CN106847513A - The preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks - Google Patents
The preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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- H—ELECTRICITY
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Abstract
The invention discloses a kind of preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks, specifically implement according to following steps：Prepare CuS nano powders；CuS nano powders are made CuS slurries；Porous C uS nanometer sheets are prepared to electrode using CuS slurries；Prepared by the sulfide nano-composite counter electrode based on porous C uS frameworks to electrode using porous C uS.Prepared by process is simple of the invention, with low cost, large area, reproducible, and the advantage of the sulfide nano-composite counter electrode prepared using the present invention is to utilize TiO2Shell quickly transmits electronics and improves electrode stability, using the electric transmission resistance in the macroporous structure reduction electrolyte between CuS nanosheet, catalysis activity is improved using the synergy of complex sulfide, and the method makes battery performance be greatly improved.
Description
Technical field
The invention belongs to quantum dot sensitized technical field of solar batteries, and in particular to a kind of based on porous C uS frameworks
The preparation method of sulfide nano-composite counter electrode.
Background technology
In recent years, as people are continuously increased to the demand of the energy and the lasting reduction of fossil fuel reserves, find a kind of
New abundance, the alternative energy source of environmental protection have turned into one of important topic of current scientific research.Solar energy takes as one kind
Natural energy source not to the utmost be increasingly subject to global concern, especially solar energy is converted into the solar cell of electric energy
Research turned into the focus of current research.
Quantum dot sensitized solar cell (QDSSC) is the third generation solar cell that the nineties in last century occurs, i.e. profit
The base material of broad stopband is sensitized with the inorganic semiconductor quantum dot (QD) of low energy gap.Quantum dot has very big excellent relative to dyestuff
Gesture, on the one hand, it has quantum confined effect, can by controlling its size and dimension come the band gap width of quantum point,
The scope of absorption spectrum is adjusted with this；On the other hand, semiconductor-quantum-point has exciton multiplier effect (MEG), a high energy
The photon excitation semiconductor-quantum-point of amount, can produce multiple electron-hole pairs (see A.Shabaev, Al.L.Efros,
A.J.Nozik, Nano.Letters 2006,6, the 22856-22863 pages).If by this two big advantage of semiconductor-quantum-point
Be applied in solar cell, the theoretical value of QDSSC efficiency can reach 44% (M.C.Hanna, A.J.Nozik,
Appl.Phys.2006,100,074510), the theoretical value 32.9% than crystal silicon solar energy battery is much higher.Therefore, whether
Still upper in application in cost, the potentiality of the development of QDSSC are very huge.
At present, the electrolyte that quantum dot sensitized solar cell is used is many sulphur (Sn 2-/S2-) liquid electrolyte, so
And study and find the I suitable for DSSC3-/I-The Pt of electrolyte is no longer appropriate for Sn 2-/S2-Electrolyte, because
S2-The catalysis activity to electrode pair electrolyte is reduced in the chemisorbed of Pt electrode surfaces, so as to have influence on the performance of battery.
In addition other are also widely studied to electrode material, for example carbon, sulfide (PbS, CoS, FeS, CuxS), noble metal
(Au) material such as.In the battery on various quantum dot sensitized optimum efficiencies, all it is utilized in without exception on Copper Foil rotten
Lose the Cu for preparingxTo electrode, one of its advantage is that the thin micro-structural of pine has catalysis activity high to S, two be Copper Foil substrate tool
There is fabulous electric conductivity；One of shortcoming be this electrode because electrolyte persistently corrodes substrate, cause adhesiveness reduction, contact resistance
Increase, two be that being contacted with light anode to electrode of coming off is caused to light anode poisoning.In addition, complex sulfide passes through to electrode
Mutual synergy can also greatly improve the catalytic performance of electrode.Therefore, for CuxThe problem that S exists to electrode with it is multiple
Condensation material is found and improves Cu to the advantage of electrodexS is to the stability of electrode and to prepare the method for combination electrode be very necessary
's.
The content of the invention
It is an object of the invention to provide a kind of preparation side of the sulfide nano-composite counter electrode based on porous C uS frameworks
Method, the method is using the electric transmission resistance in the macroporous structure reduction electrolyte between CuS nanosheet and utilizes composite
Concerted catalysis effect, the performance of battery can be greatly improved.
The technical solution adopted in the present invention is：
The preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks, specifically implements according to following steps：
Step 1, prepares CuS nano powders；
Step 2, CuS nano powders prepared by step 1 are made CuS slurries；
Step 3, the CuS slurries obtained using step 2 prepare porous C uS nanometer sheets to electrode；
Step 4, it is nano combined that the porous C uS obtained using step 3 prepares the sulfide based on porous C uS frameworks to electrode
To electrode.
The features of the present invention is also resided in：
Step 1 is specifically implemented according to following steps：
Step 1.1, the Na that concentration is 0.4-0.6M is equipped with using magnetic stirring apparatus2The S aqueous solution and CuSO4The aqueous solution；
Step 1.2, by Na2The S aqueous solution is slowly injected into CuSO4In the aqueous solution, fully it is collected by centrifugation what reaction was obtained after reaction
CuS sediments；
Step 1.3, the CuS sediment undergoes washings obtained step 1.2 using deionized water 3-5 times, then using absolute ethyl alcohol
By CuS sediment undergoes washings 3-5 times；
Step 1.4, the CuS sediments that will be cleaned are placed in 40-60 DEG C of vacuum drying chamber is dried, and will finally be dried
Dry CuS sediments grinding distribution is into CuS nano powders.
Step 2 is specifically implemented according to following steps：
Step 2.1, weighs CuS nano powders and is put into mortar, and deionized water and 50s- is ground to being added in CuS nano powders
70s, 4-6 time the step for repeat, then glacial acetic acid and grinds 50s-70s to addition in mortar, then to adding nothing in mortar
Water-ethanol simultaneously grinds 50s-70s and repeats 4-6 times；
Step 2.2, the mixture that step 2.1 is obtained is transferred in container and 15-20ml's is anhydrous to being added in container
Ethanol, the magnetic agitation and ultrasonic disperse of compartment are carried out using magnetic stirring apparatus and ultrasonic disperser to said mixture,
So operation 50-70min；Each magnetic agitation is 4-6min with the time of ultrasonic disperse；
Step 2.3, to terpinol is added in the mixture that step 2.2 is obtained, is disperseed using magnetic stirring apparatus and ultrasonic wave
Device carries out the magnetic agitation and ultrasonic disperse of compartment to said mixture, so operates 50-70min；Each magnetic agitation with
The time of ultrasonic disperse is 4-6min；
Step 2.4, the ethyl cellulose of absolute ethyl alcohol is dissolved in addition in the mixture that step 2.3 is obtained, using magnetic
Power agitator carries out the magnetic agitation and ultrasonic disperse of compartment with ultrasonic disperser to said mixture, so operates 50-
70min, each magnetic agitation is 4-6min with the time of ultrasonic disperse；Said mixture is finally placed in 60-70 DEG C of water-bath
In be stirred and fall the ethanol evaporation in mixture, obtain being applied to the CuS slurries of silk-screen printing.
CuS nano powders and the mass ratio of ethyl cellulose are 2-3 in step 2:1, the quality of terpinol and ethyl cellulose
Than being 2:3.
Every gram of CuS nano powder described in step 2.1 adds the deionized water of 0.1-0.2ml every time；Every gram of CuS nano powder is every
The glacial acetic acid of secondary addition 0.1-0.2ml, the concentration of glacial acetic acid is 99.5%；Every gram of CuS nano powder adds 0.4-0.6ml's every time
Absolute ethyl alcohol.
Step 3 is specifically implemented according to following steps：
Step 3.1, the CuS slurries obtained using step 2.4 prepare porous C uS nanometer sheet films, comprise the following steps that：
, be coated in CuS slurries in conductive substrates using screen printing technique first, then in atmosphere by step 3.1.1
Stand, after in the drying baker that conductive substrates are placed in 60-80 DEG C by CuS slurries again in conductive substrates after flow equilibrium, keep 5-
Taken out after 10min；
Step 3.1.2, repeat step 3.1.1 mono- to three times, obtain being coated with the conductive substrates of CuS slurries；
Step 3.1.3, the conductive substrates for being coated with CuS slurries that step 3.1.2 is obtained are put into Muffle furnace, with 3 DEG C/
The speed of min is cooled to room temperature from room temperature to 350-400 DEG C after annealing 90-30min, obtains porous C uS nanometer sheets
Film；
Step 3.2, TiO is prepared on porous C uS nanometer sheet films2Decorative layer, specifically using following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in being carried out using magnetic stirring apparatus in ice-water bath
Mix, be stirring evenly and then adding into butyl titanate and stir, form solution A；
Prepare B solution：Deionized water is added in absolute ethyl alcohol and uniform using magnetic stirrer, added afterwards
Concentrated hydrochloric acid simultaneously stirs to form B solution；
Above-mentioned B solution is slowly added in solution A and stirred to form TiO2The precursor solution of decorative layer, then adopts
In the space of the porous C uS nanometer sheet films for being obtained precursor solution implantation step 3.1 with spin coating proceeding, finally by porous C uS
Nanometer sheet film is put into Muffle furnace, cold after annealing 50-30min with the speed of 3 DEG C/min from room temperature to 350-400 DEG C
But to room temperature；Wherein, the rotating speed of spin coating proceeding is 3000-4000r/min；
Step 3.3, first by S powder, Na2It is 7 that S, KCl are added to volume ratio:3-5:5 methyl alcohol and deionized water mixing is molten
Many sulphur electrolyte are made in liquid, S powder, Na in many sulphur electrolyte2The concentration of S and KCl be respectively 0.5-2M, 0.5-2M and
0.2-0.5M；Then TiO will be used in step 3.2 at room temperature2The porous C uS nanometer sheet films of modified are put into many sulphur electrolyte
Carry out vulcanizing treatment 3-9 hours, obtain porous C uS nanometer sheets to electrode.
Conductive substrates described in step 3.1.1 are any one in FTO glass or titanium foil or plating titanium glass.
Acetylacetone,2,4-pentanedione, absolute ethyl alcohol, the volume ratio of butyl titanate are 1 when solution A is prepared in step 3.2:48.5:3.3-
3.5；Deionized water, absolute ethyl alcohol, the volume ratio of concentrated hydrochloric acid are 1 when preparing B solution:20:0.076；The body of solution A and B solution
Product is than being 0.8-1:1.
Step 4 is specifically implemented according to following steps：
The Pb that cation concn is 0.025-0.05M is made using water-soluble salt2+Or Ni2+Or Co2+C solution, utilizes
Concentration is the Na of 0.025-0.05M2The S aqueous solution is used as S2-Solution, then using SILAR method by step 3
The S that the porous C uS nanometer sheets for obtaining are made above to electrode immersion2-50-70s in solution, then by porous C uS nanometer sheets to electricity
Pole is taken out and uses deionized water rinsing, then the porous C uS nanometer sheets after flushing are immersed in into the C solution that the above is made to electrode
After middle 50-70s, porous C uS nanometer sheets are taken out to electrode again and uses deionized water rinsing, so repeated 3-5 times, final
To the sulfide nano-composite counter electrode based on porous C uS frameworks.
Water-soluble salt is any one in nitrate or villaumite or sulfate.
The beneficial effects of the invention are as follows：Prepared by process is simple of the invention, with low cost, large area, reproducible, use
The advantage of sulfide nano-composite counter electrode prepared by the present invention is to utilize TiO2Shell quickly transmits electronics and improves electrode
Stability, using the electric transmission resistance in the macroporous structure reduction electrolyte between CuS nanosheet, using the association of complex sulfide
Same-action improves catalysis activity, and the method makes battery performance be greatly improved.
Brief description of the drawings
Fig. 1 is CuS nanosheet SEM prepared by hybrid reaction；
Fig. 2 is the current-voltage compares figure to electrode battery based on CuS/PbS, CuS/NiS, CuS/CoS.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description：
Embodiment one：
The preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks, specifically implements according to following steps：
Step 1, prepares CuS nano powders；
Step 1.1, the Na that concentration is 0.4M is equipped with using magnetic stirring apparatus2The S aqueous solution and CuSO4The aqueous solution；
Step 1.2, by Na2The S aqueous solution is slowly injected into CuSO4In the aqueous solution, fully it is collected by centrifugation what reaction was obtained after reaction
CuS sediments；
Step 1.3, the CuS sediment undergoes washings obtained step 1.2 using deionized water 3-5 times, then using absolute ethyl alcohol
By CuS sediment undergoes washings 3-5 times；
Step 1.4, the CuS sediments that will be cleaned are placed in 40 DEG C of vacuum drying chamber is dried, finally will drying
CuS sediments grinding distribution into CuS nano powders；
Step 2, CuS nano powders prepared by step 1 are made CuS slurries；
Step 2.1, weighs 1gCuS nano powders and is put into mortar, 0.1ml deionized waters and is ground to being added in CuS nano powders
Mill 50s-70s, 4-6 time the step for repeat, then 0.1ml glacial acetic acid and grinds 50s-70s to addition in mortar, then to grinding
0.4ml absolute ethyl alcohols are added in alms bowl and is ground 50s-70s and is repeated 4-6 times；
Step 2.2, the mixture that step 2.1 is obtained is transferred in container and 15-20ml's is anhydrous to being added in container
Ethanol, the magnetic agitation and ultrasonic disperse of compartment are carried out using magnetic stirring apparatus and ultrasonic disperser to said mixture,
So operation 50-70min；Each magnetic agitation is 4-6min with the time of ultrasonic disperse；
Step 2.3, to terpinol is added in the mixture that step 2.2 is obtained, is disperseed using magnetic stirring apparatus and ultrasonic wave
Device carries out the magnetic agitation and ultrasonic disperse of compartment to said mixture, so operates 50-70min；Each magnetic agitation with
The time of ultrasonic disperse is 4-6min；
Step 2.4, the ethyl cellulose of absolute ethyl alcohol is dissolved in addition in the mixture that step 2.3 is obtained, using magnetic
Power agitator carries out the magnetic agitation and ultrasonic disperse of compartment with ultrasonic disperser to said mixture, so operates 50-
70min, each magnetic agitation is 4-6min with the time of ultrasonic disperse；Finally said mixture is placed in 60 DEG C of water-bath
Row stirring falls the ethanol evaporation in mixture, obtains being applied to the CuS slurries of silk-screen printing；CuS nano powders and ethyl cellulose
The mass ratio of element is 2:1, terpinol is 2 with the mass ratio of ethyl cellulose:3.
Step 3, the CuS slurries obtained using step 2 prepare porous C uS nanometer sheets to electrode；
Step 3.1, the CuS slurries obtained using step 2.4 prepare porous C uS nanometer sheet films, comprise the following steps that：
, be coated in CuS slurries in conductive substrates using screen printing technique first, then in atmosphere by step 3.1.1
Stand, conductive substrates are placed in 60 DEG C of drying baker again after flow equilibrium in conductive substrates after CuS slurries, keep 5-
Taken out after 10min；Conventional conductive substrates are any one in FTO glass or titanium foil or plating titanium glass.
Step 3.1.2, repeat step 3.1.1 mono- to three times, obtain being coated with the conductive substrates of CuS slurries；
Step 3.1.3, the conductive substrates for being coated with CuS slurries that step 3.1.2 is obtained are put into Muffle furnace, with 3 DEG C/
The speed of min is cooled to room temperature from room temperature to 350 DEG C after annealing 90min, obtains porous C uS nanometer sheet films；
Step 3.2, TiO is prepared on porous C uS nanometer sheet films2Decorative layer, specifically using following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in being carried out using magnetic stirring apparatus in ice-water bath
Mix, be stirring evenly and then adding into butyl titanate and stir, form solution A；Wherein, acetylacetone,2,4-pentanedione, absolute ethyl alcohol,
The volume ratio of butyl titanate is 1:48.5:3.3；
Prepare B solution：Deionized water is added in absolute ethyl alcohol and uniform using magnetic stirrer, added afterwards
Concentrated hydrochloric acid simultaneously stirs to form B solution；Wherein, deionized water, absolute ethyl alcohol, the volume ratio of concentrated hydrochloric acid are 1:20:0.076；
Above-mentioned B solution is slowly added in solution A and stirred to form TiO2The precursor solution of decorative layer, solution A
It is 0.8 with the volume ratio of B solution:1.Then the porous C uS for being obtained precursor solution implantation step 3.1 using spin coating proceeding is received
Rice piece film space in, finally porous C uS nanometer sheet films are put into Muffle furnace, with the speed of 3 DEG C/min from room temperature to
350 DEG C, room temperature is cooled to after annealing 50min；Wherein, the rotating speed of spin coating proceeding is 3000r/min；
Step 3.3, first by S powder, Na2It is 7 that S, KCl are added to volume ratio:In 3 methyl alcohol and deionized water mixed solution
Many sulphur electrolyte are made, S powder, Na in many sulphur electrolyte2The concentration of S and KCl is respectively 0.5M, 0.5M and 0.2M；Then
TiO will be used in step 3.2 at room temperature2The porous C uS nanometer sheet films of modified carry out vulcanizing treatment 9 in being put into many sulphur electrolyte
Hour, porous C uS nanometer sheets are obtained to electrode.Na2S steps 4, the porous C uS obtained using step 3 is prepared based on many to electrode
The sulfide nano-composite counter electrode of hole CuS frameworks, specifically implements according to following steps：
The Pb that cation concn is 0.025M is made using water-soluble salt2+Or Ni2+Or Co2+C solution, using concentration
It is the Na of 0.025M2The S aqueous solution is used as S2-Solution, then using SILAR method (i.e. SILAR methods) by step 3
In the porous C uS nanometer sheets that obtain to the S that more than electrode immersion is made2-50-70s in solution, then by porous C uS nanometer sheets pair
Electrode takes out and uses deionized water rinsing, then that the porous C uS nanometer sheets after flushing are immersed in into the C that the above is made to electrode is molten
In liquid after 50-70s, porous C uS nanometer sheets are taken out to electrode again and uses deionized water rinsing, so repetition 3-5 times, finally
Obtain the sulfide nano-composite counter electrode based on porous C uS frameworks；Wherein, water-soluble salt is nitrate or villaumite or sulphur
Any one in hydrochlorate.
Embodiment two：
The preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks, specifically implements according to following steps：
Step 1, prepares CuS nano powders；
Step 1.1, the Na that concentration is 0.5M is equipped with using magnetic stirring apparatus2The S aqueous solution and CuSO4The aqueous solution；
Step 1.2, by Na2The S aqueous solution is slowly injected into CuSO4In the aqueous solution, fully it is collected by centrifugation what reaction was obtained after reaction
CuS sediments；
Step 1.3, the CuS sediment undergoes washings obtained step 1.2 using deionized water 3-5 times, then using absolute ethyl alcohol
By CuS sediment undergoes washings 3-5 times；
Step 1.4, the CuS sediments that will be cleaned are placed in 50 DEG C of vacuum drying chamber is dried, finally will drying
CuS sediments grinding distribution into CuS nano powders；
Step 2, CuS nano powders prepared by step 1 are made CuS slurries；
Step 2.1, weighs 1gCuS nano powders and is put into mortar, 0.15ml deionized waters and is ground to being added in CuS nano powders
Mill 50s-70s, 4-6 time the step for repeat, then 0.15ml glacial acetic acid and grinds 50s-70s, Ran Houxiang to addition in mortar
0.5ml absolute ethyl alcohols are added in mortar and is ground 50s-70s and is repeated 4-6 times；
Step 2.2, the mixture that step 2.1 is obtained is transferred in container and 15-20ml's is anhydrous to being added in container
Ethanol, the magnetic agitation and ultrasonic disperse of compartment are carried out using magnetic stirring apparatus and ultrasonic disperser to said mixture,
So operation 50-70min；Each magnetic agitation is 4-6min with the time of ultrasonic disperse；
Step 2.3, to terpinol is added in the mixture that step 2.2 is obtained, is disperseed using magnetic stirring apparatus and ultrasonic wave
Device carries out the magnetic agitation and ultrasonic disperse of compartment to said mixture, so operates 50-70min；Each magnetic agitation with
The time of ultrasonic disperse is 4-6min；
Step 2.4, the ethyl cellulose of absolute ethyl alcohol is dissolved in addition in the mixture that step 2.3 is obtained, using magnetic
Power agitator carries out the magnetic agitation and ultrasonic disperse of compartment with ultrasonic disperser to said mixture, so operates 50-
70min, each magnetic agitation is 4-6min with the time of ultrasonic disperse；Finally said mixture is placed in 65 DEG C of water-bath
Row stirring falls the ethanol evaporation in mixture, obtains being applied to the CuS slurries of silk-screen printing；CuS nano powders and ethyl cellulose
The mass ratio of element is 2.5:1, terpinol is 2 with the mass ratio of ethyl cellulose:3.
Step 3, the CuS slurries obtained using step 2 prepare porous C uS nanometer sheets to electrode；
Step 3.1, the CuS slurries obtained using step 2.4 prepare porous C uS nanometer sheet films, comprise the following steps that：
, be coated in CuS slurries in conductive substrates using screen printing technique first, then in atmosphere by step 3.1.1
Stand, conductive substrates are placed in 70 DEG C of drying baker again after flow equilibrium in conductive substrates after CuS slurries, keep 5-
Taken out after 10min；Conventional conductive substrates are any one in FTO glass or titanium foil or plating titanium glass.
Step 3.1.2, repeat step 3.1.1 mono- to three times, obtain being coated with the conductive substrates of CuS slurries；
Step 3.1.3, the conductive substrates for being coated with CuS slurries that step 3.1.2 is obtained are put into Muffle furnace, with 3 DEG C/
The speed of min is cooled to room temperature from room temperature to 375 DEG C after annealing 60min, obtains porous C uS nanometer sheet films；
Step 3.2, TiO is prepared on porous C uS nanometer sheet films2Decorative layer, specifically using following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in being carried out using magnetic stirring apparatus in ice-water bath
Mix, be stirring evenly and then adding into butyl titanate and stir, form solution A；Wherein, acetylacetone,2,4-pentanedione, absolute ethyl alcohol,
The volume ratio of butyl titanate is 1:48.5:3.4；
Prepare B solution：Deionized water is added in absolute ethyl alcohol and uniform using magnetic stirrer, added afterwards
Concentrated hydrochloric acid simultaneously stirs to form B solution；Wherein, deionized water, absolute ethyl alcohol, the volume ratio of concentrated hydrochloric acid are 1:20:0.076；
Above-mentioned B solution is slowly added in solution A and stirred to form TiO2The precursor solution of decorative layer, solution A
It is 0.9 with the volume ratio of B solution:1.Then the porous C uS for being obtained precursor solution implantation step 3.1 using spin coating proceeding is received
Rice piece film space in, finally porous C uS nanometer sheet films are put into Muffle furnace, with the speed of 3 DEG C/min from room temperature to
375 DEG C, room temperature is cooled to after annealing 40min；Wherein, the rotating speed of spin coating proceeding is 3500r/min；
Step 3.3, first by S powder, Na2It is 3 that S, KCl are added to volume ratio:In 2 methyl alcohol and deionized water mixed solution
Many sulphur electrolyte are made, S powder, Na in many sulphur electrolyte2The concentration of S and KCl is respectively 1M, 1M and 0.35M；Then in room
TiO will be used in step 3.2 under temperature2The porous C uS nanometer sheet films of modified are put into many sulphur electrolyte that to carry out vulcanizing treatment 6 small
When, porous C uS nanometer sheets are obtained to electrode.
Step 4, it is nano combined that the porous C uS obtained using step 3 prepares the sulfide based on porous C uS frameworks to electrode
To electrode, specifically implement according to following steps：
The Pb that cation concn is 0.04M is made using water-soluble salt2+Or Ni2+Or Co2+C solution, be using concentration
The Na of 0.04M2The S aqueous solution is used as S2-Solution, it is then porous by what is obtained in step 3 using SILAR method
The S that CuS nanosheet is made above to electrode immersion2-50-70s in solution, porous C uS nanometer sheets then taken out and adopted to electrode
With deionized water rinsing, then the porous C uS nanometer sheets after flushing are immersed in 50-70s in the C solution that the above is made to electrode
Afterwards, porous C uS nanometer sheets are taken out to electrode again and use deionized water rinsing, so repeated 3-5 time, finally give be based on it is many
The sulfide nano-composite counter electrode of hole CuS frameworks；Wherein, appointing during water-soluble salt is for nitrate or villaumite or sulfate
Meaning is a kind of.
Embodiment three：
The preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks, specifically implements according to following steps：
Step 1, prepares CuS nano powders；
Step 1.1, the Na that concentration is 0.6M is equipped with using magnetic stirring apparatus2The S aqueous solution and CuSO4The aqueous solution；
Step 1.2, by Na2The S aqueous solution is slowly injected into CuSO4In the aqueous solution, fully it is collected by centrifugation what reaction was obtained after reaction
CuS sediments；
Step 1.3, the CuS sediment undergoes washings obtained step 1.2 using deionized water 3-5 times, then using absolute ethyl alcohol
By CuS sediment undergoes washings 3-5 times；
Step 1.4, the CuS sediments that will be cleaned are placed in 60 DEG C of vacuum drying chamber is dried, finally will drying
CuS sediments grinding distribution into CuS nano powders；
Step 2, CuS nano powders prepared by step 1 are made CuS slurries；
Step 2.1, weighs 1gCuS nano powders and is put into mortar, 0.2ml deionized waters and is ground to being added in CuS nano powders
Mill 50s-70s, 4-6 time the step for repeat, then 0.2ml glacial acetic acid and grinds 50s-70s to addition in mortar, then to grinding
0.6ml absolute ethyl alcohols are added in alms bowl and is ground 50s-70s and is repeated 4-6 times；
Step 2.2, the mixture that step 2.1 is obtained is transferred in container and 15-20ml's is anhydrous to being added in container
Ethanol, the magnetic agitation and ultrasonic disperse of compartment are carried out using magnetic stirring apparatus and ultrasonic disperser to said mixture,
So operation 50-70min；Each magnetic agitation is 4-6min with the time of ultrasonic disperse；
Step 2.3, to terpinol is added in the mixture that step 2.2 is obtained, is disperseed using magnetic stirring apparatus and ultrasonic wave
Device carries out the magnetic agitation and ultrasonic disperse of compartment to said mixture, so operates 50-70min；Each magnetic agitation with
The time of ultrasonic disperse is 4-6min；
Step 2.4, the ethyl cellulose of absolute ethyl alcohol is dissolved in addition in the mixture that step 2.3 is obtained, using magnetic
Power agitator carries out the magnetic agitation and ultrasonic disperse of compartment with ultrasonic disperser to said mixture, so operates 50-
70min, each magnetic agitation is 4-6min with the time of ultrasonic disperse；Finally said mixture is placed in 70 DEG C of water-bath
Row stirring falls the ethanol evaporation in mixture, obtains being applied to the CuS slurries of silk-screen printing；CuS nano powders and ethyl cellulose
The mass ratio of element is 3:1, terpinol is 2 with the mass ratio of ethyl cellulose:3.
Step 3, the CuS slurries obtained using step 2 prepare porous C uS nanometer sheets to electrode；
Step 3.1, the CuS slurries obtained using step 2.4 prepare porous C uS nanometer sheet films, comprise the following steps that：
, be coated in CuS slurries in conductive substrates using screen printing technique first, then in atmosphere by step 3.1.1
Stand, conductive substrates are placed in 80 DEG C of drying baker again after flow equilibrium in conductive substrates after CuS slurries, keep 5-
Taken out after 10min；Conventional conductive substrates are any one in FTO glass or titanium foil or plating titanium glass.
Step 3.1.2, repeat step 3.1.1 mono- to three times, obtain being coated with the conductive substrates of CuS slurries；
Step 3.1.3, the conductive substrates for being coated with CuS slurries that step 3.1.2 is obtained are put into Muffle furnace, with 3 DEG C/
The speed of min is cooled to room temperature from room temperature to 400 DEG C after annealing 30min, obtains porous C uS nanometer sheet films；
Step 3.2, TiO is prepared on porous C uS nanometer sheet films2Decorative layer, specifically using following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in being carried out using magnetic stirring apparatus in ice-water bath
Mix, be stirring evenly and then adding into butyl titanate and stir, form solution A；Wherein, acetylacetone,2,4-pentanedione, absolute ethyl alcohol,
The volume ratio of butyl titanate is 1:48.5:3.5；
Prepare B solution：Deionized water is added in absolute ethyl alcohol and uniform using magnetic stirrer, added afterwards
Concentrated hydrochloric acid simultaneously stirs to form B solution；Deionized water, absolute ethyl alcohol, the volume ratio of concentrated hydrochloric acid are 1:20:0.076；
Above-mentioned B solution is slowly added in solution A and stirred to form TiO2The precursor solution of decorative layer, solution A
It is 1 with the volume ratio of B solution:1.Then porous C uS nanometers for being obtained precursor solution implantation step 3.1 using spin coating proceeding
In the space of piece film, finally porous C uS nanometer sheet films are put into Muffle furnace, with the speed of 3 DEG C/min from room temperature to 400
DEG C, it is cooled to room temperature after annealing 30min；Wherein, the rotating speed of spin coating proceeding is 4000r/min；
Step 3.3, first by S powder, Na2It is 1 that S, KCl are added to volume ratio:In 1 methyl alcohol and deionized water mixed solution
Many sulphur electrolyte are made, S powder, Na in many sulphur electrolyte2The concentration of S and KCl is respectively 2M, 2M and 0.5M；Then in room
TiO will be used in step 3.2 under temperature2The porous C uS nanometer sheet films of modified are put into many sulphur electrolyte that to carry out vulcanizing treatment 3 small
When, porous C uS nanometer sheets are obtained to electrode.
Step 4, it is nano combined that the porous C uS obtained using step 3 prepares the sulfide based on porous C uS frameworks to electrode
To electrode, specifically implement according to following steps：
The Pb that cation concn is 0.05M is made using water-soluble salt2+Or Ni2+Or Co2+C solution, be using concentration
The Na of 0.05M2The S aqueous solution is used as S2-Solution, it is then porous by what is obtained in step 3 using SILAR method
The S that CuS nanosheet is made above to electrode immersion2-50-70s in solution, porous C uS nanometer sheets then taken out and adopted to electrode
With deionized water rinsing, then the porous C uS nanometer sheets after flushing are immersed in 50-70s in the C solution that the above is made to electrode
Afterwards, porous C uS nanometer sheets are taken out to electrode again and use deionized water rinsing, so repeated 3-5 time, finally give be based on it is many
The sulfide nano-composite counter electrode of hole CuS frameworks；Wherein, appointing during water-soluble salt is for nitrate or villaumite or sulfate
Meaning is a kind of.
The present invention prepares CuS nano powders, the CuS nano powder systems that will then clean up using simple hybrid reaction first
Standby paired CuS slurries, and porous C uS nanometer sheet films are prepared with annealing process using screen printing technique, then using TiO2With
Many sulphur electrolyte carry out surface modification to porous C uS nanometer sheets film and vulcanizing treatment forms the porous C uS nanometer sheets of stabilization to electricity
Pole, finally using metal sulfide catalysts such as SILAR methods deposition PbS, NiS, CoS, forms the vulcanization based on porous C uS frameworks
Thing nano-composite counter electrode.Prepared by process is simple of the invention, with low cost, large area, reproducible, is most closed in whole technique
The technology of key is：The control of annealing temperature in air；Using TiO2The control of the surface modification and vulcanizing treatment technique that carry out.Adopt
The advantage of the sulfide nano-composite counter electrode prepared with the present invention is to utilize TiO2Shell quickly transmits electronics and improves electricity
Stabilizer pole, using the electric transmission resistance in the macroporous structure reduction electrolyte between CuS nanosheet, using complex sulfide
Synergy improves catalysis activity, and the method makes battery performance be greatly improved.If Fig. 1 is CuS prepared by hybrid reaction
Nanometer sheet SEM；Fig. 2 is the current-voltage compares figure to electrode battery based on CuS/PbS, CuS/NiS, CuS/CoS.
From figure 1 it appears that the micro-structural of sheet, particle are presented using CuS patterns prepared by simple solution mixing method
Even size distribution, about in 100nm, laminated structure is conducive to the mutually support in construction is to electrode film to form porous knot
Structure.
What Fig. 2 was presented is the CdSe quantum dot sensitization sun prepared by PbS, NiS, CoS combined counter electrode based on CuS frameworks
The current-voltage performance comparison analysis of energy battery.It can be seen that three kinds of batteries to electrode all show it is essentially identical
Open-circuit voltage, the most significant different manifestations of three in short-circuit current density, based on CuS/PbS and CuS/CoS to the electricity of electrode
Pond has close current density, but has best current density to the battery of electrode based on CuS/NiS, this test knot
Fruit illustrates that the catalysis activity that CuS/NiS shows in the battery to electrode, the electronics that can be input into external circuit passes through CuS/
The active site of NiS material surfaces quickly reduces many sulphur electrolyte for aoxidizing, while the light induced electron of more light anodes is transmitted
To external circuit.
Claims (10)
1. the preparation method of the sulfide nano-composite counter electrode of porous C uS frameworks is based on, it is characterised in that specifically according to following
Step is implemented：
Step 1, prepares CuS nano powders；
Step 2, CuS nano powders prepared by step 1 are made CuS slurries；
Step 3, the CuS slurries obtained using step 2 prepare porous C uS nanometer sheets to electrode；
Step 4, it is nano combined to electricity that the porous C uS obtained using step 3 prepares the sulfide based on porous C uS frameworks to electrode
Pole.
2. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks according to claim 1, it is special
Levy and be, the step 1 is specifically implemented according to following steps：
Step 1.1, the Na that concentration is 0.4-0.6M is equipped with using magnetic stirring apparatus2The S aqueous solution and CuSO4The aqueous solution；
Step 1.2, by Na2The S aqueous solution is slowly injected into CuSO4In the aqueous solution, the CuS that reaction is obtained fully is collected by centrifugation after reaction
Sediment；
Step 1.3, the CuS sediment undergoes washings obtained step 1.2 using deionized water 3-5 times, then using absolute ethyl alcohol by CuS
Sediment undergoes washing 3-5 times；
Step 1.4, the CuS sediments that will be cleaned are placed in 40-60 DEG C of vacuum drying chamber is dried, finally by drying
CuS sediments grinding distribution is into CuS nano powders.
3. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks according to claim 1, it is special
Levy and be, the step 2 is specifically implemented according to following steps：
Step 2.1, weighs CuS nano powders and is put into mortar, heavy to adding deionized water in CuS nano powders and grinding 50s-70s
4-6 time the step for multiple, then to addition glacial acetic acid in mortar and 50s-70s is ground, then to adding absolute ethyl alcohol in mortar
And grind 50s-70s and repeat 4-6 times；
Step 2.2, the mixture that step 2.1 is obtained is transferred in container and to the absolute ethyl alcohol that 15-20ml is added in container,
The magnetic agitation and ultrasonic disperse of compartment, so behaviour are carried out to said mixture using magnetic stirring apparatus and ultrasonic disperser
Make 50-70min；Each magnetic agitation is 4-6min with the time of ultrasonic disperse；
Step 2.3, to terpinol is added in the mixture that step 2.2 is obtained, using magnetic stirring apparatus and ultrasonic disperser pair
Said mixture carries out the magnetic agitation and ultrasonic disperse of compartment, so operates 50-70min；Each magnetic agitation and ultrasound
The scattered time is 4-6min；
Step 2.4, the ethyl cellulose of absolute ethyl alcohol is dissolved in addition in the mixture that step 2.3 is obtained, and is stirred using magnetic force
Mix device carries out the magnetic agitation and ultrasonic disperse of compartment to said mixture with ultrasonic disperser, so operates 50-
70min, each magnetic agitation is 4-6min with the time of ultrasonic disperse；Said mixture is finally placed in 60-70 DEG C of water-bath
In be stirred and fall the ethanol evaporation in mixture, obtain being applied to the CuS slurries of silk-screen printing.
4. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks according to claim 3, it is special
Levy and be, CuS nano powders and the mass ratio of ethyl cellulose are 2-3 in the step 2:1, the matter of terpinol and ethyl cellulose
Amount is than being 2:3.
5. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks according to claim 3, it is special
Levy and be, every gram of CuS nano powder described in step 2.1 adds the deionized water of 0.1-0.2ml every time；Every gram of CuS nano powder is every
The glacial acetic acid of secondary addition 0.1-0.2ml, the concentration of glacial acetic acid is 99.5%；Every gram of CuS nano powder adds 0.4-0.6ml's every time
Absolute ethyl alcohol.
6. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks according to claim 3, it is special
Levy and be, the step 3 is specifically implemented according to following steps：
Step 3.1, the CuS slurries obtained using step 2.4 prepare porous C uS nanometer sheet films, comprise the following steps that：
, be coated in CuS slurries in conductive substrates using screen printing technique first by step 3.1.1, is then stood in atmosphere,
After in the drying baker that conductive substrates are placed in 60-80 DEG C by CuS slurries again in conductive substrates after flow equilibrium, 5-10min is kept
Take out afterwards；
Step 3.1.2, repeat step 3.1.1 mono- to three times, obtain being coated with the conductive substrates of CuS slurries；
Step 3.1.3, the conductive substrates for being coated with CuS slurries that step 3.1.2 is obtained is put into Muffle furnace, with 3 DEG C/min
Speed from room temperature to 350-400 DEG C, be cooled to room temperature after annealing 90-30min, obtain porous C uS nanometer sheet films；
Step 3.2, TiO is prepared on porous C uS nanometer sheet films2Decorative layer, specifically using following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in being mixed using magnetic stirring apparatus in ice-water bath
Stirring, is stirring evenly and then adding into butyl titanate and stirs, and forms solution A；
Prepare B solution：Deionized water is added in absolute ethyl alcohol and uniform using magnetic stirrer, dense salt is added afterwards
Acid simultaneously stirs to form B solution；
Above-mentioned B solution is slowly added in solution A and stirred to form TiO2The precursor solution of decorative layer, then using rotation
In the space of the porous C uS nanometer sheet films that painting technique obtains precursor solution implantation step 3.1, finally by porous C uS nanometers
Piece film is put into Muffle furnace, with the speed of 3 DEG C/min from room temperature to 350-400 DEG C, is cooled to after annealing 50-30min
Room temperature；Wherein, the rotating speed of spin coating proceeding is 3000-4000r/min；
Step 3.3, first by S powder, Na2It is 7 that S, KCl are added to volume ratio:3-5:In 5 methyl alcohol and deionized water mixed solution
Many sulphur electrolyte are made, S powder, Na in many sulphur electrolyte2The concentration of S and KCl is respectively 0.5-2M, 0.5-2M and 0.2-
0.5M；Then TiO will be used in step 3.2 at room temperature2The porous C uS nanometer sheet films of modified are carried out in being put into many sulphur electrolyte
Vulcanizing treatment 3-9 hours, porous C uS nanometer sheets were obtained to electrode.
7. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks according to claim 6, it is special
Levy and be, the conductive substrates described in step 3.1.1 are any one in FTO glass or titanium foil or plating titanium glass.
8. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks according to claim 6, it is special
Levy and be, acetylacetone,2,4-pentanedione, absolute ethyl alcohol, the volume ratio of butyl titanate are 1 when solution A is prepared in step 3.2:48.5:3.3-
3.5；Deionized water, absolute ethyl alcohol, the volume ratio of concentrated hydrochloric acid are 1 when preparing B solution:20:0.076；The body of solution A and B solution
Product is than being 0.8-1:1.
9. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks according to claim 1, it is special
Levy and be, the step 4 is specifically implemented according to following steps：
The Pb that cation concn is 0.025-0.05M is made using water-soluble salt2+Or Ni2+Or Co2+C solution, using concentration
It is the Na of 0.025-0.05M2The S aqueous solution is used as S2-Solution, will then be obtained using SILAR method in step 3
Porous C uS nanometer sheets to the more than electrode immersion S that is made2-50-70s in solution, then takes porous C uS nanometer sheets to electrode
Go out and use deionized water rinsing, then the porous C uS nanometer sheets after flushing are immersed in the C solution that the above is made to electrode
After 50-70s, porous C uS nanometer sheets are taken out to electrode again and uses deionized water rinsing, so repeated 3-5 times, finally given
Sulfide nano-composite counter electrode based on porous C uS frameworks.
10. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks according to claim 9, its
It is characterised by, water-soluble salt is any one in nitrate or villaumite or sulfate.
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