CN111200177B - A kind of lead-halide perovskite light-driven charging electrode and preparation method thereof - Google Patents
A kind of lead-halide perovskite light-driven charging electrode and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 13
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 125000001475 halogen functional group Chemical group 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 58
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lead-halogen perovskite light-driven charging electrode, which comprises the preparation steps of manufacturing a lithium iron phosphate substrate, configuring a perovskite solution, preparing a perovskite light-driven charging electrode, preparing an electrolyte, and connecting and measuring the electrode. Compared with the prior art, the invention has the advantages of simple raw materials, small volume, environmental protection, safety, no toxicity, lower cost, simple and easy operation, simplifies the preparation process of the electrode, and simultaneously uses the sodium sulfate aqueous solution as the electrolyte to ensure that the light-driven charging electrode has the light-driven charging performance in the water phase environment.
Description
Technical Field
The invention belongs to the technical field of synthesis and application of optical functional materials, and particularly relates to a lead-halogen perovskite optical drive charging electrode and a preparation method thereof.
Background
The study of photo-charged cells, the first of which was proposed by Hodes et al in 1976 (Nature 261, 403-. In 2014 Yu et al reported charging lithium-oxygen batteries with the aid of redox-coupled dye photoelectrodes (nat. commun. 5, 5111, 2014). Meanwhile, Li et al in 2015 integrated a titania-based electrode into a three-electrode system containing lithium iron phosphate material (J. mater. chem. A3, 20903-. All these devices have two connected parts: one for solar energy conversion and the other for energy storage. In 2017, Paolella et al (nat. commu. 8, 14643, 2017) reported a two-electrode system involving a ruthenium-containing dye and lithium iron phosphate as a photocathode, lithium metal as an anode and a lithium hexafluorophosphate organocarbonate solvent as an electrolyte. Although the above system solves the problem of the need for two connection portions for photo-charging, the manufacturing process is complicated and costly.
Aiming at the problems, the invention adopts the preparation method of the lead-halogen perovskite light-driven charging electrode, simplifies the preparation process of the electrode, and simultaneously uses the sodium sulfate aqueous solution as the electrolyte to ensure that the light-driven charging electrode works in the water phase environment. This improvement not only makes the preparation method simpler, but also makes the system more environmentally friendly.
Disclosure of Invention
The invention aims to solve the problems of difficult preparation and high cost of the light charging battery material in the prior art, and provides a lead-halogen perovskite light-driven charging electrode material and a preparation method thereof.
The invention adopts the following technical scheme:
a lead-halogen perovskite light-driven charging electrode is prepared by mixing LiFePO with a metal oxide4The ball-milling mixture obtained by mixing and ball-milling SUPER P Li, PVDF, 1-methyl-2-pyrrolidone and alcohol is coated on FTO as a lithium iron phosphate substrate, and a perovskite solution is dripped on the lithium iron phosphate substrate and dried to prepare the lithium iron phosphate.
Further, the manufacturing method of the lead-halogen perovskite light-driven charging electrode comprises the following steps:
s1 and manufacturing of lithium iron phosphate substrate
Mixing LiFePO4Mixing SUPER P Li and PVDF, adding 1-methyl-2-pyrrolidone and alcohol, ball milling for 1-3 h, coating the ball milled mixture on FTO, drying, heating to 400 ℃ at a heating rate of 4-6 ℃ per minute in an argon environment, continuously heating for 1-3 h, and naturally cooling to obtain a lithium iron phosphate substrate;
s2 preparation of perovskite solution
The perovskite solution is a first solution or a second solution prepared as follows;
preparation method of solution I: uniformly mixing lead iodide, methylamine hydroiodide and DMSO solution, stirring for 30-60min, and preparing 0.1mol/l perovskite solution as a first solution;
preparation method of solution II: uniformly mixing lead iodide, methylamine hydroiodide and DMSO solution, stirring for 30-60min, and preparing 0.2mol/l perovskite solution as second solution;
s3 preparation of perovskite light-driven charging electrode
The perovskite light-driven charging electrode is one of a first electrode, a second electrode and a third electrode which are prepared in the following way;
the preparation method of the first electrode comprises the following steps: dripping 20 mul of the first solution on the lithium iron phosphate substrate prepared in S1, drying at 110 ℃, continuing dripping 20 mul of the first solution after drying, and drying at 110 ℃ to obtain a first electrode;
the preparation method of the second electrode comprises the following steps: dripping 20 mul of the second solution on the lithium iron phosphate substrate prepared in S1, and drying at 110 ℃ to obtain a second electrode;
the preparation method of the third electrode comprises the following steps: dripping 20 mul of the first solution on the lithium iron phosphate substrate prepared in S1, drying at 80 ℃, continuing dripping 20 mul of the first solution after drying, and drying at 80 ℃ to obtain a third electrode;
s4 preparation of electrolyte
Adding deionized water into sodium sulfate, and stirring to prepare 0.25mol/L sodium sulfate solution to obtain electrolyte;
s5 connection and measurement of electrodes
Taking a platinum sheet as a counter electrode; Ag/AgCl is used as a reference electrode; connecting the red copper electrode with the conductive surface of the first electrode, the second electrode or the third electrode prepared in S3 to be used as a working electrode; and the photocurrent and photovoltage of each electrode were tested in S3.
Further, in S1, LiFePO4The mixing ratio of SUPER P Li to PVDF is as follows: 7:2:1.
Further, in S1, the drying temperature is 30-50 ℃.
Further, in S2, the preparation method of the solution one is: 0.4610g of lead iodide, 0.1590g of methylamine hydroiodide and 10ml of DMSO solution are taken and uniformly mixed, and stirred for 30-60min to obtain 0.1mol/l of perovskite solution; the preparation method of the solution II comprises the following steps: 0.4610g of lead iodide, 0.1590g of methylamine hydroiodide and 5ml of DMSO solution are uniformly mixed and stirred for 30-60min to obtain 0.2mol/l of perovskite solution.
Further, in S4, the preparation method of the electrolyte solution includes: 2.1306g of sodium sulfate is taken and added into 60ml of deionized water, and the mixture is stirred for ten minutes to obtain electrolyte
The invention has the beneficial effects that:
compared with the prior art, the invention has the advantages of simple raw materials, small volume, environmental protection, safety, no toxicity, low cost, simple and easy operation and simplified preparation process of the electrode, simultaneously uses the sodium sulfate aqueous solution as the electrolyte, leads the light-driven charging electrode to have light-driven charging performance in an aqueous phase environment, skillfully combines the perovskite and the lithium iron phosphate together, and leads the charging and the discharging to be carried out in the same system. The preparation method is simple, and the electrode material does not contain noble metal elements, so that the system is more environment-friendly.
Description of the drawings:
FIG. 1 shows the photocurrent measured by the lead-halo perovskite photo-driven charging electrode material obtained in example 1;
FIG. 2 is a photo-voltage measured for the lead-halo perovskite photo-driven charging electrode material obtained in example 1;
FIG. 3 shows the photocurrent measured by the lead-halo perovskite photo-driven charging electrode material obtained in example 2;
FIG. 4 is a photo-voltage measured for the lead-halo perovskite photo-driven charging electrode material obtained in example 2;
FIG. 5 shows the photocurrent measured by the lead-halo perovskite photo-driven charging electrode material obtained in example 3;
fig. 6 is a photo-voltage measured for the lead-halo perovskite photo-driven charging electrode material obtained in example 3.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
A lead-halogen perovskite light-driven charging electrode is prepared by mixing LiFePO with a metal oxide4The ball-milling mixture obtained by mixing and ball-milling SUPER P Li, PVDF, 1-methyl-2-pyrrolidone and alcohol is coated on FTO as a lithium iron phosphate substrate, and a perovskite solution is dripped on the lithium iron phosphate substrate and dried to prepare the lithium iron phosphate.
Specifically, the manufacturing method of the lead-halogen perovskite light-driven charging electrode comprises the following steps:
s1 and manufacturing of lithium iron phosphate substrate
Mixing LiFePO4SUPER P Li mixed with PVDF, LiFePO4The mixing ratio of SUPER P Li to PVDF is as follows: 7:2:1, adding 1-methyl-2-pyrrolidone and alcohol, ball milling for 1-3 h, coating the ball milling mixture on FTO by scraping, drying at 30-50 ℃, heating to 400 ℃ at a heating rate of 5 ℃ per minute in an argon environment, continuously heating for 1-3 h, and naturally cooling to obtain a lithium iron phosphate substrate;
s2 preparation of perovskite solution
The perovskite solution is a first solution or a second solution prepared as follows;
preparation method of solution I: 0.4610g of lead iodide, 0.1590g of methylamine hydroiodide and 10ml of DMSO solution are taken and uniformly mixed, and stirred for 30-60min to obtain 0.1mol/l of perovskite solution as a first solution;
preparation method of solution II: 0.4610g of lead iodide, 0.1590g of methylamine hydroiodide and 5ml of DMSO solution are taken and uniformly mixed, and stirred for 30-60min to obtain 0.2mol/l of perovskite solution as a second solution;
s3 preparation of perovskite light-driven charging electrode
The perovskite light-driven charging electrode is one of a first electrode, a second electrode and a third electrode which are prepared in the following way;
the preparation method of the first electrode comprises the following steps: dripping 20 mul of the first solution on the lithium iron phosphate substrate prepared in S1, drying at 110 ℃, continuing dripping 20 mul of the first solution after drying, and drying at 110 ℃ to obtain a first electrode;
the preparation method of the second electrode comprises the following steps: dripping 20 mul of the second solution on the lithium iron phosphate substrate prepared in S1, and drying at 110 ℃ to obtain a second electrode;
the preparation method of the third electrode comprises the following steps: dripping 20 mul of the first solution on the lithium iron phosphate substrate prepared in S1, drying at 80 ℃, continuing dripping 20 mul of the first solution after drying, and drying at 80 ℃ to obtain a third electrode;
s4 preparation of electrolyte
2.1306g of sodium sulfate is taken and added into 60ml of deionized water, and stirring is carried out for ten minutes to obtain electrolyte;
s5 connection and measurement of electrodes
Taking a platinum sheet as a counter electrode; Ag/AgCl is used as a reference electrode; connecting the red copper electrode with the conductive surface of the first electrode, the second electrode or the third electrode prepared in S3 to be used as a working electrode; and the photocurrent and photovoltage of each electrode were tested in S3.
Example 1
A preparation method of a lead-halogen perovskite light-driven charging electrode comprises the following steps:
s1, mixing LiFePO 4: SUPER P Li: PVDF =7:2:1, adding 1-methyl-2-pyrrolidone and alcohol, ball-milling for two hours, coating the mixture on FTO by scraping, drying at 40 ℃, heating to 400 ℃ at a heating rate of 5 ℃ per minute in an argon environment, continuously heating for two hours, and then naturally cooling to obtain a lithium iron phosphate substrate;
s2, 0.4610g of lead iodide, 0.1590g of methylamine hydroiodide and 10ml of DMSO solution are uniformly mixed and stirred for thirty minutes to obtain 0.1mol/l of perovskite solution;
s3, dropwise adding 20 mu l of perovskite solution on the lithium iron phosphate substrate prepared in S1, drying at 110 ℃, continuously dropwise adding 20 mu l of perovskite solution, and drying at 110 ℃ to obtain a light-driven charging electrode;
s4, adding 2.1306g of sodium sulfate into 60ml of deionized water, and stirring for ten minutes to obtain electrolyte;
s5, taking a platinum sheet as a counter electrode; Ag/AgCl is used as a reference electrode; the red copper electrode is connected with the conductive surface of the light-driven charging electrode prepared in S3 and used as a working electrode to respectively test the photocurrent and the photovoltage of the light-driven charging electrode, the test results are shown in figures 1 and 2, as can be seen from figure 1, the maximum value of the photocurrent can reach 20 microamperes per square centimeter, the photoelectric conversion efficiency of the system is very high, as can be seen from figure 2, the increase of the photovoltage exceeds 0.04V, and the light-driven charging performance of the system is very good, so that the light-driven charging performance of the charging electrode prepared in the embodiment is good.
Example 2
A preparation method of a lead-halogen perovskite light-driven charging electrode comprises the following steps:
s1, mixing LiFePO 4: SUPER P Li: PVDF =7:2:1, adding 1-methyl-2-pyrrolidone and alcohol, ball-milling for two hours, coating the mixture on FTO by scraping, drying at 40 ℃, heating to 400 ℃ at a heating rate of 5 ℃ per minute in an argon environment, continuously heating for two hours, and then naturally cooling to obtain a lithium iron phosphate substrate;
s2, 0.4610g of lead iodide, 0.1590g of methylamine hydroiodide and 5ml of DMSO solution are uniformly mixed and stirred for thirty minutes to obtain 0.2mol/l of perovskite solution;
s3, dripping 20 mu l of perovskite solution on the lithium iron phosphate substrate prepared in the S1, and drying at 110 ℃ to obtain the light-driven charging electrode;
s4, adding 2.1306g of sodium sulfate into 60ml of deionized water, and stirring for ten minutes to obtain electrolyte;
s5, taking a platinum sheet as a counter electrode; Ag/AgCl is used as a reference electrode; the red copper electrode is connected with the conductive surface of the light-driven charging electrode prepared in S3 and used as a working electrode to respectively test the photocurrent and the photovoltage of the light-driven charging electrode, the test results are shown in figures 3 and 4, as can be seen from figure 3, the maximum numerical value of the photocurrent can reach 6 microamperes per square centimeter, the photoelectric conversion efficiency of the system is good, as can be seen from figure 4, the increase of the photovoltage exceeds 0.02V, and the light-driven charging performance of the system is good, so that the light-driven charging performance of the charging electrode prepared in the embodiment is good.
Example 3
A preparation method of a lead-halogen perovskite light-driven charging electrode comprises the following steps:
s1, mixing LiFePO 4: SUPER P Li: PVDF =7:2:1, adding 1-methyl-2-pyrrolidone and alcohol, ball-milling for two hours, coating the mixture on FTO by scraping, drying at 40 ℃, heating to 400 ℃ at a heating rate of 5 ℃ per minute in an argon environment, continuously heating for two hours, and then naturally cooling to obtain a lithium iron phosphate substrate;
s2, 0.4610g of lead iodide, 0.1590g of methylamine hydroiodide and 10ml of DMSO solution are uniformly mixed and stirred for thirty minutes to obtain 0.1mol/l of perovskite solution;
s3, dropwise adding 20 mu l of perovskite solution on the lithium iron phosphate substrate prepared in the S1, drying at 80 ℃, continuously dropwise adding 20 mu l of perovskite solution, and drying at 80 ℃ to obtain a light-driven charging electrode;
s4, adding 2.1306g of sodium sulfate into 60ml of deionized water, and stirring for ten minutes to obtain electrolyte;
s5, taking a platinum sheet as a counter electrode; Ag/AgCl is used as a reference electrode; the red copper electrode is connected with the conductive surface of the optical drive charging electrode prepared in S3 and used as a working electrode to respectively test the photocurrent and the photovoltage of the optical charge electrode, the test result is shown in figures 5 and 6, as can be seen from figure 5, the maximum value of the photocurrent can reach 5 microamperes per square centimeter, the photoelectric conversion efficiency of the system is good, as can be seen from figure 6, the increase of the photovoltage exceeds 0.03V, the optical charge performance of the system is good, and therefore, the optical drive charging performance of the charging electrode prepared in the embodiment is good.
Compared with the prior art, the invention has the advantages of simple raw materials, small volume, environmental protection, safety, no toxicity, lower cost, simple and easy operation, simplifies the preparation process of the electrode, and simultaneously uses the sodium sulfate aqueous solution as the electrolyte to ensure that the light-driven charging electrode has the light-driven charging performance in the water phase environment.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention, it should be noted that, for those skilled in the art, several modifications and decorations without departing from the principle of the present invention should be regarded as the protection scope of the present invention.
Claims (5)
1. A lead-halogen perovskite light-driven charging electrode is characterized in that the electrode is prepared by mixingLiFePO4The electrode is prepared by coating a ball-milled mixture obtained by mixing and ball milling SUPER P Li, PVDF, 1-methyl-2-pyrrolidone and alcohol on FTO as a lithium iron phosphate substrate, dripping a perovskite solution on the lithium iron phosphate substrate and drying, and the electrode is directly contacted with a sodium ion electrolyte; the manufacturing method comprises the following steps:
s1 and manufacturing of lithium iron phosphate substrate
Mixing LiFePO4Mixing SUPER P Li and PVDF, adding 1-methyl-2-pyrrolidone and alcohol, ball milling for 1-3 h, coating the ball milled mixture on FTO, drying, heating to 400 ℃ at a heating rate of 4-6 ℃ per minute in an argon environment, continuously heating for 1-3 h, and naturally cooling to obtain a lithium iron phosphate substrate;
s2 preparation of perovskite solution
The perovskite solution is a first solution or a second solution prepared as follows;
preparation method of solution I: uniformly mixing lead iodide, methylamine hydroiodide and DMSO solution, stirring for 30-60min, and preparing 0.1mol/l perovskite solution as a first solution;
preparation method of solution II: uniformly mixing lead iodide, methylamine hydroiodide and DMSO solution, stirring for 30-60min, and preparing 0.2mol/l perovskite solution as second solution;
s3 preparation of perovskite light-driven charging electrode
The perovskite light-driven charging electrode is one of a first electrode, a second electrode and a third electrode which are prepared in the following way;
the preparation method of the first electrode comprises the following steps: dripping 20 mul of the first solution on the lithium iron phosphate substrate prepared in S1, drying at 110 ℃, continuing dripping 20 mul of the first solution after drying, and drying at 110 ℃ to obtain a first electrode;
the preparation method of the second electrode comprises the following steps: dripping 20 mul of the second solution on the lithium iron phosphate substrate prepared in S1, and drying at 110 ℃ to obtain a second electrode;
the preparation method of the third electrode comprises the following steps: dripping 20 mul of the first solution on the lithium iron phosphate substrate prepared in S1, drying at 80 ℃, continuing dripping 20 mul of the first solution after drying, and drying at 80 ℃ to obtain a third electrode;
s4 preparation of electrolyte
Adding deionized water into sodium sulfate, and stirring to prepare 0.25mol/L sodium sulfate solution to obtain electrolyte;
s5 connection and measurement of electrodes
Taking a platinum sheet as a counter electrode; Ag/AgCl is used as a reference electrode; connecting the red copper electrode with the conductive surface of the first electrode, the second electrode or the third electrode prepared in S3 to be used as a working electrode; and the photocurrent and photovoltage of each electrode were tested in S3.
2. The lead-halo perovskite optically-driven charging electrode as claimed in claim 1, wherein in S1 LiFePO4The mixing ratio of SUPER P Li to PVDF is as follows: 7:2:1.
3. The lead-halo perovskite optically-driven charge electrode as claimed in claim 1, wherein in S1, the baking temperature is 30-50 ℃.
4. The lead-halo perovskite optically-driven charge electrode as claimed in claim 1, wherein in S2, the first solution is prepared by: 0.4610g of lead iodide, 0.1590g of methylamine hydroiodide and 10ml of DMSO solution are taken and uniformly mixed, and stirred for 30-60min to obtain 0.1mol/l of perovskite solution; the preparation method of the solution II comprises the following steps: 0.4610g of lead iodide, 0.1590g of methylamine hydroiodide and 5ml of DMSO solution are uniformly mixed and stirred for 30-60min to obtain 0.2mol/l of perovskite solution.
5. The lead-halo perovskite optically-driven charge electrode as claimed in claim 1, wherein in S4, the electrolyte is prepared by: 2.1306g of sodium sulfate is added into 60ml of deionized water, and stirred for ten minutes to obtain electrolyte.
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