CN115172607A - Preparation method and application of core-shell material - Google Patents
Preparation method and application of core-shell material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 27
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- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 239000000758 substrate Substances 0.000 claims abstract description 14
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- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000004729 solvothermal method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 25
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 11
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 11
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 97
- 239000011787 zinc oxide Substances 0.000 description 41
- 238000012360 testing method Methods 0.000 description 12
- 239000002243 precursor Substances 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011358 absorbing material Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
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- 239000004246 zinc acetate Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 low-toxicity Sb Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- LYTMXSRDMBKYIZ-UHFFFAOYSA-N [Ag].[Sb]=S Chemical compound [Ag].[Sb]=S LYTMXSRDMBKYIZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/152—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising zinc oxide, e.g. ZnO
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method and application of a core-shell material, belonging to the technical field of material manufacturing, wherein the preparation method comprises the following steps: coating a ZnO seed layer on an FTO substrate, and growing a ZnO nanorod by using a solvothermal method; then coating the ZnO nano-rod with AgNO 3 、SbCl 3 And mixed solution of ethanol of thioacetamide and N, N dimethylformamide, and finally annealing to obtain the core-shell material, wherein the structure of the core-shell material is ZnO @ AgSbS 2 . The preparation method is simple and has high repeatability; the obtained core-shell material is used for preparing the perovskite battery, and the conversion efficiency is high.
Description
Technical Field
The invention belongs to the technical field of material manufacturing, and particularly relates to a preparation method and application of a core-shell material.
Background
Zinc oxide is a very excellent photoelectric semiconductor material due to its diverse nanostructures and extremely fast electron transport rate; in particular, znO nanowires, nanotubes or nanorods can provide a direct path for electron transmission, effectively reduce the recombination of carriers, and are widely applied as electron transmission materials in electro-catalytic hydrogen production and photovoltaic cells. However, because of the forbidden bandwidth of ZnO, znO-based photoelectrode or electron transport material of battery can only absorb uv part, which limits its practical application in catalysis and battery.
In order to solve the above problems, attempts to broaden the absorption spectrum of ZnO by element doping and narrow bandgap semiconductor coupling have been made in many studies. Wherein, znO is used as a substrate, and a photoelectric material with other suitable band gaps is deposited or coated on the surface of the substrate, so that the method is an effective method for effectively solving the band gap defect. Such as silver antimony sulfide (AgSbS) 2 ) The material has a proper band gap of 1.72eV in a visible light region and a higher absorption coefficient, and is widely applied to the fields of electrocatalysis and the like at present, but the preparation method is more complex; in addition, among solar cells, a crystalline silicon cell is a relatively mature cell material in the market, but as the corresponding cell efficiency reaches a certain limit, the development and application of a new generation of cell material is also an important research trend. In the third generation of batteries, perovskite batteries have become a new research hotspot due to the efficiency and economy comparable to those of crystalline silicon. Although the perovskite material has high performance, the problems of high-toxicity lead contained in the original material, poor stability of the battery and the like still exist. Therefore, the development of new, highly efficient light absorbing materials is also one of the important studies in the field of photovoltaics. At present, agSbS 2 The light-absorbing material is commonly used in the fields of electrocatalysis and the like, but the application research of the light-absorbing material in solar cells is still relatively less, and sulfides of metals such as low-toxicity Sb, bi and the like are proved to be potential light-absorbing materials to be used in the solar cells at present. Thus, by ZnO and AgSbs-like 2 The sulfide is used for the composite preparation of the material, and the photoelectric material with excellent performance is expected to be developed.
Chinese patent application 201710748920.5 discloses a core-shell material, wherein a core substance of the core-shell material is selected from at least one of multi-metal oxides, and is prepared by a multilayer precursor method; the shell substance of the core-shell material is mainly a multi-metal oxide. The core-shell material is used as a positive electrode material in the field of lithium ion batteries, exerts the advantage of high capacity, and has good air stability and safety performance. However, the core-shell material in the patent needs to be obtained by repeatedly mixing the metal-containing precursor material in the core with the solution of the shell material for many times, and the process involves many pH regulation, washing, separation, drying or mixing and grinding procedures, so that the procedure is relatively complex; in the washing or separating process, the defects that the actual content of the material components cannot be accurately controlled and the repeatability of the result is not high exist.
Therefore, it is necessary to find a preparation method of the core-shell material which has simple preparation process and high repeatability and can prepare the battery with excellent electrical property.
Disclosure of Invention
The invention aims to provide a preparation method and application of a core-shell structure material. The invention takes a ZnO wire rod as a base material, and prepares the ZnO @ AgSbS by spin-coating and calcining a simple metal sulfide precursor solution 2 A rod core shell material; the core-shell material is used for preparing the perovskite battery in the later stage, and the application of the material in the perovskite battery is developed.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a core-shell material, which comprises the following steps: coating a ZnO seed layer on an FTO substrate, and growing a ZnO nanorod by using a solvothermal method; then coating the ZnO nano-rod with AgNO 3 、SbCl 3 And mixed solution of ethanol of thioacetamide and N, N-dimethylformamide, and finally annealing to obtain the core-shell material.
Further, the preparation method of the ZnO nanorod comprises the following steps: and (3) putting the FTO substrate with the ZnO seed layer into a mixed solution containing zinc nitrate, hexamethylenetetramine and hexamethylphosphoric triamide for reaction for 2-4h at 90 ℃.
Further, the molar ratio of zinc nitrate, hexamethylenetetramine and hexamethylphosphoric triamide in the mixed solution is 4-6:4-5:0.4-0.6. In some specific embodiments, the concentrations of zinc nitrate, hexamethylenetetramine and hexamethylphosphoric triamide in the mixed solution are 0.05mol/L, 0.045mol/L and 0.005mol/L, respectively.
Further, the preparation method of the solution for the ZnO seed layer comprises the following steps: 2.95g of zinc acetate was dissolved in 120mL of ethanol solution, and then an ethanol solution containing KOH (1.45 mg of KOH was dissolved in 60mL of ethanol) was dropped dropwise and heated at 65 ℃ for 20min.
Further, the AgNO-containing material 3 、SbCl 3 And thioacetamide, or other solutions containing silver ions, antimony ions, and a sulfur source, as long as a single AgSbS can be formed 2 And (4) finishing.
Further, the structure of the core-shell material is ZnO @ AgSbS 2 The structure can also be ZnO @ AgBiS 2 、ZnO@CuBiS 2 、ZnO@Ag 3 CuS 2 、ZnO@CuSbS 2 、ZnO@Ag 3 Cu X Zn 1-X S 2 、ZnO@AgBi X Sb 1-X S 2 Any one of the above, znO @ Ag 3 Cu X Zn 1-X S 2 、ZnO@AgBi X Sb 1-X S 2 Wherein X is any value between 0 and 1.
Further, the AgNO-containing material 3 、SbCl 3 And mixed solution of thioacetamide, ethanol and N, N-dimethylformamide, agNO 3 、SbCl 3 The mol ratio of thioacetamide is 0.9-1.1:1.0-1.2:1.9-2.2, the volume ratio of ethanol to N, N-dimethylformamide is 1:1-10.
Further, the AgNO-containing material 3 、SbCl 3 And mixed solution of thioacetamide with ethanol and N, N-dimethylformamide, agNO 3 The concentration of (B) is 0.01 to 1mol/L, preferably 0.1mol/L.
Further, the AgNO-containing material 3 、SbCl 3 And thioacetamide, or N, N-dimethylformamide, or dimethyl sulfoxide.
Further, theThe annealing comprises the following steps: coating ZnO nano-rod with AgNO 3 、SbCl 3 And a N, N dimethylformamide solution of thioacetamide, calcining for 4-7min at 200 ℃, and repeating the calcining step for 4-6 times; then, the core-shell material is obtained by calcining the core-shell material for 25 to 35min at 350 ℃ after being washed by N, N dimethylformamide.
Further, the core-shell material obtained by the preparation method.
Further, the core-shell material obtained by the preparation method or the application of the core-shell material in preparation of perovskite batteries.
Further, the preparation method of the perovskite battery comprises the following steps: and coating poly 3-hexylthiophene on the core-shell material, annealing at 150-170 ℃ for 8-12min, cooling, and then evaporating silver or gold electrodes to assemble the perovskite battery.
The @ s appearing throughout all represent being coated.
In some embodiments, the core-shell material is prepared by the following steps:
(1) Preparation of ZnO seed solution: dissolving 2.95g of zinc acetate in 120mL of ethanol solution, then dropping an ethanol solution containing KOH drop by drop (1.45 mg of KOH in 60mL of ethanol), and heating at 65 ℃ for 20min;
(2) Preparing a ZnO nanorod: firstly, spin-coating a ZnO seed layer on an FTO conductive glass substrate, then putting the FTO substrate with the ZnO seed layer into a thermal reaction kettle containing 189.4mg of zinc nitrate, 126.17mg of Hexamethylenetetramine (HMTA), 17.90mg of hexamethylphosphoric triamide (HMPA) and 20mL of water, reacting for 3 hours at 90 ℃, and growing uniform ZnO nanorods, wherein one surface with ZnO seeds faces the bottom of the reaction kettle;
(3)AgSbS 2 preparing a precursor solution: weighing 33.8mg AgNO 3 、45.6mg SbCl 3 30.4mg thioacetamide in 2.7mL of N, N dimethylformamide and 0.3mL of ethanol;
(4)ZnO@AgSbS 2 preparation of the core-shell material: the ZnO nano-rod is cleaned and dried by ethanol, and then is spin-coated with 30-50uL AgSbS at the rotating speed of 2500rmp 2 Calcining the precursor solution at 200 deg.C for 5min, and repeating the steps5 times; washing with N, N-dimethylformamide for 2 times, and annealing in muffle furnace at 350 deg.C for 30min to obtain ZnO @ AgSbS 2 A core-shell material.
The preparation method of the perovskite battery comprises the following steps:
in the above-obtained ZnO @ AgSbS 2 Coating poly 3-hexylthiophene on the core-shell material, annealing at 150-170 ℃ for 8-12min, cooling, and then evaporating silver or gold electrodes to assemble the perovskite battery. The effective area of the battery is 0.0625cm 2 。
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention successfully prepares the ZnO @ AgSbS by simply and precisely controlling the material components of the later-stage metal sulfur salt on the basis of the ZnO wire rod 2 The core-shell structure material of (1);
(2) The preparation method is simple and high in repeatability, realizes the structural variability of the metal sulfide, and develops the application of the material in the perovskite battery.
Drawings
FIG. 1 is an SEM photograph of ZnO nanorods in example 1 at a magnification of 2.00 um;
FIG. 2 shows ZnO @ AgSbS in example 1 2 SEM images of core-shell materials: the magnification is 2.00um (a) and 500nm (b).
Detailed Description
It should be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited.
Example 1
The preparation method of the core-shell material comprises the following steps:
(1) Preparation of ZnO seed solution: dissolving 2.95g of zinc acetate in 120mL of ethanol solution, then dropping an ethanol solution containing KOH drop by drop (1.45 mg of KOH in 60mL of ethanol), and heating at 65 ℃ for 20min;
(2) Preparing ZnO nano-rods: firstly, spin-coating a ZnO seed layer on an FTO conductive glass substrate, then putting the FTO substrate with the ZnO seed layer into a thermal reaction kettle containing 189.4mg of zinc nitrate, 126.17mg of Hexamethylenetetramine (HMTA), 17.90mg of hexamethylphosphoric triamide (HMPA) and 20mL of water, reacting for 3 hours at 90 ℃, and growing uniform ZnO nanorods, wherein one surface with the ZnO seeds faces the bottom of the reaction kettle, and FIG. 1 is an SEM image of the corresponding ZnO nanorods;
(3)AgSbS 2 preparing a precursor solution: weighing 33.8mg AgNO 3 、45.6mg SbCl 3 30.4mg thioacetamide in 2.7mL of N, N dimethylformamide and 0.3mL of ethanol;
(4)ZnO@AgSbS 2 preparation of the core-shell material: the ZnO nano-rod prepared by the method is cleaned and dried by ethanol, and is spin-coated with 30-50uL AgSbS at the rotating speed of 2500rmp 2 Calcining the precursor solution at 200 ℃ for 5min, and repeating the step for 5 times; washing with N, N-dimethylformamide for 2 times, and annealing in muffle furnace at 350 deg.C for 30min to obtain ZnO @ AgSbS 2 Core-shell material, corresponding ZnO @ AgSbS in FIG. 2 2 SEM image of core shell material.
The preparation method of the perovskite battery comprises the following steps:
in the above-obtained ZnO @ AgSbS 2 Coating poly 3-hexylthiophene on the core-shell material, annealing at 160 ℃ for 10min, cooling, and then evaporating silver or gold electrode to assemble the perovskite battery, wherein the effective area of the battery is 0.0625cm 2 (ii) a The photovoltaic efficiency test was performed under standard solar irradiance test conditions (see table 1).
Example 2
The difference from example 1 is that:
(3)AgSbS 2 preparing a precursor solution: weighing 33.8mg AgNO 3 、45.6mg SbCl 3 30.4mg thioacetamide in 3mL of N, N dimethylformamide and 3mL of dimethyl sulfoxide;
obtained ZnO @ AgSbS 2 The core-shell material is used for preparing perovskite cells, and photoelectric efficiency test is carried out under the test condition of standard solar irradiance (see table 1).
Example 3
The difference from example 1 is that:
(3)AgSbS 2 preparing a precursor solution: weighing 16.9mg AgNO 3 、22.8mg SbCl 3 15.2mg of thioacetamideDissolving in 2.7mL of N, N-dimethylformamide and 0.3mL of ethanol;
resulting ZnO @ AgSbS 2 The core-shell material is used for preparing perovskite cells, and photoelectric efficiency test is carried out under the test condition of standard solar irradiance (see table 1).
Example 4
The difference from example 1 is that:
(3)AgBiS 2 preparing a precursor solution: weighing 16.9mg AgNO 3 、39.4mg BiCl 3 15.2mg thioacetamide in 2.7mL of N, N dimethylformamide and 0.3mL of ethanol;
obtained ZnO @ AgBiS 2 The core-shell material is used for preparing perovskite cells, and photoelectric efficiency test is carried out under the test condition of standard solar irradiance (see table 1).
Example 5
The difference from example 1 is that:
(3)AgSbS 2 preparing a precursor solution: weighing 16.9mg AgNO 3 、30.0mg SbCl 3 10.0mg thioacetamide and 15.2mg thiourea were dissolved in 1.5mL of N, N dimethylformamide and 1.5mL of dimethyl sulfoxide;
resulting ZnO @ AgSbS 2 The core-shell material is used for preparing perovskite cells, and photoelectric efficiency test is carried out under the test condition of standard solar irradiance (see table 1).
Comparative example 1
The difference from example 1 is that:
(2) Modification of ZnO substrate: firstly, spin-coating a ZnO seed layer on an FTO conductive glass substrate, then putting the FTO substrate with the ZnO seed layer into a thermal reaction kettle containing 189.4mg of zinc nitrate, 126.17mg of Hexamethylenetetramine (HMTA), 17.90mg of hexamethylphosphoric triamide (HMPA) and 20mL of water, and reacting for 1h at 90 ℃ to grow uniform ZnO nanorods;
obtained ZnO @ AgSbS 2 The core-shell material is used for preparing perovskite cells, and photoelectric efficiency test is carried out under the test condition of standard solar irradiance (see table 1).
TABLE 1 summary of different solar cell performance parameters
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the core-shell material is characterized by comprising the following steps: coating a ZnO seed layer on an FTO substrate, and growing a ZnO nanorod by using a solvothermal method; then coating the ZnO nano-rod with AgNO 3 、SbCl 3 And mixed solution of ethanol of thioacetamide and N, N-dimethylformamide, and finally annealing to obtain the core-shell material.
2. The preparation method of claim 1, wherein the preparation method of the ZnO nanorod comprises the following steps: and (3) putting the FTO substrate with the ZnO seed layer into a mixed solution containing zinc nitrate, hexamethylenetetramine and hexamethylphosphoric triamide for reaction for 2-4h at 90 ℃.
3. The production method according to claim 2, wherein the molar ratio of zinc nitrate, hexamethylenetetramine and hexamethylphosphoric triamide in the mixed solution is 4 to 6:4-5:0.4-0.6.
4. The preparation method according to claim 1, wherein the core-shell material has a structure of ZnO @ AgSbS 2 The structure can also be ZnO @ AgBiS 2 、ZnO@CuBiS 2 、ZnO@Ag 3 CuS 2 、ZnO@CuSbS 2 、ZnO@Ag 3 Cu X Zn 1-X S 2 、ZnO@AgBi X Sb 1-X S 2 Any one of the above, znO @ Ag 3 Cu X Zn 1-X S 2 、ZnO@AgBi X Sb 1-X S 2 Wherein X is any value between 0 and 1.
5. The method of claim 1, wherein the AgNO-containing material is 3 、SbCl 3 And mixed solution of thioacetamide, ethanol and N, N-dimethylformamide, agNO 3 、SbCl 3 The mol ratio of thioacetamide is 0.9-1.1:1.0-1.2:1.9-2.2, the volume ratio of ethanol to N, N-dimethylformamide is 1:1-10.
6. The method of claim 5, wherein the AgNO-containing material is 3 、SbCl 3 And mixed solution of thioacetamide with ethanol and N, N-dimethylformamide, agNO 3 The concentration of (B) is 0.01-1mol/L.
7. The method of manufacturing of claim 1, wherein the annealing comprises the steps of: coating ZnO nano-rod with AgNO 3 、SbCl 3 And a N, N dimethylformamide solution of thioacetamide, calcining for 4-7min at 200 ℃, and repeating the calcining step for 4-6 times; then, the core-shell material is obtained by calcining the core-shell material for 25 to 35min at 350 ℃ after being washed by N, N dimethylformamide.
8. Core-shell material obtainable by the preparation process according to any one of claims 1 to 7.
9. Use of a core-shell material obtained by a preparation method according to any one of claims 1 to 7 or a core-shell material according to claim 8 in the preparation of a perovskite battery.
10. Use according to claim 9, wherein the perovskite battery is prepared by a method comprising the steps of: and coating poly 3-hexylthiophene on the core-shell material, annealing at 150-170 ℃ for 8-12min, cooling, and then evaporating silver or gold electrodes to assemble the perovskite battery.
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