CN103839686B - A kind of DSSC fabric light anode and preparation method thereof - Google Patents
A kind of DSSC fabric light anode and preparation method thereof Download PDFInfo
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- CN103839686B CN103839686B CN201410091354.1A CN201410091354A CN103839686B CN 103839686 B CN103839686 B CN 103839686B CN 201410091354 A CN201410091354 A CN 201410091354A CN 103839686 B CN103839686 B CN 103839686B
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The present invention relates to a kind of DSSC fabric light anode and preparation method thereof, belong to technical field of solar.The present invention is with fabric for base material, plating layer of metal nickel, obtains conductive fabric on the surface of the fabric, then on conductive fabric electrophoresis deposited porous Nanometer Semiconductor Films material, then calcine under the oxygen free condition of 300 DEG C, it is thus achieved that DSSC fabric light anode.The preparation method of the present invention is simple, and cost of material is low, consuming little energy, pollutes little.The advantages such as DSSC fabric light anode prepared by the present invention has light weight, and the adhesion between porous nano semiconductor film material and conductive fabric substrate is strong, and photoelectricity transmission is fast, flexible, any curling rear flawless.Solaode prepared by the DSSC fabric light anode of the present invention can be widely applied to curtain, tent, clothing.
Description
Technical field
The present invention relates to a kind of DSSC fabric light anode and preparation method thereof.Be specially and adopt the method for chemical nickel plating to plate layer of metal nickel on fabric substrate, and on metallic nickel surface a kind of nano-porous film material of deposition, under the oxygen free condition of 300 DEG C, calcine the light anode as DSSC after a period of time.Belong to DSSC technology of preparing.
Background technology
Solar energy as a kind of use not to the utmost, the energy of inexhaustible clean type enjoy watching attentively of people.1991, the research group of Instituto Superior Technico of Lausanne, SUI federation professor Gratzel leader successfully developed employing nanoporous TiO2Semiconductor film is as optoelectronic pole, the efficiency of the DSSC assembled reaches 7.1%, its cost of manufacture is only the 1/5～1/10 of silicon solar cell, its cheap cost, the opto-electronic conversion performance of simple processing technology and stability and high efficiency, inexpensively utilizes solar energy to provide a kind of more effective means for the mankind.
DSSC is mainly by transparent conducting glass, nano-TiO2Semiconductor porous film, photosensitizer, electrolyte and to electrode form.The general electro-conductive glass that light anode is FTO or ITO and nano-TiO2Semiconductor porous film.Electro-conductive glass is used to not only increase the weight of battery, flexible poor, and also broken.Adding the process conditions complexity that its preparation needs, cost is high, limits the DSSC application in portable electronic field.In recent years, with flexibility, flexible, light weight, portable, the conducting PET of low cost and other advantages or conduction PEN receive the great attention of Chinese scholars and research institution as the DSSC of conductive substrates.People in the flow of research of the flexibility of DSSC, China Patent Publication No. CN101944437A, January 12 2011 publication date, denomination of invention is a kind of soft-light anode for flexible dye-sensitized solar battery and preparation method thereof, it is selected flexible and transparent base material and arranges metal grill thereon, filler it is coated with in the mesh of grid, it is then coated with conductive polymer thin polymer film, although the light anode prepared has certain pliability, but it is poor, obtained semiconductor film is smooth not and fine and close, and it is also poor at the adhesive force of substrate, complicated operation.ACSAppliedMaterialInterfaces, 2012.4.1709-1715, article name (High-performanceplasticDye-sensitizedsolarcellsBasedonlo w-costcommercialP25TiO2andoriganicDye), this article utilizes plastics PEN-ITO conductive base, electrophoretic deposition nano-titanium dioxide film, then film being pressurizeed, the light anode that the method prepares has a flexibility, but film poor adhesive force and prepare the complex process of ITO in substrate.
Summary of the invention
For above-mentioned existing problems, it is an object of the invention to provide and a kind of adopt fabric as dye-sensitized solar cell anode of light anode base material and preparation method thereof.To achieve these goals, the technical solution of the present invention is:
A kind of DSSC fabric light anode, described fabric light anode is by fabric substrate, conductive nickel layer, and porous semi-conductor nano material is constituted, conductive nickel layer is adsorbed on the outer surface of fabric substrate, and porous semi-conductor nano material is attached on conductive nickel layer top layer.
Described fabric substrate is bafta or linen or acrylic fabric or nylon fabric one therein.
The preparation method of a kind of DSSC fabric light anode, it specifically comprises the following steps that
The fabric substrate cleaned up is placed in the nickel salt that concentration is 0.05～0.25g/mL and the mixed aqueous solution that concentration is 0.02～0.25g/mL hydrochloric acid and impregnates after 10～30min by A, and taking out and putting into concentration is 0.01～0.2g/mLNaBH4Take out after dipping 10～30min with in the NaOH mixed aqueous solution of concentration 0.01～0.2g/mL, clean with deionized water；
It is 25～45g/L that fabric substrate after step A processes is put into nickel salt concentration by B, succinic acid concentration is 20～30g/L, malic acid concentration is 20～30g/L, ortho phosphorous acid na concn is in the mixed aqueous solution of 25～35g/L, temperature 65～80 DEG C, react 1h when pH value 7～9, at fabric substrate plated surface last layer conducting metal nickel, form conductive fabric base material；
Wherein said nickel salt is the one in nickel sulfate or nickel acetate or Nickel dichloride.；
C is by ethanol, isopropanol, n-butyl alcohol is made into 10mL mixed solution for 1:2:4 by volume, take 0.35g nano-oxide powder and put in mixed solution, aaerosol solution is become with after ultrasonic echography 30min, put in suspension by vertical with a piece of conductive fabric base material prepared through step B for piece of metal platinized platinum, wherein metal platinized platinum is as anode, conductive fabric is as negative electrode, connect the DC voltage 10～30min of 10V, under executing alive effect, charged nano-oxide in suspension moves on the top layer of the conductive nickel layer of the conductive fabric base material of negative electrode, then in the Muffle furnace of 300 DEG C of logical argon, calcine 30min, porous nano semiconductor film layer is formed on the top layer of conductive nickel layer, obtain DSSC fabric light anode.
Described nano-oxide powder is TiO2Or ZnO or WO3One.
Owing to have employed above technical scheme, DSSC fabric light anode of the present invention and preparation method thereof, utilize fabric absorption affinity strong, compliance is good, can any feature such as bending, using the fabric base material as dye-sensitized solar cell anode, good conductivity due to nickel, the corrosion of electrolyte-resistant, cheap, it is easy to the advantages such as preparation, utilize the method for chemical nickel plating to plate layer of metal nickel on fabric substrate, metallic nickel is adsorbed on textile surface uniformly so that it is become conductive fabric；Method deposited porous Nanometer Semiconductor Films material on conductive fabric of recycling electrophoretic deposition, then the method utilizing anaerobic high temperature sintering removes the organic solvent in porous nano semiconductor film material, porous nano semiconductor film material is attached to conductive fabric surface, and and between conductive fabric adhesion strong.The soft-light anode that the light anode that the present invention obtains has than prepared by additive method is high to the utilization rate of sunlight, light weight, portable, flexible, the electronics of the battery generation that the light anode unit of preparation is dressed up quickly can be transferred to external circuit and form the features such as photoelectric current.Solaode prepared by the DSSC fabric light anode of the present invention can be widely applied to curtain, tent, clothing.
Accompanying drawing explanation
Accompanying drawing is the schematic diagram of dye-sensitized solar cell anode of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, the invention will be further described, sees accompanying drawing.
The preparation of DSSC fabric light anode sequentially includes the following steps:
A kind of DSSC fabric light anode, described fabric light anode is by fabric substrate 1, conductive nickel layer 2, and porous semi-conductor nano material 3 is constituted, conductive nickel layer 2 is adsorbed on the outer surface of fabric substrate 1, and porous semi-conductor nano material 3 is attached on conductive nickel layer 2 top layer.
Described fabric substrate is bafta or linen or acrylic fabric or nylon fabric one therein.
The preparation method of a kind of DSSC fabric light anode, it specifically comprises the following steps that
The fabric substrate cleaned up is placed in the nickel salt that concentration is 0.05～0.25g/mL and the mixed aqueous solution that concentration is 0.02～0.25g/mL hydrochloric acid and impregnates after 10～30min by A, and taking out and putting into concentration is 0.01～0.2g/mLNaBH4Take out after dipping 10～30min with in the NaOH mixed aqueous solution of concentration 0.01～0.2g/mL, clean with deionized water；
It is 25～45g/L that fabric substrate after step A processes is put into nickel salt concentration by B, succinic acid concentration is 20～30g/L, malic acid concentration is 20～30g/L, ortho phosphorous acid na concn is in the mixed aqueous solution of 25～35g/L, temperature 65～80 DEG C, react 1h when pH value 7～9, at fabric substrate plated surface last layer conducting metal nickel, form conductive fabric base material.Nickel salt of the present invention is the one in nickel sulfate or nickel acetate or Nickel dichloride..
nullThe C present invention adopts the method for electrophoretic deposition that nano-oxide deposits to conductive fabric surface，It is specially ethanol，Isopropanol，N-butyl alcohol is made into 10mL mixed solution for 1:2:4 by volume，Take 0.35g nano-oxide powder to put in mixed solution，Aaerosol solution is become with after ultrasonic echography 30min，Put into vertical with a piece of conductive fabric base material prepared through step B for piece of metal platinized platinum in suspension，Wherein metal platinized platinum is as anode，Conductive fabric is as negative electrode，Connect the DC voltage 10～30min of 10V，Under executing alive effect，Charged nano-oxide in suspension moves on the top layer of the conductive nickel layer 2 of the conductive fabric base material of negative electrode，Then in the Muffle furnace of 300 DEG C of logical argon, calcine 30min，Porous nano semiconductor film layer 3 is formed on the top layer of conductive nickel layer 2，Obtain DSSC fabric light anode.Nano-oxide powder of the present invention is TiO2Or ZnO or WO3One, wherein nano-TiO2With nano-ZnO because of abundance, low price, handling ease, the advantage such as it is widely used as preferred nano-oxide, and nano-TiO2Relatively larger with the thin film reference area that nano-ZnO is formed, it is possible to adsorb more dyestuff, be conducive to the raising of battery efficiency.
Specific embodiment
Embodiment one
Selecting bafta as base material as stated above, respectively with detergent, dehydrated alcohol, deionized water cleans and dries when 60 DEG C.
Cleaned bafta is put into 50mL concentration and is 0.05g/mL nickel sulfate and concentration is, after impregnating 10min in 0.02g/mL mixed in hydrochloric acid aqueous solution, take out and be placed in the NaBH that 50mL concentration is 0.01g/mL4Take out after dipping 10min with in the mixed aqueous solution that concentration is 0.01g/mLNaOH, clean with deionized water and be placed in 100mL chemical plating fluid, at 65 DEG C, take out after reacting 1h when pH value is 7 and dry, prepare conductive sponge fabric.Wherein, chemical plating fluid consists of: nickel sulfate 25g/L, malic acid 20g/L, succinic acid 20g/L, sodium hypophosphite 25g/L.
By ethanol, isopropanol, n-butyl alcohol is made into 10mL mixed solution for 1:2:4 by volume, takes 0.35g nano-TiO2Powder is put in mixed solution, aaerosol solution is become with after ultrasonic echography 30min, put in suspension by vertical with the conductive sponge fabric substrate that a piece of above-mentioned steps prepares for piece of metal platinized platinum, wherein metal platinized platinum is as anode, conductive sponge fabric is as negative electrode, connect the DC voltage 10min of 10V, the charged nano-TiO under executing alive effect, in suspension2Move on the top layer of conductive nickel layer of the conductive sponge fabric substrate of negative electrode, in the Muffle furnace of 300 DEG C of logical argon, then calcine 30min, form porous nano quasiconductor TiO on the top layer of conductive sponge fabric nickel dam2Thin layer, obtains DSSC bafta light anode.
Embodiment two
Selecting linen as base material as stated above, respectively with detergent, dehydrated alcohol, deionized water cleans and dries when 60 DEG C.
Cleaned linen is put into 50mL concentration and is 0.025g/mL nickel acetate and concentration is, after impregnating 20min in 0.15g/mL mixed in hydrochloric acid aqueous solution, take out and be placed in the NaBH that 50mL concentration is 0.15g/mL4Take out after dipping 20min with in the mixed aqueous solution that concentration is 0.15g/mLNaOH, clean with deionized water and be placed in 100mL chemical plating fluid, at 75 DEG C, take out after reacting 1h when pH value is 8 and dry, prepare conduction linen.Wherein, chemical plating fluid consists of: nickel acetate 35g/L, malic acid 25g/L, succinic acid 25g/L, sodium hypophosphite 30g/L.
By ethanol, isopropanol, n-butyl alcohol is made into 10mL mixed solution for 1:2:4 by volume, take 0.35g nanometer ZnO powder and put in mixed solution, aaerosol solution is become with after ultrasonic echography 30min, put in suspension by vertical with the conduction linen base material that a piece of above-mentioned steps prepares for piece of metal platinized platinum, wherein metal platinized platinum is as anode, conduction linen is as negative electrode, connect the DC voltage 20min of 10V, under executing alive effect, charged nano-ZnO in suspension moves on the top layer of the conductive nickel layer of the conduction linen base material of negative electrode, then in the Muffle furnace of 300 DEG C of logical argon, calcine 30min, porous nano quasiconductor ZnO film layer is formed on the top layer of conduction linen nickel dam, obtain DSSC hemp object light anode.
Embodiment three
Selecting acrylic fabric as base material as stated above, respectively with detergent, dehydrated alcohol, deionized water cleans and dries when 60 DEG C.
Cleaned acrylic fabric is put into 50mL concentration and is 0.25g/mL Nickel dichloride. and concentration is, after impregnating 30min in 0.25g/mL mixed in hydrochloric acid aqueous solution, take out and be placed in the NaBH that 50mL concentration is 0.2g/mL4Take out after dipping 30min with in the mixed aqueous solution that concentration is 0.2g/mLNaOH, clean with deionized water and be placed in 100mL chemical plating fluid, at 80 DEG C, take out after reacting 1h when pH value is 9 and dry, prepare conductive acrylic fibre fabric.Wherein, chemical plating fluid consists of: Nickel dichloride. 45g/L, malic acid 30g/L, succinic acid 30g/L, sodium hypophosphite 35g/L.
By ethanol, isopropanol, n-butyl alcohol is made into 10mL mixed solution for 1:2:4 by volume, takes 0.35g nanometer of WO3Powder is put in mixed solution, aaerosol solution is become with after ultrasonic echography 30min, put in suspension by vertical with the conductive acrylic fibre fabric substrate that a piece of above-mentioned steps prepares for piece of metal platinized platinum, wherein metal platinized platinum is as anode, conductive acrylic fibre fabric is as negative electrode, connect the DC voltage 30min, charged nanometer of WO under executing alive effect, in suspension of 10V3Move on the top layer of conductive nickel layer of the conductive acrylic fibre fabric substrate of negative electrode, in the Muffle furnace of 300 DEG C of logical argon, then calcine 30min, form porous nano quasiconductor WO on the top layer of conductive acrylic fibre fabric nickel dam3Thin layer, obtains DSSC acrylic fabric light anode.
Embodiment four
Selecting nylon fabric as base material as stated above, respectively with detergent, dehydrated alcohol, deionized water cleans and dries when 60 DEG C.
Cleaned nylon fabric is put into 50mL concentration and is 0.025g/mL nickel sulfate and concentration is, after impregnating 30min in 0.15g/mL mixed in hydrochloric acid aqueous solution, take out and be placed in the NaBH that 50mL concentration is 0.15g/mL4Take out after dipping 30min with in the mixed aqueous solution that concentration is 0.15g/mLNaOH, clean with deionized water and be placed in 100mL chemical plating fluid, at 75 DEG C, take out after reacting 1h when pH value is 7 and dry, prepare conduction nylon fabric.Wherein, chemical plating fluid consists of: nickel sulfate 35g/L, malic acid 25g/L, succinic acid 25g/L, sodium hypophosphite 30g/L.
nullBy ethanol，Isopropanol，N-butyl alcohol is made into 10mL mixed solution for 1:2:4 by volume，Take 0.35g nanometer ZnO powder to put in mixed solution，Aaerosol solution is become with after ultrasonic echography 30min，Put into vertical with the conduction nylon fabric base material that a piece of above-mentioned steps prepares for piece of metal platinized platinum in suspension，Wherein metal platinized platinum is as anode，Conduction nylon fabric is as negative electrode，Connect the DC voltage 30min of 10V，Under executing alive effect，Charged nano-ZnO in suspension moves on the top layer of the conductive nickel layer of the conduction nylon fabric base material of negative electrode，Then in the Muffle furnace of 300 DEG C of logical argon, calcine 30min，Porous nano quasiconductor ZnO film layer is formed on the top layer of conduction nylon fabric nickel dam，Obtain DSSC nylon fabric light anode.
Claims (1)
1. the preparation method of a DSSC fabric light anode, it is characterised in that: preparation method specifically comprises the following steps that
The fabric substrate (1) cleaned up is placed in the nickel salt that concentration is 0.05～0.25g/mL and the mixed aqueous solution that concentration is 0.02～0.25g/mL hydrochloric acid and impregnates after 10～30min by A, and taking out and putting into concentration is 0.01～0.2g/mLNaBH4Take out after dipping 10～30min with in the NaOH mixed aqueous solution of concentration 0.01～0.2g/mL, clean with deionized water；
It is 25～45g/L that fabric substrate (1) after step A processes is put into nickel salt concentration by B, succinic acid concentration is 20～30g/L, malic acid concentration is 20～30g/L, ortho phosphorous acid na concn is in the mixed aqueous solution of 25～35g/L, temperature 65～80 DEG C, react 1h when pH value 7～9, plate last layer conductive nickel layer (2) at fabric substrate (1) outer surface, form conductive fabric base material；
Wherein, described nickel salt is the one in nickel sulfate or nickel acetate or Nickel dichloride.；
nullC is by ethanol，Isopropanol，N-butyl alcohol is made into 10mL mixed solution for 1:2:4 by volume，Take 0.35g nano-oxide powder to put in mixed solution，Aaerosol solution is become with after ultrasonic echography 30min，Put into vertical with a piece of conductive fabric base material prepared through step B for piece of metal platinized platinum in suspension，Wherein metal platinized platinum is as anode，Conductive fabric base material is as negative electrode，Connect the DC voltage 10～30min of 10V，Under executing alive effect，Charged nano-oxide in suspension moves on the top layer of conductive nickel layer (2) of the conductive fabric base material of negative electrode，Then in the Muffle furnace of 300 DEG C of logical argon, calcine 30min，Porous nano semiconductor film layer (3) is formed on the top layer of conductive nickel layer (2)，Obtain DSSC fabric light anode；
Described nano-oxide powder is TiO2Or ZnO or WO3One.
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| CN105047824B (en) * | 2015-07-10 | 2017-07-04 | 福建师范大学 | A kind of fabric as substrate organic solar batteries and preparation method thereof |
| CN110676461A (en) * | 2019-10-14 | 2020-01-10 | 湖北文理学院 | High-flexibility lithium ion battery fabric with flexible self-supporting function and preparation method thereof |
| CN114566389B (en) * | 2022-02-28 | 2024-01-09 | 天津工业大学 | Method for preparing photo-anode of fabric substrate and photocell |
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| CN102623186A (en) * | 2012-04-01 | 2012-08-01 | 东华大学 | Titanium-foil-based flexible dye-sensitized solar cell and preparation method thereof |
| CN103258650A (en) * | 2013-05-16 | 2013-08-21 | 武汉纺织大学 | Dye-sensitized solar cell fabric counter electrode and preparation method thereof |
| CN103346017A (en) * | 2013-07-17 | 2013-10-09 | 重庆大学 | Dye-sensitized solar cell photo anode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102623186A (en) * | 2012-04-01 | 2012-08-01 | 东华大学 | Titanium-foil-based flexible dye-sensitized solar cell and preparation method thereof |
| CN103258650A (en) * | 2013-05-16 | 2013-08-21 | 武汉纺织大学 | Dye-sensitized solar cell fabric counter electrode and preparation method thereof |
| CN103346017A (en) * | 2013-07-17 | 2013-10-09 | 重庆大学 | Dye-sensitized solar cell photo anode and preparation method thereof |
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