CN114628711A - Light-assisted magnesium/seawater battery and preparation method thereof - Google Patents
Light-assisted magnesium/seawater battery and preparation method thereof Download PDFInfo
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- 239000013535 sea water Substances 0.000 title claims abstract description 58
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011777 magnesium Substances 0.000 title claims abstract description 42
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000005525 hole transport Effects 0.000 claims abstract description 26
- 239000004065 semiconductor Substances 0.000 claims abstract description 26
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 229960001484 edetic acid Drugs 0.000 claims description 6
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical group [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 5
- 229940112669 cuprous oxide Drugs 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000355 copper sulfate Drugs 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000010248 power generation Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 11
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 230000001976 improved effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 29
- 238000005286 illumination Methods 0.000 description 10
- 239000010949 copper Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004506 ultrasonic cleaning 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/32—Deferred-action cells activated through external addition of electrolyte or of electrolyte components
- H01M6/34—Immersion cells, e.g. sea-water cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a novel photo-assisted magnesium/seawater battery and a preparation method thereof. The photo-assisted magnesium/seawater cell comprises a photocathode (3,4,5), a magnesium alloy anode 6, a seawater electrolyte 7, a resistive load 1 and a light source 2, wherein the photocathode consists of a conductive substrate 3, a hole transport layer 4 and a photo-semiconductor 5. Under the irradiation of light, the cathode optical semiconductor absorbs light energy to generate photo-generated electrons and holes, and the photo-generated holes are transferred to the hole transport layer and are compounded with electrons generated by electrochemical oxidation of the anode magnesium; and the photo-generated electrons are transferred to the surface of the semiconductor and participate in the cathode seawater reduction reaction to generate hydrogen, so that the kinetics of the seawater reduction reaction is promoted, and the performance of the magnesium/seawater battery is improved. The photo-assisted magnesium/seawater battery disclosed by the invention can simultaneously utilize chemical energy and light energy to generate electric energy and hydrogen energy, and has the advantages of simple structure, safety, stability, environmental friendliness to the ocean, low manufacturing cost and easiness in popularization.
Description
Technical Field
The invention relates to a photo-assisted magnesium/seawater battery and a preparation method thereof, in particular to a photo-assisted magnesium/seawater battery with a photocathode and a magnesium alloy anode and a preparation method thereof, belonging to the field of new energy.
Background
The ocean is an important development space and strategic resource treasury of the country. At present, more and more countries pay attention to the development of deep and far sea resources, and the development of deep sea oil and gas resources, submarine mineral resources, deep sea biological gene resources and ocean fishery resources becomes a hot spot for international ocean resource development. In this context, high capacity power supplies are critical to the development of marine resources. The magnesium/seawater dissolved oxygen battery is a battery capable of working in seawater electrolyte, and takes magnesium alloy as an anode and dissolved oxygen in seawater as a cathode reactant, when the battery generates electricity, the anode generates a magnesium electrochemical oxidation reaction, and the cathode generates an oxygen reduction reaction; the cell performance is limited by the seawater dissolved oxygen concentration and therefore is not high. Patent CN106898788A discloses a magnesium/seawater battery, which uses magnesium alloy as anode and seawater as cathode reactant and electrolyte, when working, the anode generates magnesium electrochemical oxidation reaction, and the cathode generates water electrochemical reduction reaction, thereby realizing power generation. Because seawater is used as a cathode reactant and an electrolyte, the magnesium/seawater battery has a simple structure and high specific capacity, and is suitable for being used as an ocean power supply to supply power for ocean equipment for a long time. However, the performance of magnesium/seawater batteries depends to a large extent on the battery cathode rate, i.e. the rate of the cathode seawater electrochemical reduction reaction, the reaction kinetics are slow, and even with the most advanced noble metal platinum catalysts, the kinetics are difficult to accelerate, resulting in low battery performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a photo-assisted magnesium/seawater battery and a preparation method thereof. Compared with the prior art, the photo-assisted magnesium/seawater battery disclosed by the invention can effectively convert chemical energy and light energy into electric energy, and meanwhile, a cathode byproduct is hydrogen gas which can provide hydrogen energy. The battery has the advantages of simple structure, safety, reliability, environmental friendliness to ocean, low manufacturing cost and easy popularization.
In order to realize the invention, the specific technical scheme is as follows:
a photo-assisted magnesium/seawater battery and a preparation method thereof comprise a magnesium alloy anode, a photoelectric cathode, a seawater electrolyte and a light source. The photoelectric cathode is characterized by comprising a conductive substrate, a hole transport layer and a light semiconductor layer. The preparation method of the photocathode comprises the following specific steps:
step 1: preparation of hole transport layer
And preparing the hole transport layer in a traditional three-electrode system by adopting an electrochemical deposition method. Indium-doped tin oxide conductive glass (ITO) is used as a working electrode, a platinum sheet electrode is used as a counter electrode, and a silver/silver chloride electrode is used as a reference electrode. The electrolyte is a mixed aqueous solution of copper sulfate, ethylene diamine tetraacetic acid and potassium thiocyanate, wherein the concentration of the copper sulfate solution is 0.6-3 mmol/L; the concentration of the ethylene diamine tetraacetic acid solution is 0.6-3 mmol/L; the concentration of the potassium thiocyanate solution is 0.1-1.2 mmol/L. Before electrochemical deposition, the ITO conductive glass is sequentially subjected to ultrasonic cleaning in acetone, ethanol and deionized water for 20 minutes for later use. And applying a voltage of-0.1 to-0.5V to the working electrode by using an electrochemical workstation in a timing current mode, and keeping the voltage for 200 to 600s, namely depositing a hole transport layer with the thickness of 20 to 200nm on the surface of the ITO of the working electrode.
Step 2: preparation of photoresponsive cathode semiconductor layer
And preparing the photoresponse semiconductor layer in a traditional three-electrode system by adopting an electrochemical deposition method. And (2) taking the hole transport layer electrode prepared in the step (1) as a working electrode, a platinum sheet electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode. The electrolyte is a mixed water solution of copper sulfate, lactic acid and sodium hydroxide, wherein the concentration of the copper sulfate is 10-50 mmol/L; the concentration of the lactic acid is 0.1-1 mmol/L; the concentration of sodium hydroxide is 0.1-1 mmol/L, and the electrodeposition temperature is 60-70 ℃; controlling the current passing through the working electrode to be 0.5-2.0 mA cm by utilizing an electrochemical workstation and adopting a timing potential mode-2And keeping the temperature within the range of 200-600 s to obtain the photocathode semiconductor film with the thickness of 100-1200 nm growing on the hole transport layer.
And step 3: selection and treatment of magnesium/seawater battery anode material
The magnesium/seawater battery anode material is commercial AZ31 magnesium alloy, and a surface oxidation layer is polished by abrasive paper before use.
And 4, step 4: assembling light-assisted magnesium/seawater battery
And (3) respectively placing the conductive glass deposited with the cuprous thiocyanate hole transport layer and the cuprous oxide semiconductor film obtained in the step (2) and the commercial AZ31 magnesium alloy obtained in the step (3) into a light-permeable container filled with seawater, connecting the conductive glass and the commercial AZ31 magnesium alloy by using a lead, and connecting the conductive glass and the commercial AZ31 magnesium alloy in series with a resistance load. Light is applied to the photocathode side to obtain a light-assisted magnesium/seawater battery. Under the illumination condition, the photocathode semiconductor is excited, the semiconductor absorbs photon energy to generate photo-generated electrons and holes, the photo-generated holes rapidly migrate to the hole transport layer, and meanwhile, electrons generated by the anodic oxidation reaction of the magnesium alloy are transferred to the hole transport layer through an external circuit lead and are compounded with the photo-generated electrons; the photo-generated electrons migrate to the surface of the photocathode semiconductor to participate in a reduction reaction, thereby generating current.
Wherein, the light source can be sunlight or xenon lamp light source.
Drawings
FIG. 1 is a schematic view of a light-assisted magnesium/seawater battery according to the present invention.
Fig. 2 is a comparison of the discharge performance of the photo-assisted magnesium/seawater cell of effect example 1 when illuminated and removed from light.
Fig. 3 is a chopped light discharge curve of a light-assisted magnesium/seawater battery in effect example 2.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
The structure of the photo-assisted magnesium/seawater battery is shown in figure 1, a photoelectric cathode comprises a conductive substrate 3, a hole transport layer 4 and a photo-semiconductor 5, and an anode is magnesium alloy 6. The photocathode, the small bulb load 1 and the anode are connected by a copper wire and are placed into a seawater electrolyte 7 to form the photo-assisted magnesium/seawater battery. When light emitted by the light source 2 irradiates the photocathode semiconductor 5, photo-generated carriers can be generated, wherein photo-generated electrons reach the surface of the photocathode semiconductor 5 and participate in a water reduction reaction to generate hydrogen, and photo-generated holes migrate to the hole transport material 4 and are combined with electrons generated by electrochemical oxidation of the anode magnesium alloy 6, so that current is generated in a circuit.
Examples
In this example, the anode was commercial magnesium alloy AZ 31; the electrolyte is natural seawater; the photoelectric cathode comprises three layers, namely a conductive substrate layer, an intermediate layer and a surface layer, wherein the conductive substrate layer is indium-doped tin oxide (ITO) conductive glass, the intermediate layer is a cuprous thiocyanate (CuSCN) hole transport layer, and the surface layer is cuprous oxide (Cu)2O) a light semiconductor layer.
Step 1: electrochemical deposition of cuprous thiocyanate hole transport layer on surface of ITO (indium tin oxide) of conductive substrate layer
In an electrochemical three-electrode system, indium-doped tin oxide conductive glass (ITO) serving as a conductive substrate is used as a working electrode, a platinum sheet electrode is used as a counter electrode, and a silver/silver chloride electrode is used as a reference electrode. The electrolyte is a mixed solution of copper sulfate, ethylene diamine tetraacetic acid and potassium thiocyanate; and controlling the voltage of the working electrode to be-0.3V by the electrochemical workstation, and keeping the voltage for 400s to obtain the ITO with the cuprous thiocyanate hole transport layer deposited on the surface.
Preferably, the copper sulfate concentration is 2.4 mmol/L; the concentration of the ethylene diamine tetraacetic acid is 2.4 mmol/L; the concentration of potassium thiocyanide was 0.6 mmol/L.
Step 2: electrochemical deposition of photo-semiconductor Cu on the surface of hole transport layer2O
And (2) taking the ITO electrode with the hole transmission layer on the surface prepared in the step (1) as a working electrode, a platinum sheet electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode. The electrolyte is a mixed solution of copper sulfate, lactic acid and sodium hydroxide, and the current flowing through the working electrode is controlled to be 0.8mA cm by the electrochemical workstation-2And maintaining 480s, and electrochemically depositing a cuprous oxide semiconductor film on the surface of the cuprous thiocyanate hole transport layer to obtain the photocathode.
Preferably, the copper sulfate concentration is 20 mmol/L; the ligand concentration is 0.34 mmol/L; the alkali concentration is 0.375mmol/L, and the electrolyte temperature is controlled at 65 ℃.
And step 3: treatment of magnesium alloy anodes
The magnesium alloy anode is commercial AZ31 alloy with the size of 4cm multiplied by 1cm, and a surface oxidation layer is polished by abrasive paper before use.
And 4, step 4: assembling light-assisted magnesium/seawater battery
And (3) respectively placing the conductive glass deposited with the cuprous thiocyanate hole transport layer and the cuprous oxide semiconductor film obtained in the step (2) and the commercial AZ31 magnesium alloy obtained in the step (3) into a light-permeable container filled with seawater, connecting the conductive glass and the commercial AZ31 magnesium alloy by using a lead, and connecting the conductive glass and the commercial AZ31 magnesium alloy in series with a resistance load. Light is applied to the photocathode side to obtain a light-assisted magnesium/seawater battery.
EXAMPLES Effect example 1
The light-assisted magnesium/seawater cell obtained in the example is placed in a container with a quartz glass window on the side surface, illumination is carried out on the cathode side, a 200-watt xenon lamp is adopted as a light source, the distance between the light source and a photocathode is 6cm, and the size of an anode magnesium alloy AZ31 electrode is 1cm multiplied by 1 cm. The discharge curves of the magnesium/seawater cells in light and no light were tested in the potential step mode using an electrochemical workstation, as shown in figure 2. As can be seen from FIG. 2, the maximum discharge power density of the magnesium/seawater battery is only 0.33mW/cm under the condition of no illumination2The highest discharge power density under illumination is increased to nearly 1.18mW/cm2And is 3.6 times of the product in the absence of light. Therefore, the light-assisted magnesium/seawater battery manufactured by the invention has a remarkably improved effect under the illumination condition.
EXAMPLES Effect example 2
The light-assisted magnesium/seawater cell obtained in the example is placed in a container with a quartz glass window on the side surface, illumination is carried out on the cathode side, a 200-watt xenon lamp is adopted as a light source, the distance between the light source and a photocathode is 6cm, and the size of an anode magnesium alloy AZ31 electrode is 1cm multiplied by 1 cm. 0.1mA/cm in constant current mode by using electrochemical workstation2The cell performance was tested under chopping conditions with a chopping interval of 10s, the results are shown in figure 2. As can be seen from the figure, the cell voltage is only 0.6-0.7V in the absence of illumination, and the cell voltage is increased to 1.1-1.2V at the moment of illumination, which shows that the cathode seawater is reduced only by Cu under the condition of no illumination2Electricity of OCatalytic reduction is carried out, and the self resistance of a semiconductor is high, so that the seawater reduction reaction kinetics is slow, and the current is small; and Cu in the photocathode under illumination2The O semiconductor absorbs photon energy to generate photon-generated carriers, photo-generated holes rapidly migrate to CuSCN and are compounded with electrons generated by dissolution of the anode magnesium alloy AZ31, and photo-generated electrons migrate to Cu2The O surface participates in the water reduction reaction, thereby accelerating the dynamics of the seawater reduction reaction and improving the battery performance.
Claims (7)
1. A photo-assisted magnesium/seawater battery is characterized by comprising a photocathode, a magnesium alloy anode, a seawater electrolyte and a light source; the photoelectric cathode and the magnesium alloy anode are both arranged in the seawater electrolyte, and the battery power generation is realized when the light emitted by the light source irradiates the photoelectric cathode.
2. The photo-assisted magnesium/seawater cell of claim 1 wherein the photocathode is a three-layer structure comprising a conductive substrate, a hole transport layer and a photo-semiconductor layer.
3. The photo-assisted magnesium/seawater cell of claim 1 wherein the photo-semiconductor layer of the photocathode faces the light source.
4. The photo-assisted magnesium/seawater cell of claim 1 wherein the light source is sunlight or a xenon light source.
5. The photo-assisted magnesium/seawater cell of claim 1 wherein the preparation of the photocathode comprises:
step 1: preparation of hole transport layer
And preparing the hole transport layer in a traditional three-electrode system by adopting an electrochemical deposition method. Indium-doped tin oxide conductive glass (ITO) is used as a working electrode, a platinum sheet electrode is used as a counter electrode, and a silver/silver chloride electrode is used as a reference electrode. The electrolyte is a mixed aqueous solution of copper sulfate, ethylene diamine tetraacetic acid and potassium thiocyanate, wherein the concentration of the copper sulfate solution is 0.6-3 mmol/L; the concentration of the ethylene diamine tetraacetic acid solution is 0.6-3 mmol/L; the concentration of the potassium thiocyanate solution is 0.1-1.2 mmol/L. And applying a voltage of-0.1 to-0.5V to the working electrode by using an electrochemical workstation in a timing current mode, and keeping the voltage for 200 to 600s, namely depositing a hole transport layer with the thickness of 20 to 200nm on the surface of the ITO of the working electrode.
Step 2: preparation of photoresponsive cathode semiconductor layer
And preparing the photoresponse semiconductor layer in a traditional three-electrode system by adopting an electrochemical deposition method. And (3) taking the hole transport layer electrode prepared in the step (1) as a working electrode, a platinum sheet electrode as a counter electrode and a silver/silver chloride electrode as a reference electrode. The electrolyte is a mixed water solution of copper sulfate, lactic acid and sodium hydroxide, wherein the concentration of the copper sulfate is 10-50 mmol/L; the concentration of the lactic acid is 0.1-1 mmol/L; the concentration of sodium hydroxide is 0.1-1 mmol/L, and the electrodeposition temperature is 60-70 ℃; controlling the current passing through the working electrode to be 0.5-2.0 mA cm by utilizing an electrochemical workstation and adopting a timing potential mode-2And keeping the temperature within the range of 200-600 s to obtain the photocathode semiconductor film with the thickness of 100-1200 nm growing on the hole transport layer.
6. The photo-assisted magnesium/seawater cell of claim 1 wherein the photocathode semiconductor is cuprous oxide; the hole transport material is cuprous thiocyanate; the anode magnesium alloy is commercial AZ 31.
7. The photo-assisted magnesium/seawater cell of claim 1, wherein the more than 2 magnesium/seawater cells are connected in series or in parallel or in series-parallel connection to form a cell stack.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116581345A (en) * | 2023-05-25 | 2023-08-11 | 徐州工程学院 | Membrane-free magnesium-sodium hypochlorite seawater/sodium chloride solution battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106898788A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of magnesium water battery |
| CN108796532A (en) * | 2017-05-03 | 2018-11-13 | 天津大学 | Nickel oxide-cuprous oxide homojunction photocathode and preparation method thereof and the application in photocatalysis |
| CN110473927A (en) * | 2019-05-23 | 2019-11-19 | 中国计量大学 | A kind of cuprous oxide/cuprous sulfocyanide heterojunction photovoltaic film and preparation method thereof |
| CN112086289A (en) * | 2020-08-12 | 2020-12-15 | 华东师范大学 | Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof |
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| CN110473927A (en) * | 2019-05-23 | 2019-11-19 | 中国计量大学 | A kind of cuprous oxide/cuprous sulfocyanide heterojunction photovoltaic film and preparation method thereof |
| CN112086289A (en) * | 2020-08-12 | 2020-12-15 | 华东师范大学 | Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof |
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| CN116581345A (en) * | 2023-05-25 | 2023-08-11 | 徐州工程学院 | Membrane-free magnesium-sodium hypochlorite seawater/sodium chloride solution battery |
| CN116581345B (en) * | 2023-05-25 | 2024-01-26 | 徐州工程学院 | Membrane-free magnesium-sodium hypochlorite seawater/sodium chloride solution battery |
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