CN106847513B - The preparation method of sulfide nano-composite counter electrode based on porous C uS frameworks - Google Patents
The preparation method of sulfide nano-composite counter electrode based on porous C uS frameworks Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- 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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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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Abstract
The invention discloses a kind of preparation methods of the sulfide nano-composite counter electrode based on porous C uS frameworks, are specifically implemented according to the following steps：Prepare CuS nano powders；CuS slurries are made in CuS nano powders；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.The simple for process, of low cost of the present invention, large area prepare, are 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, and the electron-transport resistance in electrolyte is reduced using the macroporous structure between CuS nanosheet, improves catalytic activity using the synergistic effect of complex sulfide, this 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, the demand with people to the energy is continuously increased and the lasting reduction of fossil fuel reserves, searching are a kind of
New abundance, environmentally protective alternative energy source have become one of the 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 have become the hot spot studied at present.
Quantum dot sensitized solar cell (QDSSC) is the third generation solar cell occurred the nineties in last century, i.e., sharp
The base material of broad stopband is sensitized with the inorganic semiconductor quantum dot (QD) of low energy gap.Quantum dot has prodigious excellent relative to dyestuff
Gesture, on the one hand, its with quantum confined effect, can by controlling its size and shape come the band gap width of quantum point,
The range 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 generate 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), more much higher than the theoretical value 32.9% of crystal silicon solar energy battery.Therefore, whether
Still upper in application in cost, the potentiality of the development of QDSSC are very huge.
Currently, electrolyte used by quantum dot sensitized solar cell is more sulphur (Sn 2-/S2-) liquid electrolyte, so
And it studies and finds the I suitable for dye-sensitized solar cells3-/I-The Pt of electrolyte is no longer appropriate for Sn 2-/S2-Electrolyte, because
S2-The catalytic activity to electrode to electrolyte is reduced in the chemisorption of Pt electrode surfaces, to influence the performance of battery.
In addition to this other are also widely studied electrode material, such as carbon, sulfide (PbS, CoS, FeS, CuxS), noble metal
(Au) materials such as.In the battery about various quantum dot sensitized optimum efficiencies, it is adopted without exception on copper foil rotten
Lose the Cu preparedxFor S to electrode, one of advantage, which is the thin micro-structure of pine, has high catalytic activity, second is that copper foil substrate has
There is fabulous electric conductivity；One of disadvantage is this electrode since electrolyte persistently corrodes substrate, causes adhesiveness to reduce, contact resistance
Increase, second is that being contacted with light anode to electrode for falling off causes to light anode poisoning.In addition, complex sulfide passes through electrode
Mutual synergistic effect can also greatly improve the catalytic performance of electrode.Therefore, for CuxS to electrode there are the problem of with it is multiple
The advantages of condensation material is to electrode is found and improves CuxS is very necessary with the method for preparing combination electrode to the stability of electrode
's.
Invention content
The object of the present invention is to provide a kind of preparation sides of the sulfide nano-composite counter electrode based on porous C uS frameworks
Method, this method utilize the macroporous structure between CuS nanosheet to reduce the electron-transport resistance in electrolyte and utilize composite material
Concerted catalysis effect, the performance of battery can be greatly improved.
The technical solution adopted in the present invention is：
The preparation method of sulfide nano-composite counter electrode based on porous C uS frameworks, is specifically implemented according to the following steps：
Step 1, CuS nano powders are prepared；
Step 2, CuS slurries are made in CuS nano powders prepared by step 1；
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 also characterized in that：
Step 1 is specifically implemented according to the following steps：
Step 1.1, the Na that concentration is 0.4-0.6M is equipped with using magnetic stirring apparatus2S aqueous solutions and CuSO4Aqueous solution；
Step 1.2, by Na2S aqueous solutions are slowly injected into CuSO4In aqueous solution, fully it is collected by centrifugation after reaction obtained by the reaction
CuS sediments；
Step 1.3, the CuS sediment undergoes washings obtained step 1.2 using deionized water 3-5 times, then use absolute ethyl alcohol
By CuS sediment undergoes washings 3-5 times；
Step 1.4, the CuS sediments cleaned are placed in 40-60 DEG C of vacuum drying chamber and are dried, will finally dried
Dry CuS sediments grinding distribution is at CuS nano powders.
Step 2 is specifically implemented according to the following steps：
Step 2.1, CuS nano powders are weighed to be put into mortar, deionized water is added into CuS nano powders and grind 50s-
Glacial acetic acid was then added into mortar and grinds 50s-70s, nothing is then added into mortar the step for 70s, repetition 4-6 times
Water-ethanol simultaneously grinds 50s-70s and repeats 4-6 times；
Step 2.2, the mixture that step 2.1 obtains is transferred in container and the anhydrous of 15-20ml is added into container
Ethyl alcohol carries out said mixture using magnetic stirring apparatus and ultrasonic disperser the magnetic agitation and ultrasonic disperse of compartment,
So operation 50-70min；The time of each magnetic agitation and ultrasonic disperse is 4-6min；
Step 2.3, terpinol is added in the mixture obtained to step 2.2, is disperseed using magnetic stirring apparatus and ultrasonic wave
Device carries out said mixture the magnetic agitation and ultrasonic disperse of compartment, so operates 50-70min；Each magnetic agitation with
The time of ultrasonic disperse is 4-6min；
Step 2.4, the ethyl cellulose for being dissolved in absolute ethyl alcohol is added in the mixture obtained to step 2.3, using magnetic
Power blender carries out said mixture with ultrasonic disperser the magnetic agitation and ultrasonic disperse of compartment, so operates 50-
The time of 70min, each magnetic agitation and ultrasonic disperse is 4-6min；Said mixture is finally placed in 60-70 DEG C of water-bath
In be stirred the ethanol evaporation in mixture made to fall, obtain the CuS slurries suitable for silk-screen printing.
The mass ratio of CuS nano powders and ethyl cellulose is 2-3 in step 2:1, the quality of terpinol and ethyl cellulose
Than being 2:3.
The deionized water of 0.1-0.2ml is added in every gram of CuS nano powder described in step 2.1 every time；Every gram of CuS nano powder is every
The secondary glacial acetic acid that 0.1-0.2ml is added, a concentration of the 99.5% of glacial acetic acid；Every gram of CuS nano powder is added 0.4-0.6ml's every time
Absolute ethyl alcohol.
Step 3 is specifically implemented according to the following steps：
Step 3.1, porous C uS nanometer sheet films are prepared using the CuS slurries that step 2.4 obtains, be as follows：
Step 3.1.1 uses screen printing technique that CuS slurries are coated in conductive substrates, then in air first
It stands, is again placed in conductive substrates in 60-80 DEG C of drying box after flow equilibrium in conductive substrates after CuS slurries, keep 5-
It is taken out after 10min；
Step 3.1.2 repeats step 3.1.1 mono- to the conductive substrates for, obtaining being coated with CuS slurries three times；
The conductive substrates coated with CuS slurries that step 3.1.2 is obtained are put into Muffle furnace by step 3.1.3, with 3 DEG C/
The rate of min is cooled to room temperature after annealing 90-30min, obtains porous C uS nanometer sheets from room temperature to 350-400 DEG C
Film；
Step 3.2, TiO is prepared on porous C uS nanometer sheet films2Decorative layer specifically uses following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in ice-water bath and is carried out using magnetic stirring apparatus
It is mixed, is stirring evenly and then adding into butyl titanate and stirs evenly, form solution A；
Prepare B solution：Deionized water is added in absolute ethyl alcohol and uniform using magnetic stirrer, is added later
Concentrated hydrochloric acid simultaneously stirs evenly to form B solution；
It is slowly added in solution A and stirs evenly above-mentioned B solution to form TiO2The precursor solution of decorative layer, is then adopted
In the gap of porous C uS nanometer sheet films precursor solution injection step 3.1 obtained with spin coating proceeding, finally by porous C uS
Nanometer sheet film is put into Muffle furnace, cold after the 50-30min that anneals with the rate 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, Na2S, it is 7 that KCl, which is added to volume ratio,:3-5:5 methanol and deionized water mixing is molten
More sulphur electrolyte are made in liquid, S powder, Na in more 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 more sulphur electrolyte
It carries out vulcanizing treatment 3-9 hours, obtains 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.
In step 3.2 prepare solution A when acetylacetone,2,4-pentanedione, absolute ethyl alcohol, butyl titanate volume ratio be 1:48.5:3.3-
3.5；Prepare B solution when deionized water, absolute ethyl alcohol, concentrated hydrochloric acid volume ratio be 1:20:0.076；The body of solution A and B solution
Product is than being 0.8-1:1.
Step 4 is specifically implemented according to the 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
The Na of a concentration of 0.025-0.05M2S aqueous solutions are as S2-Solution, then will be in step 3 using SILAR method
Obtained porous C uS nanometer sheets immerse the above manufactured S to electrode2-50-70s in solution, then by porous C uS nanometer sheets to electricity
Pole takes out and deionized water is used to rinse, then the porous C uS nanometer sheets after flushing are immersed in the above manufactured C solution to electrode
After middle 50-70s, porous C uS nanometer sheets take out electrode again and are rinsed with deionized water, so repeats 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：The simple for process, of low cost of the present invention, large area prepare, are 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 reduces the electron-transport resistance in electrolyte using the macroporous structure between CuS nanosheet, utilizes the association of complex sulfide
Same-action improves catalytic activity, and this method makes battery performance be greatly improved.
Description of the drawings
Fig. 1 is CuS nanosheet SEM prepared by hybrid reaction；
Fig. 2 is based on CuS/PbS, CuS/NiS, CuS/CoS to the current-voltage compares figure of electrode battery.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments：
Embodiment one：
The preparation method of sulfide nano-composite counter electrode based on porous C uS frameworks, is specifically implemented according to the following steps：
Step 1, CuS nano powders are prepared；
Step 1.1, the Na that concentration is 0.4M is equipped with using magnetic stirring apparatus2S aqueous solutions and CuSO4Aqueous solution；
Step 1.2, by Na2S aqueous solutions are slowly injected into CuSO4In aqueous solution, fully it is collected by centrifugation after reaction obtained by the reaction
CuS sediments；
Step 1.3, the CuS sediment undergoes washings obtained step 1.2 using deionized water 3-5 times, then use absolute ethyl alcohol
By CuS sediment undergoes washings 3-5 times；
Step 1.4, the CuS sediments cleaned are placed in 40 DEG C of vacuum drying chamber and are dried, it finally will drying
CuS sediments grinding distribution at CuS nano powders；
Step 2, CuS slurries are made in CuS nano powders prepared by step 1；
Step 2.1,1gCuS nano powders are weighed to be put into mortar, 0.1ml deionized waters are added into CuS nano powders and are ground
The step for grinding 50s-70s, repeating 4-6 time, then into mortar, addition and grinds 50s-70s at 0.1ml glacial acetic acid, then to grinding
0.4ml absolute ethyl alcohols are added in alms bowl and grinds 50s-70s and repeats 4-6 times；
Step 2.2, the mixture that step 2.1 obtains is transferred in container and the anhydrous of 15-20ml is added into container
Ethyl alcohol carries out said mixture using magnetic stirring apparatus and ultrasonic disperser the magnetic agitation and ultrasonic disperse of compartment,
So operation 50-70min；The time of each magnetic agitation and ultrasonic disperse is 4-6min；
Step 2.3, terpinol is added in the mixture obtained to step 2.2, is disperseed using magnetic stirring apparatus and ultrasonic wave
Device carries out said mixture the magnetic agitation and ultrasonic disperse of compartment, so operates 50-70min；Each magnetic agitation with
The time of ultrasonic disperse is 4-6min；
Step 2.4, the ethyl cellulose for being dissolved in absolute ethyl alcohol is added in the mixture obtained to step 2.3, using magnetic
Power blender carries out said mixture with ultrasonic disperser the magnetic agitation and ultrasonic disperse of compartment, so operates 50-
The time of 70min, each magnetic agitation and ultrasonic disperse is 4-6min；Finally by said mixture be placed in 60 DEG C of water-bath into
Row stirring makes the ethanol evaporation in mixture fall, and obtains the CuS slurries suitable for silk-screen printing；CuS nano powders and ethyl cellulose
The mass ratio of element is 2:1, the mass ratio of terpinol and ethyl cellulose is 2:3.
Step 3, the CuS slurries obtained using step 2 prepare porous C uS nanometer sheets to electrode；
Step 3.1, porous C uS nanometer sheet films are prepared using the CuS slurries that step 2.4 obtains, be as follows：
Step 3.1.1 uses screen printing technique that CuS slurries are coated in conductive substrates, then in air first
It stands, conductive substrates is placed in 60 DEG C of drying box again after flow equilibrium in conductive substrates after CuS slurries, keep 5-
It is taken out after 10min；Common conductive substrates are any one in FTO glass or titanium foil or plating titanium glass.
Step 3.1.2 repeats step 3.1.1 mono- to the conductive substrates for, obtaining being coated with CuS slurries three times；
The conductive substrates coated with CuS slurries that step 3.1.2 is obtained are put into Muffle furnace by step 3.1.3, with 3 DEG C/
The rate of min is cooled to room temperature after annealing 90min from room temperature to 350 DEG C, obtains porous C uS nanometer sheet films；
Step 3.2, TiO is prepared on porous C uS nanometer sheet films2Decorative layer specifically uses following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in ice-water bath and is carried out using magnetic stirring apparatus
It is mixed, is stirring evenly and then adding into butyl titanate and stirs evenly, 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, is added later
Concentrated hydrochloric acid simultaneously stirs evenly to form B solution；Wherein, deionized water, absolute ethyl alcohol, concentrated hydrochloric acid volume ratio be 1:20:0.076；
It is slowly added in solution A and stirs evenly above-mentioned B solution to form TiO2The precursor solution of decorative layer, solution A
Volume ratio with B solution is 0.8:1.Then the porous C uS that precursor solution injection step 3.1 obtains is received using spin coating proceeding
Rice piece film gap in, finally porous C uS nanometer sheet films are put into Muffle furnace, with the rate of 3 DEG C/min from room temperature to
350 DEG C, annealing 50min is cooled to room temperature later；Wherein, the rotating speed of spin coating proceeding is 3000r/min；
Step 3.3, first by S powder, Na2S, it is 7 that KCl, which is added to volume ratio,:In 3 methanol and deionized water mixed solution
More sulphur electrolyte are made, S powder, Na in more 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 are put into progress vulcanizing treatment 9 in more sulphur electrolyte
Hour, porous C uS nanometer sheets are obtained to electrode.Na2S steps 4 are prepared based on more electrode using the porous C uS that step 3 obtains
The sulfide nano-composite counter electrode of hole CuS frameworks, is specifically implemented according to the following steps：
The Pb that cation concn is 0.025M is made using water-soluble salt2+Or Ni2+Or Co2+C solution utilizes concentration
For the Na of 0.025M2S aqueous solutions are as S2-Solution then uses SILAR method (i.e. SILAR methods) by step 3
In obtained porous C uS nanometer sheets to electrode immerse it is above made of S2-50-70s in solution, then by porous C uS nanometer sheets pair
Electrode take out and use deionized water rinse, then by the porous C uS nanometer sheets after flushing to electrode be immersed in it is above made of C it is molten
In liquid after 50-70s, porous C uS nanometer sheets take out electrode again and are rinsed with deionized water, 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 sulfide nano-composite counter electrode based on porous C uS frameworks, is specifically implemented according to the following steps：
Step 1, CuS nano powders are prepared；
Step 1.1, the Na that concentration is 0.5M is equipped with using magnetic stirring apparatus2S aqueous solutions and CuSO4Aqueous solution；
Step 1.2, by Na2S aqueous solutions are slowly injected into CuSO4In aqueous solution, fully it is collected by centrifugation after reaction obtained by the reaction
CuS sediments；
Step 1.3, the CuS sediment undergoes washings obtained step 1.2 using deionized water 3-5 times, then use absolute ethyl alcohol
By CuS sediment undergoes washings 3-5 times；
Step 1.4, the CuS sediments cleaned are placed in 50 DEG C of vacuum drying chamber and are dried, it finally will drying
CuS sediments grinding distribution at CuS nano powders；
Step 2, CuS slurries are made in CuS nano powders prepared by step 1；
Step 2.1,1gCuS nano powders are weighed to be put into mortar, 0.15ml deionized waters are added into CuS nano powders and are ground
The step for grinding 50s-70s, repeating 4-6 time, then into mortar, addition and grinds 50s-70s at 0.15ml glacial acetic acid, then to
0.5ml absolute ethyl alcohols are added in mortar and grinds 50s-70s and repeats 4-6 times；
Step 2.2, the mixture that step 2.1 obtains is transferred in container and the anhydrous of 15-20ml is added into container
Ethyl alcohol carries out said mixture using magnetic stirring apparatus and ultrasonic disperser the magnetic agitation and ultrasonic disperse of compartment,
So operation 50-70min；The time of each magnetic agitation and ultrasonic disperse is 4-6min；
Step 2.3, terpinol is added in the mixture obtained to step 2.2, is disperseed using magnetic stirring apparatus and ultrasonic wave
Device carries out said mixture the magnetic agitation and ultrasonic disperse of compartment, so operates 50-70min；Each magnetic agitation with
The time of ultrasonic disperse is 4-6min；
Step 2.4, the ethyl cellulose for being dissolved in absolute ethyl alcohol is added in the mixture obtained to step 2.3, using magnetic
Power blender carries out said mixture with ultrasonic disperser the magnetic agitation and ultrasonic disperse of compartment, so operates 50-
The time of 70min, each magnetic agitation and ultrasonic disperse is 4-6min；Finally by said mixture be placed in 65 DEG C of water-bath into
Row stirring makes the ethanol evaporation in mixture fall, and obtains the CuS slurries suitable for silk-screen printing；CuS nano powders and ethyl cellulose
The mass ratio of element is 2.5:1, the mass ratio of terpinol and ethyl cellulose is 2:3.
Step 3, the CuS slurries obtained using step 2 prepare porous C uS nanometer sheets to electrode；
Step 3.1, porous C uS nanometer sheet films are prepared using the CuS slurries that step 2.4 obtains, be as follows：
Step 3.1.1 uses screen printing technique that CuS slurries are coated in conductive substrates, then in air first
It stands, conductive substrates is placed in 70 DEG C of drying box again after flow equilibrium in conductive substrates after CuS slurries, keep 5-
It is taken out after 10min；Common conductive substrates are any one in FTO glass or titanium foil or plating titanium glass.
Step 3.1.2 repeats step 3.1.1 mono- to the conductive substrates for, obtaining being coated with CuS slurries three times；
The conductive substrates coated with CuS slurries that step 3.1.2 is obtained are put into Muffle furnace by step 3.1.3, with 3 DEG C/
The rate of min is cooled to room temperature after annealing 60min from room temperature to 375 DEG C, obtains porous C uS nanometer sheet films；
Step 3.2, TiO is prepared on porous C uS nanometer sheet films2Decorative layer specifically uses following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in ice-water bath and is carried out using magnetic stirring apparatus
It is mixed, is stirring evenly and then adding into butyl titanate and stirs evenly, 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, is added later
Concentrated hydrochloric acid simultaneously stirs evenly to form B solution；Wherein, deionized water, absolute ethyl alcohol, concentrated hydrochloric acid volume ratio be 1:20:0.076；
It is slowly added in solution A and stirs evenly above-mentioned B solution to form TiO2The precursor solution of decorative layer, solution A
Volume ratio with B solution is 0.9:1.Then the porous C uS that precursor solution injection step 3.1 obtains is received using spin coating proceeding
Rice piece film gap in, finally porous C uS nanometer sheet films are put into Muffle furnace, with the rate of 3 DEG C/min from room temperature to
375 DEG C, annealing 40min is cooled to room temperature later；Wherein, the rotating speed of spin coating proceeding is 3500r/min；
Step 3.3, first by S powder, Na2S, it is 3 that KCl, which is added to volume ratio,:In 2 methanol and deionized water mixed solution
More sulphur electrolyte are made, S powder, Na in more sulphur electrolyte2The concentration of S and KCl is respectively 1M, 1M and 0.35M；Then in room
TiO will be used under temperature in step 3.22It is small that the porous C uS nanometer sheet films of modified are put into progress vulcanizing treatment 6 in more sulphur electrolyte
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, it is specifically implemented according to the following steps：
The Pb that cation concn is 0.04M is made using water-soluble salt2+Or Ni2+Or Co2+C solution, utilization are a concentration of
The Na of 0.04M2S aqueous solutions are as S2-Solution then uses SILAR method porous by what is obtained in step 3
CuS nanosheet immerses the above manufactured S to electrode2-Then porous C uS nanometer sheets are taken out and are adopted to electrode by 50-70s in solution
It is rinsed with deionized water, then the porous C uS nanometer sheets after flushing is immersed in 50-70s in the above manufactured C solution to electrode
Afterwards, porous C uS nanometer sheets take out electrode again and is rinsed with deionized water, so repeated 3-5 times, finally obtained based on more
The sulfide nano-composite counter electrode of hole CuS frameworks；Wherein, water-soluble salt is times in nitrate or villaumite or sulfate
Meaning is a kind of.
Embodiment three：
The preparation method of sulfide nano-composite counter electrode based on porous C uS frameworks, is specifically implemented according to the following steps：
Step 1, CuS nano powders are prepared；
Step 1.1, the Na that concentration is 0.6M is equipped with using magnetic stirring apparatus2S aqueous solutions and CuSO4Aqueous solution；
Step 1.2, by Na2S aqueous solutions are slowly injected into CuSO4In aqueous solution, fully it is collected by centrifugation after reaction obtained by the reaction
CuS sediments；
Step 1.3, the CuS sediment undergoes washings obtained step 1.2 using deionized water 3-5 times, then use absolute ethyl alcohol
By CuS sediment undergoes washings 3-5 times；
Step 1.4, the CuS sediments cleaned are placed in 60 DEG C of vacuum drying chamber and are dried, it finally will drying
CuS sediments grinding distribution at CuS nano powders；
Step 2, CuS slurries are made in CuS nano powders prepared by step 1；
Step 2.1,1gCuS nano powders are weighed to be put into mortar, 0.2ml deionized waters are added into CuS nano powders and are ground
The step for grinding 50s-70s, repeating 4-6 time, then into mortar, addition and grinds 50s-70s at 0.2ml glacial acetic acid, then to grinding
0.6ml absolute ethyl alcohols are added in alms bowl and grinds 50s-70s and repeats 4-6 times；
Step 2.2, the mixture that step 2.1 obtains is transferred in container and the anhydrous of 15-20ml is added into container
Ethyl alcohol carries out said mixture using magnetic stirring apparatus and ultrasonic disperser the magnetic agitation and ultrasonic disperse of compartment,
So operation 50-70min；The time of each magnetic agitation and ultrasonic disperse is 4-6min；
Step 2.3, terpinol is added in the mixture obtained to step 2.2, is disperseed using magnetic stirring apparatus and ultrasonic wave
Device carries out said mixture the magnetic agitation and ultrasonic disperse of compartment, so operates 50-70min；Each magnetic agitation with
The time of ultrasonic disperse is 4-6min；
Step 2.4, the ethyl cellulose for being dissolved in absolute ethyl alcohol is added in the mixture obtained to step 2.3, using magnetic
Power blender carries out said mixture with ultrasonic disperser the magnetic agitation and ultrasonic disperse of compartment, so operates 50-
The time of 70min, each magnetic agitation and ultrasonic disperse is 4-6min；Finally by said mixture be placed in 70 DEG C of water-bath into
Row stirring makes the ethanol evaporation in mixture fall, and obtains the CuS slurries suitable for silk-screen printing；CuS nano powders and ethyl cellulose
The mass ratio of element is 3:1, the mass ratio of terpinol and ethyl cellulose is 2:3.
Step 3, the CuS slurries obtained using step 2 prepare porous C uS nanometer sheets to electrode；
Step 3.1, porous C uS nanometer sheet films are prepared using the CuS slurries that step 2.4 obtains, be as follows：
Step 3.1.1 uses screen printing technique that CuS slurries are coated in conductive substrates, then in air first
It stands, conductive substrates is placed in 80 DEG C of drying box again after flow equilibrium in conductive substrates after CuS slurries, keep 5-
It is taken out after 10min；Common conductive substrates are any one in FTO glass or titanium foil or plating titanium glass.
Step 3.1.2 repeats step 3.1.1 mono- to the conductive substrates for, obtaining being coated with CuS slurries three times；
The conductive substrates coated with CuS slurries that step 3.1.2 is obtained are put into Muffle furnace by step 3.1.3, with 3 DEG C/
The rate of min is cooled to room temperature after annealing 30min from room temperature to 400 DEG C, obtains porous C uS nanometer sheet films；
Step 3.2, TiO is prepared on porous C uS nanometer sheet films2Decorative layer specifically uses following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in ice-water bath and is carried out using magnetic stirring apparatus
It is mixed, is stirring evenly and then adding into butyl titanate and stirs evenly, 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, is added later
Concentrated hydrochloric acid simultaneously stirs evenly to form B solution；Deionized water, absolute ethyl alcohol, concentrated hydrochloric acid volume ratio be 1:20:0.076；
It is slowly added in solution A and stirs evenly above-mentioned B solution to form TiO2The precursor solution of decorative layer, solution A
Volume ratio with B solution is 1:1.Then uS nanometers of porous C for using spin coating proceeding to obtain precursor solution injection step 3.1
In the gap of piece film, finally porous C uS nanometer sheet films are put into Muffle furnace, with the rate 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, Na2S, it is 1 that KCl, which is added to volume ratio,:In 1 methanol and deionized water mixed solution
More sulphur electrolyte are made, S powder, Na in more sulphur electrolyte2The concentration of S and KCl is respectively 2M, 2M and 0.5M；Then in room
TiO will be used under temperature in step 3.22It is small that the porous C uS nanometer sheet films of modified are put into progress vulcanizing treatment 3 in more sulphur electrolyte
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, it is specifically implemented according to the following steps：
The Pb that cation concn is 0.05M is made using water-soluble salt2+Or Ni2+Or Co2+C solution, utilization are a concentration of
The Na of 0.05M2S aqueous solutions are as S2-Solution then uses SILAR method porous by what is obtained in step 3
CuS nanosheet immerses the above manufactured S to electrode2-Then porous C uS nanometer sheets are taken out and are adopted to electrode by 50-70s in solution
It is rinsed with deionized water, then the porous C uS nanometer sheets after flushing is immersed in 50-70s in the above manufactured C solution to electrode
Afterwards, porous C uS nanometer sheets take out electrode again and is rinsed with deionized water, so repeated 3-5 times, finally obtained based on more
The sulfide nano-composite counter electrode of hole CuS frameworks；Wherein, water-soluble salt is times in 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 pairs of CuS slurries, and porous C uS nanometer sheet films are prepared using screen printing technique and annealing process, then use TiO2With
More sulphur electrolyte are surface modified porous C uS nanometer sheet films and vulcanizing treatment forms stable porous C uS nanometer sheets to electricity
Pole finally uses the metal sulfide catalysts such as SILAR methods deposition PbS, NiS, CoS, forms the vulcanization based on porous C uS frameworks
Object nano-composite counter electrode.The simple for process, of low cost of the present invention, large area prepare, are reproducible, are most closed in entire technique
The technology of key is：The control of annealing temperature in air；Using TiO2The control of the surface modification and vulcanizing treatment technique of progress.It adopts
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 reduces the electron-transport resistance in electrolyte using the macroporous structure between CuS nanosheet, utilizes complex sulfide
Synergistic effect improves catalytic activity, and this method makes battery performance be greatly improved.If Fig. 1 is CuS prepared by hybrid reaction
Nanometer sheet SEM；Fig. 2 is based on CuS/PbS, CuS/NiS, CuS/CoS to the current-voltage compares figure of electrode battery.
From figure 1 it appears that the micro-structure 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 and forms 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 from the figure that three kinds of batteries to electrode all show it is essentially identical
Open-circuit voltage, the most significant different manifestations of three are in short-circuit current density, based on CuS/PbS and CuS/CoS to the electricity of electrode
Pond has similar current density, however has best current density, this test knot to the battery of electrode based on CuS/NiS
Fruit illustrates that the electronics that external circuit inputs can be passed through CuS/ by the catalytic activity that CuS/NiS has shown electrode in the battery
The active site of NiS material surfaces quickly restores more sulphur electrolyte of oxidation, while the light induced electron of more light anodes being transmitted
To external circuit.
Claims (8)
1. the preparation method of the sulfide nano-composite counter electrode based on porous C uS frameworks, which is characterized in that specifically according to following
Step is implemented：
Step 1, CuS nano powders are prepared；
Step 2, CuS slurries are made in CuS nano powders prepared by step 1；
Step 3, the CuS slurries obtained using step 2 prepare porous C uS nanometer sheets to electrode, are specifically implemented according to the following steps：
Step 3.1, porous C uS nanometer sheet films are prepared using the CuS slurries that step 2 obtains, be as follows：
Step 3.1.1 uses screen printing technique that CuS slurries are coated in conductive substrates, then stands in air first,
Conductive substrates are placed in again in 60-80 DEG C of drying box after flow equilibrium in conductive substrates after CuS slurries, keep 5-10min
It takes out later；
Step 3.1.2 repeats step 3.1.1 mono- to the conductive substrates for, obtaining being coated with CuS slurries three times；
The conductive substrates coated with CuS slurries that step 3.1.2 is obtained are put into Muffle furnace, with 3 DEG C/min by step 3.1.3
Rate 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 uses following methods：
Prepare solution A：Acetylacetone,2,4-pentanedione is added in absolute ethyl alcohol, is placed in ice-water bath and is mixed using magnetic stirring apparatus
Stirring, is stirring evenly and then adding into butyl titanate and stirs evenly, and forms solution A；
Prepare B solution：Deionized water is added in absolute ethyl alcohol and uniform using magnetic stirrer, dense salt is added later
Acid simultaneously stirs evenly to form B solution；
It is slowly added in solution A and stirs evenly above-mentioned B solution to form TiO2The precursor solution of decorative layer, then using rotation
It applies in the gap of porous C uS nanometer sheet films that technique obtains precursor solution injection step 3.1, finally by uS nanometers of porous C
Piece film is put into Muffle furnace, with the rate 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, Na2S, it is 7 that KCl, which is added to volume ratio,:3-5:In 5 methanol and deionized water mixed solution
More sulphur electrolyte are made, S powder, Na in more 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, which are put into more sulphur electrolyte, to carry out
Vulcanizing treatment 3-9 hours obtains 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 is specifically implemented according to the 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
For the Na of 0.025-0.05M2S aqueous solutions are as S2-Solution then uses SILAR method that will be obtained in step 3
Porous C uS nanometer sheets to electrode immerse it is above made of S2-Then 50-70s in solution takes electrode porous C uS nanometer sheets
Go out and deionized water is used to rinse, then the porous C uS nanometer sheets after flushing are immersed in the above manufactured C solution electrode
After 50-70s, porous C uS nanometer sheets take out electrode again and are rinsed with deionized water, so repeats 3-5 times, finally obtain
Sulfide nano-composite counter electrode based on porous C uS frameworks.
2. the preparation method of the sulfide nano-composite counter electrode according to claim 1 based on porous C uS frameworks, special
Sign is that the step 1 is specifically implemented according to the following steps：
Step 1.1, the Na that concentration is 0.4-0.6M is equipped with using magnetic stirring apparatus2S aqueous solutions and CuSO4Aqueous solution；
Step 1.2, by Na2S aqueous solutions are slowly injected into CuSO4In aqueous solution, CuS obtained by the reaction 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 cleaned are placed in 40-60 DEG C of vacuum drying chamber and are dried, finally by drying
CuS sediments grinding distribution is at CuS nano powders.
3. the preparation method of the sulfide nano-composite counter electrode according to claim 1 based on porous C uS frameworks, special
Sign is that the step 2 is specifically implemented according to the following steps：
Step 2.1, CuS nano powders are weighed to be put into mortar, deionized water is added into CuS nano powders and grind 50s-70s, weight
Glacial acetic acid was then added into mortar and grinds 50s-70s, absolute ethyl alcohol is then added into mortar the step for multiple 4-6 times
And it grinds 50s-70s and repeats 4-6 times；
Step 2.2, the mixture that step 2.1 obtains is transferred in container and is added into container the absolute ethyl alcohol of 15-20ml,
The magnetic agitation and ultrasonic disperse for being carried out compartment to said mixture using magnetic stirring apparatus and ultrasonic disperser, are so grasped
Make 50-70min；The time of each magnetic agitation and ultrasonic disperse is 4-6min；
Step 2.3, terpinol is added in the mixture obtained to step 2.2, 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 time of dispersion is 4-6min；
Step 2.4, the ethyl cellulose for being dissolved in absolute ethyl alcohol is added in the mixture obtained to step 2.3, is stirred using magnetic force
Magnetic agitation and ultrasonic disperse that device carries out said mixture with ultrasonic disperser compartment are mixed, 50- is so operated
The time of 70min, each magnetic agitation and ultrasonic disperse is 4-6min；Said mixture is finally placed in 60-70 DEG C of water-bath
In be stirred the ethanol evaporation in mixture made to fall, obtain the CuS slurries suitable for silk-screen printing.
4. the preparation method of the sulfide nano-composite counter electrode according to claim 3 based on porous C uS frameworks, special
Sign is that the mass ratio of CuS nano powders and ethyl cellulose is 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 according to claim 3 based on porous C uS frameworks, special
Sign is that the deionized water of 0.1-0.2ml is added in every gram of CuS nano powder every time in step 2.1；Every gram of CuS nano powder adds every time
Enter the glacial acetic acid of 0.1-0.2ml, a concentration of the 99.5% of glacial acetic acid；The anhydrous of 0.4-0.6ml is added in every gram of CuS nano powder every time
Ethyl alcohol.
6. the preparation method of the sulfide nano-composite counter electrode according to claim 1 based on porous C uS frameworks, special
Sign is that the conductive substrates described in step 3.1.1 are any one in FTO glass or titanium foil or plating titanium glass.
7. the preparation method of the sulfide nano-composite counter electrode according to claim 1 based on porous C uS frameworks, special
Sign is, acetylacetone,2,4-pentanedione when preparing solution A in step 3.2, absolute ethyl alcohol, butyl titanate volume ratio be 1:48.5:3.3-
3.5；Prepare B solution when deionized water, absolute ethyl alcohol, concentrated hydrochloric acid volume ratio be 1:20:0.076；The body of solution A and B solution
Product is than being 0.8-1:1.
8. the preparation method of the sulfide nano-composite counter electrode according to claim 1 based on porous C uS frameworks, special
Sign is that water-soluble salt is any one in nitrate or villaumite or sulfate.
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