CN105679544B - A kind of DSSC copper manganese germanium sulphur is to electrode and preparation method thereof - Google Patents
A kind of DSSC copper manganese germanium sulphur is to electrode and preparation method thereof Download PDFInfo
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- CN105679544B CN105679544B CN201610015111.9A CN201610015111A CN105679544B CN 105679544 B CN105679544 B CN 105679544B CN 201610015111 A CN201610015111 A CN 201610015111A CN 105679544 B CN105679544 B CN 105679544B
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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
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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
- 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 DSSC copper manganese germanium sulphur to electrode and preparation method thereof, this includes conductive substrates to electrode, and copper manganese germanium sulphur of the conductive substrates surface coated with one layer of wurtzite structure is nanocrystalline；And the preparation to electrode is realized by the nanocrystalline ink of coated copper manganese germanium sulphur on conductive substrates.Nanocrystalline copper manganese germanium sulphur prepared by the application is synthesized by low temperature liquid polymerization process, has the advantages that size uniformity, crystallinity are high, monodispersity is good.Nanocrystalline copper manganese germanium sulphur prepared by this method is super cell's structure derived from buergerite, is rhombic system.When for DSSC to electrode, to I3 ‑The reduction of ion shows good catalytic activity.Compared with prior art, present invention process is simple, and prepared to electrode catalyst, not only catalytic effect is excellent, and cheap, and preparation method is simple, greatly reduces the production cost of DSSC, is adapted to industrialization large-scale production.
Description
Technical field
The present invention relates to a kind of area of solar cell, more particularly, to a kind of DSSC copper manganese germanium sulphur
To electrode and preparation method thereof.
Background technology
In recent years, with increasingly serious, the dye sensitization as one of third generation solar cell technology of energy problem
Solar cell is because with the advantages such as simple, the more low advantage of cost and higher energy conversion efficiency are assembled, causing section
Worker is ground widely to pay close attention to.Typical DSSC has " sandwich " structure, i.e., by light anode, electrolyte
Formed with to electrode.The operation principle of this kind of device is similar to the photosynthesis of nature.Under light illumination, dye molecule absorbs too
Sunlight is changed into excitation state from ground state, but excitation state is unstable, and ground state is returned to by discharging electronics.The electronics discharged passes through
The conduction band of titanium dioxide is simultaneously collected by conductive base, is transferred to external circuit and load is done work.To electrode/electrolyte interface
Generation catalytic reduction reaction, the electrolyte of oxidation state is reduced into middle condition, and the electrolyte of ground state further diffuses to light sun
Pole simultaneously reduces the dye molecule of oxidation state, so as to complete a circulation.It is therefore seen that it is dye sensitization of solar electricity to electrode
Important composition composition in pond, it is not only the medium of external circuit electronics circulation, and prior effect is the electricity of oxidation state
Solution matter is reduced into ground state, ensures the regeneration of dye molecule.Preferably should possess following condition to electrode material：(1) have high
Electronic catalytic activity, beneficial to catalysis I3 -Ion reduction is into I-；(2) resistance of electronics transfer is small；(3) in the environment of electrolyte,
With good electrochemical stability.What is be currently widely used for is the electro-conductive glass that surface is coated with one layer of platinum to electrode, and due to
The influence of the factors such as cost, abundance and the long-time stability of platinum, limit large-scale industrialization application.Therefore, substitute
Noble metal platinum turns into an important job in the application of field of dye-sensitized solar cells.
Up to now, researcher is prepared for a series of non-platinum to electrode material, such as carbon material
(Angew.Chem.Int.Ed.2013,52,3996；Energy Environ.Sci.2009,2,426), organic polymer
(J.Mater.Chem.2012,22,21624), and oxide (Chem.Commun.2013,49,5945；ChemSusChem2014,
7,442), nitride (ChemSusChem 2013,6,261) and metal chalcogenides (J.Am.Chem.Soc.2012,134,
10953；Angew.Chem.Int.Ed.2013,52,6694) etc..Conventional preparation method includes blade coating
(Chem.Eur.J.2015,doi:10.1002/chem.201406124), growth in situ (Chem.Commun.2014,50,
4824；Chem.Commun.2015,51,1846), electrochemical deposition (Chem.Eur.J.2014,20,474) and drop coating
(Chem.Eur.J.2013,19,10107) etc..
Chinese patent CN 104835649A disclose a kind of preparation side of DSSC silver sulfide to electrode
Method, including：Prepare silver sulfide nanocrystalline；Silver sulfide nanocrystalline is dissolved in solvent, handles to obtain silver sulfide through ultrasonic disperse and receives
The brilliant ink of rice；By silver sulfide nanocrystalline ink coated in substrate, substrate is heat-treated, dye sensitization of solar electricity is made
Pond silver sulfide is to electrode.However, these common binary semiconductor limited amounts, and nature parameters be all it is fixed, often not
Requirement of the DSSC ideal to electrode material can be met.For example, Ag2S, the band edge of the semiconductor such as CoS, NiS
What position was to determine, thus its electric conductivity and the physicochemical properties of material surface are also with fixation, thus be difficult to further
It is lifted to I3 -The electro catalytic activity of electricity pair.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of excellent performance, preparation
Simply, it is adapted to the DSSC copper manganese germanium sulphur of large-scale industrial production to electrode and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of DSSC copper manganese germanium sulphur is coated with to electrode, including conductive substrates, conductive substrates surface
The copper manganese germanium sulphur of one layer of wurtzite structure is nanocrystalline.
The nanocrystalline particle diameter of described copper manganese germanium sulphur is 10~100nm, the thickness of copper manganese germanium sulphur nano-crystalline layers for 0.01~
10μm。
Described conductive substrates include FTO, ITO, stainless steel, compliant conductive macromolecule or graphite.
The preparation method that the copper manganese germanium sulphur of described wurtzite structure is nanocrystalline comprises the following steps：
(1) mantoquita, manganese salt, ge source, surfactant and solvent are mixed, vacuumizes water removal deoxygenation, magnetic agitation, heating
To 60~120 DEG C and maintain 0.5~3 hour reactant is fully dissolved, whole reaction system is then passed through protection gas；
(2) above-mentioned reaction system is heated to 130~160 DEG C, injects sulphur source rapidly, be afterwards further heated to system
200~280 DEG C, and kept for 0.5~6 hour；
(3) question response terminates, and naturally cools to room temperature, and separation of solid and liquid operation, obtained precipitation are carried out after adding demulsifier
As copper manganese germanium sulphur is nanocrystalline.
Heating-up temperature in described step (1) is 100 DEG C；
The reaction system that step (1) obtains is heated to 140 DEG C in described step (2), 280 are heated to after injecting sulphur source
℃；
Demulsifier in described step (3) is absolute ethyl alcohol；Separation of solid and liquid is centrifuged using 8000rpm rotating speed.
Described mantoquita, manganese salt, the mol ratio of ge source and sulphur source are：(2~2.2):(l~1.2):(1~1.2):(4~
4.2)。
Described mantoquita in copper nitrate, copper acetate, acetylacetone copper, copper chloride, stannous chloride or copper bromide one
Kind is a variety of；
The one kind or more of described manganese salt in manganese acetylacetonate, manganous chloride, manganese nitrate, manganese acetate or manganese sulfate
Kind；
One or more of the described ge source in germanium tetrachloride, germanium oxide or germanium powder；
Described sulphur source is selected from sublimed sulfur, n- dodecyl mereaptan, tert-dodecyl mercaptan, thioacetamide, carbon disulfide or vulcanization
One or more in sodium；
One kind in n-octyl amine, lauryl amine, cetylamine, oleyl amine, octadecylamine, oleic acid, diphenyl ether of described solvent or
It is several；
Described surfactant be selected from trioctyl phosphine oxide, 1,2- dodecanediols, tri octyl phosphine, n- dodecyl mereaptan,
It is one or more of in tert-dodecyl mercaptan.
A kind of DSSC copper manganese germanium sulphur comprises the following steps to the preparation method of electrode：
(a) it is dissolved in copper manganese germanium sulphur is nanocrystalline in non-polar solven, copper manganese germanium sulphur nanometer is obtained after ultrasonic disperse is handled
Brilliant ink；
(b) the nanocrystalline ink of copper manganese germanium sulphur is coated in conductive substrates surface, be then heat-treated, dye sensitization is made
Solar cell copper manganese germanium sulphur is to electrode.
Described step (a) can also use short chain part is nanocrystalline to copper manganese germanium sulphur to carry out surface ligand replacement, make copper
Manganese germanium sulphur nanocrystal surface carries hydrophilic radical, is then dissolved in polar solvent, polar solvent is obtained after ultrasonic disperse is handled
The scattered nanocrystalline ink of copper manganese germanium sulphur；Described short chain part includes ammonium polysulfide, dithioglycol, n-butylamine, pyridine or just
Caproic acid.
The concentration of the described nanocrystalline ink of copper manganese germanium sulphur is 1~200mg/mL；
Non-polar solven in described step (a) includes chloroform, n-hexane or dichloromethane；
Painting method in described step (b) includes dip-coating, spin coating, blade coating, inkjet printing or silk-screen printing, coating time
Number is 1~10 time；
Heat treatment in described step (b) is under nitrogen, helium or argon gas atmosphere and condition of normal pressure, controls the temperature to be
100~500 DEG C are heated 0.5~10 hour.
By carrying out rational ion replacement to binary sulfide, the polynary sulfide of a series of new is can obtain, these
Not only property and the binary sulfide of " former generation " keep certain inheritance to new sulfide compounds, as electronic structure, semiconductor are special
Sign etc., and abundant variable property, such as valence band location, electric conductivity are provided, this is chalcogenide for design low cost, high activity
Compound provides new opportunity to electrode.
Copper manganese germanium sulphur is a kind of new copper-based germanium base quaternary sulfide, and its energy gap is wanted with semiconductor solar cell
The optimal energy gap (1.5eV) asked is sufficiently close to, and is a kind of useful light absorbing material.Two kinds of crystal knots be present in copper manganese germanium sulphur
Structure：Stannite (low-temperature phase) and buergerite (high-temperature-phase).Stannite usually requires to occur more than 700 DEG C to buergerite,
This means traditional high-temperature melting method is used, only temperature, which reaches more than 700 DEG C, could prepare buergerite copper manganese germanium sulphur nanometer
It is brilliant.Polynary sulfide with wurtzite structure than stannite structure polynary sulfide with more preferable I3 -Catalytic activity, this
Mean that the polynary sulfide of metastable state wurtzite structure is more suitable for DSSCs to electrode catalytic materialses.At present on fine zinc
The nanocrystalline preparation of the copper manganese germanium sulphur of ore deposit structure is also in blank.Therefore, the copper of low temperature solution polycondensation compounding wurtzite structure is explored
Manganese germanium sulphur and explore its application study in DSSCs there is important scientific meaning.
Compared with prior art, preparation process of the present invention is simple, and the copper manganese germanium sulphur of preparation is fitted to the technique and process of electrode
For large-scale industrial production；This method provides to prepare the DSSC of other materials to electrode simultaneously
The thinking that can be used for reference.
It is size uniformity (about 18 nanometers) that the copper manganese germanium sulphur for the wurtzite structure that the application synthesizes is nanocrystalline, dispersed good
The nano particle of good (easily forming nanocrystalline ink), the copper nanocrystalline ink of manganese germanium sulphur are used by being attached in the conductive substrates such as FTO
To substitute conventional precious metal platinum electrode to be used for the catalysis electrode of DSSC, i.e., to electrode, what is utilized is that it will
I3 -It is reduced to I-Catalysis characteristics, and obtain excellent performance.In addition, the nanocrystalline ink of copper manganese germanium sulphur obtained by the application can
For modes such as inkjet printing or sprayings, for preparing on a large scale to electrode.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrogram that copper manganese germanium sulphur is nanocrystalline made from embodiment 1；
Fig. 2 is the nanocrystalline Raman spectrum of copper manganese germanium sulphur made from embodiment 1；
Fig. 3 is transmission electron microscope photo of the copper manganese germanium sulphur made from embodiment 1 to electrode；
Fig. 4 is that Cyclic voltamogram of the copper manganese germanium sulphur of the present invention to electrode with pyrolysis platinum to electrode in iodine electrolyte is bent
Line；
Fig. 5 is current density-electricity containing copper manganese germanium sulphur made from embodiment 1 to the DSSC of electrode
Press (J-V) curve map.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings, but is not limited only to this.
Institute of the embodiment of the present invention is analysis net product purchased in market using raw material, and is not further purified.
The thing of material prepared by the present invention mutually passes through XRD-6000 (Shimadzu) types x-ray diffractometer (Cu targets, nickel filter
Wave plate filters, λ=0.154 nanometer, 40 kilovolts of tube voltage, 30 milliamperes of tube current, 20 degree~60 degree of scanning range) characterized.
The pattern of material prepared by the present invention carries out observation by JEOL companies JEM-2010 types transmission electron microscope and obtained
, gained is entered to the configuration of surface top view and film thickness of electrode by Hitachi companies S-4800 type SEM
Row observation obtains.
Embodiment 1
A kind of DSSC copper manganese germanium sulphur is to electrode, including FTO conductive substrates, FTO conductive substrates surface
Copper manganese germanium sulphur coated with the wurtzite structure that a layer thickness is 0.08 μm is nanocrystalline, and the nanocrystalline particle diameter of copper manganese germanium sulphur is
18nm。
The preparation method to electrode is：
(1) by 1 mM of acetylacetone copper, 0.5 mM of manganese acetylacetonate, 0.5 mM of germanium tetrachloride, 1.5 mmoles
That trioctyl phosphine oxide and 10 milliliters of oleyl amines are added in three-neck flask, vacuumize water removal deoxygenation, magnetic agitation, temperature control is heated to
100 DEG C and maintain to make pre-reaction material fully dissolve in 0.5 hour, whole reaction system is hereafter passed through protection gas until reaction is tied
Beam；
(2) above-mentioned reaction system temperature control is heated to 140 DEG C, 4 mMs of n- dodecyl mereaptan, heating is injected with syringe
To 280 DEG C and kept for 2 hours；
(3) question response terminates, and naturally cools to room temperature, after adding absolute ethyl alcohol, is centrifuged with 8000rpm rotating speed solid
Liquid system, obtained precipitation are that the copper manganese germanium sulphur of wurtzite structure is nanocrystalline；
(4) it is dissolved in above-mentioned copper manganese germanium sulphur is nanocrystalline in chloroform, handles to obtain copper manganese germanium sulphur nanometer through ultrasonic disperse
Brilliant ink, the nanocrystalline concentration control of copper manganese germanium sulphur is 50mg/mL；
(5) the nanocrystalline ink of above-mentioned copper manganese germanium sulphur is spun in FTO conductive substrates, coated five times, be placed in 400 DEG C of pipe
It is heat-treated in formula stove under the protection of nitrogen and obtains within 0.5 hour DSSC copper manganese germanium sulphur to electrode.
Fig. 1 is the nanocrystalline X-ray diffraction spectrogram of obtained DSSC copper manganese germanium sulphur, and its result is shown
Products therefrom is the copper manganese germanium sulphur of wurtzite structure.Fig. 2 is that obtained DSSC copper manganese germanium sulphur is nanocrystalline
SERS figure, product prepared by the display of its result is the copper manganese germanium sulphur of single no phase, without Cu2-xS(475cm-1), Cu3GeS4(290cm-1), GeS2(342cm-1) etc. thing phase.Fig. 3 shows that the nanocrystalline size of the copper manganese germanium sulphur of gained is about
18 nanometers.
Electrode is urged using cyclic voltammetry (German Zahner electrochemical workstations) the measurement embodiment of the present invention is used
Change performance and electrode is compared with pyrolysis platinum.As a result it is as shown in Figure 4.Test uses traditional three-electrode system, with the present invention
Described copper manganese germanium sulphur is working electrode to electrode to electrode or pyrolysis Pt, using Ag/AgCl as reference electrode, with Pt pieces to electricity
Pole, electrolyte are 10mM LiI, 1mM I2With 0.1M LiClO4Acetonitrile solution.Test result shows copper manganese germanium sulphur pair of the present invention
There are obvious two pairs of redox peaks in the conversion of catalytic iodine electricity pair in electrode, shows effectively be catalyzed these processes
Occur.Wherein, a pair of relatively negative redox peaks of current potential correspond to I-/I3 -Conversion, and a pair of redox peaks pair of calibration
Should be in I3 -/I2Conversion.Prepared copper manganese germanium sulphur is to electrode cycle voltammetric scan take-off potential less than platinum to electrode, spike potential
Difference is better than platinum electrode less than platinum to electrode, and to electrode current density value, so as to show that the present invention is excellent to electrode catalyst performance
In pyrolysis platinum.The present invention has used the preparation method simplified while catalytic performance is ensured, greatly reduces preparation cost, body
The potential value of this method is showed.
The stability used in the present invention to electrode in iodine electrolyte is weighed using multi-turn cyclic voltammetry.Test uses
Traditional three-electrode system, using copper manganese germanium sulphur of the present invention to electrode as working electrode, using Ag/AgCl as reference electrode, with
For Pt pieces to electrode, electrolyte is 10mM LiI, 1mM I2With 0.1M LiClO4Acetonitrile solution, sweep speed is 50mV s-1。
With the increase of surface sweeping number, cyclic voltammetry curve does not change especially, shows substantially not decay to electrode activity, illustrates
The present invention is sufficiently stable in electrolyte to electrode.
New by the embodiment of the present invention into dye-sensitized solar cells and tests its electricity conversion to electrode assembling.
As a result it is as shown in Figure 5.Battery photovoltaic performance test be by titanium dioxide membrane electrode provided and to electrode distinguish extraction wire,
It is connected in the photovoltaic test system of battery.The light-receiving area of battery is 0.16cm2.With solar simulator (Oriel
Simulated solar irradiation 94023A) is exported, luminous intensity is adjusted to 100mW cm2, measure the voltage curve of current density one of the battery
As shown in Figure 5.The photovoltaic parameter of device can be calculated according to curve：Open-circuit voltage (Voc) it is 722mV, short-circuit current density
(Jsc) it is 15.74mA cm-2, fill factor, curve factor (FF) is 57.2%, and gained solar cell transformation efficiency (η) is 6.63%, is less than
It is pyrolyzed the device efficiency (V of platinum electrode assemblingoc=725mV, Jsc=15.89mA cm-2, FF=63.8%, η=7.36%).
Embodiment 2
A kind of DSSC copper manganese germanium sulphur is to electrode, including ITO conductive substrates, ITO conductive substrates surface
Copper manganese germanium sulphur coated with the wurtzite structure that a layer thickness is 10 μm is nanocrystalline, and the nanocrystalline particle diameter of copper manganese germanium sulphur is 100nm.
The preparation method to electrode is：
(1) by 2 mMs of copper nitrates, 1.2 mMs of manganese nitrates, 1 mM of germanium oxide, 2 mMs of trioctyl phosphine oxides
It is added to 12 milliliters of oleyl amines in three-neck flask, vacuumizes water removal deoxygenation, magnetic agitation, temperature control is heated to 60 DEG C and maintenance 3 is small
When pre-reaction material is fully dissolved, hereafter by whole reaction system be passed through protection gas until reaction terminate；
(2) above-mentioned reaction system temperature control is heated to 130 DEG C, 4 mMs of thioacetamide, heating is injected with syringe
To 200 DEG C, and kept for 6 hours；
(3) question response terminates, and naturally cools to room temperature, after adding absolute ethyl alcohol, is centrifuged with 8000rpm rotating speed solid
Liquid system, obtained precipitation are that the copper manganese germanium sulphur of wurtzite structure is nanocrystalline；
(4) it is dissolved in above-mentioned copper manganese germanium sulphur is nanocrystalline in chloroform, handles to obtain copper manganese germanium sulphur nanometer through ultrasonic disperse
Brilliant ink, the nanocrystalline concentration control of copper manganese germanium sulphur is 200mg/mL；
(5) by the above-mentioned nanocrystalline ink dip-coating of copper manganese germanium sulphur in ITO conductive substrates, coating is repeatedly placed in 100 DEG C of pipe
It is heat-treated in formula stove under the protection of argon gas and obtains within 10 hours DSSC copper manganese germanium sulphur to electrode.
Embodiment 3
A kind of DSSC copper manganese germanium sulphur is to electrode, including graphite substrate, graphite substrate table
Copper manganese germanium sulphur of the face coated with the wurtzite structure that a layer thickness is 0.01 μm is nanocrystalline, and the nanocrystalline particle diameter of copper manganese germanium sulphur is
10nm。
The preparation method to electrode is：
(1) by 2.2 mMs of copper chlorides and the mixture of stannous chloride, the mixing of 1 mM of manganese sulfate and manganous chloride
Thing, 1.2 mMs of germanium powder, 1.5 mMs of trioctyl phosphine oxides and 10 milliliters of oleyl amines are added in three-neck flask, vacuumize water removal
Deoxygenation, magnetic agitation, temperature control are heated to 120 DEG C and maintain 0.5 hour pre-reaction material is fully dissolved, hereafter will entirely react
System is passed through protection gas until reaction terminates；
(2) above-mentioned reaction system temperature control is heated to 160 DEG C, 4.2 mMs of sublimed sulfur and two sulphur is injected with syringe
Change the mixture of carbon, be heated to 260 DEG C, and kept for 0.5 hour；
(3) question response terminates, and naturally cools to room temperature, after adding absolute ethyl alcohol, is centrifuged with 8000rpm rotating speed solid
Liquid system, obtained precipitation are that the copper manganese germanium sulphur of wurtzite structure is nanocrystalline；
(4) it is dissolved in above-mentioned copper manganese germanium sulphur is nanocrystalline in chloroform, handles to obtain copper manganese germanium sulphur nanometer through ultrasonic disperse
Brilliant ink, the nanocrystalline concentration control of copper manganese germanium sulphur is 1mg/mL；
(5) the nanocrystalline ink of above-mentioned copper manganese germanium sulphur is scratched in graphite substrate, coating once, is placed in 500 DEG C
It is heat-treated in tube furnace under the protection of helium and obtains within 0.5 hour DSSC copper manganese germanium sulphur to electrode.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, and difference is, the mantoquita in the present embodiment uses copper acetate
Embodiment 5
The present embodiment is substantially the same manner as Example 1, and difference is, the mantoquita in the present embodiment uses copper bromide.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, and difference is, the manganese salt in the present embodiment uses manganese acetate.
Embodiment 7
The present embodiment is substantially the same manner as Example 1, and difference is, the sulphur source in the present embodiment uses vulcanized sodium.
Embodiment 8
The present embodiment is substantially the same manner as Example 1, difference in the present embodiment copper manganese germanium sulphur it is nanocrystalline in conduction
Painting method in substrate is ink-jet printing process.
Embodiment 9
The present embodiment is substantially the same manner as Example 1, difference in the present embodiment copper manganese germanium sulphur it is nanocrystalline in conduction
Painting method in substrate is screen printing mode.
Embodiment 10
The present embodiment is substantially the same manner as Example 1, and difference is, the conductive substrates in the present embodiment are stainless steel.
Embodiment 11
The present embodiment is substantially the same manner as Example 1, and difference is, the conductive substrates in the present embodiment are compliant conductive
Macromolecule.
Embodiment 12
The method used of step (4) in the present embodiment for using short chain part to the nanocrystalline carry out surface of copper manganese germanium sulphur
Part is replaced, and it is nanocrystalline to obtain water miscible copper manganese germanium sulphur, and water miscible copper manganese germanium sulphur is nanocrystalline soluble in water, through ultrasound point
The nanocrystalline ink of copper manganese germanium sulphur is obtained after dissipating processing, short chain part is ammonium polysulfide.
Embodiment 13
The present embodiment is substantially the same manner as Example 12, and difference is ethylene dithiol in the short chain part in the present embodiment
Alcohol.
Embodiment 14
The present embodiment is substantially the same manner as Example 12, and difference is n-butylamine in the short chain part in the present embodiment.
Embodiment 15
The present embodiment is substantially the same manner as Example 12, and difference is pyridine in the short chain part in the present embodiment.
Embodiment 16
The present embodiment is substantially the same manner as Example 12, and difference is n-caproic acid in the short chain part in the present embodiment.
Embodiment 17
The present embodiment is substantially the same manner as Example 1, and solvent of the difference in the step (1) in the present embodiment is just
Octylame.
Embodiment 18
The present embodiment is substantially the same manner as Example 1, and solvent of the difference in the step (1) in the present embodiment is ten
Diamines.
Embodiment 19
The present embodiment is substantially the same manner as Example 1, and solvent of the difference in the step (1) in the present embodiment is ten
Hexamine.
Embodiment 20
The present embodiment is substantially the same manner as Example 1, and solvent of the difference in the step (1) in the present embodiment is ten
Hexamine and octadecylamine.
Embodiment 21
The present embodiment is substantially the same manner as Example 1, and solvent of the difference in the step (1) in the present embodiment is oil
Acid.
Embodiment 22
The present embodiment is substantially the same manner as Example 1, and solvent of the difference in the step (1) in the present embodiment is two
Phenylate.
Embodiment 23
The present embodiment is substantially the same manner as Example 1, surface-active of the difference in the step (1) in the present embodiment
Agent is 1,2- dodecanediols.
Embodiment 24
The present embodiment is substantially the same manner as Example 1, surface-active of the difference in the step (1) in the present embodiment
Agent is tri octyl phosphine.
Embodiment 25
The present embodiment is substantially the same manner as Example 1, surface-active of the difference in the step (1) in the present embodiment
Agent is n- dodecyl mereaptan
Embodiment 26
The present embodiment is substantially the same manner as Example 1, surface-active of the difference in the step (1) in the present embodiment
Agent is tert-dodecyl mercaptan.
Claims (9)
1. a kind of DSSC copper manganese germanium sulphur is to electrode, including conductive substrates, it is characterised in that conductive substrates table
Copper manganese germanium sulphur of the face coated with one layer of wurtzite structure is nanocrystalline；
Described DSSC copper manganese germanium sulphur comprises the following steps to the preparation method of electrode：
(a) surface ligand replacement is carried out using short chain part is nanocrystalline to copper manganese germanium sulphur, carries copper manganese germanium sulphur nanocrystal surface
Hydrophilic radical, it is then dissolved in polar solvent, it is nanocrystalline that the scattered copper manganese germanium sulphur of polar solvent is obtained after ultrasonic disperse is handled
Ink；Described short chain part includes ammonium polysulfide, dithioglycol, n-butylamine, pyridine or n-caproic acid；
(b) the nanocrystalline ink of copper manganese germanium sulphur is coated in conductive substrates surface, be then heat-treated, the dye sensitization sun is made
Energy battery copper manganese germanium sulphur is to electrode.
2. a kind of DSSC copper manganese germanium sulphur according to claim 1 is to electrode, it is characterised in that described
The nanocrystalline particle diameter of copper manganese germanium sulphur be 10~100nm, the thickness of copper manganese germanium sulphur nano-crystalline layers is 0.01~10 μm.
3. a kind of DSSC copper manganese germanium sulphur according to claim 1 is to electrode, it is characterised in that described
Conductive substrates include FTO, ITO, stainless steel, compliant conductive macromolecule or graphite.
4. a kind of DSSC copper manganese germanium sulphur according to claim 1 is to electrode, it is characterised in that described
The nanocrystalline preparation method of copper manganese germanium sulphur of wurtzite structure comprise the following steps：
(1) mantoquita, manganese salt, ge source, surfactant and solvent are mixed, vacuumizes water removal deoxygenation, magnetic agitation, be heated to 60
~120 DEG C and maintain to make reactant fully dissolve in 0.5~3 hour, whole reaction system is then passed through protection gas；
(2) above-mentioned reaction system is heated to 130~160 DEG C, injects sulphur source rapidly, system is further heated to 200 afterwards
~280 DEG C, and kept for 0.5~6 hour；
(3) question response terminates, and naturally cools to room temperature, carries out separation of solid and liquid operation after adding demulsifier, obtained precipitation is
Copper manganese germanium sulphur is nanocrystalline.
5. a kind of DSSC copper manganese germanium sulphur according to claim 4 is to electrode, it is characterised in that
Heating-up temperature in described step (1) is 100 DEG C；
The reaction system that step (1) obtains is heated to 140 DEG C in described step (2), 280 DEG C are heated to after injecting sulphur source；
Demulsifier in described step (3) is absolute ethyl alcohol；Separation of solid and liquid is centrifuged using 8000rpm rotating speed.
6. a kind of DSSC copper manganese germanium sulphur according to claim 4 is to electrode, it is characterised in that described
Mantoquita, manganese salt, the mol ratio of ge source and sulphur source be：(2~2.2):(l~1.2):(1~1.2):(4~4.2).
7. a kind of DSSC copper manganese germanium sulphur according to claim 4 is to electrode, it is characterised in that
One kind in copper nitrate, copper acetate, acetylacetone copper, copper chloride, stannous chloride or copper bromide of described mantoquita or
It is a variety of；
One or more of the described manganese salt in manganese acetylacetonate, manganous chloride, manganese nitrate, manganese acetate or manganese sulfate；
One or more of the described ge source in germanium tetrachloride, germanium oxide or germanium powder；
Described sulphur source is in sublimed sulfur, n- dodecyl mereaptan, tert-dodecyl mercaptan, thioacetamide, carbon disulfide or vulcanized sodium
One or more；
One or more of the described solvent in n-octyl amine, lauryl amine, cetylamine, oleyl amine, octadecylamine, oleic acid, diphenyl ether；
Described surfactant is selected from trioctyl phosphine oxide, 1,2- dodecanediols, tri octyl phosphine, n- dodecyl mereaptan, uncle ten
It is one or more of in two mercaptan.
8. a kind of DSSC copper manganese germanium sulphur as claimed in claim 1 is to the preparation method of electrode, its feature
It is, comprises the following steps：
(a) surface ligand replacement is carried out using short chain part is nanocrystalline to copper manganese germanium sulphur, carries copper manganese germanium sulphur nanocrystal surface
Hydrophilic radical, it is then dissolved in polar solvent, it is nanocrystalline that the scattered copper manganese germanium sulphur of polar solvent is obtained after ultrasonic disperse is handled
Ink；Described short chain part includes ammonium polysulfide, dithioglycol, n-butylamine, pyridine or n-caproic acid；
(b) the nanocrystalline ink of copper manganese germanium sulphur is coated in conductive substrates surface, be then heat-treated, the dye sensitization sun is made
Energy battery copper manganese germanium sulphur is to electrode.
9. for a kind of DSSC copper manganese germanium sulphur according to claim 8 to the preparation method of electrode, it is special
Sign is,
The concentration of the described nanocrystalline ink of copper manganese germanium sulphur is 1~200mg/mL；
Non-polar solven in described step (a) includes chloroform, n-hexane or dichloromethane；
Painting method in described step (b) includes dip-coating, spin coating, blade coating, inkjet printing or silk-screen printing, and coating number is
1~10 time；
Heat treatment in described step (b) is under nitrogen, helium or argon gas atmosphere and condition of normal pressure, and it is 100 to control temperature
~500 DEG C are heated 0.5~10 hour.
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