CN106783185B - A kind of novel environmental solar energy collector based on sensitizing dyestuff - Google Patents

A kind of novel environmental solar energy collector based on sensitizing dyestuff Download PDF

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CN106783185B
CN106783185B CN201611162774.XA CN201611162774A CN106783185B CN 106783185 B CN106783185 B CN 106783185B CN 201611162774 A CN201611162774 A CN 201611162774A CN 106783185 B CN106783185 B CN 106783185B
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graphene
porous semiconductor
layer
tio
semiconductor layer
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CN106783185A (en
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李晓宁
吴婷婷
易晶正
宫大为
刘洋
叶小龙
梁巍
陈亮
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a kind of novel environmental solar energy collector based on sensitizing dyestuff, belong to new energy source energy-saving technical field, the laminated laminated formation electrical contact of nano porous semiconductor with light anode of the electro-conductive glass of light anode, the lower surface of the conductive glass layer is nano porous semiconductor layer, the lower surface of nano porous semiconductor layer is sensitizing dyestuff layer, the lower surface of sensitizing dyestuff layer is redox electrolyte layer, and the lower surface of redox electrolyte layer is to electrode.The present invention advantage strong using graphene intensity height and current-carrying capability, makes graphene and TiO2Nano porous semiconductor film is made in certain process conditions, improves the efficiency of photoelectric conversion, and further decrease the manufacturing cost of dye-sensitized nano-crystalline solar collector, stability is further enhanced for manufacturing to electrode using graphene substitution Pt.

Description

A kind of novel environmental solar energy collector based on sensitizing dyestuff
Technical field
The present invention relates to a kind of new energy source energy-saving technical field, in particular to a kind of novel environmental based on sensitizing dyestuff is too Positive energy collecting device.
Background technique
How solar energy is developed and used, is one of the effective means for solving current energy problem.Solar energy at present Battery is the device that can preferably convert solar energy into electrical energy, and there are two systems for the solar battery being relatively expected.One For siliceous polysilicon semiconductor solid state battery module, another is the dye-sensitized solar cells containing liquid electrolyte.At present Developing most mature solar battery is silica-based solar cell, and the efficiency of monocrystaline silicon solar cell has reached 25% or more, But it to the purity requirement height of material, complex manufacturing technology, expensive, this greatly limits its extensive uses.Separately A kind of dye sensitized nano crystal salar battery, the cost of material used is low, and manufactures and be easy, it is only necessary to which simple manufacture is set It is standby, therefore the cost of manufacture of solar battery can be greatly reduced, it is acknowledged as one of most potential renewable sources of energy at present, But its incident photon-to-electron conversion efficiency is only 7.1%.
Typical dye sensitized nano crystal salar battery is by light anode, electrolyte, sensitizer and to four part group of electrode At wherein light anode is generally TiO2Membrane electrode is generally platinum to electrode to electrode.Catalysis reduction is wherein mainly played to electrode The effect of electrolyte, in order to guarantee to have electrode enough catalytic activity, typical way is to introduce platinum as catalysis material. But platinum not only increases the cost of material as noble metal, and because long-time is impregnated in the electrolyte, exists easily rotten The phenomenon that erosion, (generates PtI4).Therefore, development cost is low, catalysis material of high stability becomes problem in the urgent need to address.
Semiconductor material in DSSC light anode mostly uses porous TiO2, it is the carrier of dye molecule, while being separated simultaneously Transmit charge.And currently, two methods are mainly used in order to improve the incident photon-to-electron conversion efficiency of dye cell, first is that increasing TiO2 Specific surface area and improvement TiO2Surface-active；Second is that finding substitution TiO2Other semiconductor materials.
For increase TiO2Specific surface area and improvement TiO2The settling mode of surface-active, a kind of dye sensitization of denomination of invention Solar battery, application No. is 201610123180.1, provide similar settling mode optoelectronic pole far from conductive media one Side sets light absorbing layer, increases the uptake of light, is being equipped with reflection layer far from the side of conductive media to electrode, can make to penetrate Second transparent substrate in electrode is reflected back into solar battery without absorbed light, weight and to solve light utilization efficiency not high The problem of, but its reaction efficiency without fundamentally solving the problems, such as light.
TiO can be substituted for finding2Other semiconductor materials solution, denomination of invention one kind is based on surface etc. The solar battery and preparation method thereof of gas ions enhancing principle is disclosed application No. is 201410126280.0 in broad stopband One layer of light is assembled above semiconductor and excites dyestuff, while the deposited metal film on graphene film, and metal is formed by annealing and is received Rice grain；Then the graphene for being formed with metal nanoparticle is assembled on the semiconductor for being adsorbed with dyestuff, under light illumination, gold The local surface phasmon of metal nano-particle can greatly enhance circumgranular local electromagnetic field, the light field energy converged Amount can be such that the electron hole pair of light excitation dyestuff is efficiently separated, and then by wide bandgap semiconductor by light induced electron and hole It separates, improves the incident photon-to-electron conversion efficiency of battery device, but it could not promote electronics using technique and technology to greatest extent and pass Conductance and inhibition charge recombination rate, the effect for promoting incident photon-to-electron conversion efficiency are very limited.
Therefore, it is necessary to be directed to above-mentioned problem, existing dye-sensitized solar cells is improved, can overcome makes Use platinum as the etching problem to electrode, and substitution TiO2When semiconductor material, the photoelectricity of promotion dye cell that can be more efficient Transformation efficiency.
Summary of the invention
In order to overcome the problems in background technique, the present invention proposes a kind of novel environmental solar energy based on sensitizing dyestuff Collector uses graphene and TiO2The semiconductor of nanoporous is prepared, is solved using coating process to dye-sensitized nano Brilliant solar cell photoelectric transformation efficiency promotes little problem, while graphene being used to replace platinum to make to electrode as catalyst Bring etching problem.
To achieve the goals above, the present invention realizes in the following way: described a kind of based on sensitizing dyestuff Novel environmental solar energy collector include light anode, sensitizing dyestuff layer, redox electrolyte layer, to electrode, the light Anode includes conductive glass layer and nano porous semiconductor layer, and the electro-conductive glass is laminated with nano porous semiconductor layer one Face forms electrical contact；The lower surface of conductive glass layer is nano porous semiconductor layer, the lower surface of nano porous semiconductor layer Lower surface for sensitizing dyestuff layer, sensitizing dyestuff layer is redox electrolyte layer, and the lower surface of redox electrolyte layer is To electrode, the nano porous semiconductor layer is by graphene and TiO2It is mixed with；Described is prepared electrode by graphene.
The preparation is nano-sheet to the graphene of electrode.
The nano porous semiconductor layer with a thickness of 40-50um.
The graphene nanometer sheet is with a thickness of 40-50um.
The manufacturing step of the nano porous semiconductor layer is as follows:
Step a. is by TiO2Respectively with 60-80 DEG C of heating, drying 10-20min, it is extra to remove for crystalline flour and graphene powder Moisture.
Step b. that 2.5-3g is heavy nanoscale TiO2Crystalline flour and 0.5g graphene powder are put into mortar, then with grinding Pestle will generate the TiO of agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
Step c.1-2min after, be added 5-6 drop through diluting, pH value be 3-4 acetic acid solution, continue to grind, repeatedly it is above-mentioned Process is until form the smooth colloidal suspension object of texture.
Step d. stops grinding, obtains graphene and TiO2The nano porous semiconductor layer material being mixed with.
Further, the TiO in the manufacturing step a of the nano porous semiconductor layer2The temperature of crystalline flour heating is 65 DEG C, heating time 15min.
Further, the interval time in the manufacturing step c of the nano porous semiconductor layer is 1min, is diluted to PH Value is 3-4.
Described is as follows to the manufacturing step of electrode:
Step a. is by graphene GNs, carboxyl methyl cellulose, ethanol water by ground and mixed until forming carbon slurry State, wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 5-10:1.
Step b. uses scraper by graphene GNs, the carboxyl methyl cellulose, second of the carbon pulpous state state in the step a of acquisition The mixture of alcohol solution forms the carbon film with a thickness of 40-50um coated on the electro-conductive glass of fluorine-doped tin oxide FTO.
C. the electro-conductive glass for being coated with carbon film obtained in step b is kept the temperature 1-2h and be made under conditions of 100-150 DEG C To electrode.
Further, in the manufacturing step to electrode in step b by graphene GNs, the carboxymethyl of carbon pulpous state state Cellulose CMC, ethanol water mixture coated in fluorine-doped tin oxide FTO electro-conductive glass on, make the thickness to form carbon film Degree is 45um.
Beneficial effects of the present invention: the present invention manufactures dye sensitized nano crystal using the good physical-chemical performance of graphene Solar battery, the high feature of the performance and carrier mobility for making full use of its intensity high, on the one hand using graphene and TiO2Nano porous semiconductor layer is made by certain process conditions, improves the light of dye sensitized nano crystal salar battery On the other hand electrotransformation rate uses graphene to improve substitution Pt as the catalyst to electrode by science, overcomes Pt conduct It is easily corroded to electrode, the problem that material cost is high, stability is low reduces the manufacture of dye sensitized nano crystal salar battery Cost.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention；
Fig. 2 is dye sensitized nano crystal salar battery operation principle schematic diagram；
Fig. 3 is TiO2Crystalline flour and the asynchronous short circuit current curve graph of graphene mass ratio；
Fig. 4 is the asynchronous short circuit current curve graph of mass ratio of graphene GNs and carboxyl methyl cellulose.
In figure, 1- conductive glass layer, 2- nano porous semiconductor layer, 3- light anode, 4- sensitizing dyestuff layer, 5- redox Electrolyte layer, 6- are to electrode.
Specific embodiment
It is right below in conjunction with attached drawing in order to be clearer and more clear the purpose of the present invention, technical scheme and beneficial effects The preferred embodiment of the present invention is described in detail, to facilitate the technical staff to understand.
As shown in Fig. 2, in solar cells, photoelectric conversion process is commonly divided into light excitation and generates electron hole pair, The separation of electron hole pair, to conveying of external circuit etc. three.The wherein excitation state of S3 sensitizers, S0 are the base of sensitizer State, S+ is that the oxidation state of sensitizer is different with traditional p-n junction solar battery, in dye sensitization sodium rice crystalline substance solar cell, The capture of light and the transmission of charge are carried out separately, and the capture of light is completed by dye molecule, and dye molecule absorbs photon Afterwards, the dye molecule for being in excitation state produces central ion to the charge migration of ligand, and electronics is injected into TiO by ligand2 Conduction band, then pass through porous TiO2Film is transferred to light anode, from external circuit by load transmission to counterelectrode, while dyestuff Molecule realizes the separation of charge by the I- ion reduction in electrolyte, and the redox electronics in electrolyte is passed to by hole It is defeated arrive counterelectrode, it is compound with electronics, complete one circulation.Since space charge layer, dyestuff electricity being not present in nano crystal semiconductor It is not to realize by space charge layer, and must rely on the velocity constant and electronics for controlling each reaction that charge in pond, which efficiently separates, Movement speed is realized.
Embodiment 1
A kind of novel environmental solar energy collector based on sensitizing dyestuff includes light anode 3, sensitizing dyestuff layer 4, redox electrolyte layer 5, to electrode 6, the light anode 3 includes conductive glass layer 1 and nano porous semiconductor layer 2； The conductive glass layer 1 forms electrical contact, the lower surface of conductive glass layer 1 while with nano porous semiconductor layer 2 For nano porous semiconductor layer 2, the lower surface of nano porous semiconductor layer 2 is sensitizing dyestuff layer 4, the following table of sensitizing dyestuff layer 4 Face is redox electrolyte layer 5, and the lower surface of redox electrolyte layer 5 is to electrode 6, the nano porous semiconductor Layer 2 is by graphene and TiO2It is mixed with.
The nano porous semiconductor layer 2 with a thickness of 40-50um, the nano porous semiconductor layer of production can be made flat It is whole, it is firmly combined, and defect is few.
The graphene nanometer sheet is with a thickness of 40-50um, and the smooth to electrode surface of acquisition, defect are small, electro-conductive glass The porous electrode being firmly combined.
The manufacturing step of the nano porous semiconductor layer is as follows:
Step a. is by TiO2Respectively with 60-80 DEG C of heating, drying 10-20min, it is extra to remove for crystalline flour and graphene powder Moisture.
Step b. that 2.5-3g is heavy nanoscale TiO2Crystalline flour and 0.5g graphene powder are put into mortar, then with grinding Pestle will generate the TiO of agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
Step c.1-2min after, be added 5-6 drop through diluting, pH value be 3-4 acetic acid solution, continue to grind, repeatedly it is above-mentioned Process is until form the smooth colloidal suspension object of texture.
Step d. stops grinding, obtains graphene and TiO2The nano porous semiconductor layer material being mixed with.
Further, the TiO in the manufacturing step a of the nano porous semiconductor layer2The temperature of crystalline flour heating is 65 DEG C, heating time 15min.
Further, the nanoscale TiO of the 3g weight in the manufacturing step b of the nano porous semiconductor layer2Crystalline flour The graphene powder of 0.5g weight be put into mortar, uniformly grind, cost-saved to be conducive to manufacture, and discharge current is larger.
Further, the interval time in the manufacturing step c of the nano porous semiconductor layer is 1min, is diluted to PH Value is 3-4, and the Nano semiconductor layer defects produced can be made few, smooth.
Described is as follows to the manufacturing step of electrode:
Step a. is by graphene GNs, carboxyl methyl cellulose, ethanol water by ground and mixed until forming carbon slurry State, wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 5-10:1.
Step b. uses scraper by graphene GNs, the carboxyl methyl cellulose, second of the carbon pulpous state state in the step a of acquisition The mixture of alcohol solution forms the carbon film with a thickness of 40-50um coated on the electro-conductive glass of fluorine-doped tin oxide FTO.
C. the electro-conductive glass for being coated with carbon film obtained in step b is kept the temperature 1-2h and be made under conditions of 100-150 DEG C To electrode.
Further, by graphene GNs, carboxyl methyl cellulose, ethanol water in the manufacturing step b to electrode Solution is by ground and mixed until form carbon pulpous state state, and wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 5:1, Conducive to reducing cost, and the voltage stabilization of battery.
Further, by graphene GNs, the carboxymethyl cellulose of carbon pulpous state state in the manufacturing step b to electrode CMC, ethanol water mixture coated on the electro-conductive glass of fluorine-doped tin oxide FTO, make to be formed carbon film with a thickness of 45um。
Further, item of the manufacture to the electro-conductive glass in the step c of electrode coated with carbon film at 125-150 DEG C Under part, heat preservation 1-2h is made to electrode.
Embodiment 2
A kind of novel environmental solar energy collector based on sensitizing dyestuff includes light anode 3, sensitizing dyestuff layer 4, redox electrolyte layer 5, to electrode 6, the light anode 3 includes conductive glass layer 1 and nano porous semiconductor layer 2； The conductive glass layer 1 forms electrical contact, the lower surface of conductive glass layer 1 while with nano porous semiconductor layer 2 For nano porous semiconductor layer 2, the lower surface of nano porous semiconductor layer 2 is sensitizing dyestuff layer 4, the following table of sensitizing dyestuff layer 4 Face is redox electrolyte layer 5, the lower surface of redox electrolyte layer 5 be to electrode 6, it is described to electrode 6 by graphite Alkene preparation.
The preparation is nano-sheet to the graphene of electrode 6, and the graphene nanometer sheet GNs that multi-layer graphene is piled up is not Only preferably inherit the characteristic of graphene, and diversity and adjustability with pattern and crystal structure.
The graphene nanometer sheet keeps the smooth to electrode surface of acquisition, defect small, conductive glass with a thickness of 40-50um The porous electrode that glass is firmly combined.The manufacturing step of the nano porous semiconductor layer is as follows:
Step a. is by TiO2Respectively with 60-80 DEG C of heating, drying 10-20min, it is extra to remove for crystalline flour and graphene powder Moisture.
Step b. that 2.5-3g is heavy nanoscale TiO2Crystalline flour and 0.5g graphene powder are put into mortar, then with grinding Pestle will generate the TiO of agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
Step c.1-2min after, be added 5-6 drop through diluting, pH value be 3-4 acetic acid solution, continue to grind, repeatedly it is above-mentioned Process is until form the smooth colloidal suspension object of texture.
Step d. stops grinding, obtains graphene and TiO2The nano porous semiconductor layer material being mixed with.
Further, the TiO in the manufacturing step a of the nano porous semiconductor layer2The temperature of crystalline flour heating is 75 DEG C, heating time 15min is cost-saved to be conducive to manufacture, and discharge current is larger.
Further, the nanoscale TiO of the 3g weight in the manufacturing step b of the nano porous semiconductor layer2Crystalline flour 0.5g weight graphene powder be put into mortar, uniformly grind.
Further, the interval time in the manufacturing step c of the nano porous semiconductor layer is 1min, is diluted to PH Value is 3-4, keeps the smooth to electrode surface of acquisition, defect small, the porous electrode that electro-conductive glass is firmly combined.
Described is as follows to the manufacturing step of electrode:
Step a. is by graphene GNs, carboxyl methyl cellulose, ethanol water by ground and mixed until forming carbon slurry State, wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 5-10:1.
Step b. uses scraper by graphene GNs, the carboxyl methyl cellulose, second of the carbon pulpous state state in the step a of acquisition The mixture of alcohol solution forms the carbon film with a thickness of 40-50um coated on the electro-conductive glass of fluorine-doped tin oxide FTO.
C. the electro-conductive glass for being coated with carbon film obtained in step b is kept the temperature 1-2h and be made under conditions of 100-150 DEG C To electrode.
Further, by graphene GNs, carboxyl methyl cellulose, ethanol water in the manufacturing step b to electrode Solution is by ground and mixed until form carbon pulpous state state, and wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 5:1, Conducive to reducing cost, and the voltage stabilization of battery.
Further, by graphene GNs, the carboxymethyl cellulose of carbon pulpous state state in the manufacturing step b to electrode CMC, ethanol water mixture coated on the electro-conductive glass of fluorine-doped tin oxide FTO, make to be formed carbon film with a thickness of 45- 50um, what is produced is few to electrode defects, smooth.
Further, item of the manufacture to the electro-conductive glass in the step c of electrode coated with carbon film at 125-150 DEG C Under part, heat preservation 1-2h is made to electrode.
Embodiment 3 is as shown in Figure 1, a kind of novel environmental solar energy collector based on sensitizing dyestuff includes light Anode 3, sensitizing dyestuff layer 4, redox electrolyte layer 5, to electrode 6, the light anode 3 includes conductive glass layer 1 and receives Rice porous semiconductor layer 2；The conductive glass layer 1 forms electrical contact while with nano porous semiconductor layer 2, conductive The lower surface of glassy layer 1 is nano porous semiconductor layer 2, and the lower surface of nano porous semiconductor layer 2 is sensitizing dyestuff layer 4, quick The lower surface for changing dye coating 4 is redox electrolyte layer 5, and the lower surface of redox electrolyte layer 5 is to electrode 6, oxidation Restore electrolyte layer 5 lower surface be to electrode 6, it is described that electrode 6 is prepared by graphene.
The preparation is nano-sheet to the graphene of electrode 6, and the graphene nanometer sheet GNs that multi-layer graphene is piled up is not Only preferably inherit the characteristic of graphene, and diversity and adjustability with pattern and crystal structure.
The graphene nanometer sheet is with a thickness of 40-50um, and the smooth to electrode surface of acquisition, defect are small, electro-conductive glass The porous electrode being firmly combined.
The nano porous semiconductor layer 2 with a thickness of 40-50um, the nano porous semiconductor layer of production is smooth, knot It closes securely, and defect is few.
The manufacturing step of the nano porous semiconductor layer is as follows:
Step a. is by TiO2Respectively with 60-80 DEG C of heating, drying 10-20min, it is extra to remove for crystalline flour and graphene powder Moisture.
Step b. that 2.5-3g is heavy nanoscale TiO2Crystalline flour and 0.5g graphene powder are put into mortar, then with grinding Pestle will generate the TiO of agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
Step c.1-2min after, be added 5-6 drop through diluting, pH value be 3-4 acetic acid solution, continue to grind, repeatedly it is above-mentioned Process is until form the smooth colloidal suspension object of texture.
Step d. stops grinding, obtains graphene and TiO2The nano porous semiconductor layer material being mixed with.
Further, the TiO in the manufacturing step a of the nano porous semiconductor layer2The temperature of crystalline flour heating is 75 DEG C, heating time 15min.
Further, the nanoscale TiO of the 3g weight in the manufacturing step b of the nano porous semiconductor layer2Crystalline flour The graphene powder of 0.5g weight be put into mortar, uniformly grind, cost-saved to be conducive to manufacture, and discharge current is larger.
Further, the interval time in the manufacturing step c of the nano porous semiconductor layer is 1min, is diluted to PH Value is 3-4.
Described is as follows to the manufacturing step of electrode:
Step a. is by graphene GNs, carboxyl methyl cellulose, ethanol water by ground and mixed until forming carbon slurry State, wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 5-10:1.
Step b. uses scraper by graphene GNs, the carboxyl methyl cellulose, second of the carbon pulpous state state in the step a of acquisition The mixture of alcohol solution forms the carbon film with a thickness of 40-50um coated on the electro-conductive glass of fluorine-doped tin oxide FTO.
C. the electro-conductive glass for being coated with carbon film obtained in step b is kept the temperature 1-2h and be made under conditions of 100-150 DEG C To electrode.
Further, by graphene GNs, carboxyl methyl cellulose, ethanol water in the manufacturing step b to electrode Solution is by ground and mixed until form carbon pulpous state state, and wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 5:1, Conducive to reducing cost, and the voltage stabilization of battery.
Further, by graphene GNs, the carboxymethyl cellulose of carbon pulpous state state in the manufacturing step b to electrode CMC, ethanol water mixture coated on the electro-conductive glass of fluorine-doped tin oxide FTO, make to be formed carbon film with a thickness of 45- 50um。
Further, item of the manufacture to the electro-conductive glass in the step c of electrode coated with carbon film at 125-150 DEG C Under part, heat preservation 1-2h is made to electrode.
Experiment 1
Now embodiment 1 and semiconductor porous film are not added with the quick dye cell of graphene identical illumination condition, Short circuit current and open-circuit voltage are verified in the case where identical experiment material
Table one:
Experiment conclusion: illumination condition under the same conditions, the bulb brightness of embodiment 1, electric current are greater than TiO2Film Dye cell light bulb, embodiment 1 is compared to TiO2Dye cell short circuit current, the bulb brightness increase of metal film are coated, but not Obviously, it was demonstrated that graphene and TiO2The preparation process condition of the dye cell for the nano porous semiconductor layer being mixed with is conducive to Improve the optoelectronic transformation efficiency of dye cell.
Now by embodiment 2 and using Pt to the common dye battery of electrode section in different times, under the conditions of same light is shone Brightness, the current strength of light bulb are verified, the time interval set is 15 day.
Table two:
Table three:
After 15 days
Experiment conclusion: with the extension of time, the intensity of illumination of the lamp of common quick dye cell, electric current, which are less than, uses stone The preparation of black alkene nano material to electrode, it was demonstrated that Pt is easy to be corroded as catalyst generates PtI4.
Now by embodiment 1, implement 2, embodiment 3 tested under identical illumination condition, verify light bulb short circuit current and Open-circuit voltage
Table four:
Experiment conclusion: the light bulb intensity of illumination of embodiment 3, electric current are significantly greater than remaining two groups, and embodiment 3 was manufacturing It is overcome in journey single using graphene and TiO2The nano porous semiconductor film or single use graphene nano material of film The problem short to pole strength and service life is prepared, is furthermore also overcomed by graphene and TiO2It is film-made bring lamp current Strength Changes very little, the preparation of graphene nano material carry out electrode band, just start current strength and open-circuit voltage is all smaller.
Experiment 2
The manufacturing step of the nano porous semiconductor layer is as follows:
1. 0.5g graphene powder is put on the basis of mortar, nanoscale TiO2The ratio between crystalline flour and graphene powder are 3:1, It is put into mortar, then to grind the TiO that pestle will generate agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
2. 0.5g graphene powder is put on the basis of mortar, nanoscale TiO2The ratio between crystalline flour and graphene powder are 4:1, It is put into mortar, then to grind the TiO that pestle will generate agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
3. 0.5g graphene powder is put on the basis of mortar, nanoscale TiO2The ratio between crystalline flour and graphene powder are 6:1, It is put into mortar, then to grind the TiO that pestle will generate agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
4. 0.5g graphene powder is put on the basis of mortar, nanoscale TiO2The ratio between crystalline flour and graphene powder are 8:1, It is put into mortar, then to grind the TiO that pestle will generate agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
5. 0.5g graphene powder is put on the basis of mortar, nanoscale TiO2The ratio between crystalline flour and graphene powder are 10: 1, it is put into mortar, then to grind the TiO that pestle will generate agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
6. 0.5g graphene powder is put on the basis of mortar, nanoscale TiO2The ratio between crystalline flour and graphene powder are 15: 1, it is put into mortar, then to grind the TiO that pestle will generate agglomeration2Crystalline flour uniformly grinds with graphene powder and comes.
The TiO in manufacturing step in identical process conditions, by changing nano porous semiconductor layer2Crystalline flour and graphite Alkene powder mass ratio examines light bulb short circuit current
Experiment conclusion: as shown in figure 3, in the case where meeting manufacturing cost and photoelectric conversion rate is optimal, TiO2Crystalline flour and The mass ratio of graphene powder is abscissa, and ordinate is short circuit current, TiO2The mass ratio of crystalline flour and graphene powder is 5- 6:1, the short circuit current of dye cell is 4-4.3mA at this time.
Experiment 3
1. by graphene GNs, carboxyl methyl cellulose, ethanol water by ground and mixed up to forming carbon pulpous state state, Wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 1:1.
2. by graphene GNs, carboxyl methyl cellulose, ethanol water by ground and mixed up to forming carbon pulpous state state, Wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 5:1.
3. by graphene GNs, carboxyl methyl cellulose, ethanol water by ground and mixed up to forming carbon pulpous state state, Wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 10:1.
4. by graphene GNs, carboxyl methyl cellulose, ethanol water by ground and mixed up to forming carbon pulpous state state, Wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 15:1.
5. by graphene GNs, carboxyl methyl cellulose, ethanol water by ground and mixed up to forming carbon pulpous state state, Wherein the mass ratio of graphene GNs and carboxyl methyl cellulose is 20:1.
In identical process conditions, by changing to the graphene GNs and carboxymethyl cellulose in the manufacturing step of electrode The mass ratio of CMC examines light bulb short circuit current
Experiment conclusion: as shown in figure 4, in the case where meeting that manufacturing cost is low and stability is good, graphene GNS, carboxylic first Base cellulose CMC mass ratio is abscissa, and ordinate is short circuit current, and graphene GNS, carboxyl methyl cellulose mass ratio are 5-10:1, the short circuit current of dye cell is 3-3.5mA at this time.
Experimental method described in above-described embodiment is unless otherwise specified conventional method.
Finally, it is stated that described above is the preferred embodiment of the present invention, although by above preferred embodiment, Through invention is explained in detail, however, those skilled in the art should understand that, can be in the form and details to it It is variously modified, without departing from range required by claims of the present invention.

Claims (4)

1. a kind of novel environmental solar energy collector based on sensitizing dyestuff, the novel environmental solar energy based on sensitizing dyestuff Collector include light anode, sensitizing dyestuff layer, redox electrolyte layer, to electrode, the light anode includes electro-conductive glass Layer and nano porous semiconductor layer, the electro-conductive glass are laminated with the laminated formation electrical contact of nano porous semiconductor； The lower surface of conductive glass layer is nano porous semiconductor layer, and the lower surface of nano porous semiconductor layer is sensitizing dyestuff layer, quick The lower surface for changing dye coating is redox electrolyte layer, and the lower surface of redox electrolyte layer is to electrode, and described receives Rice porous semiconductor layer is by graphene and TiO2It is mixed with；Described is prepared electrode by graphene, it is characterised in that: nanometer The manufacturing step of porous semiconductor layer is as follows:
Step a. is by TiO2Crystalline flour and graphene powder remove extra moisture respectively with 60-80 DEG C of heating, drying 10-20min；
Step b. that 2.5-3g is heavy nanoscale TiO2Crystalline flour and 0.5g graphene powder are put into mortar, then will to grind pestle Generate the TiO of agglomeration2Crystalline flour uniformly grinds with graphene powder and comes；
Step c.1-2min after, be added 5-6 drop through diluting, pH value be 3-4 acetic acid solution, continue to grind, repeat the above process Until forming the smooth colloidal suspension object of texture；
Step d. stops grinding, obtains graphene and TiO2The nano porous semiconductor layer material being mixed with.
2. a kind of novel environmental solar energy collector based on sensitizing dyestuff according to claim 1, it is characterised in that: TiO in the manufacturing step a of the nano porous semiconductor layer2The temperature of crystalline flour heating is 65 DEG C, and drying time is 15min。
3. a kind of novel environmental solar energy collector based on sensitizing dyestuff according to claim 1, it is characterised in that: The nano porous semiconductor layer with a thickness of 40-50um.
4. a kind of novel environmental solar energy collector based on sensitizing dyestuff according to claim 1, it is characterised in that: The preparation is nano-sheet to the graphene of electrode.
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