CN102610394B - Preparation method of transition metal doped alpha-Fe2O3 nano rod array - Google Patents

Preparation method of transition metal doped alpha-Fe2O3 nano rod array Download PDF

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CN102610394B
CN102610394B CN201210087299.XA CN201210087299A CN102610394B CN 102610394 B CN102610394 B CN 102610394B CN 201210087299 A CN201210087299 A CN 201210087299A CN 102610394 B CN102610394 B CN 102610394B
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preparation
substrate
solution
transition metal
stick array
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CN102610394A (en
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董立峰
刘春廷
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Qingdao University of Science and Technology
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Abstract

The invention belongs to the technical field of battery materials, and relates to a preparation method of a transition metal doped alpha-Fe2O3 nano rod array. The preparation method comprises the following steps: carrying out ultrasonic cleaning pretreatment respectively on acetone, absolute ethyl alcohol and deionized water successively for a selected substrate, and mixing FeCl3.6H2O, a polyvinyl alcohol water solution and an HCl (hydrogen chloride) solution, thereby obtaining a gelatin solution; preparing and forming an alpha-Fe2O3 buffer layer by the gelatin solution for the pretreatment substrate by adopting a spin-coating technique; dissolving FeCl3.6H2O and 1NaNo3 in a mixed solution of the HCl solution and alcohol, thereby preparing the reaction liquid; placing the substrate alpha-Fe2O3 buffer layer into a high-pressure kettle of a teflon inner lining, also pouring the reaction liquid into the high-pressure kettle, tightening a cap of the high-pressure kettle, and placing into an electric heating constant-temperature air blast drying box for heat preservation and drying, thereby obtaining the reaction product; and preparing an alpha-Fe2O3 nano rod array by a step-by-step temperature rising mode for the reaction product. The preparation process is simple, the repeatability is good, the cost is low, the application range is wide, and the application effects are good.

Description

A kind of transient metal doped formula α-Fe 2o 3the preparation method of nanometer stick array
Technical field:
The invention belongs to battery material technical field, relate to a kind of transient metal doped formula α-Fe 2o 3the preparation method of nanometer stick array.
Background technology:
Along with global energy crisis is day by day serious, the urgent exploitation of people needs new energy materials and utilizes new forms of energy, and solar energy, as a kind of natural energy source of inexhaustible, clean and safe, receives the concern of countries in the world day by day.DSSC is compared with traditional monocrystaline silicon solar cell, and the advantage of the simple and stable performance of, technique low with cost, becomes both at home and abroad the competitively focus of research.In order to improve the electricity conversion of battery, researcher updates sensitizer, electrolyte and the semiconductor optical anode material of battery, and wherein, selecting suitable semiconductor optical anode material is the important channel of improving the electricity conversion of solar cell; As far back as the 1991 Nian, Lausanne, SUI Michael of higher technical school research group has developed a kind of DSSC (Dye sensitized solar cell, be called for short DSSC), with porous TiO 2film is to have obtained breakthrough in the research work of light anode, at < < Nature > > (1991,353:737~740) on, delivered and be entitled as " A Low-cost, High-efficiency Solar-cell Based on Dye-sensitized Colloidal TiO 2films " research article, but because TiO 2there is the bottleneck that cannot break through in semiconductor self, as greater band gap (3.2eV) etc., has reduced to a certain extent the electricity conversion of DSSC, restricted TiO 2the process of industrialization of base DSSC.
At present, because iron oxide material has nontoxic pollution-free, with low cost, aboundresources, the advantageous feature such as biocompatibility, environment friendly, stability, catalytic and magnetic, more and more extensively by the general fields such as biomedicine, pigment, catalysis, air-sensitive, sensing and semiconductor that are applied to.In recent years, along with the pay attention to day by day of the development He Dui energy problem of film preparing technology, Michael deng research, find that sull energy gap is 1.5~1.7eV, approach the best energy gap of solar cell, its absorption coefficient is large, makes it under AM 1.5 conditions, can absorb in theory approximately 40% sunlight, well beyond other wide bandgap semiconductor as TiO 2, therefore increasing Chinese scholars is gathered in research sight in the photoelectric characteristic of sull, is expected to be applied in its photovoltaic conversion and solar cell.Yet, α-Fe 2o 3as the battery efficiency of light anode still very low reason, be low (the about 0.01cm of movement of hole speed under room temperature 2v -1s -1), the carrier diffusion path short (approximately 2~4nm) producing, the life-span that charge carrier exists is very short by (~10 -12s), therefore cell photoelectric conversion efficiency is low.In order to overcome above-mentioned deficiency and to improve the utilization of semiconductor optical anode to sunlight, at present the method for report mainly contains the methods such as the design of ferric oxide nano structure and morphology, doping ion surface chemical modification and compound other sulls of semiconductor, but existing these technical methods again ubiquity many deficiencies and shortcoming.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, seek to design a kind of transient metal doped formula α-Fe 2o 3the preparation method of nanometer stick array, the ferric oxide nano rod of take improves the efficiency of semiconductor optical anode transmission light induced electron as substrate, and then raising open circuit voltage, reduce the recombination probability in light induced electron and hole, widen the response of light anode to visible ray, improve sunlight utilization ratio, realize the raising of solar cell photoelectric transformation efficiency.
To achieve these goals, the present invention aligns with nanometer one-dimentional structure, high length-diameter ratio and the high density of ferric oxide nano rod, adopt transient metal doped technology to change its physical property, light conducting excites the charge carrier of generation faster and better, improve electric charge transmission rate, can effectively reduce the compound of photogenerated charge, be conducive to strengthen nanostructured alpha-Fe 2o 3photoelectrochemical behaviour, and then improve photoelectric conversion efficiency; Take ferric oxide nano rod as base material containing transition metal ion Sn 4+, Sn 2+, Ti 4+, Cu 2+, Cu +and Zn 2+deng obtaining low energy gap Nano semiconductor photo-anode film, and be applied in DSSC field.
The present invention includes following steps:
(1) substrate pretreatment: acetone, absolute ethyl alcohol and the deionized water for substrate selected are carried out respectively to Ultrasonic Cleaning 10~30min successively and carry out substrate pretreatment, its base material comprises glass, FTO, PET, silicon chip, titanium, copper and zinc;
(2) preparation gelatin solution: by 0.1~0.4mol/L FeCl 3.6H 2o, the HCl solution of the polyvinyl alcohol of 3~5wt% (PVA) aqueous solution and 0.1~0.5wt% is mixed to get gelatin solution;
(3) resilient coating preparation: adopt whirl coating, print, smear or dipping technique will through in pretreated substrate with gelatin solution preparation formation α-Fe 2o 3resilient coating, the mode of then taking substep to heat up in chamber type electric resistance furnace, from room temperature to 150 ℃, programming rate is 1~10 ℃/min, is warming up to 300~600 ℃ afterwards with 1~5 ℃/min, then in the time of 300~600 ℃ sintering 1~5 hour, make substrate α-Fe 2o 3resilient coating;
(4) preparation reactant liquor: by 0.1~0.4mol/L FeCl 3.6H 2o and 1.0~1.5mol/LNaNO 3be dissolved in 20mL volume ratio and be in the mixed solution of 3: 3~7 HCl solution and ethanol and make reactant liquor;
(5) by step (3) gained substrate α-Fe 2o 3resilient coating is put into polytetrafluoroethyllining lining autoclave, and reactant liquor prepared by step (4) falls in autoclave, tightens high pressure kettle cover;
(6) autoclave in step (5) is put into 70~120 ℃ of heat preservation and drynesses of electric heating constant-temperature blowing drying box 1~6 hour, obtain product;
(7) the mode sintering of step (6) gained product being taked in chamber type electric resistance furnace substep heat up, from room temperature to 150 ℃, programming rate is 1~10 ℃/min, is warming up to 300~600 ℃ afterwards with 1~5 ℃/min, then sintering 1~5 hour in the time of 300~600 ℃, makes α-Fe 2o 3nanometer stick array;
(8) α-Fe step (7) being made 2o 3nanometer stick array adopts solid-phase sintering diffusion method to carry out transient metal doped, the mode of taking substep to heat up to electrode in chamber type electric resistance furnace, from room temperature to 400 ℃, programming rate is 1~10 ℃/min, be incubated 2 hours, with 1~3 ℃/min, be warming up to 600~1200 ℃ of solid-phase sintering DIFFUSION TREATMENT 20~40 minutes afterwards, obtain the α-Fe of containing transition metal ion 2o 3nanometer stick array.
Of the present invention to α-Fe 2o 3nanometer stick array carries out transient metal doped or adopts liquid-phase chemical reaction, first prepares the ethanolic solution 20~30mL of 0.001~0.05g/mL containing transition metal ion; Again step (7) gained is had to α-Fe 2o 3polytetrafluoroethyllining lining autoclave is put in the substrate of nanometer stick array, and the ethanolic solution of transition metal ions is transferred to wherein and tightened high pressure kettle cover, puts into 70~120 ℃ of heat preservation and drynesses of electric heating constant-temperature blowing drying box 4~6 hours; Then, put into after adopting successively deionized water and absolute ethyl alcohol to clean at 40~80 ℃, baking oven dry 6~12 hours, obtain the α-Fe of containing transition metal ion 2o 3nanometer stick array.
The slaine that the selected transition metal of the present invention mixes is Sn 4+, Sn 2+, Ti 4+, Mn 2+, Cu 2+, Cu +and Zn 2+one or two or more kinds in the hydrochloride of transition metal ions, nitrate and sulfate.
The present invention relates to transient metal doped be by prepared α-Fe 2o 3nanometer stick array carries out solid-phase sintering DIFFUSION TREATMENT at 600~1200 ℃ of sintering, be conducive in substrate with nanometer stick array in transition metal ions diffusion; Or put it into 0.001~0.05g/mL containing transition metal ion Sn 4+, Sn 2+, Ti 4+, Mn 2+, Cu +, Cu 2+and Zn 2+deng ethanolic solution in 70~120 ℃ insulation 4~6 hours, carry out liquid-phase chemical reaction, realize α-Fe 2o 3nanometer stick array doped metal ion; The ferric oxide nano rod nano-crystal film light anode of containing transition metal is for making by nano crystal semiconductor optical anode, dye sensitizing agent, electrolyte and DSSC that electrode four parts are formed.
The present invention compared with prior art, by different element dopings, realize the control to semiconductor ferric oxide nano rod energy gap size and level of energy thereof, widen the absorbing band of photo-anode film, improve sunlight utilance, one-dimentional structure, high length-diameter ratio and high density due to ferric oxide nano rod aligns simultaneously, make the transmission electronic that light anode can be faster and better, improve significantly open circuit voltage, and then improve the photoelectric conversion efficiency of solar cell; Ferric oxide nano rod excites the charge carrier of generation with its unique nanostructure better light conducting faster in the structure of solar battery light anode, improve electric transmission rate, and then improve photoelectric conversion efficiency; Take the low-energy gap nanocrystalline semiconductor photo-anode film of ferric oxide nano rod after substrate containing transition metal ion, Fermi level and the light induced electron transmission rate of light anode have been improved, widened the absorption band of light anode to sunlight, make light anode in transmission electronic, self also absorbs visible ray, produce light induced electron, dyestuff and photo-anode film have better energy level matching effect; The preparation of resilient coating has not only strengthened the adhesion of nanometer rods iron oxide and substrate, also effectively stops the light induced electron on light anode conduction band electrolytical compound with dye well; Its preparation technology is simple, and repeatability is good, with low cost, applied range, and effect is good.
Accompanying drawing explanation:
Fig. 1 is technical process flow process principle schematic of the present invention.
Fig. 2 is the stereoscan photograph of substrate FTO doping Sn ferric oxide nano rod array.
Fig. 3 is substrate FTO doping Sn ferric oxide nano rod array current density voltage curve under visible ray.
Fig. 4 is the stereoscan photograph of substrate Ti paper tinsel doped Ti ferric oxide nano rod array.
Fig. 5 is the current density voltage curve under substrate Ti paper tinsel doped Ti ferric oxide nano rod array visible ray.
Embodiment:
Below by embodiment, also the invention will be further described by reference to the accompanying drawings.
Embodiment 1:FTO is the α-Fe of substrate 2o 3the preparation of nanometer rods light anode
(1) preparation FTO electro-conductive glass substrate: FTO is cut to slivering, and with acetone, absolute ethyl alcohol and deionized water successively each Ultrasonic Cleaning 10~30min, ultrasonic power is 200 watts;
(2) by 0.540~1.622g FeCl 3.6H 2o, HCl (36.5%~38%) solution of the polyvinyl alcohol of 5wt% (PVA) aqueous solution and 0.3wt%, preparation 20mL gelatin solution;
(3) by whirl coating technology, at FTO electro-conductive glass, obtain yellowish green FeOOH prefabricated membrane;
(4) 300~500 ℃ of sintering 1~5 hour, make bronzing α-Fe 2o 3resilient coating;
(5) preparation reactant liquor: 0.540~1.622g FeCl 3.6H 2o and 1.70~2.55g NaNO 3be dissolved in 20mL volume ratio and be in 3: 3~7 HCl solution and ethanol;
(6) FTO that step (4) gained is had to resilient coating puts into polytetrafluoroethyllining lining autoclave, and the reactant liquor in step (5) is transferred to wherein;
(7) autoclave of step (6) gained is placed in electric heating constant-temperature blowing drying box to 70~120 ℃ of insulations 1~6 hour;
(8) product is carried out 300~500 ℃ of sintering 1~6 hour in chamber type electric resistance furnace, obtains α-Fe 2o 3nanometer rods light anode; See the α-Fe shown in accompanying drawing 1 2o 3the preparation flow figure of nanometer stick array light anode.
Embodiment 2: α-Fe 2o 3nanometer rods light anode carries out transition metal Sn by liquid-phase chemical reaction 4+doping
(1) 0.01~0.5g SnCl 45H 2o is dissolved in 10mL ethanol, prepares the ethanolic solution 20~30mL of 1~2mg/mL containing transition metal ion;
(2) step (8) gained in example 1 is had to α-Fe 2o 3polytetrafluoroethyllining lining autoclave is put in the substrate of nanometer stick array, and high pressure kettle cover is transferred to wherein and tightened to the transition metal ions ethanolic solution in step (1);
(3) autoclave in step (2) is put into 70~120 ℃ of insulations of electric heating constant-temperature blowing drying box 4~6 hours;
(4) step (3) products therefrom is adopted successively deionized water and absolute ethyl alcohol clean, put at 40~80 ℃, baking oven dry 6~12 hours, obtain the α-Fe of containing transition metal ion 2o 3nanometer stick array.
The present embodiment transition metal ions Ti 4+, Sn 2+, Mn 2+, Cu 2+, Cu +and Zn 2+deng α-Fe 2o 3the doping of nanometer rods light anode, the slaine that selected transition metal mixes is respectively Cu 2+and Zn 2+the hydrochloride of metal ion is as TiCl 44H 2o, SnCl 22H 2o, MnCl 22H 2o, CuCl 24H 2o, CuCl2H 2o and ZnCl 24H 2o, substrate is FTO.
Embodiment 3: α-Fe that metal Ti is substrate 2o 3the preparation method of nanometer rods light anode
(1) preparation substrate Ti paper tinsel: FTO is cut to slivering, polishing, and with acetone, absolute ethyl alcohol and deionized water successively each Ultrasonic Cleaning 10~30min, ultrasonic power is 200 watts;
(2) by 0.540~1.622g FeCl 3.6H 2o, HCl (36.5%~38%) solution of the polyvinyl alcohol of 5wt% (PVA) aqueous solution and 0.3wt%, preparation 20mL gelatin solution;
(3) repeated multiple times use printing technology obtains FeOOH prefabricated membrane on Ti paper tinsel;
(4) 300~500 ℃ of sintering 1~5 hour, make α-Fe 2o 3resilient coating;
(5) preparation reactant liquor: 0.540~1.622g FeCl 3.6H 2o and 1.70~2.55g NaNO 3be dissolved in 20mL volume ratio and be in 3: 3~7 HCl solution and ethanol;
(6) the Ti paper tinsel that step (4) gained is had to resilient coating is put into polytetrafluoroethyllining lining autoclave, and the reactant liquor in step (5) is transferred to wherein;
(7) autoclave of step (6) gained is placed in electric heating constant-temperature blowing drying box to 70~120 ℃ of insulations 1~6 hour;
(8) product is carried out 300~500 ℃ of sintering 1~6 hour in chamber type electric resistance furnace, obtains α-Fe 2o 3nanometer rods light anode.
Embodiment 4: α-Fe 2o 3nanometer rods light anode diffuses into row transition metal Ti by solid-phase sintering 4+doping
By prepared α-Fe 2o 3nanometer stick array, carries out solid-phase sintering DIFFUSION TREATMENT 20~40 minutes at 600~1200 ℃, obtains the α-Fe of containing transition metal ion 2o 3nanometer stick array.

Claims (3)

1. a transient metal doped formula α-Fe 2o 3the preparation method of nanometer stick array, is characterized in that comprising the following steps:
(1) substrate pretreatment: acetone, absolute ethyl alcohol and the deionized water for substrate selected are carried out respectively to Ultrasonic Cleaning 10~30min successively and carry out substrate pretreatment, its base material is selected from a kind of in glass, FTO, PET, silicon chip, titanium, copper or zinc;
(2) preparation gelatin solution: by 0.1~0.4mol/L FeCl 36H 2o, the HCl solution of the polyvinyl alcohol of 3~5wt% (PVA) aqueous solution and 0.1~0.5wt% is mixed to get gelatin solution;
(3) resilient coating preparation: adopt whirl coating, print, smear or dipping technique will through in pretreated substrate with gelatin solution preparation formation α-Fe 2o 3resilient coating, the mode of then taking substep to heat up in chamber type electric resistance furnace, from room temperature to 150 ℃, programming rate is 1~10 ℃/min, is warming up to 300~600 ℃ afterwards with 1~5 ℃/min, then in the time of 300~600 ℃ sintering 1~5 hour, make substrate α-Fe 2o 3resilient coating;
(4) preparation reactant liquor: by 0.1~0.4mol/L FeCl 36H 2o and 1.0~1.5mol/LNaNO 3being dissolved in 20mL volume ratio is to make reactant liquor in the HCl solution of 3:3~7 and the mixed solution of ethanol;
(5) by step (3) gained substrate α-Fe 2o 3resilient coating is put into polytetrafluoroethyllining lining autoclave, and reactant liquor prepared by step (4) falls in autoclave, tightens high pressure kettle cover;
(6) autoclave in step (5) is put into 70~120 ℃ of heat preservation and drynesses of electric heating constant-temperature blowing drying box 1~6 hour, obtain product;
(7) the mode sintering of step (6) gained product being taked in chamber type electric resistance furnace substep heat up, from room temperature to 150 ℃, programming rate is 1~10 ℃/min, is warming up to 300~600 ℃ afterwards with 1~5 ℃/min, then sintering 1~5 hour in the time of 300~600 ℃, makes α-Fe 2o 3nanometer stick array;
(8) α-Fe step (7) being made 2o 3nanometer stick array adopts solid-phase sintering diffusion method to carry out transient metal doped, the mode of taking substep to heat up to electrode in chamber type electric resistance furnace, from room temperature to 400 ℃, programming rate is 1~10 ℃/min, be incubated 2 hours, with 1~3 ℃/min, be warming up to 600~1200 ℃ of solid-phase sintering DIFFUSION TREATMENT 20~40 minutes afterwards, obtain the α-Fe of containing transition metal ion 2o 3nanometer stick array.
2. transient metal doped formula α-Fe according to claim 1 2o 3the preparation method of nanometer stick array, is characterized in that adopting liquid-phase chemical reaction to α-Fe 2o 3nanometer stick array carries out transient metal doped, first prepares the ethanolic solution 20~30mL of 0.001~0.05g/mL containing transition metal ion; Again step (7) gained is had to α-Fe 2o 3polytetrafluoroethyllining lining autoclave is put in the substrate of nanometer stick array, and the ethanolic solution of transition metal ions is transferred to wherein and tightened high pressure kettle cover, puts into 70~120 ℃ of heat preservation and drynesses of electric heating constant-temperature blowing drying box 4~6 hours; Then, put into after adopting successively deionized water and absolute ethyl alcohol to clean at 40~80 ℃, baking oven dry 6~12 hours, obtain the α-Fe of containing transition metal ion 2o 3nanometer stick array.
3. transient metal doped formula α-Fe according to claim 1 2o 3the preparation method of nanometer stick array, is characterized in that the slaine that selected transition metal mixes is Sn 4+, Sn 2+, Ti 4+, Mn 2+, Cu 2+, Cu +and Zn 2+one or two or more kinds in the hydrochloride of transition metal ions, nitrate and sulfate.
CN201210087299.XA 2012-03-29 2012-03-29 Preparation method of transition metal doped alpha-Fe2O3 nano rod array Expired - Fee Related CN102610394B (en)

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CN106745311B (en) * 2017-01-20 2018-01-09 济南大学 A kind of α Fe2O3The preparation method of nanometer rods
CN108878858B (en) * 2018-05-07 2022-03-18 青岛大学 Tin dioxide thin film material, lithium battery and preparation method
CN109132997A (en) * 2018-09-29 2019-01-04 华南理工大学 (In) the GaN nano-pillar and the preparation method and application thereof being grown on Ti substrate
CN110586100A (en) * 2019-10-08 2019-12-20 扬州大学 Fe2O3/FeO heterostructure and preparation method and application thereof
CN111261413B (en) * 2019-12-27 2021-10-08 武汉科技大学 Ti-doped alpha-Fe2O3Nanorod composite MOFs heterojunction photo-anode and preparation method and application thereof
CN111346641A (en) * 2020-04-14 2020-06-30 天津大学 Doped α -ferric oxide, preparation method thereof and application thereof in hydrogenation reaction

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CN101062790A (en) * 2007-04-20 2007-10-31 南京大学 Simple preparation method of alpha-FeOOH and alpha-Fe2O3 nano stick
CN101767767A (en) * 2010-03-17 2010-07-07 哈尔滨工程大学 Ferroferric oxide and zinc oxide nuclear shell nano-rod for absorbing high-frequency electromagnetic waves and manufacturing method thereof

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CN101767767A (en) * 2010-03-17 2010-07-07 哈尔滨工程大学 Ferroferric oxide and zinc oxide nuclear shell nano-rod for absorbing high-frequency electromagnetic waves and manufacturing method thereof

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