CN106328381B - All solid state quantum dot sensitized solar cell of one kind and preparation method thereof - Google Patents
All solid state quantum dot sensitized solar cell of one kind and preparation method thereof Download PDFInfo
- Publication number
- CN106328381B CN106328381B CN201611037388.8A CN201611037388A CN106328381B CN 106328381 B CN106328381 B CN 106328381B CN 201611037388 A CN201611037388 A CN 201611037388A CN 106328381 B CN106328381 B CN 106328381B
- Authority
- CN
- China
- Prior art keywords
- solution
- solid
- electrode
- electrolytic solution
- quantum dot
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- 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
- H01G9/0029—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of all solid state quantum dot sensitized solar cells, including the electro-conductive glass and copper base being oppositely arranged, and solid-state electrolytic solution is filled between electro-conductive glass and copper base, and the side that solid-state electrolytic solution is located on electro-conductive glass is provided with light anode；It is provided with to electrode positioned at the side of solid-state electrolytic solution on copper base, is copper-based Cu to electrode2For S nanometer sheets to electrode, light anode is the quantum dot sensitized ZnO nanowire array light anodes of CdS/CdSe.The present invention, by heating solid-state electrolytic solution, makes it be adequately filled in ZnO nanowire array light anode and copper-based Cu by synthesizing solid-state electrolytic solution with good conductivity2Micro-structure gap of the S nanometer sheets to electrode, the electrolyte that will appear during performance is unstable and encapsulation process for not only overcoming the quantum dot sensitized solar cell of liquid omits problem, and preparation process is simple, of low cost, large area prepares reproducible, there is good use value.
Description
Technical field
The invention belongs to quantum dot sensitized technical field of solar batteries, and in particular to it is a kind of it is all solid state it is quantum dot sensitized too
Positive energy battery, the invention further relates to a kind of preparation methods of all solid state quantum dot sensitized solar cell.
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, the environmentally protective energy have become one of the important topic of current scientific research.Solar energy as one kind take no
Most natural energy source is increasingly subject to global concern, and the solar cell for especially solar energy being converted into electric energy is studied
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, with
This adjusts the range of absorption spectrum；On the other hand, semiconductor-quantum-point has exciton multiplier effect (MEG), a high-energy
Photon excitation semiconductor-quantum-point, multiple electron-hole pairs can be generated.If the two of semiconductor-quantum-point big advantages answered
It uses in solar cell, the theoretical value of quantum dot sensitized solar battery efficiency can reach 44%, and significantly larger than crystalline silicon is too
The theoretical value 32.9% of positive energy battery.Therefore, the potentiality of the development of quantum dot sensitized solar cell are huge.
Currently, electrolyte used by quantum dot sensitized solar cell is more sulphur (Sn2-/S2-) liquid electrolyte, so
And it studies and finds (the I suitable for dye-sensitized solar cells3-/I-) platinum of electrolyte is no longer appropriate for (Sn2-/S2-) electrolyte,
Because of S2-Catalytic activity of the electrode to electrolyte is reduced in the chemisorption of platinum electrode surface, to affect the property of battery
Energy.In the battery about various quantum dot sensitized optimum efficiencies, without exception be all to be prepared using copper foil substrate
Cu2S is to electrode, the advantages of because of electrode thus：First, the micro-structure that pine is dredged has huge catalytic activity, second is that copper foil is as substrate
With fabulous electric conductivity.However, this Cu2S causes battery performance unstable at electrode, first, liquid electrolyte is to Cu substrates
It is continuous corrosion cause adhesiveness reduce, contact resistance increase, second is that the Cu to fall off2S is contacted with light anode to be caused in light anode
Poison preserves will appear electrolyte omission for a long time, lead third, liquid electrolyte encapsulation is difficult in quantum dot sensitized solar cell
Cause battery performance heavy losses.
Invention content
The object of the present invention is to provide a kind of all solid state quantum dot sensitized solar cells, are solved by the battery structure
The existing quantum dot sensitized solar cell of the liquid problem that performance is unstable in use, encapsulation is difficult.
It is a further object to provide a kind of preparation methods of all solid state quantum dot sensitized solar cell.
The technical solution adopted in the present invention is a kind of all solid state quantum dot sensitized solar cell, including is oppositely arranged
Electro-conductive glass and copper base, solid-state electrolytic solution is filled between electro-conductive glass and copper base, solid-state is located on electro-conductive glass
The side of electrolyte is provided with light anode；Side on copper base positioned at solid-state electrolytic solution is provided with to electrode.
It is a feature of the present invention that
Solid-state electrolytic solution is more sulphur electrolyte.
It is copper-based Cu to electrode2For S nanometer sheets to electrode, light anode is the quantum dot sensitized ZnO nano linear arrays of CdS/CdSe
Row light anode.
Another technical solution of the present invention is a kind of preparation side of all solid state quantum dot sensitized solar cell
Method includes the following steps：
Step 1, ZnO nanowire array is prepared on electro-conductive glass；
Step 2, the ZnO nanowire array in step 1 is subjected to CdS/CdSe quantum spot depositions, obtains light anode；
Step 3, Cu is prepared on copper base2S is to electrode；
Step 4, solid-state electrolytic solution is prepared；
Step 5, the light anode in heating stepses 2, going forward side by side to the solid-state electrolytic solution in electrode and step 4 in step 3
Row encapsulation, forms battery.
It is of the invention to be further characterized in that,
Step 1 is specially：
Step 1.1, the precursor solution for preparing ZnO seed layers uses the forerunner of ZnO seed layers in the side of electro-conductive glass
Liquid solution prepares ZnO seed layers by spin-coating method and heat treatment process, and wherein spin speed is 3000-4500r/min, heat
The temperature for the treatment of process is 300-350 DEG C, and the thickness of ZnO seed layers is 50-100nm；
Step 1.2, the ZnO seed layers in step 1.1 are put into growth-promoting media, use temperature for 80-90 DEG C of immersion method
ZnO nanowire array is prepared, wherein growth-promoting media is molar concentration rate 20:1 NaOH and Zn (NO3)2Mixed solution or molar concentration
Than 1:1 hexamethylenetetramine and Zn (NO3)2Mixed solution or molar concentration rate 1:1 ammonium hydroxide and Zn (NO3)2Mixed solution.
Step 2 is specially：
Step 2.1, the ZnO nanowire array in step 1 is repeatedly alternately immersed to the Na of same molar ratio2S solution with
Cd(NO3)2Methanol solution obtains the ZnO nanowire array of CdS quantum dot sensitization；
Step 2.2, it is 1-1.5 that molar ratio is added in methanol solution:1 KBH4Powder and SeO2Powder, heating restore
To solution a, the ZnO nanowire array that step 2.1 processing obtains repeatedly alternately is immersed into Cd (NO3)2Methanol solution and solution a, obtain
The ZnO nanowire array quantum dot sensitized to CdS/CdSe, i.e. light anode, wherein Cd (NO3)2Methanol solution and SeO2Powder rubs
Your concentration is identical.
Step 3 is specially：
Step 3.1, copper base is placed on through sand paper polishing in ethanol solution, carries out ultrasonic cleaning 20-30min；
Step 3.2, the processed copper base side of step 3.1 is blocked and is placed in 5-10min in 70 DEG C of concentrated hydrochloric acid, taken
It rinses and dries using deionized water and methanol after going out；
Step 3.3, the processed copper base of step 3.2 is placed in progress vulcanizing treatment 10-15min in more sulphur electrolyte,
It rinses and dries using deionized water and methanol after taking-up, obtain the Cu of copper-based black2S places it in indifferent gas to electrode
It is preserved in body.
Step 4 is specially：
Step 4.1, suitable dextran is slowly added in the KCL aqueous solutions that quality is 3-5g, is stirred at 85-100 DEG C
It mixes uniformly, the wherein a concentration of 20-30% of KCL aqueous solutions；
Step 4.2, the high-purity sulphur powders of 0.09-0.10g and 0.65-0.75g are sequentially added in the solution that step 4.1 obtains
Na2S·9H2O stirs evenly postcooling to room temperature, obtains hydrosol electrolyte, i.e. solid-state electrolytic solution.
Step 5 is specially：
Step 5.1, by the light anode in step 2, being preheated to electrode and the solid-state electrolytic solution in step 4 in step 3
To 60-80 DEG C；
Step 5.2, step 5.1 will be added dropwise to through the solid-state electrolytic solution that step 5.1 is handled treated light anode table in right amount
Face is engraved in the closed container of identical temperature and vacuumizes 5-10min；
Step 5.3, step 5.1 is added dropwise to through the solid-state electrolytic solution that step 5.1 is handled by right amount treated to electrode table
Face is engraved in the closed container of identical temperature and vacuumizes 5-10min；
Step 5.4, take step 5.2 handle light anode and step 5.3 handle to electrode, be respectively placed in certain thickness
The interval body both sides face contact of degree, and heating makes solid-state electrolytic solution fully merge, and is packaged into battery.
The beneficial effects of the invention are as follows：The present invention is by synthesizing solid-state electrolytic solution with good conductivity, by heating solid-state
Electrolyte makes it be adequately filled in ZnO nanowire array light anode and copper-based Cu2S nanometer sheets to the micro-structure gap of electrode,
The electrolyte that will appear during performance is unstable and encapsulation process for not only overcoming the quantum dot sensitized solar cell of liquid is lost
Leakage problem, and preparation process is simple, of low cost, large area prepares reproducible, there is good use value.
Description of the drawings
Fig. 1 is a kind of structural schematic diagram of all solid state quantum dot sensitized solar cell of the present invention.
In figure, 1. solid-state electrolytic solutions, 2. electro-conductive glass, 3. copper bases, 4. pairs of electrodes, 5. light anodes.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of all solid state quantum dot sensitized solar cell of the invention, as shown in Figure 1, including the electro-conductive glass being oppositely arranged
2 and copper base 3, it is filled with solid-state electrolytic solution 1 between electro-conductive glass 2 and copper base 3, is located at solid state electrolysis on electro-conductive glass 2
The side of liquid 1 is provided with light anode 5；Side on copper base 3 positioned at solid-state electrolytic solution 1 is provided with to electrode 4.
Solid-state electrolytic solution 1 is more sulphur electrolyte.
A kind of preparation method of all solid state quantum dot sensitized solar cell of the present invention, includes the following steps：
Step 1, ZnO nanowire array is prepared on electro-conductive glass 2
Step 1.1, the precursor solution for preparing ZnO seed layers, before the side of electro-conductive glass 2 is using ZnO seed layers
Liquid solution to be driven, ZnO seed layers are prepared by spin-coating method and heat treatment process, wherein spin speed is 3000-4500r/min,
The temperature of heat treatment process is 300-350 DEG C, and the thickness of ZnO seed layers is 50-100nm；
The precursor solution of ZnO seed layers is specially：By 16.46g zinc acetates be added 4.5ml monoethanolamine (MEA) with
In the mixed solution of 100ml ethylene glycol monomethyl ethers, the then magnetic agitation 30min under 60 DEG C of hydrothermal conditions, later in 30 DEG C of perseverance
It is aged for 24 hours in incubator；
Step 1.2, the ZnO seed layers in step 1.1 are put into growth-promoting media, use temperature for 80-90 DEG C of immersion method
ZnO nanowire array is prepared, wherein growth-promoting media is molar concentration rate 20:1 NaOH and Zn (NO3)2Mixed solution or molar concentration
Than 1:1 hexamethylenetetramine and Zn (NO3)2Mixed solution or molar concentration rate 1:1 ammonium hydroxide and Zn (NO3)2Mixed solution；
Wherein, molar concentration rate 20:1 NaOH and Zn (NO3)2The specific preparation of mixed solution：Under magnetic agitation, first
By the Zn (NO of the NaOH of 0.08mol and 0.004mol3)2·6H2O is dissolved separately in 50ml deionized waters, then by Zn
(NO3)2·6H2O solution is slowly added NaOH solution and stirs evenly under magnetic stirring；
Molar concentration rate 1:1 hexamethylenetetramine and Zn (NO3)2The specific preparation of mixed solution：It is first under magnetic agitation
First by the Zn (NO of the hexamethylenetetramine of 0.1mol and 0.1mol3)2·6H2O is dissolved separately in 50ml deionized waters, then
By Zn (NO3)2·6H2It is uniform that hexamethylenetetramine solution ＆ stir is slowly added in O solution under magnetic stirring；
Molar concentration rate 1:1 ammonium hydroxide and Zn (NO3)2The specific preparation of mixed solution：Under magnetic agitation, match respectively for the first time
Make the Zn (NO of a concentration of 0.1mol/L3)2·6H2O solution and each 50ml of ammonia spirit, then by Zn (NO3)2﹒ 6H2O solution exists
Ammonia spirit is slowly added under magnetic agitation and stirs evenly.
Step 2, the ZnO nanowire array in step 1 is subjected to CdS/CdSe quantum spot depositions, obtains light anode 5
Step 2.1, the ZnO nanowire array in step 1 is repeatedly alternately immersed to the Na of same molar ratio2S solution with
Cd(NO3)2Methanol solution obtains the ZnO nanowire array of CdS quantum dot sensitization；
Step 2.2, it is 1-1.5 that molar ratio is added in methanol solution:1 KBH4Powder and SeO2Powder, heating restore
To solution a；The ZnO nanowire array that step 2.1 processing obtains repeatedly alternately is immersed into Cd (NO3)2Methanol solution and solution a, obtain
The ZnO nanowire array quantum dot sensitized to CdS/CdSe, i.e. light anode 5, wherein Cd (NO3)2Methanol solution and SeO2Powder rubs
Your concentration is identical.
Step 3, Cu is prepared on copper base 32S is to electrode 4；
Step 3.1, copper base 3 is placed on through sand paper polishing in ethanol solution, carries out ultrasonic cleaning 20-30min；
Step 3.2, processed 3 side of copper base of step 3.1 is blocked and is placed in 5-10min in 70 DEG C of concentrated hydrochloric acid,
It rinses and dries using deionized water and methanol after taking-up；
Step 3.3, the processed copper base of step 3.2 3 is placed in progress vulcanizing treatment 10-15min in more sulphur electrolyte,
It rinses and dries using deionized water and methanol after taking-up, obtain the Cu of copper-based black2S places it in indifferent gas to electrode 4
It is preserved in body, wherein more sulphur electrolyte are：It is respectively the Na of 2mol/L by concentration2S, the high-purity sulphur powder and 0.2mol/L of 2mol/L
KCl be dissolved in volume ratio be 7:It is prepared in 3 methanol and the mixed solution of deionized water.
Step 4, solid-state electrolytic solution 1 is prepared
Step 4.1, suitable dextran is slowly added in the KCL aqueous solutions that quality is 3-5g, is stirred at 85-100 DEG C
It mixes uniformly, the wherein a concentration of 20-30% of KCL aqueous solutions；
Step 4.2, the high-purity sulphur powders of 0.09-0.10g and 0.65-0.75g are sequentially added in the solution that step 4.1 obtains
Na2S·9H2O stirs evenly postcooling to room temperature, obtains hydrosol electrolyte, i.e. solid-state electrolytic solution 1.
Step 5, the light anode 5 in heating stepses 2, in step 3 to the solid-state electrolytic solution 1 in electrode 4 and step 4 simultaneously
It is packaged, forms battery
Step 5.1, by the light anode 5, pre- to the solid-state electrolytic solution 1 in electrode 4 and step 4 in step 3 in step 2
Heat is to 60-80 DEG C；
Step 5.2, the solid-state electrolytic solution 1 handled in right amount through step 5.1 is added dropwise to step 5.1 treated light anode 5
Surface is engraved in the closed container of identical temperature and vacuumizes 5-10min；
Step 5.3, the solid-state electrolytic solution 1 handled in right amount through step 5.1 is added dropwise to step 5.1 treated to electrode 4
Surface is engraved in the closed container of identical temperature and vacuumizes 5-10min；
Step 5.4, take that light anode 5 that step 5.2 is handled and step 5.3 handle to electrode 4, be respectively placed in certain
The interval body both sides face contact of thickness, and heating makes solid-state electrolytic solution 1 fully merge, and is packaged into battery.
Embodiment 1
(1) light anode 5 is prepared
Prepare the precursor solution of ZnO seed layers：4.5ml monoethanolamine (MEA) and 100ml is added in 16.46g zinc acetates
In the mixed solution of ethylene glycol monomethyl ether, then the magnetic agitation 30min under 60 DEG C of hydro-thermals, is aged in 30 DEG C of insulating box later
24h。
Prepare solution a：It is 1 that molar ratio is added in methanol solution:1 KBH4Powder and SeO2Powder, heating reduction obtain
Solution a.
The precursor solution of ZnO seed layers is used in the side of electro-conductive glass 2, is prepared by spin-coating method and heat treatment process
ZnO seed layers, wherein spin speed are 3000r/min, and the temperature of heat treatment process is 300 DEG C, obtains the thickness of ZnO seed layers
For 50nm；ZnO seeds are placed on molar concentration rate 20:1 NaOH and Zn (NO3)2Mixed solution, it is raw in 80 DEG C of water-bath
Long ZnO nanowire array；ZnO nanowire array is repeatedly alternately immersed to the Na of same molar ratio2S solution and Cd (NO3)2First
Then alcoholic solution repeatedly replaces immersion and SeO again2Identical Cd (the NO of powder molar concentration3)2In methanol solution and solution a, obtain
To light anode 5.
(2) it prepares to electrode 4
Prepare more sulphur electrolyte：It is respectively the Na of 2mol/L by concentration2S, high-purity sulphur powder of 2mol/L and 0.2mol/L
It is 7 that KCl, which is dissolved in volume ratio,:It is prepared in 3 methanol and the mixed solution of deionized water.
Copper base 3 is placed on through sand paper polishing in ethanol solution, ultrasonic cleaning 20min is carried out, then by copper base 3
Side, which is blocked, is placed in 5min in 70 DEG C of concentrated hydrochloric acid, and deionized water and methanol rinsing, drying are used after taking-up；It is placed in more sulphur again
Vulcanizing treatment 10min is carried out in electrolyte, and deionized water and methanol rinsing, drying are used after taking-up, obtains copper-based black
Cu2S is placed in inert gas electrode 4 and preserves, spare.
(3) solid-state electrolytic solution 1 is prepared
Suitable dextran is slowly added in the KCL aqueous solutions that quality is 3g, is stirred evenly at 85 DEG C, wherein KCL
A concentration of the 20% of aqueous solution；Then the Na of 0.09g high-purity sulphur powder and 0.65g is sequentially added into mixed solution2S·9H2O is stirred
Uniform postcooling is mixed to room temperature, obtains hydrosol electrolyte, i.e. solid-state electrolytic solution 1.
(4) battery is assembled
It is preheated to 60 DEG C by light anode 5, to electrode 4 and solid-state electrolytic solution 1；The solid-state electrolytic solution 1 preheated in right amount is dripped
5 surface of light anode for adding to preheating, that is, be engraved in 60 DEG C of closed container and vacuumize 5min；The solid-state electrolytic solution 1 of preheating is dripped
Add to preheating to 4 surface of electrode, that is, be engraved in 60 DEG C of closed container and vacuumize 5min；Then by light anode 5 and to electrode 4
It is respectively placed in the face contact of certain thickness interval body both sides, and heating makes solid-state electrolytic solution 1 fully merge, and is packaged into battery.
Embodiment 2
(1) light anode 5 is prepared
Prepare the precursor solution of ZnO seed layers：4.5ml monoethanolamine (MEA) and 100ml is added in 16.46g zinc acetates
In the mixed solution of ethylene glycol monomethyl ether, then the magnetic agitation 30min under 60 DEG C of hydro-thermals, is aged in 30 DEG C of insulating box later
24h。
Prepare solution a：It is 1.2 that molar ratio is added in methanol solution:1 KBH4Powder and SeO2Powder, heating restore
To solution a.
It is prepared by spin-coating method and heat treatment process using the precursor solution of ZnO seed layers in the side of electro-conductive glass 2
ZnO seed layers, wherein spin speed are 3800r/min, and the temperature of heat treatment process is 320 DEG C, obtains the thickness of ZnO seed layers
For 80nm；ZnO seeds are placed on molar concentration rate 1:1 hexamethylenetetramine and Zn (NO3)2Mixed solution, in 85 DEG C of water
Growing ZnO nano-wire array in bath；ZnO nanowire array is repeatedly alternately immersed to the Na of same molar ratio2S solution and Cd
(NO3)2Then methanol solution repeatedly replaces immersion and SeO again2Identical Cd (the NO of powder molar concentration3)2Methanol solution and solution
In a, light anode 5 is obtained.
(2) it prepares to electrode 4
Prepare more sulphur electrolyte：It is respectively the Na of 2mol/L by concentration2S, high-purity sulphur powder of 2mol/L and 0.2mol/L
It is 7 that KCl, which is dissolved in volume ratio,:It is prepared in 3 methanol and the mixed solution of deionized water.
Copper base 3 is placed on through sand paper polishing in ethanol solution, ultrasonic cleaning 25min is carried out, then by copper base 3
Side, which is blocked, is placed in 8min in 70 DEG C of concentrated hydrochloric acid, and deionized water and methanol rinsing, drying are used after taking-up；It is placed in more sulphur again
Vulcanizing treatment 12min is carried out in electrolyte, and deionized water and methanol rinsing, drying are used after taking-up, obtains copper-based black
Cu2S is placed in inert gas electrode 4 and preserves, spare.
(3) solid-state electrolytic solution 1 is prepared
Suitable dextran is slowly added in the KCL aqueous solutions that quality is 4g, is stirred evenly at 90 DEG C, wherein KCL
A concentration of the 25% of aqueous solution；Then the Na of 0.096g high-purity sulphur powder and 0.70g is sequentially added into mixed solution2S·9H2O,
Postcooling is stirred evenly to room temperature, obtains hydrosol electrolyte, i.e. solid-state electrolytic solution 1.
(4) battery is assembled
It is preheated to 70 DEG C by light anode 5, to electrode 4 and solid-state electrolytic solution 1；By the solid-state electrolytic solution 1 of suitable preheating
It is added dropwise to 5 surface of light anode of preheating, that is, is engraved in 70 DEG C of closed container and vacuumizes 8min；By the solid-state electricity of suitable preheating
Solution liquid 1 be added dropwise to preheating to 4 surface of electrode, that is, be engraved in 70 DEG C of closed container and carry out vacuumizing 8min；Then by light sun
Pole 5 and faces contact in certain thickness interval body both sides is respectively placed in electrode 4, and heating makes solid-state electrolytic solution 1 fully merge,
It is packaged into battery.
Embodiment 3
(1) light anode 5 is prepared
Prepare the precursor solution of ZnO seed layers：4.5ml monoethanolamine (MEA) and 100ml is added in 16.46g zinc acetates
In the mixed solution of ethylene glycol monomethyl ether, then the magnetic agitation 30min under 60 DEG C of hydro-thermals, is aged in 30 DEG C of insulating box later
24h。
Prepare solution a：It is 1.5 that molar ratio is added in methanol solution:1 KBH4Powder and SeO2Powder, heating restore
To solution a.
It is prepared by spin-coating method and heat treatment process using the precursor solution of ZnO seed layers in the side of electro-conductive glass 2
ZnO seed layers, wherein spin speed are 4500r/min, and the temperature of heat treatment process is 350 DEG C, obtains the thickness of ZnO seed layers
For 100nm；ZnO seeds are placed on molar concentration rate 1:1 ammonium hydroxide and Zn (NO3)2Mixed solution, it is raw in 90 DEG C of water-bath
Long ZnO nanowire array；ZnO nanowire array is repeatedly alternately immersed to the Na of same molar ratio2S solution and Cd (NO3)2First
Then alcoholic solution repeatedly replaces immersion and SeO again2Identical Cd (the NO of powder molar concentration3)2In methanol solution and solution a, obtain
To light anode 5.
(2) it prepares to electrode 4
Prepare more sulphur electrolyte：It is respectively the Na of 2mol/L by concentration2S, high-purity sulphur powder of 2mol/L and 0.2mol/L
It is 7 that KCl, which is dissolved in volume ratio,:It is prepared in 3 methanol and the mixed solution of deionized water.
Copper base 3 is placed on through sand paper polishing in ethanol solution, ultrasonic cleaning 30min is carried out, then by copper base 3
Side, which is blocked, is placed in 10min in 70 DEG C of concentrated hydrochloric acid, and deionized water and methanol rinsing, drying are used after taking-up；It is placed in again more
Vulcanizing treatment 15min is carried out in sulphur electrolyte, and deionized water and methanol rinsing, drying are used after taking-up, obtains copper-based black
Cu2S is placed in inert gas electrode 4 and saves backup.
(3) solid-state electrolytic solution 1 is prepared
Suitable dextran is slowly added in the KCL aqueous solutions that quality is 5g, is stirred evenly at 100 DEG C, wherein KCL
A concentration of the 30% of aqueous solution；Then the Na of 0.10g high-purity sulphur powder and 0.75g is sequentially added into mixed solution2S·9H2O is stirred
Uniform postcooling is mixed to room temperature, obtains hydrosol electrolyte, i.e. solid-state electrolytic solution 1.
(4) battery is assembled
It is preheated to 80 DEG C by light anode 5, to electrode 4 and solid-state electrolytic solution 1；Take the solid-state electrolytic solution 1 of suitable preheating
It is added dropwise to 5 surface of light anode of preheating, that is, is engraved in 80 DEG C of closed container and vacuumizes 10min；Take the solid-state of suitable preheating
Electrolyte 1 be added dropwise to preheating to 4 surface of electrode, that is, be engraved in 80 DEG C of closed container and vacuumize 10min；Then by light anode
5 and faces contact in certain thickness interval body both sides is respectively placed in electrode 4, and heating makes solid-state electrolytic solution 1 fully merge, envelope
Dress up battery.
The present invention, by heating solid-state electrolytic solution 1, makes it fully by synthesizing solid-state electrolytic solution 1 with good conductivity
It is filled in ZnO nanowire array light anode and copper-based Cu2S nanometer sheets not only overcome liquid amount to the micro-structure gap of electrode
The electrolyte of son point sensitization solar battery occurred during performance is unstable and encapsulation process omits problem, and preparation process
Simply, of low cost, large area prepares reproducible, there is good use value.
Claims (3)
1. a kind of preparation method of all solid state quantum dot sensitized solar cell, which is characterized in that include the following steps：
Step 1, ZnO nanowire array is prepared on electro-conductive glass (2), specially：
Step 1.1, the precursor solution for preparing ZnO seed layers uses the forerunner of ZnO seed layers in the side of electro-conductive glass (2)
Liquid solution prepares ZnO seed layers by spin-coating method and heat treatment process, and wherein spin speed is 3000-4500r/min, heat
The temperature for the treatment of process is 300-350 DEG C, and the thickness of ZnO seed layers is 50-100nm；
Step 1.2, the ZnO seed layers in step 1.1 are put into growth-promoting media, temperature is used to be prepared for 80-90 DEG C of immersion method
ZnO nanowire array, wherein growth-promoting media are molar concentration rate 20:1 NaOH and Zn (NO3)2Mixed solution or molar concentration rate 1:
1 hexamethylenetetramine and Zn (NO3)2Mixed solution or molar concentration rate 1:1 ammonium hydroxide and Zn (NO3)2Mixed solution；
Step 2, the ZnO nanowire array in step 1 is subjected to CdS/CdSe quantum spot depositions, obtains light anode (5)；
Step 3, Cu is prepared on copper base (3)2S is to electrode (4)；
Step 4, solid-state electrolytic solution (1) is prepared；
Step 4.1, suitable dextran is slowly added in the KCL aqueous solutions that quality is 3-5g, is stirred at 85-100 DEG C equal
It is even, the wherein a concentration of 20-30% of KCL aqueous solutions；
Step 4.2, the high-purity sulphur powders of 0.09-0.10g and 0.65-0.75g Na are sequentially added in the solution that step 4.1 obtains2S·
9H2O stirs evenly postcooling to room temperature, obtains hydrosol electrolyte, i.e. solid-state electrolytic solution (1)；
Step 5, the light anode (5) in heating stepses 2, in step 3 to the solid-state electrolytic solution (1) in electrode (4) and step 4
And be packaged, battery is formed, specially：
Step 5.1, by the light anode (5), equal to the solid-state electrolytic solution (1) in electrode (4) and step 4 in step 3 in step 2
It is preheated to 60-80 DEG C；
Step 5.2, the solid-state electrolytic solution (1) handled in right amount through step 5.1 is added dropwise to step 5.1 treated light anode (5)
Surface is engraved in the closed container of identical temperature and vacuumizes 5-10min；
Step 5.3, the solid-state electrolytic solution (1) handled in right amount through step 5.1 is added dropwise to step 5.1 treated to electrode (4)
Surface is engraved in the closed container of identical temperature and vacuumizes 5-10min；
Step 5.4, take step 5.2 handle light anode (5) and step 5.3 handle to electrode (4), be respectively placed in centainly
The interval body both sides face contact of thickness, and heating makes solid-state electrolytic solution (1) fully merge, and is packaged into battery.
2. a kind of preparation method of all solid state quantum dot sensitized solar cell according to claim 1, which is characterized in that
The step 2 is specially：
Step 2.1, the ZnO nanowire array in step 1 is repeatedly alternately immersed to the Na of same molar ratio2S solution and Cd
(NO3)2Methanol solution obtains the ZnO nanowire array of CdS quantum dot sensitization；
Step 2.2, it is 1-1.5 that molar ratio is added in methanol solution:1 KBH4Powder and SeO2Powder, heating reduction obtain molten
Liquid a；The ZnO nanowire array that step 2.1 processing obtains repeatedly alternately is immersed into Cd (NO3)2Methanol solution and solution a, obtain
ZnO nanowire array quantum dot sensitized CdS/CdSe, i.e. light anode (5), wherein Cd (NO3)2Methanol solution and SeO2Powder rubs
Your concentration is identical.
3. a kind of preparation method of all solid state quantum dot sensitized solar cell according to claim 1, which is characterized in that
The step 3 is specially：
Step 3.1, copper base (3) is placed on through sand paper polishing in ethanol solution, carries out ultrasonic cleaning 20-30min；
Step 3.2, the processed copper base of step 3.1 (3) side is blocked and is placed in 5-10min in 70 DEG C of concentrated hydrochloric acid, taken
It rinses and dries using deionized water and methanol after going out；
Step 3.3, the processed copper base of step 3.2 (3) is placed in progress vulcanizing treatment 10-15min in more sulphur electrolyte, taken
It rinses and dries using deionized water and methanol after going out, obtain the Cu of copper-based black2S places it in indifferent gas to electrode (4)
It is preserved in body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611037388.8A CN106328381B (en) | 2016-11-23 | 2016-11-23 | All solid state quantum dot sensitized solar cell of one kind and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611037388.8A CN106328381B (en) | 2016-11-23 | 2016-11-23 | All solid state quantum dot sensitized solar cell of one kind and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106328381A CN106328381A (en) | 2017-01-11 |
| CN106328381B true CN106328381B (en) | 2018-09-07 |
Family
ID=57816863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611037388.8A Active CN106328381B (en) | 2016-11-23 | 2016-11-23 | All solid state quantum dot sensitized solar cell of one kind and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106328381B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107248450A (en) * | 2017-05-18 | 2017-10-13 | 山东大学 | The preparation method of flexible quanta sensitization solar battery based on titanium net |
| CN109326445B (en) * | 2018-11-19 | 2020-04-03 | 河南师范大学 | Nano composite counter electrode for quantum dot sensitized solar cell and preparation method |
| CN110556480A (en) * | 2019-09-12 | 2019-12-10 | 合肥工业大学 | All-solid-state solar cell based on synchronous deposition quantum dots and preparation method thereof |
| CN115512972B (en) * | 2022-08-18 | 2023-11-03 | 河北大学 | Preparation method of quasi-solid electrolyte for quantum dot sensitized solar cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811186A (en) * | 2014-01-26 | 2014-05-21 | 中国科学院物理研究所 | Method for preparing quantum dot sensitized solar cell metal sulfide counter electrode |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002289271A (en) * | 2001-03-26 | 2002-10-04 | Sharp Corp | Pigment sensitized solar cell |
| CN101013742A (en) * | 2007-02-01 | 2007-08-08 | 复旦大学 | Solid-state electrolyte Dye-sensitized nano-crystalline solar battery and method for making same |
| CN101901692B (en) * | 2010-04-21 | 2012-05-30 | 苏州大学 | Solar cell gel electrolyte and preparation method and application thereof |
| CN102543471B (en) * | 2012-01-17 | 2013-11-06 | 西安交通大学 | Method for preparing CdS and CdSe quantum dot sectional compound sensitized double-layer ZnO nanometer rod photo-anode |
| CN104409218B (en) * | 2014-11-26 | 2018-02-16 | 东华大学 | A kind of Cu for quantum dot sensitized solar cellXS is to electrode and its preparation and application |
-
2016
- 2016-11-23 CN CN201611037388.8A patent/CN106328381B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811186A (en) * | 2014-01-26 | 2014-05-21 | 中国科学院物理研究所 | Method for preparing quantum dot sensitized solar cell metal sulfide counter electrode |
Non-Patent Citations (1)
| Title |
|---|
| 量子点敏化太阳能电池研究进展;卫会云，等;《物理化学学报》;20160115;第201-213页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106328381A (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Du et al. | Performance improvement strategies for quantum dot-sensitized solar cells: a review | |
| CN106328381B (en) | All solid state quantum dot sensitized solar cell of one kind and preparation method thereof | |
| CN101899701B (en) | Method for preparing composite material of copper sulfide and titanium dioxide nano-tube | |
| CN109267096B (en) | Efficient and stable silicon-based photolysis water hydrogen production electrode and preparation method and application thereof | |
| Zhou et al. | Copper selenide (Cu 3 Se 2 and Cu 2− x Se) thin films: electrochemical deposition and electrocatalytic application in quantum dot-sensitized solar cells | |
| CN102268706A (en) | Methods for preparing ZnO/Cu2O heterojunction material and ZnO/Cu2O three-dimensional heterojunction solar cell | |
| Kim et al. | Cost-effective and morphology controllable PVP based highly efficient CuS counter electrodes for high-efficiency quantum dot-sensitized solar cells | |
| CN102623195A (en) | Method for preparing solar cell through quantum dot and dye synergistic sensitization of TiO2 nanorod array | |
| Zhang et al. | Novel bilayer structure ZnO based photoanode for enhancing conversion efficiency in dye-sensitized solar cells | |
| CN108832114B (en) | Preparation method of graphene-coated CuFeO2 composite negative electrode material | |
| CN106847513B (en) | The preparation method of sulfide nano-composite counter electrode based on porous C uS frameworks | |
| CN107130256B (en) | Boron doping carbonitride modified titanic oxide complex light electrode and preparation method thereof, application | |
| Wu et al. | Soft processing of hierarchical oxide nanostructures for dye-sensitized solar cell applications | |
| Chen et al. | CdS/CdSe quantum dots and ZnPc dye co-sensitized solar cells with Au nanoparticles/graphene oxide as efficient modified layer | |
| CN104332315A (en) | Preparation method of porous nanocrystalline Cu2S counter electrode of quantum-dot-sensitized solar cell | |
| Guo et al. | Electrodeposited CuInSe2 counter electrodes for efficient and stable quantum dot-sensitized solar cells | |
| CN102324316A (en) | Compound light anode and preparation method thereof | |
| CN102965711B (en) | The anodic oxidation two-step preparation method of cuprous nano flaky powder material | |
| CN110808333A (en) | Perovskite solar cell based on copper-zinc-tin-sulfur-selenium hole transport layer and preparation method thereof | |
| JP2008243752A (en) | Electrode, its manufacturing method, and dye-sensitized solar cell | |
| CN112735835B (en) | Vanadium diselenide-doped nickel-cobalt selenide yolk shell structure micro cuboid counter electrode catalyst and preparation method and application thereof | |
| CN111962090B (en) | Ti3C2-MXene modified alpha-iron oxide photoelectrode and preparation method thereof | |
| CN105551811B (en) | The porous SnO of graded structure2And TiO2The Ag@C nanos ball of cladding, preparation method and applications | |
| Yang et al. | A strategy of combining SILAR with solvothermal process for In2S3 sensitized quantum dot-sensitized solar cells | |
| CN100541822C (en) | DSSC of a kind of nano-crystal film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |