CN107633949A - A kind of erbium list mixes C 12 A 7 up-conversion dopant dye sensitization light anode and its preparation method and application - Google Patents
A kind of erbium list mixes C 12 A 7 up-conversion dopant dye sensitization light anode and its preparation method and application Download PDFInfo
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- CN107633949A CN107633949A CN201710681614.4A CN201710681614A CN107633949A CN 107633949 A CN107633949 A CN 107633949A CN 201710681614 A CN201710681614 A CN 201710681614A CN 107633949 A CN107633949 A CN 107633949A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention belongs to novel energy resource material technology field, discloses a kind of erbium list and mixes C 12 A 7 up-conversion dopant dye sensitization light anode and its preparation method and application.First C12A7：Er is applied to DSSC.This method is to scrape method C12A7 using painting：Er is coated on electro-conductive glass with P25 mixed slurries and is prepared into light anode, and is assembled into DSSC.The battery is made up of light anode, platinum to electrode and electrolyte.The battery uses C12A7:Er adulterates light anode, and the sunshine beyond 700nm is converted into visible ray, thus widens the spectral response range of battery, improves battery efficiency.
Description
Technical field
The invention belongs to novel energy resource material technology field, more particularly to a kind of erbium list mixes C 12 A 7 up-conversion
Dopant dye sensitization light anode and preparation method thereof and the application in DSSC.
Background technology
DSSC (DSSC) has the advantages that cost is low, preparation technology is simple and pollution-free, in recent years
To show one's talent in numerous solar cells.DSSC to three electrode, light anode and electrolyte parts mainly by forming.To electricity
Lifting of the development of pole and electrolyte to DSSC battery efficiencies does not have much affect, and to improve the photoelectric transformation efficiency of battery, right
It is maximally effective that light anode, which is improved,.Light anode is mainly by conductive optical glass, nano porous semiconductor layer and dye sensitization
Agent forms.Dye sensitizing agent is adsorbed on nano porous semiconductor layer, and when sunshine is radiated in light anode, dye molecule is inhaled
Photon is received, by ground state transition to excitation state.The dye molecule of excitation state can be rapidly by electron injection semiconductor conduction band, and electronics exists
Transmitted in semiconductor nano crystal boundary to electro-conductive glass, then external circuit is transferred to by electro-conductive glass.External circuit passes through to electrode handle electricity
Son is transmitted into electrolyte, and electrolyte passes through redox reaction, and electric transmission is returned in dye molecule, one is formed with this and follows
Ring.But dyestuff concentrates on 400~700nm to the response range of sunshine at present, only accounts for the 45% of solar spectrum, and it is remaining
The sunshine of wavelength is then most of to be scattered and disappeared with form of thermal energy.
Up-conversion be it is a kind of absorb long wave and then give off a kind of material of shortwave, it by host material and rare earth from
Son composition.Host material is used as using C 12 A 7 (C12A7), doping with rare-earth ions, chemical stability can be prepared into
By force, free of contamination up-conversion.Then C12A7 up-conversions can radiate the sun light absorbs beyond the 700nm of part
Go out the photon of visible wavelength range.
The content of the invention
In order to overcome shortcoming and deficiency present in prior art, primary and foremost purpose of the invention is that providing a kind of erbium list mixes
C 12 A 7 up-conversion dopant dye is sensitized the preparation method of light anode.
The erbium list being prepared another object of the present invention is to provide a kind of above-mentioned preparation method mixes C 12 A 7
Up-conversion dopant dye is sensitized light anode.
It is still another object of the present invention to provide above-mentioned erbium list to mix the sensitization of C 12 A 7 up-conversion dopant dye
The application of light anode.
The purpose of the present invention is achieved through the following technical solutions：
A kind of erbium list mixes the preparation method of C 12 A 7 up-conversion dopant dye sensitization light anode, and its feature exists
According to following operating procedure：
S1：Weigh ethyl cellulose and be dissolved in absolute ethyl alcohol, solution A is prepared；
S2：Erbium list is mixed into C 12 A 7 up-conversion (C12A7:Er) added with titanium dioxide P25 in solution A,
OP emulsifying agents, acetylacetone,2,4-pentanedione and terpinol are added afterwards, are prepared into solution B；
S3：Solution B is ultrasonically treated；
S4：The solution B after supersound process in a water bath, constant temperature stirs, and treats that absolute ethyl alcohol is evaporated completely, is prepared into colloid C；
S5：Colloid C is coated on FTO electro-conductive glass；
S6：Electro-conductive glass is placed in drying box and dried, moves to Muffle furnace calcining afterwards；
S7：The electrode calcined is soaked under the conditions of lucifuge with dyestuff, carries out sensitized treatment；
S8：The light anode washes of absolute alcohol being sensitized, dried afterwards in drying box, obtain erbium list and mix seven aluminic acids
Ten dicalcium up-conversion dopant dyes are sensitized light anode.
The mass ratio of ethyl cellulose and absolute ethyl alcohol described in step S1 is 0.112：1.
Erbium list described in step S2 mix C 12 A 7 up-conversion and titanium dioxide P25 mass ratio for 0.01~
0.1：1；Titanium dioxide P25 and the mass ratio of solution A are 0.038：1；OP emulsifying agents and the mass ratio of solution A are 0.001：1；
Acetylacetone,2,4-pentanedione and the mass ratio of solution A are 0.011：1；Terpinol and the mass ratio of solution A are 0.14：1.
Erbium list, which mixes C 12 A 7 up-conversion, described in step S2 is prepared according to following steps：Weigh and rub
You are than being 0.4569：0.5331：0.01 calcium hydroxide, aluminium hydroxide and five water erbium nitrates, add 150 DEG C of insulations in reactor
6h, question response kettle are down to room temperature, filter simultaneously 90 DEG C of dry 12h, and white solid is moved into 800 DEG C of calcining 5h of Muffle furnace, final system
C 12 A 7 up-conversion is mixed for erbium list is obtained.
Ultrasonic time described in step S3 is 10~30min.
Bath temperature described in step S4 is 70~100 DEG C.
The temperature dried described in step S6 is 70~100 DEG C, and the dry time is 10~60min；The temperature of the calcining
Spend for 450~500 DEG C, the time of calcining is 30~60min.
The time soaked described in step S7 is 24~48h.
The temperature dried described in step S8 is 70~100 DEG C, and the dry time is 10~60min；Time of the cleaning
Number is 2 times.
A kind of erbium list obtained according to above-mentioned preparation method mixes the sensitization of C 12 A 7 up-conversion dopant dye
Light anode.
Above-mentioned erbium list mixes C 12 A 7 up-conversion dopant dye sensitization light anode and is preparing dye sensitization too
Application in positive energy battery, the efficiency of DSSC batteries can be effectively improved.
Above-mentioned application, comprises the following steps：Erbium list is mixed into C 12 A 7 up-conversion dopant dye sensitization light
Anode is prepared into sandwich structure to electrode with Pt, and injects electrolyte therebetween, and dye sensitization of solar electricity is prepared
Pond.
C12A7 in the present invention:Er up-conversions can absorb the sunshine of wavelength beyond the 700nm of part, and radiate
Go out visible ray, itself and P25 are prepared by mixing into slurry, be prepared into dye sensitization light anode with knife coating, it is quick dyestuff can be increased
Change the spectral response range of light anode, after the light anode is prepared into DSSC, battery efficiency is improved.
The present invention is had the following advantages relative to prior art and effect：
(1) C12A7 in the present invention:Er up-conversions can absorb the sunshine of wavelength beyond the 700nm of part, and spoke
Visible ray is projected, itself and P25 are prepared by mixing into slurry, dye sensitization light anode is prepared into knife coating, dyestuff can be increased
The spectral response range of light anode is sensitized, after the light anode is prepared into DSSC, battery efficiency is improved.
(2) by C12A7:Er up-conversions are used in DSSC light anodes, can widen sound of the light anode to sunshine
Scope is answered, the sunshine beyond 700nm is effectively utilized, so as to improve DSSC battery efficiencies.
Brief description of the drawings
Fig. 1 is the structural representation that erbium list mixes C 12 A 7 up-conversion dopant dye sensitization light anode, and 1 is
FTO electro-conductive glass, 2 be titanium dioxide P25, and 3 be C12A7:Er.
Fig. 2 is the C12A7 of embodiment 1 and embodiment 2:The DSSC of Er up-conversions doping light anode I-V curve
Figure, A are not add C12A7:Er DSSC samples, B are that embodiment 1 adds C12A7:Er DSSC samples, C are that embodiment 2 adds
Add C12A7：Er DSSC samples.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Erbium list, which mixes C 12 A 7 up-conversion, used in following examples is prepared according to following steps：
5g mol ratios are weighed as 0.4569：0.5331：0.01 calcium hydroxide, aluminium hydroxide and five water erbium nitrates add 100ml reactions
150 DEG C of insulation 6h, question response kettle are down to room temperature in kettle, filter simultaneously 90 DEG C of dry 12h, white solid is moved into 800 DEG C of Muffle furnace
5h is calcined, erbium list is finally prepared into and mixes C 12 A 7 up-conversion (C12A7:Er).
Embodiment 1
1. the ethyl cellulose for weighing 2.65g is dissolved in 23.67g absolute ethyl alcohols, solution A is prepared；
2. by 0.02gC12A7:Er and 1g titanium dioxide P25 are added in solution A, add afterwards 0.026gOP emulsifying agents,
0.294g acetylacetone,2,4-pentanediones and 3.73g terpinols, are prepared solution B；
3. solution B is subjected to supersound process 20min；
4. the solution B after a supersound process is placed in water-bath, 80 DEG C of constant temperature stirrings, treats that absolute ethyl alcohol is evaporated completely, make
It is standby to obtain colloid C；
5. a FTO electro-conductive glass is fixed with 3M adhesive tapes, colloid C is coated on electro-conductive glass with glass bar；
6. an electro-conductive glass is placed in drying box, 80 DEG C of dry 10min, Muffle furnace, 450 DEG C of calcinings are moved to afterwards
30min；
7. an electrode calcined soaks 24h with dyestuff, lucifuge is handled therebetween；
8. with washes of absolute alcohol for several times, 80 DEG C of dry 2h in drying box, obtain erbium to a light anode being sensitized afterwards
C 12 A 7 up-conversion dopant dye sensitization light anode is singly mixed, its structural representation is as shown in figure 1, wherein 1 is FTO
Electro-conductive glass, 2 be titanium dioxide P25, and 3 be C12A7:Er.
9. a light anode prepared is prepared into sandwich structure to electrode with Pt, and injects electrolyte therebetween, make
It is standby into C12A7:Er adulterates the DSSC of light anode.
Fig. 2 is the C12A7 that the present embodiment 1 is prepared into embodiment 2:The DSSC of Er doping light anodes I-V curve figure.
Wherein, A is not add C12A7:Er DSSC samples, B are that the present embodiment adds C12A7:Er DSSC samples, C are embodiment 2
Add C12A7：Er DSSC samples.As can be known from Fig. 2, B samples peak power (I*V) is higher than A and C sample, according to following public affairs
Formula：
Battery efficiency=peak power/incident intensity/illuminating area
Therefore, the battery efficiency highest of B samples, the battery efficiency of A samples are minimum.
Embodiment 2
The present embodiment and the difference of embodiment 1 are：C12A7 in step 2:Er is 0.1g.
Embodiment 3
The present embodiment and the difference of embodiment 1 are：Ultrasonic time in step 3 is 30min.
Embodiment 4
The present embodiment and the difference of embodiment 1 are：Bath temperature in step 4 is 100 DEG C.
Embodiment 5
The present embodiment and the difference of embodiment 1 are：The drying temperature of step 6 is 100 DEG C, drying time 60min, is forged
It is 500 DEG C to burn temperature, calcination time 60min.
Embodiment 6
The present embodiment and the difference of embodiment 1 are：The soak time of step 7 is 48h.
Embodiment 7
The present embodiment and the difference of embodiment 1 are：The drying temperature of step 8 is 100 DEG C, drying time 60min.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of erbium list mixes the preparation method of C 12 A 7 up-conversion dopant dye sensitization light anode, it is characterised in that
According to following operating procedure：
S1：Weigh ethyl cellulose and be dissolved in absolute ethyl alcohol, solution A is prepared；
S2：Erbium list is mixed into C 12 A 7 up-conversion to add in solution A with titanium dioxide P25, adds OP emulsifications afterwards
Agent, acetylacetone,2,4-pentanedione and terpinol, are prepared into solution B；
S3：Solution B is ultrasonically treated；
S4：The solution B after supersound process in a water bath, constant temperature stirs, and treats that absolute ethyl alcohol is evaporated completely, is prepared into colloid C；
S5：Colloid C is coated on FTO electro-conductive glass；
S6：Electro-conductive glass is placed in drying box and dried, moves to Muffle furnace calcining afterwards；
S7：The electrode calcined is soaked under the conditions of lucifuge with dyestuff, carries out sensitized treatment；
S8：The light anode washes of absolute alcohol being sensitized, dried afterwards in drying box, obtain erbium list and mix seven aluminic acids 12
Calcium up-conversion dopant dye is sensitized light anode.
2. preparation method according to claim 1, it is characterised in that：Ethyl cellulose and absolute ethyl alcohol described in step S1
Mass ratio be 0.112：1.
3. preparation method according to claim 1, it is characterised in that：Erbium list is mixed on C 12 A 7 described in step S2
Transition material and titanium dioxide P25 mass ratio are 0.01~0.1：1；Titanium dioxide P25 and the mass ratio of solution A are 0.038：
1；OP emulsifying agents and the mass ratio of solution A are 0.001：1；Acetylacetone,2,4-pentanedione and the mass ratio of solution A are 0.011：1；Terpinol and A
The mass ratio of solution is 0.14：1.
4. preparation method according to claim 1, it is characterised in that：Erbium list is mixed on C 12 A 7 described in step S2
Transition material is prepared according to following steps：Mol ratio is weighed as 0.4569：0.5331：0.01 calcium hydroxide, hydrogen-oxygen
Change aluminium and five water erbium nitrates, add 150 DEG C of insulation 6h, question response kettle in reactor and be down to room temperature, filter simultaneously 90 DEG C of dry 12h,
White solid is moved into 800 DEG C of calcining 5h of Muffle furnace, erbium list is finally prepared and mixes C 12 A 7 up-conversion.
5. preparation method according to claim 1, it is characterised in that：Ultrasonic time described in step S3 is 10~30min；
Bath temperature described in step S4 is 70~100 DEG C.
6. preparation method according to claim 1, it is characterised in that：The temperature dried described in step S6 is 70~100
DEG C, the dry time is 10~60min；The temperature of the calcining is 450~500 DEG C, and the time of calcining is 30~60min；Step
The time soaked described in rapid S7 is 24~48h.
7. preparation method according to claim 1, it is characterised in that：The temperature dried described in step S8 is 70~100
DEG C, the dry time is 10~60min；The number of the cleaning is 2 times.
8. the erbium list that a kind of preparation method according to claim any one of 1-7 obtains, which is mixed, changes material on C 12 A 7
Expect dopant dye sensitization light anode.
Prepared 9. erbium list according to claim 8 mixes C 12 A 7 up-conversion dopant dye sensitization light anode
Application in DSSC.
10. application according to claim 9, it is characterised in that comprise the following steps：Erbium list is mixed on C 12 A 7
Transition material dopant dye is sensitized light anode and sandwich structure is prepared into electrode with Pt, and injects electrolyte therebetween, makes
It is standby to obtain DSSC.
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| CN201710681614.4A CN107633949A (en) | 2017-08-10 | 2017-08-10 | A kind of erbium list mixes C 12 A 7 up-conversion dopant dye sensitization light anode and its preparation method and application |
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| CN201710681614.4A CN107633949A (en) | 2017-08-10 | 2017-08-10 | A kind of erbium list mixes C 12 A 7 up-conversion dopant dye sensitization light anode and its preparation method and application |
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| CN104966618A (en) * | 2015-07-31 | 2015-10-07 | 合肥工业大学 | Dye-sensitized solar cell photo anode and preparation method thereof |
| CN105694887A (en) * | 2016-01-18 | 2016-06-22 | 广东工业大学 | Preparation method of Ho<3+>-Yb<3+>-F<-> codoped TiO2 upconversion nanopowder and application of preparation method |
-
2017
- 2017-08-10 CN CN201710681614.4A patent/CN107633949A/en active Pending
Patent Citations (5)
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|---|---|---|---|---|
| CN101157856A (en) * | 2007-11-16 | 2008-04-09 | 东北师范大学 | Visible and infrared luminescent C12A7 powder and preparation method thereof |
| US20110155227A1 (en) * | 2009-12-25 | 2011-06-30 | Tadao Yagi | Electrolyte composition for photoelectric transformation device and photoelectric transformation device manufactured by using the same |
| CN103762082A (en) * | 2014-01-22 | 2014-04-30 | 广东工业大学 | Method for preparing dye sensitization solar cell photo-anode film |
| CN104966618A (en) * | 2015-07-31 | 2015-10-07 | 合肥工业大学 | Dye-sensitized solar cell photo anode and preparation method thereof |
| CN105694887A (en) * | 2016-01-18 | 2016-06-22 | 广东工业大学 | Preparation method of Ho<3+>-Yb<3+>-F<-> codoped TiO2 upconversion nanopowder and application of preparation method |
Non-Patent Citations (1)
| Title |
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| 吴继波: "Er3+,Na+共掺12CaO·7Al2O3的制备及光学性质的研究", 《中国优秀硕士学位论文全文数据库 基础科学辑》 * |
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