CN108550701A - The titanium dioxide spindle and its preparation method and application of Nb doping - Google Patents
The titanium dioxide spindle and its preparation method and application of Nb doping Download PDFInfo
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- CN108550701A CN108550701A CN201810361066.1A CN201810361066A CN108550701A CN 108550701 A CN108550701 A CN 108550701A CN 201810361066 A CN201810361066 A CN 201810361066A CN 108550701 A CN108550701 A CN 108550701A
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Abstract
The invention discloses a kind of preparation methods of the TiOx nano spindle of Nb doping, including：Butyl titanate is added in glacial acetic acid solution, stirs, the doping ratio of Nb/ (Nb+Ti) 0% 20%, ethyl alcohol niobium is added in above-mentioned solution, clear precursor solution is persistently stirred to get in molar ratio；Above-mentioned solution is poured into the stainless sodium reaction kettle with poly- first vinyl fluoride liner, after reaction, cooled to room temperature obtains white or blue precipitate；All precipitations deionized water and ethyl alcohol are cleaned repeatedly to get the TiOx nano spindle adulterated to Nb.The invention also discloses the TiOx nano spindle of Nb doping and its applications.The present invention obtains the titanium dioxide Spindle of Nb doping, and preparation method is simple, of low cost, uniform particle diameter and highly crystalline.Meanwhile by Nb doping titanium dioxide Spindle be used as electron transport material, obtained flat plate cell it is efficient, lag it is small, stability is good.
Description
Technical field
The present invention relates to a kind of battery materials, and in particular to a kind of titanium dioxide spindle and preparation method thereof of Nb doping
And application, belong to technical field of solar batteries.
Background technology
Ideal electron transfer layer is the important component of efficient plane perovskite solar cell, in transmission electronics
It is very crucial with inhibiting compound aspect to play the role of, high Voc and FF may be implemented.Currently, in perovskite solar cell
In, the most commonly used electron transfer layer is TiO2.However, TiO2It is conductive bad, the low disadvantage of electron mobility, and it is golden
Its conductivity can effectively be increased by belonging to ion doping, adjust its bandgap structure and defect state.Currently used for titanium oxide into
The metallic element of row doping has：Magnesium, lithium, samarium, tantalum etc..And niobium doping titanium oxide transparent conductive electrode, photocatalysis, lithium electricity or
It is widely used in sodium electricity, dye sensitization etc., however the application in tablet perovskite battery is but rarely reported.
2004, it has been reported that：By in TiO2NbCl is added in growth course5The titanium oxide of Nb doping is obtained, and is answered
For in tablet perovskite battery, compared with the titania based perovskite battery undoped with Nb, efficiency be doubled (from
4.9% to 7.5%).2016, it has been reported that, by the way that NbCl is added5The TiOx nano for synthesizing Nb doping is brilliant, obtained electricity
Pond efficiency is 16.3%, however efficiency is relatively low.2017, with NbCl5Obtain 1%Nb:TiO2, it is used for tablet perovskite
When the electron transfer layer of battery, the battery efficiency in counter sweep is 19.2%, while battery shows the stability improved, however
It but shows certain lag (efficiency when just sweeping is 16.21%).And the authentication efficiency of flat plate cell is 21.6% now,
Nb in result above:TiO2The efficiency of obtained flat plate cell is slightly lower, while the predecessor of Nb used in them is
NbCl5, niobium chloride is a kind of substance easily hydrolyzed, and can release HCl, to the substrate ITO of human body and perovskite battery
Have certain corrosiveness.
Invention content
The two of the Nb doping that one of the objects of the present invention is to provide a kind of methods is simple, battery efficiency is high, stability is good
The preparation method of titanium oxide spindle.
The invention is realized in this way：
A kind of preparation method of the TiOx nano spindle of Nb doping, including：
A certain amount of butyl titanate is added in the glacial acetic acid solution of certain volume, then during stirring, by Nb/
(Nb+Ti) the doping ratio of (molar ratio) 0%~20%, ethyl alcohol niobium is added in above-mentioned solution, and persistently stir to get clarification
Niobium doping titanium oxide precursor solution；
Then above-mentioned solution is poured into the stainless sodium reaction kettle with poly- first vinyl fluoride liner；It is anti-after later will be closed
Kettle is answered to be put into thermostatic drying chamber, after reacting the regular hour at a certain temperature, cooled to room temperature obtains white
Or blue precipitate；All precipitations deionized water and ethyl alcohol are cleaned repeatedly to get the TiOx nano spindle adulterated to Nb
Body.
Further scheme is：
The addition of the butyl titanate is the 1/5~1/3 of glacial acetic acid solution volume.
Further scheme is：
The regular hour is reacted at certain temperature, refers to 16~48h of reaction at 150~240 DEG C.
The present invention also provides a kind of TiOx nano spindles of Nb doping, are the titanium oxide adulterated by Nb above-mentioned
What the preparation method of nanometer spindle was prepared.
It is to be applied to tablet perovskite battery the present invention also provides the application of the TiOx nano spindle of Nb doping
In, as electron transfer layer.
Further scheme is：
Applied to being as follows in tablet perovskite battery：
Step 1: depositing the titanium oxide electron transfer layer of Nb doping on the FTO electro-conductive glass cleaned up
The precipitation being centrifuged repeatedly after cleaning is redispersed in ethyl alcohol, the glue of the titanium oxide of certain density Nb doping is formed
Liquid solution.The spin coating liquid of various concentration is obtained by the way that the terpinol of different proportion is added in this colloidal solution, then one
Under fixed rotating speed and acceleration, pass through spin coating, you can the surfaces FTO after plasma processing form one layer of fine and close electronics and pass
Defeated layer.
Step 2: the spin coating perovskite cell material layers on the titanium oxide compacted zone of Nb doping；
Step 3: the spin coating hole mobile material on calcium titanium ore bed；
Step 4: vapor deposition gold electrode.
Wherein, for core of the present invention mainly in step 1, step 2 to four is this field conventional steps, therefore not herein in detail
It states.
A kind of tablet perovskite battery is also claimed in the present invention, is the TiOx nano spindle adulterated by Nb above-mentioned
Obtained from the application of body.
The present invention preparation method it is simple, of low cost, uniform particle diameter, highly crystalline and with well repeatability.
And since the carrier concentration of the titanium oxide of Nb doping with conductivity is corresponding undoped 2 times；Defect simultaneously
State concentration decreases.The tablet perovskite battery of undoped titanium oxide composition, its anti-performance parameter swept are respectively：Electricity
Current density JSC=23.2mA/cm2, open pressure VOC=1.07V, fill factor FF=77.0%, energy conversion efficiency PCE=
19.1%, and it is 18.2% just to scan PCE, it is positive and negative to sweep test and have a degree of lag.And accordingly, the titanium oxide of Nb doping
The device J formedSC=23.6mA/cm2,VOC=1.13V, FF=78.4%, PCE=20.8%；The PCE=just swept
20.2%, exist almost without hysteresis.
And in the application, the titanium dioxide spindle structure of Nb doping is obtained by simple step solvent-thermal method,
Used in the predecessor of Nb be friendly five ethyl alcohol niobiums.It is equal by the conductivity and carrier concentration of the adulterated TiOx of Nb
There is the raising of certain degree, and when the doping of Nb is 3%, the efficiency of obtained flat plate cell is best, is
20.8%, and lag very little (efficiency when just sweeping is 20.2%).Meanwhile battery shows good stability, in non-envelope
It under conditions of dress, preserves at room temperature, after 1400h, the efficiency of battery still can be maintained at 20%.
Description of the drawings
Fig. 1 is the structural model schematic diagram of the TiOx nano spindle for the Nb doping that the present invention is prepared；
Fig. 2 is the TiOx nano spindle high-resolution electronic micro-image of Nb doping.
Fig. 3 is the basic structure schematic diagram for the tablet perovskite battery that the present invention applies.
Specific implementation mode
The present invention is further illustrated in the following with reference to the drawings and specific embodiments.
Embodiment 1
A kind of preparation method of the TiOx nano spindle of Nb doping, including：
The butyl titanate of 5ml is added in the glacial acetic acid solution of 15~25ml, then during stirring, by Nb/ (Nb
+ Ti) (molar ratio) 0%--20% doping ratio, ethyl alcohol niobium is added in above-mentioned solution, and persistently stir to get clear niobium
The precursor solution of the titanium oxide of doping；
Then above-mentioned solution is poured into the stainless sodium reaction kettle with poly- first vinyl fluoride liner；It is anti-after later will be closed
Kettle is answered to be put into thermostatic drying chamber, after reacting 16~48h at 150~240 DEG C, cooled to room temperature obtains white or blue
Color precipitates；All precipitation deionized waters and ethyl alcohol are cleaned repeatedly and (is generally first cleaned one time with deionized water, then uses second
Alcohol cleans repeatedly, is centrifuged after cleaning every time, when centrifuged supernatant clarify, cleaning completion) and to get to such as 1,2 institute of attached drawing
The TiOx nano spindle for the Nb doping shown.Wherein, attached drawing 1 is that the structural model of the TiOx nano spindle of Nb doping shows
It is intended to, attached drawing 2 is the high-resolution electronic micro-image (TEM) of the TiOx nano spindle of Nb doping, inserting wherein in attached drawing 2
Figure is fast Fourier transform (FFT) figure.By detection, Spindle uniform particle diameter, average grain diameter 25nm, and highly crystalline,
Readily available smooth electron-transport layer film.And in attached drawing 1, { 001 } and the TiOx nano spindle that { 101 } refer to Nb doping
The crystal face that body is exposed.
Embodiment 2
It is to be applied to tablet perovskite battery the present invention also provides the application of the TiOx nano spindle of Nb doping
In, as electron transfer layer.
Applied to being as follows in tablet perovskite battery：
Step 1: depositing the titanium oxide electron transfer layer of Nb doping on the FTO electro-conductive glass cleaned up
The precipitation being centrifuged repeatedly after cleaning is redispersed in ethyl alcohol, the glue of the titanium oxide of certain density Nb doping is formed
Liquid solution.The spin coating liquid of various concentration is obtained by the way that the terpinol of different proportion is added in this colloidal solution, then one
Under fixed rotating speed and acceleration, pass through spin coating, you can the surfaces FTO after plasma processing form one layer of fine and close electronics and pass
Defeated layer.
Step 2: the spin coating perovskite cell material layers on the titanium oxide compacted zone of Nb doping；
Step 3: the spin coating hole mobile material on calcium titanium ore bed；
Step 4: vapor deposition gold electrode.
The perovskite solar cell that the present embodiment obtains, structure is as shown in Fig. 3, including is followed successively by FTO from bottom to top
Conducting Glass 1；The TiOx nano spindle compacted zone 2 of niobium doping；Perovskite light-absorbing material layer 3；Hole transmission layer 4；
Metal electrode layer 5.
And when the doping of Nb is 3%, the efficiency of obtained flat plate cell is best, is 20.8%, and lags very
Small (efficiency when just sweeping is 20.2%).Meanwhile battery shows good stability, under conditions of encapsulation, in room temperature
Lower preservation, after 1400h, the efficiency of battery still can be maintained at 20%.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modification and implementations, these modifications and implementations will be fallen in principle disclosed in the present application
Within scope and spirit.
Claims (8)
1. a kind of preparation method of the TiOx nano spindle of Nb doping, it is characterised in that including：
A certain amount of butyl titanate is added in the glacial acetic acid solution of certain volume, then during stirring, in molar ratio
The doping ratio that Nb/ (Nb+Ti) is 0%~20%, ethyl alcohol niobium is added in above-mentioned solution, and persistently stir to get clear niobium
The precursor solution of the titanium oxide of doping；
Then above-mentioned solution is poured into the stainless sodium reaction kettle with poly- first vinyl fluoride liner；Reaction kettle after later will be closed
It is put into thermostatic drying chamber, after reacting the regular hour at a certain temperature, cooled to room temperature obtains white or blue
Color precipitates；All precipitations deionized water and ethyl alcohol are cleaned repeatedly to get the TiOx nano spindle adulterated to Nb.
2. the preparation method of the TiOx nano spindle of Nb doping according to claim 1, it is characterised in that：
The addition of the butyl titanate is the 1/5~1/3 of glacial acetic acid solution volume.
3. the preparation method of the TiOx nano spindle of Nb doping according to claim 1, it is characterised in that：
The regular hour is reacted at certain temperature, refers to 16~48h of reaction at 150~240 DEG C.
4. a kind of TiOx nano spindle of Nb doping is by the Nb doping described in claims 1 to 3 any claim
The preparation method of TiOx nano spindle be prepared.
5. the TiOx nano spindle of Nb doping according to claim 4, it is characterised in that：
The TiOx nano spindle highly crystalline of the Nb doping, average grain diameter 25nm.
6. the application of the TiOx nano spindle of the Nb doping of claim 4 or 5, it is characterised in that：It is to be applied to tablet
In perovskite battery, as electron transfer layer.
7. the application of the TiOx nano spindle of Nb doping according to claim 6, it is characterised in that：
Applied to being as follows in tablet perovskite battery：
Step 1: depositing the titanium oxide electron transfer layer of Nb doping on the FTO electro-conductive glass cleaned up
The precipitation being centrifuged repeatedly after cleaning is redispersed in ethyl alcohol, the colloid for forming the titanium oxide of certain density Nb doping is molten
Liquid.The spin coating liquid of various concentration is obtained by the way that the terpinol of different proportion is added in this colloidal solution, then certain
Rotating speed passes through spin coating under acceleration, you can the surfaces FTO after plasma processing form one layer of fine and close electron-transport
Layer；
Step 2: the spin coating perovskite cell material layers on the titanium oxide compacted zone of Nb doping；
Step 3: the spin coating hole mobile material on calcium titanium ore bed；
Step 4: vapor deposition gold electrode.
8. a kind of tablet perovskite battery, it is characterised in that：The tablet perovskite battery is by described in claim 6 or 7
Obtained from the application of the TiOx nano spindle of Nb doping.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111509063A (en) * | 2020-04-24 | 2020-08-07 | 中国科学院山西煤炭化学研究所 | Preparation method and application of niobium-doped titanium dioxide nano material |
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|---|---|---|---|---|
| CN102560649A (en) * | 2012-01-12 | 2012-07-11 | 中国科学院合肥物质科学研究院 | Flowerlike-structure titanium dioxide formed by spindle single crystal and preparation method thereof |
| CN104078244A (en) * | 2013-03-26 | 2014-10-01 | 中国科学院大连化学物理研究所 | Metallic-niobium-doping titanium dioxide nanometer sheet, and preparing method and application of metallic-niobium-doping titanium dioxide nanometer sheet |
| CN107919438A (en) * | 2017-11-06 | 2018-04-17 | 南京航空航天大学 | Titanic oxide electronic transport layer and preparation method for perovskite solar cell |
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2018
- 2018-04-20 CN CN201810361066.1A patent/CN108550701B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560649A (en) * | 2012-01-12 | 2012-07-11 | 中国科学院合肥物质科学研究院 | Flowerlike-structure titanium dioxide formed by spindle single crystal and preparation method thereof |
| CN104078244A (en) * | 2013-03-26 | 2014-10-01 | 中国科学院大连化学物理研究所 | Metallic-niobium-doping titanium dioxide nanometer sheet, and preparing method and application of metallic-niobium-doping titanium dioxide nanometer sheet |
| CN107919438A (en) * | 2017-11-06 | 2018-04-17 | 南京航空航天大学 | Titanic oxide electronic transport layer and preparation method for perovskite solar cell |
Non-Patent Citations (3)
| Title |
|---|
| JO SAITO等: "Fabrication and characterization of perovskite-type solar cells with Nb-doped TiO2 layers", 《AIP CONFERENCE PROCEEDINGS》 * |
| YINHUA LV等: "High performance perovskite solar cells using TiO 2 nanospindles as ultrathin mesoporous layer", 《JOURNAL OF ENERGY CHEMISTRY》 * |
| YINHUA LV等: "supporting information High Performance Perovskite Solar Cells Using TiO2 Nanospindles as ultrathin mesoporous layer", 《JOURNAL OF ENERGY CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111509063A (en) * | 2020-04-24 | 2020-08-07 | 中国科学院山西煤炭化学研究所 | Preparation method and application of niobium-doped titanium dioxide nano material |
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