CN113299481A - Near-infrared quantum dot sensitized photo-anode, preparation method thereof and battery comprising photo-anode - Google Patents
Near-infrared quantum dot sensitized photo-anode, preparation method thereof and battery comprising photo-anode Download PDFInfo
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Abstract
The invention discloses a near-infrared quantum dot sensitized photo-anode, a preparation method thereof and a battery comprising the photo-anode, the near-infrared quantum dot sensitized photo-anode comprises the preparation method of the near-infrared quantum dot sensitized photo-anode, and the synthesis steps are as follows: synthesizing quantum dot CuInSeS; synthesizing core-shell quantum dots CuInSeS @ ZnS; synthesizing a near-infrared quantum dot CuInSeS @ ZnS sensitized bismuth vanadate photo-anode; the solar cell also comprises a near-infrared quantum dot sensitized photoanode and a cell of the photoanode. The common titanium dioxide photo-anode with ultraviolet response is replaced by the bismuth vanadate photo-anode with visible light response, so that the problems that the traditional titanium dioxide photo-anode is weak in visible light absorption, and the existing photoelectrochemical cell is low in activity, low in stability, high in toxicity, strong in electrolyte alkalinity and consumes a sacrificial agent are solved.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a near-infrared quantum dot sensitized photo-anode, a preparation method thereof and a battery comprising the photo-anode.
Background
The photoelectrochemical cell technology is a novel cell technology which directly utilizes light energy and converts the light energy into chemical energy, generally comprises a photoelectrode with light activity, electrolyte and a circuit, and has the characteristics of simple structure, high efficiency, low cost and the like. Compared with the technology of hydrogen production by adopting photovoltaic power generation and water re-electrolysis, the method has the advantage of lower device preparation cost. At present, the photoelectrochemical cell hydrogen production technology is not put into practical application in a large scale, and the activity and the stability of photoelectrode materials are low; the electrolyte is usually strong in alkalinity, and a large amount of sacrificial agents are required to be added additionally to consume the photogenerated holes; the area of the photoelectrode is only 0.1-10 cm mostly at present2Far below the working area of the photovoltaic panel, limiting the practical application of this technique. Therefore, the preparation of the photoelectrochemical cell by adopting the novel photoelectrochemical cell technology has important significance for expanding the technical field of the photoelectrochemical cell and meeting the requirements of social production and life.
At present, quantum dots have the characteristics of adjustable energy band structure, wide spectrum absorption and the like and are widely applied to photoelectrochemical cells, but most of the quantum dots contain toxic heavy metals such as lead, cadmium and the like, and in recent years, the economic development concept of environmental protection is vigorously carried out at home and abroad, so that the further development of the technology is limited. Therefore, there is a need for a near-infrared quantum dot sensitized photo-anode, a method for preparing the same, and a battery including the photo-anode to solve the above technical problems.
Disclosure of Invention
Aiming at the prior art, the invention provides a near-infrared quantum dot sensitized photoanode, a preparation method thereof and a battery comprising the photoanode, so as to solve the problems that the traditional titanium dioxide photoanode has weak visible light absorption and the existing photoelectrochemical battery has low activity, low stability, high toxicity, strong alkalinity of electrolyte and sacrificial agent consumption.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of the near-infrared quantum dot sensitized photo-anode comprises the following steps:
s1: co-dissolving cuprous iodide and indium acetate in the mixed solution I to obtain a copper indium solution; dissolving selenium powder in the mixed solution II to obtain a selenium solution; mixed solution one was prepared from dodecyl mercaptan and oleylamine in a ratio of 5: 0.5-2, wherein the mixed solution is prepared by mixing dodecyl mercaptan and oleylamine according to a volume ratio of 1: 2-4 by volume ratio;
s2: dropwise adding the selenium solution into a copper indium solution heated to 200-220 ℃, carrying out heat preservation reaction for 8-15 min, then heating to 230-240 ℃, and carrying out heat preservation reaction for 15-25 min to obtain a quantum dot CuInSeS solution;
s3: dissolving oleic acid and zinc acetate in octadecene to obtain a zinc oleate solution; dropwise adding the quantum dot CuInSeS solution into a zinc oleate solution heated to 150-180 ℃, and carrying out heat preservation reaction for 15-25 min to obtain core-shell quantum dot CuInSeS @ ZnS;
s4: and (3) constructing an electrophoresis device by using a bismuth vanadate electrode as a working electrode, a blank FTO glass as a counter electrode and a core-shell quantum dot CuInSeS @ ZnS toluene solution as a deposition solution, and depositing for 1.5-3 h under the voltage of 180-220V to obtain the near-infrared quantum dot CuInSeS @ ZnS sensitized photoanode.
Further, the concentration of cuprous iodide in the copper indium solution is 0.1-0.2 mmol/ml, and the concentration of indium acetate in the copper indium solution is 0.1-0.2 mmol/ml; the concentration of selenium in the selenium solution is 0.8-1.2 mmol/ml.
Further, the volume ratio of the dodecanethiol to the oleylamine in the mixed solution one is 5: 1; the volume ratio of the dodecanethiol to the oleylamine in the mixed solution was 1: 3.
further, in S2, dropwise adding a selenium solution into a copper indium solution with the temperature of 210 ℃, carrying out heat preservation reaction for 10min, then heating to 235 ℃, and carrying out heat preservation reaction for 20min to obtain a quantum dot CuInSeS solution; the volume ratio of the selenium solution to the copper indium solution is 1: 2-4.
Further, the concentration of zinc acetate in the zinc oleate solution is 0.02-0.03 g/ml; the concentration of the oleic acid is 0.08-0.10 g/ml.
Further, in S3, dropwise adding the quantum dot CuInSeS solution into a zinc oleate solution heated to 160 ℃, and carrying out heat preservation reaction for 20min to obtain the core-shell quantum dot CuInSeS @ ZnS; the volume ratio of the quantum dot CuInSeS solution to the zinc oleate solution is 1: 8-10.
Further, the bismuth vanadate in the bismuth vanadate electrode is prepared by the following steps:
s1: constructing an electrochemical deposition device by taking FTO (fluorine-doped tin oxide) glass as a deposition electrode, an Ag/AgCl electrode containing 3mol/L potassium chloride as a reference electrode and a mixed solution of potassium iodide/bismuth nitrate/p-benzoquinone as an electrolyte, applying a voltage of-0.1V to the deposition electrode relative to the Ag/AgCl reference electrode containing 3mol/L potassium chloride, and depositing for 280-320 s to obtain bismuth oxyiodide; the pH value of the electrolyte is 1.7, wherein the concentration of potassium iodide is 0.27-0.29 mol/L, the concentration of bismuth nitrate is 0.27-0.29 mol/L, and the concentration of p-benzoquinone is 0.05-0.07 mol/L;
s2: dissolving vanadyl acetylacetonate in an organic solvent to prepare a solution with the concentration of 0.2 mol/L; and then coating the obtained solution on the surface of bismuth oxyiodide, heating to 430-460 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 1-3 h, and then naturally cooling and washing to obtain the bismuth vanadate.
In addition, the invention also provides a near-infrared quantum dot sensitized photo-anode. The obtained photo-anode has obvious performance advantages as the anode of the electrochemical cell, and the absorption efficiency of the photo-anode to the light energy is greatly improved compared with the photoelectrochemical cell prepared by the traditional photo-anode structure.
In addition, the invention also provides a photoelectrochemical cell which comprises a photoanode, a platinum counter electrode, a reference electrode and electrolyte; the photo-anode is the near-infrared quantum dot sensitized photo-anode prepared by the method; the reference electrode is a 3mol/L potassium chloride Ag/AgCl reference electrode; the electrolyte is a potassium borate solution, and the pH value is 8.8-9.2. Compared with the pH value (generally 12.5) of other quantum dot sensitized photoelectrochemical cells, the pH value of the photoelectrochemical cell is lower, the consumption of alkali is reduced, and the requirement on alkali resistance of cell equipment is lowered.
The invention has the beneficial effects that: the method is simple and easy to operate; the preparation method of the invention is adopted to prepare the near-infrared response photo-anode to obtain the photo-anode structure, bismuth vanadate is used as a sensitization electrode for the first time to replace the prior titanium dioxide electrode, the photoelectrochemical cell prepared by using the photo-anode structure does not contain any toxic heavy metal such as lead, cadmium and the like, no sacrificial agent such as sodium sulfite and the like is added, the electrolyte is a potassium borate solution, the pH value is only 8.8-9.2, the use of a strong alkaline high-concentration sodium sulfide solution containing a cavity sacrificial agent sodium sulfite and commonly used for quantum dot photoelectrochemical cells is avoided, and the absorption and utilization of visible light are enhanced.
Drawings
FIG. 1 is a schematic diagram of a near-infrared responsive photoanode;
FIG. 2 is an electron microscope scan of a near-infrared responsive photoanode;
fig. 3 is a diagram of the operating state of a near-infrared responsive photoelectrochemical cell.
Detailed Description
The following examples are provided to illustrate specific embodiments of the present invention.
Example 1:
a photoelectrochemical cell, prepared by the steps of:
s1: and (3) preparing bismuth oxyiodide. Firstly, preparing 50.0mL of electrochemical deposition solution containing potassium iodide and bismuth nitrate, wherein the concentrations of the potassium iodide and the bismuth nitrate are both 0.4 mol/L; adding nitric acid solution into the prepared electrochemical deposition solution to adjust the pH value to 1.7; then, adding 20mL of p-benzoquinone water solution with the concentration of 0.23mol/L into the electrochemical deposition solution with the adjusted pH value, and stirring for 20 minutes; finally, using FTO conductive glass as a working electrode, a platinum sheet electrode as a counter electrode, and an Ag/AgCl electrode containing 3mol/L potassium chloride as a reference electrode; and applying a voltage of-0.1V to the electrochemical deposition electrode by adopting an Ag/AgCl reference electrode corresponding to 3mol/L potassium chloride for electrochemical deposition, wherein the three-electrode electrochemical deposition method is to deposit 1.0cm multiplied by 1.0cm bismuth oxyiodide on 1.0cm multiplied by 2.0cm FTO conductive glass, and the deposition time is 300 seconds, so that the bismuth oxyiodide is prepared.
S2: the bismuth oxyiodide is converted into bismuth vanadate. Firstly, preparing a dimethyl sulfoxide solution containing 0.2mol/L vanadyl acetylacetonate, and dropwise adding 100 mu L of the prepared dimethyl sulfoxide solution on bismuth oxyiodide by using a liquid transfer gun; then, heating the dropwise added bismuth oxyiodide to 450 ℃ in a muffle furnace at the heating rate of 2 ℃/min, maintaining for 2 hours, naturally cooling to obtain a mixture containing bismuth vanadate and vanadium pentoxide, putting the mixture into 1mol/L potassium hydroxide solution, and soaking for 30 minutes to dissolve the vanadium pentoxide; and finally, washing the bismuth vanadate with deionized water to prepare the bismuth vanadate converted from the bismuth oxyiodide.
S3: and (3) constructing the photoelectrochemical cell by using the prepared bismuth vanadate as a photoanode, a platinum electrode as a counter electrode, a 3mol/L potassium chloride Ag/AgCl electrode as a reference electrode and a potassium borate aqueous solution with the pH value of 9.0 and the concentration of 0.5mol/L as an electrolyte.
Example 2:
a photoelectrochemical cell, prepared by the steps of:
s1: and (3) preparing bismuth oxyiodide. Firstly, preparing 50.0mL of electrochemical deposition solution containing potassium iodide and bismuth nitrate, wherein the concentrations of the potassium iodide and the bismuth nitrate are both 0.4 mol/L; adding nitric acid solution into the prepared electrochemical deposition solution to adjust the pH value to 1.7; then, adding 20mL of p-benzoquinone water solution with the concentration of 0.23mol/L into the electrochemical deposition solution with the adjusted pH value, and stirring for 20 minutes; finally, using FTO conductive glass as a working electrode, a platinum sheet electrode as a counter electrode, and an Ag/AgCl electrode containing 3mol/L potassium chloride as a reference electrode; and applying a voltage of-0.1V to the electrochemical deposition electrode by adopting an Ag/AgCl reference electrode corresponding to 3mol/L potassium chloride for electrochemical deposition, wherein the three-electrode electrochemical deposition method is to deposit 1.0cm multiplied by 1.0cm bismuth oxyiodide on 1.0cm multiplied by 2.0cm FTO conductive glass, and the deposition time is 300 seconds, so that the bismuth oxyiodide is prepared.
S2: the bismuth oxyiodide is converted into bismuth vanadate. Firstly, preparing a dimethyl sulfoxide solution containing 0.2mol/L vanadyl acetylacetonate, and dropwise adding 100 mu L of the prepared dimethyl sulfoxide solution on bismuth oxyiodide by using a liquid transfer gun; then, heating the dropwise added bismuth oxyiodide to 450 ℃ in a muffle furnace at the heating rate of 2 ℃/min, maintaining for 2 hours, naturally cooling to obtain a mixture containing bismuth vanadate and vanadium pentoxide, putting the mixture into 1mol/L potassium hydroxide solution, and soaking for 30 minutes to dissolve the vanadium pentoxide; and finally, washing the bismuth vanadate with deionized water to prepare the bismuth vanadate converted from the bismuth oxyiodide.
S3: and synthesizing the quantum dot CuInSeS. First, 1mmol of cuprous iodide, 1mmol of indium acetate, 5mL of dodecanethiol, and 1mL of oleylamine were taken in a 50mL three-necked flask, degassed at 90 ℃ for 30 minutes under vacuum, and then heated to 140 ℃ for 15 minutes under a nitrogen atmosphere to ensure complete dissolution of the starting materials to form a copper-indium solution. Meanwhile, 0.5mL of dodecyl mercaptan and 1.5mL of oleylamine are used for dissolving 2mmol of selenium powder to prepare a selenium solution; then, continuously heating the copper indium solution to 210 ℃, slowly dripping the selenium solution into the copper indium solution by using an injector, and after the selenium solution is added, keeping the temperature of 210 ℃ and heating for 10 minutes to nucleate the quantum dots; after the quantum dots are nucleated, heating to 235 ℃ for maintaining for 20 minutes to enable the quantum dots to grow; finally, the reaction apparatus three-necked flask was placed in cold water to quench the reaction, and the reaction liquid was transferred to a centrifuge tube to be collected and stored in a 4 ℃ refrigerator.
S4: the prepared CuInSeS quantum dot sensitized bismuth vanadate is used as a photoanode, a platinum electrode is used as a counter electrode, a 3mol/L potassium chloride Ag/AgCl electrode is used as a reference electrode, and a potassium borate aqueous solution with the pH value of 9.0 and the concentration of 0.5mol/L is used as an electrolyte, so that the photoelectrochemical cell is constructed.
Example 3:
a photoelectrochemical cell, prepared by the steps of:
s1: and (3) preparing bismuth oxyiodide. Firstly, preparing 50.0mL of electrochemical deposition solution containing potassium iodide and bismuth nitrate, wherein the concentrations of the potassium iodide and the bismuth nitrate are both 0.4 mol/L; adding nitric acid solution into the prepared electrochemical deposition solution to adjust the pH value to 1.7; then, adding 20mL of p-benzoquinone water solution with the concentration of 0.23mol/L into the electrochemical deposition solution with the adjusted pH value, and stirring for 20 minutes; finally, using FTO conductive glass as a working electrode, a platinum sheet electrode as a counter electrode, and an Ag/AgCl electrode containing 3mol/L potassium chloride as a reference electrode; and applying a voltage of-0.1V to the electrochemical deposition electrode by adopting an Ag/AgCl reference electrode corresponding to 3mol/L potassium chloride for electrochemical deposition, wherein the three-electrode electrochemical deposition method is to deposit 1.0cm multiplied by 1.0cm bismuth oxyiodide on 1.0cm multiplied by 2.0cm FTO conductive glass, and the deposition time is 300 seconds, so that the bismuth oxyiodide is prepared.
S2: the bismuth oxyiodide is converted into bismuth vanadate. Firstly, preparing a dimethyl sulfoxide solution containing 0.2mol/L vanadyl acetylacetonate, and dropwise adding 100 mu L of the prepared dimethyl sulfoxide solution on bismuth oxyiodide by using a liquid transfer gun; then, heating the dropwise added bismuth oxyiodide to 450 ℃ in a muffle furnace at the heating rate of 2 ℃/min, maintaining for 2 hours, naturally cooling to obtain a mixture containing bismuth vanadate and vanadium pentoxide, putting the mixture into 1mol/L potassium hydroxide solution, and soaking for 30 minutes to dissolve the vanadium pentoxide; and finally, washing the bismuth vanadate with deionized water to prepare the bismuth vanadate converted from the bismuth oxyiodide.
S3: and synthesizing the quantum dot CuInSeS. First, 1mmol of cuprous iodide, 1mmol of indium acetate, 5mL of dodecanethiol, and 1mL of oleylamine were taken in a 50mL three-necked flask, degassed at 90 ℃ for 30 minutes under vacuum, and then heated to 140 ℃ for 15 minutes under a nitrogen atmosphere to ensure complete dissolution of the starting materials to form a copper-indium solution. Meanwhile, 0.5mL of dodecyl mercaptan and 1.5mL of oleylamine are used for dissolving 2mmol of selenium powder to prepare a selenium solution; then, continuously heating the copper indium solution to 210 ℃, slowly dripping the selenium solution into the copper indium solution by using an injector, and after the selenium solution is added, keeping the temperature of 210 ℃ and heating for 10 minutes to nucleate the quantum dots; after the quantum dots are nucleated, heating to 235 ℃ for maintaining for 20 minutes to enable the quantum dots to grow; finally, the reaction apparatus three-necked flask was placed in cold water to quench the reaction, and the reaction liquid was transferred to a centrifuge tube to be collected and stored in a 4 ℃ refrigerator.
S4: synthesizing the core-shell quantum dot CuInSeS @ ZnS. Firstly, 3mmol of oleic acid, 1mmol of zinc acetate and 9mL of octadecene are taken in a 50mL three-necked flask, degassed for 30 minutes at 90 ℃ in a vacuum state, and then heated to 160 ℃ for 15 minutes under a nitrogen atmosphere to ensure that the raw materials are completely dissolved to prepare a zinc oleate solution. Taking 1mL of CuInSeS solution by using an injector, slowly dripping the CuInSeS solution into the prepared zinc oleate solution, keeping the temperature of 160 ℃ for heating for 20 minutes after the addition is finished, and then placing a three-necked flask of the reaction device into cold water for quenching reaction; finally, the reaction liquid was transferred to a centrifuge tube and collected, and stored in a refrigerator at 4 ℃.
S5: a bismuth vanadate photo-anode sensitized by near-infrared quantum dots. Depositing quantum dots into a bismuth vanadate electrode by using an electrophoretic deposition method, firstly, preparing a deposition solution, taking 1mL of CuInSeS @ ZnS solution, adding 4mL of toluene and 7mL of ethanol, fully oscillating, centrifuging to obtain a precipitate, and re-dispersing in 7mL of toluene to serve as the deposition solution; an electrophoresis device is adopted to take the obtained bismuth vanadate electrode as a working electrode, blank FTO glass as a counter electrode, the electrode distance is 1cm, the electrode area is 1cm multiplied by 1cm, a voltage of 200V is applied, and deposition is carried out for 2 hours; and finally obtaining the near-infrared quantum dot CuInSeS @ ZnS sensitized bismuth vanadate photo-anode.
S6: the prepared near-infrared quantum dot CuInSeS @ ZnS sensitized bismuth vanadate is used as a photo-anode, a platinum electrode is used as a counter electrode, a 3mol/L potassium chloride Ag/AgCl electrode is used as a reference electrode, and a potassium borate aqueous solution with the pH value of 9.0 and the concentration of 0.5mol/L is used as an electrolyte, so that the photoelectrochemical cell is constructed.
Example 4:
a photoelectrochemical cell, prepared by the steps of:
s1: and (3) preparing bismuth oxyiodide. Firstly, preparing 50.0mL of electrochemical deposition solution containing potassium iodide and bismuth nitrate, wherein the concentrations of the potassium iodide and the bismuth nitrate are both 0.38 mol/L; adding nitric acid solution into the prepared electrochemical deposition solution to adjust the pH value to 1.7; then, adding 20mL of p-benzoquinone water solution with the concentration of 0.18mol/L into the electrochemical deposition solution with the adjusted pH value, and stirring for 20 minutes; finally, using FTO conductive glass as a working electrode, a platinum sheet electrode as a counter electrode, and an Ag/AgCl electrode containing 3mol/L potassium chloride as a reference electrode; and applying a voltage of-0.1V to the electrochemical deposition electrode by adopting an Ag/AgCl reference electrode corresponding to 3mol/L potassium chloride to perform electrochemical deposition, wherein the three-electrode electrochemical deposition method is to deposit 1.0cm multiplied by 1.0cm bismuth oxyiodide on 1.0cm multiplied by 2.0cm FTO conductive glass, and the deposition time is 280 seconds, so that the bismuth oxyiodide is prepared.
S2: the bismuth oxyiodide is converted into bismuth vanadate. Firstly, preparing a dimethyl sulfoxide solution containing 0.2mol/L vanadyl acetylacetonate, and dropwise adding 100 mu L of the prepared dimethyl sulfoxide solution on bismuth oxyiodide by using a liquid transfer gun; then, heating the dropwise added bismuth oxyiodide to 430 ℃ in a muffle furnace at the heating rate of 2 ℃/min, maintaining for 1 hour, naturally cooling to obtain a mixture containing bismuth vanadate and vanadium pentoxide, putting the mixture into 1mol/L potassium hydroxide solution, and soaking for 30 minutes to dissolve the vanadium pentoxide; and finally, washing the bismuth vanadate with deionized water to prepare the bismuth vanadate converted from the bismuth oxyiodide.
S3: and synthesizing the quantum dot CuInSeS. First, 1mmol of cuprous iodide, 1mmol of indium acetate, 5mL of dodecanethiol and 0.5mL of oleylamine were taken in a 50mL three-necked flask, degassed at 90 ℃ for 30 minutes under vacuum, and then heated to 140 ℃ for 15 minutes under a nitrogen atmosphere to ensure complete dissolution of the starting materials to form a copper-indium solution. Meanwhile, 0.5mL of dodecyl mercaptan and 1mL of oleylamine are used for dissolving 2mmol of selenium powder to prepare a selenium solution; then, continuously heating the copper indium solution to 200 ℃, slowly dripping the selenium solution into the copper indium solution by using an injector, and after the selenium solution is added, keeping the temperature of 200 ℃ and heating for 8 minutes to nucleate the quantum dots; after the quantum dots are nucleated, heating to 230 ℃ and maintaining for 15 minutes to enable the quantum dots to grow; finally, the reaction apparatus three-necked flask was placed in cold water to quench the reaction, and the reaction liquid was transferred to a centrifuge tube to be collected and stored in a 4 ℃ refrigerator.
S4: synthesizing the core-shell quantum dot CuInSeS @ ZnS. Firstly, 2.3mmol of oleic acid, 0.9mmol of zinc acetate and 8mL of octadecene are taken to be placed in a 50mL three-necked flask, degassed at 90 ℃ in a vacuum state for 30 minutes, heated to 160 ℃ in a nitrogen atmosphere for 15 minutes to ensure that the raw materials are completely dissolved to prepare a zinc oleate solution; then, 1mL of CuInSeS solution is taken by an injector, and is slowly dripped into zinc oil solution, after the addition is finished, the reaction device is heated for 15 minutes at 150 ℃, and then a three-necked flask is placed in cold water for quenching reaction; finally, the reaction liquid was transferred to a centrifuge tube and collected, and stored in a refrigerator at 4 ℃.
S5: a bismuth vanadate photo-anode sensitized by near-infrared quantum dots. Depositing quantum dots into a bismuth vanadate electrode by using an electrophoretic deposition method, firstly, preparing a deposition solution, taking 1mL of CuInSeS @ ZnS solution, adding 4mL of toluene and 7mL of ethanol, fully oscillating, centrifuging to obtain a precipitate, and re-dispersing in 7mL of toluene to serve as the deposition solution; an electrophoresis device is adopted to take the obtained bismuth vanadate electrode as a working electrode, blank FTO glass as a counter electrode, the electrode distance is 1cm, the electrode area is 1cm multiplied by 1cm, 180V voltage is applied, and deposition is carried out for 1.5 hours; and finally obtaining the near-infrared quantum dot CuInSeS @ ZnS sensitized bismuth vanadate photo-anode.
S6: the prepared near-infrared quantum dot CuInSeS @ ZnS sensitized bismuth vanadate is used as a photo-anode, a platinum electrode is used as a counter electrode, a 3mol/L potassium chloride Ag/AgCl electrode is used as a reference electrode, and a potassium borate aqueous solution with the pH value of 8.8 and the concentration of 0.5mol/L is used as an electrolyte to construct a photoelectrochemical cell.
Example 5:
a photoelectrochemical cell, prepared by the steps of:
s1: and (3) preparing bismuth oxyiodide. Firstly, preparing 50.0mL of electrochemical deposition solution containing potassium iodide and bismuth nitrate, wherein the concentrations of the potassium iodide and the bismuth nitrate are both 0.41 mol/L; adding nitric acid solution into the prepared electrochemical deposition solution to adjust the pH value to 1.7; then, adding 20mL of p-benzoquinone water solution with the concentration of 0.25mol/L into the electrochemical deposition solution with the adjusted pH value, and stirring for 20 minutes; finally, using FTO conductive glass as a working electrode, a platinum sheet electrode as a counter electrode, and an Ag/AgCl electrode containing 3mol/L potassium chloride as a reference electrode; and applying a voltage of-0.1V to the electrochemical deposition electrode by adopting an Ag/AgCl reference electrode corresponding to 3mol/L potassium chloride for electrochemical deposition, wherein the three-electrode electrochemical deposition method is to deposit 1.0cm multiplied by 1.0cm bismuth oxyiodide on 1.0cm multiplied by 2.0cm FTO conductive glass, and the deposition time is 320 seconds, so that the bismuth oxyiodide is prepared.
S2: the bismuth oxyiodide is converted into bismuth vanadate. Firstly, preparing a dimethyl sulfoxide solution containing 0.2mol/L vanadyl acetylacetonate, and dropwise adding 100 mu L of the prepared dimethyl sulfoxide solution on bismuth oxyiodide by using a liquid transfer gun; then, heating the dropwise added bismuth oxyiodide to 460 ℃ in a muffle furnace at the heating rate of 2 ℃/min, maintaining for 3 hours, naturally cooling to obtain a mixture containing bismuth vanadate and vanadium pentoxide, putting the mixture into 1mol/L potassium hydroxide solution, and soaking for 30 minutes to dissolve the vanadium pentoxide; and finally, washing the bismuth vanadate with deionized water to prepare the bismuth vanadate converted from the bismuth oxyiodide.
S3: and synthesizing the quantum dot CuInSeS. First, 1mmol of cuprous iodide, 1mmol of indium acetate, 5mL of dodecanethiol and 2mL of oleylamine were taken in a 50mL three-necked flask, degassed at 90 ℃ for 30 minutes under vacuum, and then heated to 140 ℃ for 15 minutes under a nitrogen atmosphere to ensure complete dissolution of the starting materials to form a copper-indium solution. Meanwhile, 0.5mL of dodecyl mercaptan and 2mL of oleylamine are used for dissolving 2mmol of selenium powder to prepare a selenium solution; then, continuously heating the copper indium solution to 220 ℃, slowly dripping the selenium solution into the copper indium solution by using an injector, and after the selenium solution is added, keeping the temperature of 220 ℃ and heating for 15 minutes to nucleate the quantum dots; after the quantum dots are nucleated, heating to 240 ℃ for 25 minutes to enable the quantum dots to grow; finally, the reaction apparatus three-necked flask was placed in cold water to quench the reaction, and the reaction liquid was transferred to a centrifuge tube to be collected and stored in a 4 ℃ refrigerator.
S4: synthesizing the core-shell quantum dot CuInSeS @ ZnS. Firstly, 3.5mmol of oleic acid, 1.6mmol of zinc acetate and 10mL of octadecene are taken to be placed in a 50mL three-necked flask, degassed at 90 ℃ in a vacuum state for 30 minutes, heated to 180 ℃ in a nitrogen atmosphere for 25 minutes to ensure that the raw materials are completely dissolved to prepare a zinc oleate solution; then, 1mL of CuInSeS solution is taken by an injector, and is slowly dripped into zinc oil solution, after the addition is finished, the reaction device is heated for 15 minutes at 150 ℃, and then a three-necked flask is placed in cold water for quenching reaction; finally, the reaction liquid was transferred to a centrifuge tube and collected, and stored in a refrigerator at 4 ℃.
S5: a bismuth vanadate photo-anode sensitized by near-infrared quantum dots. Depositing quantum dots into a bismuth vanadate electrode by using an electrophoretic deposition method, firstly, preparing a deposition solution, taking 1mL of CuInSeS @ ZnS solution, adding 4mL of toluene and 7mL of ethanol, fully oscillating, centrifuging to obtain a precipitate, and re-dispersing in 7mL of toluene to serve as the deposition solution; an electrophoresis device is adopted to take the obtained bismuth vanadate electrode as a working electrode, blank FTO glass as a counter electrode, the electrode distance is 1cm, the electrode area is 1cm multiplied by 1cm, a voltage of 220V is applied, and deposition is carried out for 3 hours; and finally obtaining the near-infrared quantum dot CuInSeS @ ZnS sensitized bismuth vanadate photo-anode.
S6: the prepared near-infrared quantum dot CuInSeS @ ZnS sensitized bismuth vanadate is used as a photo-anode, a platinum electrode is used as a counter electrode, a 3mol/L potassium chloride Ag/AgCl electrode is used as a reference electrode, and a potassium borate aqueous solution with the pH value of 9.2 and the concentration of 0.5mol/L is used as an electrolyte, so that the photoelectrochemical cell is constructed.
For the above examples, the performance of the photoelectrochemical cell prepared according to the present invention was tested using a standard am1.5g solar simulator as a light source, 0.5mol/L potassium borate solution as an electrolyte, and PH of the potassium borate solution was 8.8 to 9.2, and the results are shown in table 1.
TABLE 1 photoelectrochemical cell Performance test results parameter Table
As can be seen from the above table, the near-infrared quantum dot sensitized bismuth vanadate photo-anode has excellent efficiency of converting sunlight into hydrogen energy, and the conversion efficiency is improved by more than 2 times; meanwhile, the stability is improved by about 2 times.
While the present invention has been described in detail with reference to the embodiments, it should not be construed as limited to the scope of the patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (9)
1. A preparation method of a near-infrared quantum dot sensitized photo-anode is characterized by comprising the following steps:
s1: co-dissolving cuprous iodide and indium acetate in the mixed solution I to obtain a copper indium solution; dissolving selenium powder in the mixed solution II to obtain a selenium solution; the mixed solution I is prepared from dodecyl mercaptan and oleylamine according to the weight ratio of 5: 0.5-2, wherein the mixed solution is prepared by mixing dodecyl mercaptan and oleylamine according to a volume ratio of 1: 2-4 by volume ratio;
s2: dropwise adding the selenium solution into a copper indium solution heated to 200-220 ℃, carrying out heat preservation reaction for 8-15 min, then heating to 230-240 ℃, and carrying out heat preservation reaction for 15-25 min to obtain a quantum dot CuInSeS solution;
s3: dissolving oleic acid and zinc acetate in octadecene to obtain a zinc oleate solution; dropwise adding the quantum dot CuInSeS solution into a zinc oleate solution heated to 150-180 ℃, and carrying out heat preservation reaction for 15-25 min to obtain core-shell quantum dot CuInSeS @ ZnS;
s4: and (3) constructing an electrophoresis device by using a bismuth vanadate electrode as a working electrode, a blank FTO glass as a counter electrode and a core-shell quantum dot CuInSeS @ ZnS toluene solution as a deposition solution, and depositing for 1.5-3 h under the voltage of 180-220V to obtain the near-infrared quantum dot CuInSeS @ ZnS sensitized photoanode.
2. The method for preparing the near-infrared quantum dot sensitized photo-anode according to claim 1 is characterized in that: the concentration of cuprous iodide in the copper indium solution is 0.1-0.2 mmol/ml, and the concentration of indium acetate in the copper indium solution is 0.1-0.2 mmol/ml; the concentration of selenium in the selenium solution is 0.8-1.2 mmol/ml.
3. The method for preparing the near-infrared quantum dot sensitized photo-anode according to claim 1 is characterized in that: the volume ratio of the dodecyl mercaptan to the oleylamine in the first mixed solution is 5: 1; the volume ratio of the dodecanethiol to the oleylamine in the mixed solution is 1: 3.
4. the method for preparing the near-infrared quantum dot sensitized photo-anode according to claim 1 is characterized in that: s2, dropwise adding the selenium solution into the copper indium solution at the temperature of 210 ℃, carrying out heat preservation reaction for 10min, then heating to 235 ℃, and carrying out heat preservation reaction for 20min to obtain a quantum dot CuInSeS solution; the volume ratio of the selenium solution to the copper indium solution is 1: 2-4.
5. The method for preparing the near-infrared quantum dot sensitized photo-anode according to claim 1 is characterized in that: the concentration of zinc acetate in the zinc oleate solution is 0.02-0.03 g/ml; the concentration of the oleic acid is 0.08-0.10 g/ml.
6. The method for preparing the near-infrared quantum dot sensitized photo-anode according to claim 1 is characterized in that: in S3, dropwise adding the quantum dot CuInSeS solution into a zinc oleate solution heated to 160 ℃, and carrying out heat preservation reaction for 20min to obtain core-shell quantum dot CuInSeS @ ZnS; the volume ratio of the quantum dot CuInSeS solution to the zinc oleate solution is 1: 8-10.
7. The method for preparing a near-infrared quantum dot sensitized photoanode according to claim 1, wherein bismuth vanadate in the bismuth vanadate electrode is prepared by the following steps:
s1: an electrochemical deposition device is constructed by taking FTO glass as a deposition electrode, an Ag/AgCl electrode as a reference electrode and a mixed solution of potassium iodide, bismuth nitrate and p-benzoquinone as an electrolyte, then, a voltage of-0.1V is applied to the deposition electrode relative to the Ag/AgCl reference electrode of 3mol/L potassium chloride, and the deposition is carried out for 280-320 s, so as to obtain bismuth oxyiodide; the pH value of the electrolyte is 1.7, wherein the concentration of potassium iodide is 0.27-0.29 mol/L, the concentration of bismuth nitrate is 0.27-0.29 mol/L, and the concentration of p-benzoquinone is 0.05-0.07 mol/L;
s2: dissolving vanadyl acetylacetonate in an organic solvent to prepare a solution with the concentration of 0.2 mol/L; and then coating the obtained solution on the surface of bismuth oxyiodide, heating to 430-460 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 1-3 h, and then naturally cooling and washing to obtain the bismuth vanadate.
8. The near-infrared quantum dot sensitized photo-anode prepared by the method for preparing the near-infrared quantum dot sensitized photo-anode according to claims 1-7.
9. A photoelectrochemical cell, comprising: comprises a photo-anode, a platinum counter electrode, a reference electrode and electrolyte; the photo-anode is the near-infrared quantum dot sensitized photo-anode of claim 8; the reference electrode is a 3mol/L potassium chloride Ag/AgCl reference electrode; the electrolyte is a potassium borate water solution, and the pH value is 8.8-9.2.
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