CN108550701B - Nb-doped titanium dioxide spindle and preparation method and application thereof - Google Patents

Nb-doped titanium dioxide spindle and preparation method and application thereof Download PDF

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CN108550701B
CN108550701B CN201810361066.1A CN201810361066A CN108550701B CN 108550701 B CN108550701 B CN 108550701B CN 201810361066 A CN201810361066 A CN 201810361066A CN 108550701 B CN108550701 B CN 108550701B
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doped titanium
titanium oxide
oxide nano
solution
spindle
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CN108550701A (en
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张文华
吕银花
蔡冰
马青山
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Abstract

The invention discloses a preparation method of a Nb-doped titanium oxide nano spindle, which comprises the following steps: adding butyl titanate into glacial acetic acid solution, stirring, adding niobium ethoxide into the solution according to the doping ratio of Nb/(Nb + Ti) of 0% -20%, and continuously stirring to obtain clear precursor solution; pouring the solution into a stainless sodium reaction kettle with a polymethyl vinyl fluoride lining, and naturally cooling to room temperature after reaction to obtain white or blue precipitate; and repeatedly cleaning all the precipitates by using deionized water and ethanol to obtain the Nb-doped titanium oxide nano spindle body. The invention also discloses the Nb-doped titanium oxide nano spindle body and application thereof. The Nb-doped titanium dioxide spindle body obtained by the invention has the advantages of simple preparation method, low cost, uniform particle size and high degree of crystallization. Meanwhile, the Nb-doped titanium dioxide spindle body is used as an electron transport material, and the obtained flat cell is high in efficiency, small in hysteresis and good in stability.

Description

Nb-doped titanium dioxide spindle and preparation method and application thereof
Technical Field
The invention relates to a battery material, in particular to a Nb-doped titanium dioxide spindle and a preparation method and application thereof, belonging to the technical field of solar batteries.
Background
The ideal electron transport layer is a highly efficient planar perovskiteThe important components of the mine solar cell play a very key role in the aspects of electron transmission and recombination inhibition, and can realize high Voc and FF. Currently, in perovskite solar cells, the most commonly used electron transport layer is TiO2. However, TiO2The metal ion doping can effectively increase the conductivity of the metal ion and adjust the band gap structure and defect state of the metal ion. The metal elements currently used for doping titanium oxide are: magnesium, lithium, samarium, tantalum, and the like. Niobium-doped titanium oxide has wide application in transparent conductive electrodes, photocatalysis, lithium or sodium batteries, dye sensitization and the like, but the application in flat perovskite batteries is rarely reported.
In 2004, there were reports that: by reaction on TiO2NbCl is added during the growth process5Nb doped titania was obtained and applied to a flat plate perovskite cell with a doubling of efficiency (from 4.9% to 7.5%) compared to the Nb undoped titania based perovskite cell. In 2016, it was reported that by adding NbCl5The battery efficiency obtained by synthesizing the Nb-doped titanium oxide nanocrystal is 16.3%, but the efficiency is lower. 2017 using NbCl5Obtaining 1% Nb: TiO2When used in the electron transport layer of a flat-plate perovskite cell, the cell efficiency at reverse scan was 19.2% while the cell exhibited improved stability, however it exhibited some hysteresis (16.21% efficiency at forward scan). The authentication efficiency of the prior flat-plate battery is 21.6 percent, and the results show that the Nb is TiO2The obtained flat cells are slightly less efficient, and the precursors of Nb used by the flat cells are all NbCl5Niobium chloride is a substance which is very easy to hydrolyze, and can release HCl, so that the niobium chloride has a certain corrosion effect on a human body and the substrate ITO of the perovskite battery.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of the Nb-doped titanium dioxide spindle body, which has the advantages of simple method, high cell efficiency and good stability.
The invention is realized by the following steps:
a preparation method of a Nb-doped titanium oxide nano spindle body comprises the following steps:
adding a certain amount of butyl titanate into glacial acetic acid solution with a certain volume, then adding niobium ethoxide into the solution according to the doping ratio of Nb/(Nb + Ti) (molar ratio) of 0-20% in the stirring process, and continuously stirring to obtain clear precursor solution of niobium-doped titanium oxide;
then pouring the solution into a stainless sodium reaction kettle with a poly (methyl vinyl fluoride) lining; then putting the sealed reaction kettle into a constant-temperature drying box, reacting for a certain time at a certain temperature, and naturally cooling to room temperature to obtain white or blue precipitate; and repeatedly cleaning all the precipitates by using deionized water and ethanol to obtain the Nb-doped titanium oxide nano spindle body.
The further scheme is as follows:
the addition amount of the butyl titanate is 1/5-1/3 of the volume of the glacial acetic acid solution.
The further scheme is as follows:
the reaction is carried out at a certain temperature for a certain time, namely at 150-240 ℃ for 16-48 h.
The invention also provides a Nb-doped titanium oxide nano spindle body which is prepared by the preparation method of the Nb-doped titanium oxide nano spindle body.
The invention also provides application of the Nb-doped titanium oxide nano spindle body, which is applied to a flat perovskite battery and used as an electron transport layer.
The further scheme is as follows:
the specific steps applied to the flat-plate perovskite battery are as follows:
step one, depositing a Nb-doped titanium oxide electron transport layer on cleaned FTO conductive glass
And dispersing the precipitate after repeated centrifugal cleaning in ethanol to form a colloidal solution of Nb-doped titanium oxide with a certain concentration. The spin coating liquid with different concentrations is obtained by adding terpineol with different proportions into the colloidal solution, and then a compact electron transmission layer can be formed on the surface of the FTO treated by the plasma through spin coating at a certain rotating speed and acceleration.
Step two, spin-coating a perovskite battery material layer on the Nb-doped titanium oxide compact layer;
step three, spin-coating a hole transport material on the perovskite layer;
and step four, evaporating the gold electrode.
The core of the present invention is mainly the first step, and the second to fourth steps are conventional in the art, and therefore, are not described in detail herein.
The invention also claims a flat perovskite cell obtained by the application of the Nb-doped titanium oxide nano spindle.
The preparation method is simple, low in cost, uniform in particle size, highly crystalline and good in repeatability.
And because the carrier concentration and the conductivity of the Nb-doped titanium oxide are 2 times of those of the corresponding undoped titanium oxide; meanwhile, the defect state concentration is reduced. The flat perovskite battery composed of undoped titanium oxide has the following performance parameters of reverse scanning: current density JSC＝23.2mA/cm2Opening pressure VOC1.07V, fill factor FF 77.0%, energy conversion efficiency PCE 19.1%, and positive scan PCE 18.2%, with some degree of hysteresis in the positive and negative scan test. And correspondingly, a device J composed of Nb-doped titanium oxideSC＝23.6mA/cm2,VOC1.13V, FF is 78.4%, PCE is 20.8%; the PCE for the forward sweep is 20.2%, and almost no hysteresis exists.
In the application, the Nb-doped titanium dioxide spindle body structure is obtained by a simple one-step solvothermal method, wherein the precursor of the Nb is friendly niobium pentaethanolate. The conductivity and carrier concentration of the Nb-doped titanium oxide were improved to some extent, and when the Nb doping amount was 3%, the efficiency of the obtained flat cell was the best, 20.8%, and the hysteresis was small (efficiency in the normal scan was 20.2%). Meanwhile, the battery shows good stability, and the efficiency of the battery can still be maintained at 20% after 1400h when the battery is stored at room temperature under a non-packaging condition.
Drawings
FIG. 1 is a schematic view of a structural model of a Nb-doped titanium oxide nano-spindle prepared according to the present invention;
FIG. 2 is a high resolution electron micrograph of Nb doped titanium oxide nano-spindles.
Fig. 3 is a schematic diagram of the basic structure of a flat perovskite cell applied in the invention.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
Example 1
A preparation method of a Nb-doped titanium oxide nano spindle body comprises the following steps:
adding 5ml of butyl titanate into 15-25 ml of glacial acetic acid solution, then adding niobium ethoxide into the solution according to the doping ratio of Nb/(Nb + Ti) (molar ratio) of 0% -20% in the stirring process, and continuously stirring to obtain a clear precursor solution of the niobium-doped titanium oxide;
then pouring the solution into a stainless sodium reaction kettle with a poly (methyl vinyl fluoride) lining; then placing the sealed reaction kettle into a constant-temperature drying box, reacting for 16-48 h at 150-240 ℃, and naturally cooling to room temperature to obtain white or blue precipitate; and (3) repeatedly cleaning all precipitates with deionized water and ethanol (generally, cleaning with deionized water once, then repeatedly cleaning with ethanol, centrifuging after each cleaning, and cleaning when supernatant is clarified after centrifuging), thus obtaining the Nb-doped titanium oxide nano spindle shown in the attached figures 1 and 2. Wherein, fig. 1 is a schematic view of a structural model of the Nb-doped titanium oxide nano-spindle, fig. 2 is a high-resolution electron micrograph (TEM) of the Nb-doped titanium oxide nano-spindle, wherein the inset in fig. 2 is a Fast Fourier Transform (FFT) diagram. Through detection, the spindle has uniform particle size, average particle size of 25nm, high crystallinity and easy obtaining of a flat electron transport layer film. In FIG. 1, {001} and {101} refer to the crystal planes exposed by the Nb-doped Titania nano-spindles.
Example 2
The invention also provides application of the Nb-doped titanium oxide nano spindle body, which is applied to a flat perovskite battery and used as an electron transport layer.
The specific steps applied to the flat-plate perovskite battery are as follows:
step one, depositing a Nb-doped titanium oxide electron transport layer on cleaned FTO conductive glass
And dispersing the precipitate after repeated centrifugal cleaning in ethanol to form a colloidal solution of Nb-doped titanium oxide with a certain concentration. The spin coating liquid with different concentrations is obtained by adding terpineol with different proportions into the colloidal solution, and then a compact electron transmission layer can be formed on the surface of the FTO treated by the plasma through spin coating at a certain rotating speed and acceleration.
Step two, spin-coating a perovskite battery material layer on the Nb-doped titanium oxide compact layer;
step three, spin-coating a hole transport material on the perovskite layer;
and step four, evaporating the gold electrode.
The perovskite solar cell obtained in the embodiment has a structure shown in fig. 3, and comprises an FTO conductive glass substrate 1 from bottom to top in sequence; a niobium doped titanium oxide nano spindle compact layer 2; a layer of perovskite light absorbing material 3; a hole transport layer 4; and a metal electrode layer 5.
When the doping amount of Nb is 3%, the efficiency of the resulting flat cell is the best, 20.8%, and the hysteresis is small (efficiency in normal scan is 20.2%). Meanwhile, the battery shows good stability, and the efficiency of the battery can still be maintained at 20% after 1400h when the battery is stored at room temperature under a non-packaging condition.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.

Claims (8)

1. A preparation method of a Nb-doped titanium oxide nano spindle body is characterized by comprising the following steps:
adding a certain amount of butyl titanate into glacial acetic acid solution with a certain volume, then adding niobium ethoxide into the solution according to the doping ratio of Nb/(Nb + Ti) of 0-20% in the stirring process, and continuously stirring to obtain clear precursor solution of niobium-doped titanium oxide;
then pouring the solution into a stainless sodium reaction kettle with a poly (methyl vinyl fluoride) lining; then putting the sealed reaction kettle into a constant-temperature drying box, reacting for a certain time at a certain temperature, and naturally cooling to room temperature to obtain white or blue precipitate; and repeatedly cleaning all the precipitates by using deionized water and ethanol to obtain the Nb-doped titanium oxide nano spindle body.
2. The method of producing the Nb-doped titanium oxide nanospindle of claim 1, wherein:
the addition amount of the butyl titanate is 1/5-1/3 of the volume of the glacial acetic acid solution.
3. The method of producing the Nb-doped titanium oxide nanospindle of claim 1, wherein:
the reaction is carried out at a certain temperature for a certain time, namely at 150-240 ℃ for 16-48 h.
4. An Nb-doped titanium oxide nano-spindle produced by the production method of an Nb-doped titanium oxide nano-spindle according to any one of claims 1 to 3.
5. The Nb doped titanium oxide nanospindle of claim 4, wherein:
the Nb-doped titanium oxide nano spindle body is highly crystalline, and the average grain size is 25 nm.
6. Use of the Nb-doped titanium oxide nanospindle according to claim 4 or 5, characterized in that: the material is applied to a flat perovskite battery and is used as an electron transport layer.
7. Use of the Nb-doped titanium oxide nanospindle according to claim 6, characterized in that:
the specific steps applied to the flat-plate perovskite battery are as follows:
step one, depositing a Nb-doped titanium oxide electron transport layer on cleaned FTO conductive glass
And dispersing the precipitate after repeated centrifugal cleaning in ethanol to form a colloidal solution of Nb-doped titanium oxide with a certain concentration. The method comprises the steps of adding terpineol in different proportions into the colloidal solution to obtain spin-coating solutions with different concentrations, and then forming a compact electron transmission layer on the surface of the FTO treated by the plasma through spin coating at a certain rotating speed and acceleration;
step two, spin-coating a perovskite battery material layer on the Nb-doped titanium oxide compact layer;
step three, spin-coating a hole transport material on the perovskite layer;
and step four, evaporating the gold electrode.
8. A flat-plate perovskite battery, characterized in that: the flat perovskite cell is obtained by the use of the Nb-doped titanium oxide nano-spindles according to claim 6 or 7.
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Citations (3)

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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
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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
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