current (mA cm -2) Open circuit voltage (V) Fill factor, curve factor Electricity conversion (%)
TiO 2 0.43 0.60 0.46 0.12
Si-W-TiO 2 0.69 0.60 0.56 0.23
With reference to selected works
[[1]]0’Regan B, Gratzel M. Nature 353 (1991) 737.
[2]Su,Y.; Wu, J. ; Quan, X.; Chen, S. Desalination 252(2010) 143.
[3]Khan, S. U. M.; Al-Shahry, M.; Ingler, W. B. Jr. Science297(2002) 2243.
[4]Asahi, R.; Morikawa, T.; Ohwaki, T.; Aoki, K.; Taga, Y. Science293 (2001) 269.
[5]K. Bapna, D.M. Phase, R.J. Choudhary, J. Appl. Phys. 110 (2011) 043910.
[6]X. Zhang, F. Liu, Q.L. Huang, G. Zhou, Z. S. Wang, J. Phys. Chem. C 115(2011) 12665.
[7] X.S. Zhou, F. Peng, H.J. Wang, H. Yu, J.A. Yang, Electrochem. Commun. 13 (2011) 121.
[8] W. Shi, Q. Chen, Y. Xu, D. Wu, C. Huo, Appl. Surf. Sci. 257 (2011) 3000.
[9]X. Y. Zhang, X. L. Cui, Acta Phys. -Chim. Sin., 25 (2009) 1829.
[[1]0]L. Lin, R. Zheng, J. Xie, Y. Zhu, Y. Xie, Appl. Catal. B 76 (2007) 196.
[[1]1] R. Long, N.J. English, Appl. Phys. Lett. 94 (2009) 132102.
[[1]2] X.J. You, L.L. Jiang, H.L. Chen, Y. Tang, L.F. Li, K. Feng, J.L. Xie, Journal of Sichuan University(Natural Science Edition) 44 (2007) 873。.

Claims (2)

1. in-situ preparing silicon tungsten codope TiO 2The method of nano-tube film light anode is characterized in that material adopts Titanium, 0.5%HF solution and silico-tungstic acid, and equipment adopts D.C. regulated power supply, tube furnace; Concrete steps are: as anode, graphite flake as electrolyte, adds 0.1-0.8 M silico-tungstic acid H with 0.5%HF solution as negative electrode in electrolyte with pretreated metal Ti sheet 4[SiO 4(W 3O 9) 4], D.C. regulated power supply control voltage is 18-20V, anodic oxidation 35-45 min under the magnetic agitation; In tube furnace, be warming up to 400 at last oC-600 oC, heat treatment 2 h-3 h promptly obtain silicon tungsten doped Ti O 2Nano-tube film.
2. method according to claim 1 is characterized in that controlling the doping of silicon and tungsten through the consumption of control silico-tungstic acid.
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Cited By (11)

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CN103943365A (en) * 2014-04-25 2014-07-23 中南大学 Manufacturing method of dye-sensitized solar cell modified photo anode
CN104071831A (en) * 2014-06-25 2014-10-01 复旦大学 Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays
CN105575668A (en) * 2015-12-15 2016-05-11 哈尔滨工业大学 Preparation method of SiW11Ni heteropoly acid modified dye-sensitized solar cell photocathode
CN105575667A (en) * 2015-12-15 2016-05-11 哈尔滨工业大学 Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2
CN105679546A (en) * 2016-01-18 2016-06-15 黑龙江大学 InWO4:Eu<3+>/TiO2 composite photo anode and preparation method thereof
CN106757115A (en) * 2016-11-14 2017-05-31 中北大学 The electrochemistry of continuous poriferous titanium dioxide powder is prepared and doping method
CN107841777A (en) * 2017-11-01 2018-03-27 西南交通大学 A kind of preparation method of witch culture Nano tube array of titanium dioxide
CN108922783A (en) * 2018-07-24 2018-11-30 长江大学 A kind of dye-sensitized solar cell anode scattering layer and preparation method thereof
CN109537021A (en) * 2018-11-26 2019-03-29 天津师范大学 A kind of preparation method of the titanium oxide for sodium-ion battery cathode/tin oxide composite membrane
CN109637816A (en) * 2018-12-27 2019-04-16 东北师范大学 Cu2S-SiW12/MoS2Combined counter electrode and preparation method thereof and quantum dot sensitized solar battery
CN109713127A (en) * 2018-12-26 2019-05-03 西安电子科技大学 A kind of preparation method of perovskite solar battery

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CN103943365A (en) * 2014-04-25 2014-07-23 中南大学 Manufacturing method of dye-sensitized solar cell modified photo anode
CN103943365B (en) * 2014-04-25 2016-08-24 中南大学 A kind of preparation method of DSSC modification light anode
CN104071831A (en) * 2014-06-25 2014-10-01 复旦大学 Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays
CN105575668A (en) * 2015-12-15 2016-05-11 哈尔滨工业大学 Preparation method of SiW11Ni heteropoly acid modified dye-sensitized solar cell photocathode
CN105575667A (en) * 2015-12-15 2016-05-11 哈尔滨工业大学 Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2
CN105679546A (en) * 2016-01-18 2016-06-15 黑龙江大学 InWO4:Eu<3+>/TiO2 composite photo anode and preparation method thereof
CN106757115A (en) * 2016-11-14 2017-05-31 中北大学 The electrochemistry of continuous poriferous titanium dioxide powder is prepared and doping method
CN107841777A (en) * 2017-11-01 2018-03-27 西南交通大学 A kind of preparation method of witch culture Nano tube array of titanium dioxide
CN107841777B (en) * 2017-11-01 2019-11-01 西南交通大学 A kind of preparation method of witch culture Nano tube array of titanium dioxide
CN108922783A (en) * 2018-07-24 2018-11-30 长江大学 A kind of dye-sensitized solar cell anode scattering layer and preparation method thereof
CN109537021A (en) * 2018-11-26 2019-03-29 天津师范大学 A kind of preparation method of the titanium oxide for sodium-ion battery cathode/tin oxide composite membrane
CN109537021B (en) * 2018-11-26 2020-07-21 天津师范大学 Preparation method of titanium oxide/tin oxide composite membrane for sodium ion battery cathode
CN109713127A (en) * 2018-12-26 2019-05-03 西安电子科技大学 A kind of preparation method of perovskite solar battery
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Application publication date: 20120620