CN101740228A - Method for preparing counter electrode based on electrochemical synthesized polyaniline on surface of stainless steel - Google Patents
Method for preparing counter electrode based on electrochemical synthesized polyaniline on surface of stainless steel Download PDFInfo
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- CN101740228A CN101740228A CN200910264462A CN200910264462A CN101740228A CN 101740228 A CN101740228 A CN 101740228A CN 200910264462 A CN200910264462 A CN 200910264462A CN 200910264462 A CN200910264462 A CN 200910264462A CN 101740228 A CN101740228 A CN 101740228A
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 82
- 239000010935 stainless steel Substances 0.000 title claims abstract description 82
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 76
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 75
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 43
- 239000012153 distilled water Substances 0.000 claims abstract description 23
- 238000005498 polishing Methods 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 12
- 239000012895 dilution Substances 0.000 claims description 12
- 238000011010 flushing procedure Methods 0.000 claims description 12
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 238000002848 electrochemical method Methods 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 238000013019 agitation Methods 0.000 description 10
- 238000005282 brightening Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- NTOLGSSKLPLTDW-UHFFFAOYSA-N hydrogen sulfate;phenylazanium Chemical compound OS(O)(=O)=O.NC1=CC=CC=C1 NTOLGSSKLPLTDW-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000010963 304 stainless steel Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- SFPQDYSOPQHZAQ-UHFFFAOYSA-N 2-methoxypropanenitrile Chemical compound COC(C)C#N SFPQDYSOPQHZAQ-UHFFFAOYSA-N 0.000 description 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a method for preparing a counter electrode based on electrochemical synthesized polyaniline on the surface of stainless steel. The method comprises the following steps: firstly, washing and chemically polishing a stainless steel sheet to eliminate an oxide layer on the surface; secondly, taking a washed stainless steel substrate as a working electrode, and taking another stainless steel sheet with slightly large size as the counter electrode; thirdly, placing the working electrode and the counter electrode in mixed solution, of aniline and sulphuric acid, with a certain concentration; fourthly, performing electrochemical polymerization with continuous stirring; and finally, rinsing sample sheets with dilute sulfuric acid solution and distilled water orderly after reaction, and drying the sample sheets in vacuum to obtain a stainless steel base polyaniline counter electrode. The stainless steel base polyaniline counter electrode prepared by an electrochemistry method has low cost and simple manufacturing process, and can obtain wide application prospect in the field of dye-sensitized solar cells.
Description
Technical field
The present invention relates to a kind of based on the preparation method of stainless steel base surface electrochemistry synthesized polyaniline to electrode.
Background technology
DSSC is a kind of novel photovoltaic cell of efficient and cheap.Battery is mainly by nano-TiO
2Light anode, electrolyte reach to be formed electrode.Commonly used is the platinized electrode that obtains by magnetron sputtering or vacuum vapor deposition method on the transparent conducting glass matrix to electrode at present, yet this platinum electrode manufacturing cost costliness has limited the production and the application of DSSC greatly.Therefore adopt conducting polymer to do when reducing cost of material, further raising to have promoted the process of DSSC practical applicationization to the catalytic capability of electrode to electrode.At present existing people has studied by chemical oxidization method and has generated polyaniline, and be coated in the conductive glass surface preparation to electrode (Li Qinghua, Wu Jihuai, Tang Qunwei, LanZhang, Li Pinjiang, Lin Jianming, Fan Leqing, Electrochem Commun, 2008,10 (9) 1299-1302), but the subject matter that exists is the poorly soluble of polyaniline, by polyaniline solutions is coated in matrix surface, the polyaniline film that obtains of evaporating solvent is very inhomogeneous again, and is poor with the glass basis adhesion.So, need consideration a kind of both simple and convenient, can guarantee the new method of film quality again.The electrochemical preparation polyaniline is the key that solves this difficult problem to electrode on stainless steel substrates.Overcome the frangible shortcoming of electro-conductive glass matrix with the stainless steel thin slice as matrix, laid the first stone for preparing flexible DSSC.Electrochemical process can make starting monomer directly at the substrate surface polymerization film formation, it is good to have controllability, the non-oxidation agent, product is pure, advantages such as environmental friendliness and operating process are easy, the high molecular main electrochemical method of compositing conducting has at present: galvanostatic method, constant voltage method, cyclic voltammetry and pulse current method etc.
Prepare the technological difficulties of polyaniline with the stainless steel for the matrix electrochemical process to electrode: the pre-treatment of (1) stainless steel substrates, all can there be layer oxide film on the stainless steel substrates surface usually, and this layer oxide-film has a significant impact the preparation product.Therefore select suitable clean very important that seem for use.(2) selection of electrolyte is the product that will select suitable acid and concentration just can obtain expecting on the one hand.Secondly, electrolyte also will provide the ion that can mix simultaneously.(3) selection of electrochemical synthetic process parameter, different technological parameters obtain the shape characteristic of polyaniline, and the oxidation state structure has nothing in common with each other, and the polyaniline of selecting the preparation of suitable technological parameter is to electrode, further the assembling solar battery.
Summary of the invention
The purpose of this invention is to provide a kind of simply in the preparation method of stainless steel surfaces electrochemical synthesized polyaniline to electrode, comprise the preliminary treatment of stainless steel substrates, the electrochemistry of polyaniline is synthetic.This method operation is simple and easy, with low cost, and the polyaniline of preparation can replace original platinized electrode to electrode, is successfully applied to DSSC.
The present invention for the above-mentioned technical scheme that purpose adopted of realization is: a kind of based on the preparation method of stainless steel surfaces electrochemical synthesized polyaniline to electrode, comprise the steps:
The first step, the preliminary treatment of stainless steel substrate:
Two stainless steel substrate → alkali cleaning oil removing → 50~80 ℃ hot water wash → 0~30 ℃ of cold wash → chemical polishing → distillation washing → oven dry that size differs;
In second step, polyaniline is to the preparation of electrode:
(a) aniline monomer and sulfuric acid are added stir in the entry that to form aniline monomer concentration be 0.1~0.5mol/L, sulfuric acid solution concentration is the mixed solution of 0.1~1.5mol/L;
(b) choose the little stainless steel substrate of size and make the work electrode, the stainless steel substrate that size is big is done electrode;
(c) two electrodes are placed mixed solution, continue to stir;
(d) in mixed solution, make aniline monomer at the stainless steel base surface aggregate, form the cyan polyaniline film of one deck by electrochemical method for synthesizing;
(e) take out electrode, with carrying out vacuum drying treatment behind 0.01mol/L~0.1mol/L dilution heat of sulfuric acid, the distilled water flushing, obtain polyaniline successively electrode.
2, according to claim 1 a kind of based on the preparation method of stainless steel surfaces electrochemical synthesized polyaniline to electrode, it is characterized in that: described electrochemical method for synthesizing is a potentiostatic method, the work electrode current potential is 0.8~1.2V, and polymerization time is 1000~4000s; Perhaps galvanostatic method, Faradaic current is 0.2~5mA/cm
2, polymerization time is 100~1000s; Or cyclic voltammetry, CONTROLLED POTENTIAL is at-0.2~0.9V, and sweep speed is 10~200mV/s, and the scan round number of times is 100~1000 times.
The present invention compared with prior art, its remarkable advantage is: (1) realizes that electrochemical process prepares polyaniline film, compares with chemical method, the advantage of electrochemical method is the technological process simplification, need not oxidant, can be by the control electrochemical parameter, the pattern of control product; By the control electrode electric weight, the thickness of control film; (2) adopt the polyaniline of the present invention's preparation that electrode is compared with platinized electrode, this stainless steel base has obvious decline than the cost of electro-conductive glass, and the electrode cost of manufacture is cheap, can be in DSSC, and there are good application prospects and economic benefit in fields such as flexible electrode material.
Description of drawings
The polyaniline that makes under the different constant voltages of Fig. 1 is to the stereoscan photograph (1-a:0.8V of electrode surface; 1-b:1.0V; 1-c:1.1V; 1-d:1.2V).
Fig. 2 is based on the polyaniline of the constant voltage method preparation photoelectric current-photovoltage curve to the DSSC of electrode and platinum electrode.
Embodiment
Mode below by embodiment is elaborated to technical solution of the present invention, but protection scope of the present invention is not limited to described embodiment.
The first step earlier soaks a slice stainless steel substrates and another large-sized slightly stainless steel substrates in the alkali lye oil removing, takes out the back with 50 ℃ of hot water injections, use 0 ℃ of cold water flush clean again after, substrate is put into chemical brightening solution carries out polishing, remove surperficial oxide layer.At last will be clean and dry stand-by with distilled water flushing through the substrate of polishing.
Second step added aniline and sulfuric acid in the entry, and being made into aniline monomer concentration is 0.1mol/L, and sulfuric acid solution concentration is the solution of 0.1mol/L, formed uniform and transparent mixed solution by magnetic agitation.Make the work electrode with slightly little stainless steel substrate, do electrode is put into the aniline-sulfuric acid solution for preparing with another large-sized slightly stainless steel substrates, adopt potentiostatic method in the time of continuous stirring, electrochemical polymerization is 1000 seconds under 0.8V voltage.Question response finishes the back and takes out print, rinses well repeatedly with dilution heat of sulfuric acid and the distilled water of 0.01mol/L successively, removes the reactant of surface attachment, and vacuumize can obtain stainless steel-based polyaniline to electrode.
Testing result: the stereoscan photograph of polymerization 1000s gained polyaniline material is shown in accompanying drawing 1-a under the 0.8V constant voltage.(Fig. 1-a) as can be known, when constant voltage is 0.8V, formed the fine and close polyaniline film of layer on the stainless steel substrates is made up of at the granule of 30~40nm diameter by the stereoscan photograph of polyaniline.This layer dense film is the oligomer of polyaniline, also is the initial product that the polyaniline nucleation is grown up.
The first step earlier soaks a slice stainless steel substrates and another large-sized slightly stainless steel substrates in the alkali lye oil removing, takes out the back with 60 ℃ of hot water injections, use 10 ℃ of cold water flush clean again after, substrate is put into chemical brightening solution carries out polishing, remove surperficial oxide layer.At last will be clean and dry stand-by with distilled water flushing through the substrate of polishing.
Second step added aniline and sulfuric acid in the entry, and being made into aniline monomer concentration is 0.3mol/L, and sulfuric acid solution concentration is the solution of 0.5mol/L, formed uniform and transparent mixed solution by magnetic agitation.Make the work electrode with slightly little stainless steel substrate, do electrode is put into the aniline-sulfuric acid solution for preparing with another large-sized slightly stainless steel substrates, adopt potentiostatic method in the time of continuous stirring, electrochemical polymerization is 2000 seconds under 1.0V voltage.Question response finishes the back and takes out print, rinses well repeatedly with dilution heat of sulfuric acid and the distilled water of 0.05mol/L successively, removes the reactant of surface attachment, and vacuumize can obtain stainless steel-based polyaniline to electrode.
Testing result: by stereoscan photograph (Fig. 1-b) as can be known, when constant voltage is 1.0V, formed the mixing pattern that coexists by some big polyaniline spheric granules and short nanometer rods on the stainless steel substrates of polyaniline.This mixture helps to improve the specific area of polyaniline owing to a large amount of open loose structures occur, adsorbs more liquid electrolyte.Through the test of four point probe conductivity meter, this polyaniline is 6.173S/cm to the conductivity of electrode.
Preparation method to electrode may further comprise the steps based on the stainless steel surfaces electrochemical synthesized polyaniline:
The first step earlier soaks a slice stainless steel substrates and another large-sized slightly stainless steel substrates in the alkali lye oil removing, takes out the back with 70 ℃ of hot water injections, use 20 ℃ of cold water flush clean again after, substrate is put into chemical brightening solution carries out polishing, remove surperficial oxide layer.At last will be clean and dry stand-by with distilled water flushing through the substrate of polishing.
Second step added the sulfuric acid of 0.4mol/L aniline and 1.0mol/L in the entry, and magnetic agitation forms the 50ml uniform and transparent mixed solution.304 stainless steel substrates of getting after a slice is cleaned, polished are made the work electrode, do electrode is put into the aniline-aqueous sulfuric acid for preparing with another large-sized slightly 304 stainless steel substrates, adopt potentiostatic method in the time of continuous stirring, electrochemical polymerization is 3000 seconds under 1.1V voltage.Question response finishes the back and takes out print, rinses well repeatedly with 0.1mol/L dilution heat of sulfuric acid and distilled water successively, removes the reactant of surface attachment, and at 60 ℃ of vacuumize 24h, can obtain stainless steel-based polyaniline to electrode.
Testing result: (Fig. 1-c) as can be known, when constant voltage was 1.1V, the spheric granules of polyaniline disappeared, and having formed diameter is 300nm, the nanorod structure of length about 800nm by the stereoscan photograph of polyaniline.The rising of this phenomenon account for voltage help the growth of polyaniline one-dimensional rod-like structure, and the growth of spheric granules only occurs when the low-voltage polymerization.Through the test of four point probe conductivity meter, this polyaniline is 1.811S/cm to the conductivity of electrode.
The first step earlier soaks a slice stainless steel substrates and another large-sized slightly stainless steel substrates in the alkali lye oil removing, takes out the back with 80 ℃ of hot water injections, use 30 ℃ of cold water flush clean again after, substrate is put into chemical brightening solution carries out polishing, remove surperficial oxide layer.At last will be clean and dry stand-by with distilled water flushing through the substrate of polishing.
Second step added aniline and sulfuric acid in the entry, and being made into aniline monomer concentration is 0.5mol/L, and sulfuric acid solution concentration is the solution of 1.5mol/L, formed uniform and transparent mixed solution by magnetic agitation.Make the work electrode with slightly little stainless steel substrate, do electrode is put into the aniline-sulfuric acid solution for preparing with another large-sized slightly stainless steel substrates, adopt potentiostatic method in the time of continuous stirring, electrochemical polymerization is 4000 seconds under 1.2V voltage.Question response finishes the back and takes out print, rinses well repeatedly with dilution heat of sulfuric acid and the distilled water of 0.1mol/L successively, removes the reactant of surface attachment, and vacuumize can obtain stainless steel-based polyaniline to electrode.
Testing result: by the stereoscan photograph of polyaniline (Fig. 1-d) as can be known, when constant voltage is 1.2V, polyaniline grows is that diameter is in the 500nm scope, length is the nanofiber pattern about 1.5 μ m, explanation is along with voltage continues to raise, it is large-sized polyaniline fiber that short nanometer rods increases thick growth, has caused the specific area of polyaniline to descend, and is unfavorable for the absorption of liquid electrolyte.Through the test of four point probe conductivity meter, this polyaniline is 1.303S/cm to the conductivity of electrode.
The first step earlier soaks a slice stainless steel substrates and another large-sized slightly stainless steel substrates in the alkali lye oil removing, takes out the back with 50 ℃ of hot water injections, use 0 ℃ of cold water flush clean again after, substrate is put into chemical brightening solution carries out polishing, remove surperficial oxide layer.At last will be clean and dry stand-by with distilled water flushing through the substrate of polishing.
Second step added aniline and sulfuric acid in the entry, and being made into aniline monomer concentration is 0.1mol/L, and sulfuric acid solution concentration is the solution of 0.1mol/L, formed uniform and transparent mixed solution by magnetic agitation.Make the work electrode with slightly little stainless steel substrate, do electrode is put into the aniline-sulfuric acid solution for preparing, adopt galvanostatic method in the time of continuous stirring, at 0.2mA/cm with another large-sized slightly stainless steel substrates
2Electrochemical polymerization is 100 seconds under the electric current.Question response finishes the back and takes out print, rinses well repeatedly with dilution heat of sulfuric acid and the distilled water of 0.01mol/L successively, removes the reactant of surface attachment, and vacuumize can obtain stainless steel-based polyaniline to electrode.
The first step, earlier a slice stainless steel substrates and another large-sized slightly stainless steel substrates are soaked in the alkali lye oil removing, take out back with 65 ℃ of hot water injections, after using 15 ℃ of cold water flush clean again, substrate is put into chemical brightening solution carry out polishing, remove the oxide layer on surface, at last will be with distilled water flushing totally and dry stand-by through the substrate of polishing.
Second step added aniline and sulfuric acid in the entry, and being made into aniline monomer concentration is 0.3mol/L, and sulfuric acid solution concentration is the solution of 0.8mol/L, formed uniform and transparent mixed solution by magnetic agitation.Make the work electrode with slightly little stainless steel substrate, do electrode is put into the aniline-sulfuric acid solution for preparing, adopt galvanostatic method in the time of continuous stirring, at 2.5mA/cm with another large-sized slightly stainless steel substrates
2Electrochemical polymerization is 500 seconds under the electric current.Question response finishes the back and takes out print, rinses well repeatedly with dilution heat of sulfuric acid and the distilled water of 0.05mol/L successively, removes the reactant of surface attachment, and vacuumize can obtain stainless steel-based polyaniline to electrode.
Embodiment 7
The first step earlier soaks a slice stainless steel substrates and another large-sized slightly stainless steel substrates in the alkali lye oil removing, takes out the back with 80 ℃ of hot water injections, use 30 ℃ of cold water flush clean again after, substrate is put into chemical brightening solution carries out polishing, remove surperficial oxide layer.At last will be clean and dry stand-by with distilled water flushing through the substrate of polishing.
Second step added aniline and sulfuric acid in the entry, and being made into aniline monomer concentration is 0.5mol/L, and sulfuric acid solution concentration is the solution of 1.5mol/L, formed uniform and transparent mixed solution by magnetic agitation.Make the work electrode with slightly little stainless steel substrate, do electrode is put into the aniline-sulfuric acid solution for preparing, adopt galvanostatic method in the time of continuous stirring, at 5mA/cm with another large-sized slightly stainless steel substrates
2Electrochemical polymerization is 1000 seconds under the electric current.Question response finishes the back and takes out print, rinses well repeatedly with dilution heat of sulfuric acid and the distilled water of 0.1mol/L successively, removes the reactant of surface attachment, and vacuumize can obtain stainless steel-based polyaniline to electrode.
Embodiment 8
The first step earlier soaks a slice stainless steel substrates and another large-sized slightly stainless steel substrates in the alkali lye oil removing, takes out the back with 50 ℃ of hot water injections, use 0 ℃ of cold water flush clean again after, substrate is put into chemical brightening solution carries out polishing, remove surperficial oxide layer.At last will be clean and dry stand-by with distilled water flushing through the substrate of polishing.
Second step added aniline and sulfuric acid in the entry, and being made into aniline monomer concentration is 0.1mol/L, and sulfuric acid solution concentration is the solution of 0.1mol/L, formed uniform and transparent mixed solution by magnetic agitation.With the saturated calomel electrode is reference electrode, make the work electrode with slightly little stainless steel substrate, do electrode is put into the aniline-sulfuric acid solution for preparing with another large-sized slightly stainless steel substrates, adopt cyclic voltammetry in the time of continuous stirring, CONTROLLED POTENTIAL is at-0.2~0.9V, sweep speed is 10mV/s, and the scan round number of times is 100 times.Question response finishes the back and takes out print, rinses well repeatedly with dilution heat of sulfuric acid and the distilled water of 0.01mol/L successively, removes the reactant of surface attachment, and vacuumize can obtain stainless steel-based polyaniline to electrode.
Embodiment 9
The first step earlier soaks a slice stainless steel substrates and another large-sized slightly stainless steel substrates in the alkali lye oil removing, takes out the back with 65 ℃ of hot water injections, use 15 ℃ of cold water flush clean again after, substrate is put into chemical brightening solution carries out polishing, remove surperficial oxide layer.At last will be clean and dry stand-by with distilled water flushing through the substrate of polishing.
Second step added aniline and sulfuric acid in the entry, and being made into aniline monomer concentration is 0.3mol/L, and sulfuric acid solution concentration is the solution of 0.8mol/L, formed uniform and transparent mixed solution by magnetic agitation.With the saturated calomel electrode is reference electrode, make the work electrode with slightly little stainless steel substrate, do electrode is put into the aniline-sulfuric acid solution for preparing with another large-sized slightly stainless steel substrates, adopt cyclic voltammetry in the time of continuous stirring, CONTROLLED POTENTIAL is at-0.2~0.9V, sweep speed is 100mV/s, and the scan round number of times is 500 times.Question response finishes the back and takes out print, rinses well repeatedly with dilution heat of sulfuric acid and the distilled water of 0.05mol/L successively, removes the reactant of surface attachment, and vacuumize can obtain stainless steel-based polyaniline to electrode.
Embodiment 10
The first step earlier soaks a slice stainless steel substrates and another large-sized slightly stainless steel substrates in the alkali lye oil removing, takes out the back with 80 ℃ of hot water injections, use 30 ℃ of cold water flush clean again after, substrate is put into chemical brightening solution carries out polishing, remove surperficial oxide layer.At last will be clean and dry stand-by with distilled water flushing through the substrate of polishing.
Second step added aniline and sulfuric acid in the entry, and being made into aniline monomer concentration is 0.5mol/L, and sulfuric acid solution concentration is the solution of 1.5mol/L, formed uniform and transparent mixed solution by magnetic agitation.With the saturated calomel electrode is reference electrode, make the work electrode with slightly little stainless steel substrate, do electrode is put into the aniline-sulfuric acid solution for preparing with another large-sized slightly stainless steel substrates, adopt cyclic voltammetry in the time of continuous stirring, CONTROLLED POTENTIAL is at-0.2~0.9V, sweep speed is 200mV/s, and the scan round number of times is 1000 times.Question response finishes the back and takes out print, rinses well repeatedly with dilution heat of sulfuric acid and the distilled water of 0.1mol/L successively, removes the reactant of surface attachment, and vacuumize can obtain stainless steel-based polyaniline to electrode.
With the foregoing description 2,3, electrode is assembled into DSSC and based on platinum plating the DSSC of electrode (Dyesol company, Australia) is carried out photoelectric properties and detect in 4.
Described DSSC is earlier with a small amount of TiO
2Slurry,, at 450 ℃ of annealing in process 30min, takes out when being cooled to 100 ℃ after drying at the ITO conductive glass surface with the glass bar roller coating, is immersed in 24h in the ethanol solution of 0.5mmol/L dyestuff N719, afterwards with TiO
2Light anode and to the electrode clamp, drip a little by the 0.05mol/L elemental iodine, 0.5mol/L lithium iodide, 0.4mol/L1-methyl-3-propyl imidazole iodine, 0.5mol/L the liquid iodophor ionic electrolytes that 4-tert .-butylpyridine and 5mL methoxypropionitrile are formed is to two electrode gaps, the DSSC of assembling paired electrode compares, and is as shown in table 1.
Table 1, difference are assembled into DSSC photoelectric properties testing result to electrode
The electrode of DSSC | Open circuit voltage mV | Short circuit current mA/cm 2 | Fill factor, curve factor | Photoelectric conversion efficiency |
Among the |
??700 | ??6.35 | ??0.596 | ??2.65% |
Among the |
??610 | ??4.92 | ??0.546 | ??1.64% |
Among the |
??610 | ??4.64 | ??0.509 | ??1.44% |
Existing platinum plating is to electrode | ??680 | ??3.72 | ??0.569 | ??1.44% |
Claims (2)
1. one kind based on the preparation method of stainless steel surfaces electrochemical synthesized polyaniline to electrode, it is characterized in that may further comprise the steps:
The first step, the preliminary treatment of stainless steel substrate:
Two stainless steel substrate → alkali cleaning oil removing → 50~80 ℃ hot water wash → 0~30 ℃ of cold wash → chemical polishing → distillation washing → oven dry that size differs;
In second step, polyaniline is to the preparation of electrode:
(a) aniline monomer and sulfuric acid are added stir in the entry that to form aniline monomer concentration be 0.1~0.5mol/L, sulfuric acid solution concentration is the mixed solution of 0.1~1.5mol/L;
(b) choose the little stainless steel substrate of size and make the work electrode, the stainless steel substrate that size is big is done electrode;
(c) two electrodes are placed mixed solution, continue to stir;
(d) in mixed solution, make aniline monomer at the stainless steel base surface aggregate, form the cyan polyaniline film of one deck by electrochemical method for synthesizing;
(e) take out electrode, with carrying out vacuum drying treatment behind 0.01mol/L~0.1mol/L dilution heat of sulfuric acid, the distilled water flushing, obtain polyaniline successively electrode.
2. according to claim 1 a kind of based on the preparation method of stainless steel surfaces electrochemical synthesized polyaniline to electrode, it is characterized in that: described electrochemical method for synthesizing is a potentiostatic method, the work electrode current potential is 0.8~1.2V, and polymerization time is 1000~4000s; Perhaps galvanostatic method, Faradaic current is 0.2~5mA/cm
2, polymerization time is 100~1000s; Or cyclic voltammetry, CONTROLLED POTENTIAL is at-0.2~0.9V, and sweep speed is 10~200mV/s, and the scan round number of times is 100~1000 times.
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