CN112086289A - Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof - Google Patents
Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof Download PDFInfo
- Publication number
- CN112086289A CN112086289A CN202010805306.XA CN202010805306A CN112086289A CN 112086289 A CN112086289 A CN 112086289A CN 202010805306 A CN202010805306 A CN 202010805306A CN 112086289 A CN112086289 A CN 112086289A
- Authority
- CN
- China
- Prior art keywords
- photo
- seawater
- anode
- oxygen
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a sunlight-driven electricity-oxygen co-production seawater battery and a preparation method thereof, wherein the method comprises the following steps: 1) an N-type semiconductor for generating electron-hole pairs under the excitation of sunlight is used as a photoanode material for providing electron and hole sources; 2) the cathode material takes the coordination crystal as a main part and provides storage sites for photo-generated electrons and alkali metal ions in seawater at the same time, and shows reversible charge-discharge characteristics of the secondary battery in the charge-discharge process; 3) the seawater solution with the salinity value of at least 0.1 percent is used as electrolyte to balance the polarization of ion concentration in the electrode brought in the power generation and oxygen production processes and stabilize the working environment of the combined power and oxygen generation device. When light is irradiated, the photo-anode simultaneously generates electrons and holes, the electrons flow to the cathode through an external circuit, and the holes react with water to generate oxygen. The invention takes sunlight as the only energy input source, has simple scientific principle, safety and stability, environmental protection, low manufacturing cost, feasible practicability and easy popularization.
Description
Technical Field
The invention relates to the field of photoelectric conversion and energy, in particular to a sunlight-driven electricity-oxygen cogeneration seawater battery and a preparation method thereof.
Background
The ocean power supply problem needs to be solved, and although the off-grid power supply technology of far continents can solve part of ocean power supply problems, the technology still has shortcomings, such as large cost, difficult maintenance and the like. The ocean contains abundant resources, which also include various renewable energy sources, such as tidal energy and wave energy. Therefore, the development of the application of the renewable energy sources in ocean energy supply has important research significance. Solar energy has been widely studied in recent years as the most abundant resource on earth. However, there has been little research on the use of solar energy in the ocean; this is mainly because the existing solar cell materials are difficult to withstand the highly corrosive environment of the ocean, and thus no suitable material capable of utilizing the ocean solar energy has been found. Therefore, a new device is needed to be developed to realize the utilization of the solar energy in the ocean. In addition, one of the important environmental issues currently facing the ocean is seawater hypoxia. The marine hypoxia causes death of animals and plants, damages marine ecology and seriously affects the diversity of marine organisms and the geochemical cycle of organisms. The problem to be solved is how to solve the problem of ocean energy supply and provide a scheme for ocean environment restoration.
The coordination crystal is a three-dimensional periodic porous framework material formed by taking metal ions or clusters as nodes and organic ligands as frameworks. The coordination crystal has the advantages of high porosity, low density, large specific surface area, adjustable pore diameter, diversity and tailorability of topological structure and the like, so that the coordination crystal can be used for reversible storage of metal ions (such as potassium ions, sodium ions and the like). In addition, the crystal structure can be kept stable during the process of embedding and extracting the guest ions. In recent years, the coordination crystal, represented by a prussian blue coordination crystal as a typical example, has shown a great potential in lithium, sodium, potassium plasma batteries. Therefore, the coordination crystal is an ideal cathode material for seawater power generation, and provides possibility for manufacturing an environment-friendly electricity-oxygen cogeneration seawater power generation device.
Disclosure of Invention
The invention aims to provide a sunlight-driven electricity-oxygen cogeneration seawater battery and a preparation method thereof, aiming at optimizing the problems of continuous energy supply and the remediation of an anoxic water body in a marine environment. The invention takes sunlight as the only energy input source, has simple scientific principle, safety and stability, is fully friendly to the environment, has low manufacturing cost, feasible practicability and easy popularization.
The specific technical scheme for realizing the purpose of the invention is as follows:
a preparation method of a sunlight-driven electricity-oxygen cogeneration seawater battery comprises the following specific steps:
step 1: selection and preparation of cathode
A1: selection of coordination crystals
Selecting Prussian blue crystals and crystals with sodium ion storage sites as coordination crystals, wherein the molecular general formula of the Prussian blue crystals is Aa MⅠ b MⅡ c[MⅢ(CN)6]d·nH2O; wherein A is an alkali metal element, a hydrogen ion or an ammonium ion; mⅠ、MⅡ、MⅢAre the same or different transition metal elements; a. b, c, d are [0,2 ]]The value of (a); n is [0,20 ]]The value of (a); the alkali metal element is Li, Na, K, Rb or Cs; the transition metal element is Fe, Co, Ni, Mn, Ti, Zn, Cr, Cu or In;
the crystal with sodium ion storage sites is: na (Na)2C6O6、Na4Fe3(PO4)2(P2O7)、NaVO2、NaCrO2、NaMnFe2(PO4)3、Na3Fe2(PO4)3、C24H8O6、C6Cl4O2、NaFePO4、Na2FeP2O7Or NaMnO2；
A2: preparation of the cathode
The preparation of the cathode adopts two modes of coating and electroplating;
i) coating: grinding the coordination crystal, a conductive agent and a binder for 5-50 minutes by using a mortar according to a mass ratio of 1: 0.1-10 under the action of a solvent; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the contained coordination crystal is 1mg/cm2～100mg/cm2And placing the anode and the cathode in an oven at 50-100 ℃ for vacuum drying for 0.2-24 hours to obtain a current collector electrode coated with the coordination crystal as the cathode; wherein the content of the first and second substances,
the conductive agent is one or a mixture of more than one of carbon black, conductive graphite, carbon fiber, carbon nano tube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, triethyl phosphate or dimethyl sulfoxide;
the current collector is carbon cloth, metal titanium, metal copper, metal nickel, ITO conductive glass or FTO conductive glass.
Ii) electroplating: preparing a mixed solution of metal salt, ligand and inorganic salt, wherein the concentration of the metal salt is 0.1 mmol/L-1 mmol/L; the ligand concentration is 0.1 mmol/L-5 mmol/L; the concentration of the inorganic salt is 0.1-3 mol/L; using conductive glass with the thickness of 1mm multiplied by 1 mm-3 m multiplied by 3m as a working electrode, a platinum sheet electrode as a counter electrode, a silver/silver chloride electrode as a reference electrode, connecting an electrochemical workstation, and using a cyclic voltammetry scanning mode to perform the operation of 0.01mVs within the voltage range of-1.5V-1～1Vs-1Continuously scanning for 50-500 times; obtaining a coordination crystal thin film electrode with the thickness of 10 nm-500 nm; the metal salt is nickel chloride, copper chloride, zinc chloride,Ferric chloride, nickel sulfate, copper sulfate, zinc nitrate, nickel nitrate, copper nitrate or ferric nitrate; the ligand is potassium ferricyanide, potassium ferrocyanide or sodium ferrocyanide; the inorganic salt is sodium sulfate, sodium nitrate, potassium nitrate or potassium sulfate.
Step 2: selection and preparation of photoanode
B1: selection of photo-anode
Titanium dioxide or zinc oxide N-type semiconductor is selected as a photo-anode, namely under the irradiation of sunlight, electron hole pairs can be generated, and the recombination rate of the electron holes is low (> 250 ns);
b2: preparation of photoanode material
The preparation of the photo-anode material adopts two modes of anodic oxidation or substrate growth:
i) an anodic oxidation process: and (3) pretreating the titanium sheet, namely polishing and grinding the titanium sheet which is 0-100%, 1cm multiplied by 1 cm-3 m multiplied by 3m in size and 0.05 mm-0.3 mm in thickness by adopting 100-1000-mesh sand paper and aluminum oxide nano particles to remove scratches in the processing process. After polishing, the glass is washed by deionized water and naturally dried. Configuring HF (40.0%), HNO3(65-68%) and deionized water at a volume ratio of 1:4: 5. And soaking the polished titanium sheet in the mixed solution for 1-60 seconds for etching to remove the oxide layer. And ultrasonically cleaning the etched titanium sheet by using deionized water, ethanol and acetone respectively, and naturally airing for later use. Preparing electrolyte, wherein the concentration of the electrolyte is 0.1 mmol/L-1 mol/L. And (2) placing the beaker filled with the electrolyte on a magnetic stirring device, setting the rotating speed of a stirrer to be 500-100 r/min, adjusting the rotating speed to be 100-400 r/min after uniformly stirring, adopting a pretreated titanium sheet as a working electrode and a platinum sheet electrode as a double-electrode system of a counter electrode, and adjusting a direct current power supply to work for 10-50 min under the voltage of 30V. And after the reaction is finished, taking out the titanium sheet, washing the titanium sheet by using deionized water and ethanol, and naturally airing the titanium sheet. Then calcining for 2-4 h in a muffle furnace at 400-550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; obtaining a metal sheet oxide film with the thickness of 1 nm-1 mu m on the surface of the titanium sheet after calcination, namely the photo-anode; wherein the content of the first and second substances,
the electrolyte is as follows: aqueous hydrofluoric acid or aqueous ammonium fluoride;
ii) substrate growth: taking conductive glass with the resistance of 1-20 omega, the size of 1cm multiplied by 1 cm-3 m multiplied by 3m and the thickness of 0.05 mm-15 mm as a substrate; respectively putting the substrate into 5-18% of acetone, absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10-40 minutes, vertically and obliquely putting the substrate into a reaction kettle, and placing the substrate with the conductive surface facing downwards; adding 1-100 ml of hydrochloric acid solution with the concentration of 18% into a reaction kettle; then sealing the reaction kettle, and transferring the reaction kettle to an oven with the temperature of 160-200 ℃ for reaction for 5-48 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and washing the substrate by deionized water; putting the conductive glass into an oven with the temperature of 40-100 ℃ for drying for 0.2-24 h; soaking the dried substrate sheet in a titanium tetrachloride solution with the concentration of 1-0.5 mol/L in an oven with the temperature of 80 ℃ for 30-60 min, then washing the substrate sheet with absolute ethyl alcohol, and drying the substrate sheet in the oven with the temperature of 50-70 ℃ for 2-15 h; finally calcining for 2-4 h in a muffle furnace at the temperature of 400-550 ℃ in the air atmosphere, wherein the heating rate is 1 ℃/min; obtaining a white oxide film with the thickness of 1 nm-1 mu m on the conductive surface of the conductive glass substrate after calcination, namely the photo-anode; wherein the content of the first and second substances,
the conductive glass is as follows: FTO;
and step 3: electrolyte solution
Seawater with the salinity of at least 0.1 percent is selected as electrolyte and used for providing metal ions required in the power generation process and balancing electrode polarization effect; the seawater is a seawater resource in the ocean that occupies about 70% of the earth;
and 4, step 4: generation of constant current
The cathode and the photo-anode are respectively put into the seawater electrolyte which flows mutually, and then the cathode and the photo-anode are connected by a lead, when the photo-anode semiconductor is excited by illumination, the photo-generated electrons are transferred to the cathode, so that constant direct current is generated;
and 5: constant oxygen generation
The cathode and the photo-anode are respectively placed in seawater electrolyte which flows mutually, the cathode and the photo-anode are connected by a lead, and when the photo-anode semiconductor is excited by light, water molecules in seawater are oxidized into oxygen and hydrogen ions by the photo-induced holes, so that oxygen is released.
The Prussian blue coordination crystal in the step 1 is as follows: fe4[Fe(CN)6]3(iron ferrocyanide Prussian blue, CAS number 14038-43-8), Ni3[Fe(CN)6]2(Nickel ferricyanide), Na2Co[Fe(CN)6](cobalt ferrocyanide), Ti [ Fe (CN)6](titanium ferrocyanide), Na2Cu[Fe(CN)6](copper ferrocyanide), Na2Zn[Fe(CN)6](Zinc ferrocyanide).
The solar-driven electricity-oxygen cogeneration seawater battery prepared by the method.
The invention takes sunlight as the only energy input source, has simple scientific principle, safety and stability, is fully friendly to the environment, has low manufacturing cost, feasible practicability and easy popularization. The N-type semiconductor is mainly used for generating photo-generated electron-hole pairs by light excitation during illumination, providing electrons in the power generation process and generating holes in the oxygen generation process. The coordination crystal is mainly used for accepting electrons and providing storage sites of metal ions; the invention can obtain the stable and reusable combined oxygen generation seawater battery under the premise of ensuring simple process and environmental protection.
Drawings
FIG. 1 is a schematic structural diagram of a solar-powered cogeneration seawater battery;
FIG. 2 is a graph of current time when the solar-powered cogeneration seawater cell prepared in example 1 is illuminated and removed and a graph of time of oxygen concentration under illumination;
FIG. 3 is a graph of the current time when the solar-powered seawater cell is illuminated and removed and a graph of the concentration of oxygen under illumination according to the embodiment 2 of the present invention;
fig. 4 is a current time chart and an oxygen concentration time chart under illumination when the solar light-driven cogeneration seawater battery prepared in example 3 is illuminated and removed;
fig. 5 is a current time chart and an oxygen concentration time chart under illumination of the solar light-driven cogeneration seawater cell according to embodiment 4 of the present invention when the cell is illuminated and removed.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Referring to fig. 1, the co-generation seawater battery of the present invention is shown in the figure, in which a conductive carbon cloth 2 coated with a coordination crystal 3 is led out by a copper wire to be connected to a cathode of a load 1, such as a small bulb; titanium foil 4 with titanium dioxide 5 grown thereon is led out with a copper wire to be connected to the photo-anode of load 1, for example, a small bulb. And then the connected conductive carbon cloth 2 and titanium foil 4 are put into a beaker filled with seawater electrolyte 6 together to form the combined oxygen and power generation seawater battery. When sunlight 7 is irradiated onto the titanium dioxide 5, a constant current can be generated while oxygen is released.
Example 1
Coating + substrate growth
The cathode material selected in this example is of the formula Ni3[Fe(CN)6]2Prussian blue coordination crystals; the photo-anode material is a titanium dioxide N-type semiconductor with a molecular formula of TiO2(ii) a The electrolyte is natural seawater.
Step 1: ni3[Fe(CN)6]2Preparation of prussian blue coordination crystal
1426mg of nickel chloride hydrate (NiCl)2·6H2O) and 3300mg of sodium citrate dihydrate (HOC (COOH) (CH)2COONa)2·1.5H2O) is dissolved in 200ml of deionized water to form a transparent clear solution A; 1313 mg of potassium ferricyanide (K)3[Fe(CN)6]) Dissolving in 200ml deionized water to form a transparent clear solution B, uniformly mixing the solution A and the solution B at room temperature to obtain a green turbid liquid, reacting at room temperature (25 ℃) for 24 hours to obtain a deep yellow prussian blue coordination crystal solution, and centrifugally separating the obtained prussian blue coordination crystal solution at 8000rpm to obtain Ni3[Fe(CN)6]2Prussian blue-based coordination crystal powder; a. the obtained Ni3[Fe(CN)6]2Putting Prussian blue coordination crystal powder into 20ml industrial alcoholDispersing by ultrasonic for 10min, and centrifuging at 8000rpm to obtain Ni3[Fe(CN)6]2Prussian blue-based coordination crystal powder; b. the Ni obtained from a3[Fe(CN)6]2The Prussian blue coordination crystal powder is placed into 20ml deionized water for ultrasonic dispersion for 10min, and then is centrifugally separated at 8000rpm to obtain Ni3[Fe(CN)6]2Prussian blue-based coordination crystal powder; repeating the steps a and b for 3 times. Placing the resulting powder at 60。C, drying in a drying oven for 10 hours in vacuum, wherein the vacuum degree is less than 0.1 Pa;
step 2: preparation of cathode of seawater battery by combined production of electricity and oxygen
Taking 70mg of Ni in step 13[Fe(CN)6]2Prussian blue coordination crystal powder, 20mg of conductive carbon powder and 10mg of polyvinylidene fluoride are placed in a mortar, 2ml of N-methyl pyrrolidone is added, and the mixture is manually ground for 15 minutes. The uniformly ground mixture was coated on a conductive carbon cloth having a size of 3cm × 4cm with a blade. And placing the mixture in an oven at 100 ℃ for vacuum drying for 6 hours, wherein the vacuum degree is less than 0.1 Pa. The obtained electrode can be used as the cathode of the seawater battery for the cogeneration of electricity and oxygen;
and step 3: preparation of photo-anode of electricity-oxygen co-production seawater battery
Growing a substrate: using conductive glass with the resistance of 10 omega, the size of 2.5cm multiplied by 4m and the thickness of 0.1mm as a substrate; respectively putting the substrate into 18% acetone, absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10 minutes, vertically and obliquely putting the substrate into a reaction kettle, and putting the substrate with the conductive surface facing downwards; adding 25ml of hydrochloric acid solution with the concentration of 18% into a 50ml reaction kettle; then sealing the reaction kettle, and transferring the reaction kettle to an oven with the temperature of 200 ℃ for reaction for 12 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and washing the substrate by deionized water; putting the substrate into an oven at 100 ℃ for drying for 24 hours; soaking the dried substrate sheet in a titanium tetrachloride solution with the concentration of 0.5mol/L in an oven at 80 ℃ for 30min, then washing the substrate sheet with absolute ethyl alcohol, and drying the substrate sheet in the oven at 70 ℃ for 2 h; finally calcining for 3h in a muffle furnace at 550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; after calcination, a white oxide film with the thickness of 10nm is obtained on the conductive surface of the substrate and can be used as a photo-anode of the electricity-oxygen cogeneration seawater battery.
And 4, step 4: assembly of electricity oxygen coproduction sea water battery
Coating the Ni-coated film obtained in step 23[Fe(CN)6]2And (3) respectively placing the conductive carbon cloth of the prussian blue coordination crystal and the conductive glass electrode plate with the titanium dioxide electric film in the step (3) in seawater electrolyte which can flow mutually, and connecting the conductive carbon cloth and the conductive glass electrode plate with the titanium dioxide electric film by using a lead to obtain the seawater battery with combined production of electricity and oxygen.
FIG. 2 is a photo-generated current time chart and an oxygen generation time chart of the seawater battery with combined generation of electricity and oxygen of the embodiment, under the test condition that the Ni-coated seawater battery obtained in the step 2 is coated with Ni3[Fe(CN)6]2And (3) respectively placing the conductive carbon cloth of the prussian blue coordination crystal and the conductive glass electrode plate with the titanium dioxide electric film obtained in the step (3) into 200mL of seawater electrolyte which can flow mutually, and placing the seawater electrolyte into a 300mL beaker. Connecting a titanium dioxide electrode to a counter electrode and a reference electrode of an electrochemical workstation, connecting a conductive carbon cloth electrode coated with Prussian blue coordination crystals to the working electrode of the electrochemical workstation, and irradiating by using a 100W xenon lamp in a current-time mode to obtain a current-time relation diagram shown in 1) in figure 2; meanwhile, in the illumination process, the oxygen concentration time chart shown in 2) in fig. 2 can be obtained by testing the oxygen concentration in the electrolyte by using a dissolved oxygen meter.
In the embodiment, the prepared cathode and the photo-anode are connected and are respectively placed in seawater electrolyte with the salinity of more than or equal to 0.1%, when the sunlight shines, because titanium dioxide can generate electron hole pairs under the excitation of the sunlight, and the prussian blue coordination crystal has the capability of accepting electrons, the photo-generated electrons flow to the cathode through an external circuit to form current, and meanwhile, in order to keep the electric neutrality, the prussian blue coordination crystal can obtain a cation from the seawater. On the other hand, the holes generated by the photo-anode react with water molecules to generate oxygen, so that the purpose of repairing the anoxic seawater is achieved. The whole process is simple and easy to implement, and is green and pollution-free to the seawater environment.
Example 2
Coating + anodizing process
The cathode material selected in this example was a Prussian blue analogue coordination crystal with the molecular formula Ni3[Fe(CN)6]2(ii) a The photo-anode material is a titanium dioxide N-type semiconductor with a molecular formula of TiO2(ii) a The electrolyte is natural seawater.
Step 1: preparation of prussian blue analogue coordination crystal
1426mg of nickel chloride hydrate (NiCl)2·6H2O) and 3300mg of sodium citrate dihydrate (HOC (COOH) (CH)2COONa)2·1.5H2O) dissolved in 200ml of deionized water to form a green clear solution A; 1313 mg of potassium ferricyanide (K)3[Fe(CN)6])3Dissolving the solution A and the solution B in 200ml of deionized water to form a red transparent clear solution B, uniformly mixing the solution A and the solution B at room temperature to obtain a green clear liquid, reacting at room temperature (25 ℃) for 24 hours to obtain yellow Prussian blue coordination crystal precipitate, and centrifugally separating the obtained yellow Prussian blue coordination crystal precipitate at 8000rpm to obtain Prussian blue coordination crystal powder; a. putting the obtained Prussian blue coordination crystal powder into 20ml of industrial alcohol, performing ultrasonic dispersion for 10min, and performing centrifugal separation at a speed of 8000rpm to obtain Prussian blue analogue coordination crystal powder; b. b, putting the Prussian blue coordination analogue crystal powder obtained in the step a into 20ml of deionized water, performing ultrasonic dispersion for 10min, and performing centrifugal separation at a speed of 8000rpm to obtain Prussian blue analogue coordination crystal powder; repeating the steps a and b for 3 times. Placing the finally obtained powder at room temperature, and drying for 20 hours in vacuum with the vacuum degree less than 0.1 Pa;
step 2: preparation of cathode of seawater battery by combined production of electricity and oxygen
Taking 70mg of Prussian blue coordination crystal powder in the step 1, 20mg of conductive carbon powder and 10mg of polyvinylidene fluoride, putting the mixture into a mortar, adding 2ml of N-methylpyrrolidone, and manually grinding for 15 minutes. The uniformly ground mixture was coated on a conductive carbon cloth having a size of 3cm × 4cm with a blade. And placing the mixture in an oven at 100 ℃ for vacuum drying for 6 hours, wherein the vacuum degree is less than 0.1 Pa. The obtained electrode plate can be used as the cathode of the seawater battery for the cogeneration of electricity and oxygen;
and step 3: preparation of photo-anode of electricity-oxygen co-production seawater battery
And (3) pretreating the titanium sheet, namely polishing and grinding the titanium sheet with the size of 4cm multiplied by 3cm and the thickness of 0.3mm by adopting 1000-mesh sand paper and aluminum oxide nano particles so as to remove scratches in the processing process. After polishing, the glass is washed by deionized water and naturally dried. Configuring HF (40.0%), HNO3(65-68%) and deionized water at a volume ratio of 1:4: 5. And soaking the polished titanium sheet in the mixed solution for 30s for etching to remove the oxide layer. And ultrasonically cleaning the etched titanium sheet by using deionized water, ethanol and acetone respectively, and naturally airing for later use. And preparing electrolyte, wherein the concentration of the electrolyte is 1 mol/L. And (3) placing the beaker filled with the electrolyte on a magnetic stirrer, setting the rotating speed of the stirrer to be 100r/min, adjusting the rotating speed to be 400r/min after uniformly stirring, adopting a pretreated titanium sheet as a working electrode and a platinum sheet electrode as a double-electrode system of a counter electrode, and adjusting a direct-current power supply to work for 30min under the voltage of 30V. And after the reaction is finished, taking out the titanium sheet, washing the titanium sheet by using deionized water and ethanol, and naturally airing the titanium sheet. Then calcining for 3h in a muffle furnace at 550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; calcining to obtain a titanium dioxide film with the thickness of 0.5 mu m, which grows on the surface of the titanium sheet substrate and is the photo-anode;
and 4, step 4: assembly of electricity oxygen coproduction sea water battery
Coating the Ni-coated film obtained in step 23[Fe(CN)6]2And (3) respectively placing the conductive carbon cloth of the Prussian blue analogue coordination crystal and the titanium dioxide titanium sheet obtained in the step (3) in seawater electrolyte which can be mutually circulated, and connecting the conductive carbon cloth and the titanium dioxide titanium sheet by using a wire clamp to obtain the electricity-oxygen co-production seawater battery.
Fig. 3 is a photo-generated current time chart and an oxygen production time chart of the seawater battery for cogeneration of electricity and oxygen in the present embodiment, under the test conditions that the conductive carbon cloth coated with the prussian blue coordination crystal obtained in step 1 and the titanium dioxide titanium sheet obtained in step 2 are respectively placed in 200mL seawater electrolytes which can be circulated, and the seawater electrolyte is placed in a 300mL beaker. Connecting a titanium dioxide electrode to a counter electrode and a reference electrode of an electrochemical workstation, connecting a conductive carbon cloth electrode coated with Prussian blue coordination crystals to the working electrode of the electrochemical workstation, and irradiating by using a 100W xenon lamp in a current-time mode to obtain a current-time relation diagram shown in 1) in figure 3; meanwhile, in the illumination process, the oxygen concentration time chart shown in 2) in fig. 3 can be obtained by testing the oxygen concentration in the electrolyte by using a dissolved oxygen meter.
In the embodiment, the prepared cathode and the photoanode are connected and respectively placed in seawater electrolyte with salinity of more than or equal to 0.1%, when the sunlight shines, titanium dioxide can generate electron hole pairs under the excitation of the sunlight, and the prussian blue coordination crystal has the ability of accepting electrons, so that the photoproduction electrons flow to the cathode through an external circuit to form current, and meanwhile, in order to keep the electroneutrality, the prussian blue coordination crystal can obtain a cation from the seawater. On the other hand, the holes generated by the photo-anode react with water molecules to generate oxygen, so that the purpose of repairing the anoxic seawater is achieved. The whole process is simple and easy to implement, and is green and pollution-free to the seawater environment.
Example 3
Electroplating + substrate growth
The cathode material selected in this example is a Prussian blue coordination crystal with the molecular formula Ni3[Fe(CN)6]2(ii) a The photo-anode material is a titanium dioxide N-type semiconductor with a molecular formula of TiO2(ii) a The electrolyte is natural seawater.
Step 1: prussian blue analogue coordination crystal film and preparation of seawater battery cathode
745mg potassium chloride, 82.31mg potassium ferricyanide, 67.57mg nickel chloride, and 0.836ml concentrated hydrochloric acid were dissolved in 100ml deionized water to form a mixed solution. Using ITO conductive glass of 2cm multiplied by 1cm multiplied by 0.1cm as a working electrode, a platinum electrode of 1cm multiplied by 0.1cm as a counter electrode, a silver/silver chloride electrode as a reference electrode, connecting an electrochemical workstation, and using a cyclic voltammetry scanning mode to scan 50m Vs within the voltage range of 0V-0.9V-1Is continuously scanned for 60 times to obtain Ni with the thickness of 100nm3[Fe(CN)6]2Prussian blue coordination crystal film. The obtained electroplated Ni3[Fe(CN)6]2The conducting glass of the Prussian blue coordination crystal film is used as the cathode of the seawater battery for the combined production of electricity and oxygen.
Step 2: preparation of photo-anode of electricity-oxygen co-production seawater battery
Growing a substrate: using conductive glass with the resistance of 10 omega, the size of 2.5cm multiplied by 4m and the thickness of 0.1mm as a substrate; respectively putting the substrate into 18% acetone, absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10 minutes, vertically and obliquely putting the substrate into a reaction kettle, and putting the substrate with the conductive surface facing downwards; adding 25ml of hydrochloric acid solution with the concentration of 18% into a 50ml reaction kettle; then sealing the reaction kettle, and transferring the reaction kettle to an oven with the temperature of 200 ℃ for reaction for 12 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and washing the substrate by deionized water; putting the substrate into an oven at 100 ℃ for drying for 24 hours; soaking the dried substrate sheet in a titanium tetrachloride solution with the concentration of 0.5mol/L in an oven at 80 ℃ for 30min, then washing the substrate sheet with absolute ethyl alcohol, and drying the substrate sheet in the oven at 70 ℃ for 2 h; finally calcining for 3h in a muffle furnace at 550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; and (3) obtaining a titanium dioxide oxide film with the thickness of 10nm on the conductive surface of the substrate after calcination, and the titanium dioxide oxide film can be used as a photo-anode of the electricity-oxygen cogeneration seawater battery.
And step 3: assembly of electricity oxygen coproduction sea water battery
Electroplating the obtained product in the step 1 with Ni3[Fe(CN)6]2And (3) respectively placing the conductive glass of the Prussian blue analogue coordination crystal film and the titanium dioxide electrode slice obtained in the step (2) in seawater electrolyte which can flow mutually, and connecting the conductive glass and the titanium dioxide electrode slice by using a lead to obtain the electricity-oxygen co-production seawater battery.
FIG. 4 is a photo-generated current time chart and an oxygen generation time chart of the seawater battery with combined generation of electricity and oxygen according to the embodiment, under the test condition that the Ni-plated film obtained in the step 1 is plated with Ni3[Fe(CN)6]2And (3) respectively placing the conductive glass of the Prussian blue analogue coordination crystal film and the titanium dioxide electrode slice obtained in the step (2) into 200mL of seawater electrolyte which can mutually circulate, and placing the seawater electrolyte into a 300mL beaker. The titanium dioxide electrode is connected with a counter electrode and a reference electrode of an electrochemical workstation and is electroplated with Ni3[Fe(CN)6]2The conductive glass electrode of the Prussian blue analogue coordination crystal thin film is connected to a working electrode of an electrochemical workstation, and a 100W xenon lamp is used for irradiation in a current-time mode, so that a current-time relation graph shown in 1) in figure 4 can be obtained; meanwhile, in the illumination process, the oxygen concentration time chart shown in 2) in fig. 4 can be obtained by testing the oxygen concentration in the electrolyte by using a dissolved oxygen meter.
In the embodiment, the prepared cathode and the photoanode are connected and respectively placed in seawater electrolyte with salinity of more than or equal to 0.1%, when the sunlight shines, titanium dioxide can generate electron hole pairs under the excitation of the sunlight, and the prussian blue coordination crystal has the ability of accepting electrons, so that the photoproduction electrons flow to the cathode through an external circuit to form current, and meanwhile, in order to keep the electroneutrality, the prussian blue coordination crystal can obtain a cation from the seawater. On the other hand, the holes generated by the photo-anode react with water molecules to generate oxygen, so that the purpose of repairing the anoxic seawater is achieved. The whole process is simple and easy to implement, and is green and pollution-free to the seawater environment.
Example 4
Electroplating + anodizing process
The cathode material selected in this example is a Prussian blue coordination crystal with the molecular formula Ni3[Fe(CN)6]2(ii) a The photo-anode material is a titanium dioxide N-type semiconductor with a molecular formula of TiO2(ii) a The electrolyte is natural seawater
Step 1: prussian blue coordination crystal film and preparation of photoelectric oxygen coproduction seawater battery cathode
745mg potassium chloride, 82.31mg potassium ferricyanide, 67.57mg nickel chloride and 0.836ml concentrated hydrochloric acid were dissolved in 100ml deionized water to form a mixed solution. Using ITO conductive glass of 2cm multiplied by 1cm multiplied by 0.1cm as a working electrode, a platinum electrode of 1cm multiplied by 0.1cm as a counter electrode, a silver/silver chloride electrode as a reference electrode, connecting an electrochemical workstation, and using a cyclic voltammetry scanning mode to use 50m Vs within the voltage range of 0V-0.9V-1Is continuously scanned for 60 times to obtain Ni with the thickness of 100nm3[Fe(CN)6]2Prussian blue coordination crystal film.The obtained electroplated Ni3[Fe(CN)6]2The conducting glass of the Prussian blue coordination crystal is used as the cathode of the seawater battery for the combined production of electricity and oxygen.
Step 2: preparation of photo-anode of electricity-oxygen co-production seawater battery
And (3) pretreating the titanium sheet, namely polishing and grinding the titanium sheet with the size of 4cm multiplied by 3cm and the thickness of 0.3mm by adopting 1000-mesh sand paper and aluminum oxide nano particles so as to remove scratches in the processing process. After polishing, the glass is washed by deionized water and naturally dried. Configuring HF (40.0%), HNO3(65-68%) and deionized water at a volume ratio of 1:4: 5. And soaking the polished titanium sheet in the mixed solution for 30s for etching to remove the oxide layer. And ultrasonically cleaning the etched titanium sheet by using deionized water, ethanol and acetone respectively, and naturally airing for later use. And preparing electrolyte, wherein the concentration of the electrolyte is 1 mol/L. And (3) placing the beaker filled with the electrolyte on a magnetic stirrer, setting the rotating speed of the stirrer to be 100r/min, adjusting the rotating speed to be 400r/min after uniformly stirring, adopting a pretreated titanium sheet as a working electrode and a platinum sheet electrode as a double-electrode system of a counter electrode, and adjusting a direct-current power supply to work for 30min under the voltage of 30V. And after the reaction is finished, taking out the titanium sheet, washing the titanium sheet by using deionized water and ethanol, and naturally airing the titanium sheet. Then calcining for 3h in a muffle furnace at 550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; calcining to obtain a titanium dioxide film with the thickness of 0.5 mu m, which grows on the surface of the titanium sheet substrate and is the photo-anode;
and step 3: assembly of electricity oxygen coproduction sea water battery
The Ni obtained in the step 13[Fe(CN)6]2And (3) respectively placing the conductive glass film of the Prussian blue coordination crystal and the titanium dioxide film electrode obtained in the step (2) in seawater electrolyte which can mutually circulate, and connecting the conductive glass film and the titanium dioxide film electrode by using a lead to obtain the electricity-oxygen co-production seawater battery.
FIG. 5 is a photo-generated current time chart and an oxygen generation time chart of the seawater battery with combined generation of electricity and oxygen according to the embodiment, under the test condition that the Ni obtained in the step 1 is used3[Fe(CN)6]2Conductive glass film of Prussian blue coordination crystal and preparation method thereofAnd (3) putting the titanium dioxide film electrodes obtained in the step (2) into 200mL of seawater electrolyte which can be mutually circulated, and putting the seawater electrolyte into a 300mL beaker. The titanium dioxide electrode is connected with a counter electrode and a reference electrode of an electrochemical workstation and is electroplated with Ni3[Fe(CN)6]2The conducting glass film electrode of the Prussian blue coordination crystal is connected to a working electrode of an electrochemical workstation, and a 100W xenon lamp is used for irradiation in a current-time mode, so that a current-time relation graph shown in 1) in figure 5 can be obtained; meanwhile, in the process of illumination, the oxygen concentration time chart shown in 2) in fig. 5 can be obtained by testing the oxygen concentration in the electrolyte by using a dissolved oxygen meter.
In the embodiment, the prepared cathode and the photoanode are connected and respectively placed in seawater electrolyte with salinity of more than or equal to 0.1%, when the sunlight shines, titanium dioxide can generate electron hole pairs under the excitation of the sunlight, and the prussian blue coordination crystal has the ability of accepting electrons, so that the photoproduction electrons flow to the cathode through an external circuit to form current, and meanwhile, in order to keep the electroneutrality, the prussian blue coordination crystal can obtain a cation from the seawater. On the other hand, the holes generated by the photo-anode react with water molecules to generate oxygen, so that the purpose of repairing the anoxic seawater is achieved. The whole process is simple and easy to implement, and is green and pollution-free to the seawater environment.
Claims (3)
1. A preparation method of a sunlight-driven electricity-oxygen cogeneration seawater battery is characterized by comprising the following specific steps:
step 1: selection and preparation of cathode
A1: selection of coordination crystals
Selecting a Prussian blue coordination crystal and a crystal with an alkali metal ion storage site as coordination crystals, wherein the molecular general formula of the Prussian blue coordination crystal is AaMⅠ bMⅡ c[MⅢ(CN)6]d·nH2O; wherein A is an alkali metal element, a hydrogen ion or an ammonium ion; mⅠ、MⅡ、MⅢAre the same or differentA transition metal element; a. b, c, d are [0,2 ]]The value of (a); n is [0,20 ]]The value of (a); the alkali metal element is Li, Na, K, Rb or Cs; the transition metal element is Fe, Co, Ni, Mn, Ti, Zn, Cr, Cu or In;
the crystal with sodium ion storage sites is: na (Na)2C6O6、Na4Fe3(PO4)2(P2O7)、NaVO2、NaCrO2、NaMnFe2(PO4)3、Na3Fe2(PO4)3、C24H8O6、C6Cl4O2、NaFePO4、Na2FeP2O7Or NaMnO2；
A2: preparation of the cathode
The preparation of the cathode adopts a coating or electroplating mode:
i) coating: grinding the coordination crystal, a conductive agent and a binder for 5-50 minutes by using a mortar according to a certain proportion under the action of a solvent, wherein the mass ratio is 1-10: 0.1; coating the uniformly ground slurry on a current collector, wherein the thickness of the coated film is 100 nm-1 dm, and the contained coordination crystal is 1mg/cm2～100mg/cm2And placing the anode and the cathode in an oven at 50-100 ℃ for vacuum drying for 0.2-24 hours to obtain a current collector electrode coated with the coordination crystal as the cathode; wherein the content of the first and second substances,
the conductive agent is one or a mixture of a plurality of carbon black, conductive graphite, carbon fiber, carbon nano tube and graphene;
the binder is polyvinylidene fluoride, styrene butadiene rubber or carboxymethyl cellulose;
the solvent is N-methyl pyrrolidone, dimethylacetamide, N-dimethylformamide, triethyl phosphate or dimethyl sulfoxide;
the current collector is carbon cloth, metal titanium, metal copper or metal nickel;
ii) electroplating: preparing a mixed solution of metal salt, ligand and inorganic salt, wherein the concentration of the metal salt is 0.1 mmol/L-1 mmol/L; ligand concentration of 0.1mmol/L E5 mmol/L; the concentration of the inorganic salt is 0.1-3 mol/L; using conductive glass with the thickness of 1mm multiplied by 1 mm-3 m multiplied by 3m as a working electrode, a platinum sheet electrode as a counter electrode, a silver/silver chloride electrode as a reference electrode, connecting an electrochemical workstation, and using a cyclic voltammetry scanning mode to perform the operation of 0.01mVs within the voltage range of-1.5V-1～1Vs-1Continuously scanning for 50-500 times; obtaining a coordination crystal thin film electrode with the thickness of 10 nm-500 nm; the metal salt is nickel chloride, copper chloride, zinc chloride, ferric chloride, nickel sulfate, copper sulfate, zinc nitrate, nickel nitrate, copper nitrate or ferric nitrate; the ligand is potassium ferricyanide, potassium ferrocyanide or sodium ferrocyanide; the inorganic salt is sodium sulfate, sodium nitrate, potassium nitrate or potassium sulfate;
step 2: selection and preparation of photoanode
B1: selection of photo-anode
The titanium dioxide or zinc oxide N-type semiconductor is selected as the photo-anode, namely under the irradiation of sunlight, electron hole pairs can be generated, and the recombination rate of the electron holes is low;
b2: preparation of photo-anode
The preparation of the photo-anode material adopts an anode oxidation or substrate growth mode:
i) anodizing: pretreating a titanium sheet, namely polishing and grinding the titanium sheet with the size of 1cm multiplied by 1 cm-3 m multiplied by 3m and the thickness of 0.05 mm-0.3 mm by adopting 100-1000-mesh sand paper and aluminum oxide nano particles to remove scratches in the processing process; after polishing, washing with deionized water and naturally drying; preparing 40.0% of HF and 65-68% of HNO3And deionized water at a volume ratio of 1:4: 5; soaking the polished titanium sheet in the mixed solution for 1-60 s for etching to remove an oxide layer; ultrasonically cleaning the etched titanium sheet by using deionized water, ethanol and acetone respectively, and naturally airing for later use; preparing electrolyte, wherein the concentration of the electrolyte is 0.1 mmol/L-1 mol/L; placing a beaker filled with electrolyte on a magnetic stirring device, setting the rotating speed of a stirrer to be 500-100 r/min, after the stirring is uniform, adjusting the rotating speed to be 100-400 r/min, adopting a pretreated titanium sheet as a working electrode and a platinum sheet electrode as a double-electrode system of a counter electrode, and adjusting a direct current power supply to enable the double-electrode system to be under 30V voltageWorking for 10-50 min; after the reaction is finished, taking out the titanium sheet, washing the titanium sheet by using deionized water and ethanol, and naturally airing the titanium sheet; then calcining for 2-4 h in a muffle furnace at 400-550 ℃ in the air atmosphere at the heating speed of 1-5 ℃/min; calcining to obtain a metal sheet oxide film with the thickness of 1 nm-1 mu m growing on the surface of the substrate, namely the photo-anode; wherein the content of the first and second substances,
the electrolyte is as follows: 0.1 to 0.5 percent of hydrofluoric acid aqueous solution or 0.1 to 0.5 percent of ammonium fluoride aqueous solution;
ii) substrate growth: taking conductive glass with the resistance of 1-20 omega, the size range of 1cm multiplied by 1 cm-3 m multiplied by 3m and the thickness of 0.05 mm-15 mm as a substrate; respectively putting the substrate into 5-18% of acetone, absolute ethyl alcohol and deionized water, ultrasonically cleaning for 10-40 minutes, vertically and obliquely putting the substrate into a reaction kettle, and placing the substrate with the conductive surface facing downwards; adding 1-100 ml of hydrochloric acid solution with the concentration of 18% into a reaction kettle; then sealing the reaction kettle, and transferring the reaction kettle to an oven with the temperature of 160-200 ℃ for reaction for 5-48 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and washing the substrate by deionized water; putting the substrate into an oven with the temperature of 40-100 ℃ for drying for 0.2-24 h; soaking the dried substrate in a titanium tetrachloride solution with the concentration of 1-0.5 mol/L in an oven at 80 ℃ for 30-60 min, then washing the substrate with absolute ethyl alcohol, and drying the substrate in the oven at 50-70 ℃ for 2-15 h; finally calcining for 2-4 h in a muffle furnace at 400-550 ℃ in the air atmosphere, wherein the heating rate is 5 ℃/min; after calcination, growing a white oxide film with the thickness of 1 nm-1 mu m on the conductive surface of the substrate, namely the photo-anode; wherein the content of the first and second substances,
the conductive glass is as follows: FTO;
and step 3: electrolyte solution
Seawater with the salinity of at least 0.1 percent is selected as electrolyte and used for providing metal ions required in the power generation process and balancing electrode polarization effect; the seawater is water in the ocean that occupies about 70% of the earth;
and 4, step 4: generation of constant photocurrent
Respectively putting the photo-anode and the cathode into seawater electrolyte which flows mutually, connecting the cathode and the photo-anode by using a wire, and generating constant direct current due to the transfer of photo-generated electrons to the cathode when the photo-anode semiconductor is excited by illumination;
and 5: constant oxygen generation
The cathode and the photo-anode are respectively placed in seawater electrolyte which flows mutually, the cathode and the photo-anode are connected by a lead, and when the photo-anode semiconductor is excited by light, water molecules in seawater are oxidized into oxygen and hydrogen ions by the photo-induced holes, so that oxygen is released.
2. The solar-powered cogeneration seawater battery of claim 1, wherein the prussian blue-like crystals are: fe4[Fe(CN)6]3、NaFe[Fe(CN)6] 、Fe[Fe(CN)6] 、NaMn[Fe(CN)6] 、Na2Mn[Fe(CN)6] 、NaMn[Fe(CN)6] 、 Ni3[Fe(CN)6]2、Na2Ni[Fe(CN)6] 、Na2Co[Fe(CN)6]、NaTi[Fe(CN)6]、Na2Cu[Fe(CN)6]Or Na2Zn[Fe(CN)6]。
3. A solar-powered cogeneration seawater cell made according to the method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010805306.XA CN112086289A (en) | 2020-08-12 | 2020-08-12 | Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010805306.XA CN112086289A (en) | 2020-08-12 | 2020-08-12 | Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112086289A true CN112086289A (en) | 2020-12-15 |
Family
ID=73729148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010805306.XA Pending CN112086289A (en) | 2020-08-12 | 2020-08-12 | Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112086289A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113104862A (en) * | 2021-03-17 | 2021-07-13 | 山东师范大学 | Method for rapidly preparing Prussian blue or analogues thereof in batches and application of method |
| CN113293292A (en) * | 2021-05-25 | 2021-08-24 | 上海大学 | Seawater lithium extraction system based on solar drive and preparation method thereof |
| CN114628711A (en) * | 2022-03-31 | 2022-06-14 | 青岛科技大学 | Light-assisted magnesium/seawater battery and preparation method thereof |
| CN114804303A (en) * | 2022-04-25 | 2022-07-29 | 上海大学 | System and method for degrading organic pollutants in water body and recovering heavy metal ions at same time |
| CN114853103A (en) * | 2022-04-19 | 2022-08-05 | 南京理工大学 | Local heating type saline solution water separation device based on isotropic ion exclusion |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
| WO2013057079A1 (en) * | 2011-10-17 | 2013-04-25 | Fundació Privada Institut Català D'investigació Química (Iciq) | Process for water oxidation comprising the use of a polyoxometalate compound as water oxidation catalyst |
| CN109637813A (en) * | 2018-11-12 | 2019-04-16 | 华东师范大学 | A kind of sunlight helps seawater battery and preparation method |
| CN109821559A (en) * | 2019-03-27 | 2019-05-31 | 泉州师范学院 | A kind of preparation method and applications of core-shell structure composite photoelectric material |
-
2020
- 2020-08-12 CN CN202010805306.XA patent/CN112086289A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
| WO2013057079A1 (en) * | 2011-10-17 | 2013-04-25 | Fundació Privada Institut Català D'investigació Química (Iciq) | Process for water oxidation comprising the use of a polyoxometalate compound as water oxidation catalyst |
| CN109637813A (en) * | 2018-11-12 | 2019-04-16 | 华东师范大学 | A kind of sunlight helps seawater battery and preparation method |
| CN109821559A (en) * | 2019-03-27 | 2019-05-31 | 泉州师范学院 | A kind of preparation method and applications of core-shell structure composite photoelectric material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113104862A (en) * | 2021-03-17 | 2021-07-13 | 山东师范大学 | Method for rapidly preparing Prussian blue or analogues thereof in batches and application of method |
| CN113293292A (en) * | 2021-05-25 | 2021-08-24 | 上海大学 | Seawater lithium extraction system based on solar drive and preparation method thereof |
| CN114628711A (en) * | 2022-03-31 | 2022-06-14 | 青岛科技大学 | Light-assisted magnesium/seawater battery and preparation method thereof |
| CN114853103A (en) * | 2022-04-19 | 2022-08-05 | 南京理工大学 | Local heating type saline solution water separation device based on isotropic ion exclusion |
| CN114853103B (en) * | 2022-04-19 | 2023-10-31 | 南京理工大学 | Local heating type saline solution water separation device based on homopolar ion repulsion |
| CN114804303A (en) * | 2022-04-25 | 2022-07-29 | 上海大学 | System and method for degrading organic pollutants in water body and recovering heavy metal ions at same time |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112086289A (en) | Sunlight-driven electricity-oxygen co-production seawater battery and preparation method thereof | |
| CN109637813B (en) | Sunlight sea water assisting battery and preparation method thereof | |
| CN105200450B (en) | A kind of molybdenum disulfide/carbon black is combined Electrocatalytic Activity for Hydrogen Evolution Reaction material and preparation method thereof | |
| CN108499585B (en) | Phosphorus-containing compound and preparation and application thereof | |
| CN105132941B (en) | A kind of two selenizing molybdenums/carbon black is combined Electrocatalytic Activity for Hydrogen Evolution Reaction material and preparation method thereof | |
| CN109616674B (en) | Hybrid battery based on seawater solute and preparation method | |
| CN106868563B (en) | A kind of preparation method and applications of selenide thin film modifying foam nickel electrode | |
| He et al. | NiFe-layered double hydroxide decorated BiVO4 photoanode based bi-functional solar-light driven dual-photoelectrode photocatalytic fuel cell | |
| CN106252616A (en) | A kind of nickelous selenide/hollow carbon fiber composite and preparation method thereof | |
| CN110655656A (en) | Cobalt metal organic framework material and preparation method and application thereof | |
| CN108597886B (en) | A kind of organic solution and its application for modified oxidized iron light anode | |
| CN110350200A (en) | A kind of lithium ion battery three-dimensional Arrays of Copper Nanowires collector and preparation method thereof | |
| CN114481192B (en) | Cd doped titanium dioxide/indium zinc sulfide photo-anode and preparation method thereof | |
| CN113299928A (en) | Preparation method of high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material | |
| CN108842168A (en) | A kind of two-step electrochemical method preparation g-C3N4/ MMO compound film optoelectronic pole | |
| CN110205638B (en) | Z-shaped CuBi2O4/SnO2Photoelectric cathode film and preparation method and application thereof | |
| CN111816890A (en) | Fluid seawater battery and preparation method thereof | |
| CN108364792A (en) | A kind of preparation method and applications of nickel cobalt selenium hollow ball-shape multilevel structure material | |
| CN113571812B (en) | Bio-photo-electrochemical cell based on photo/chemical integrated energy conversion | |
| CN113089020B (en) | Co(OH) 2 /FePO 4 Photoelectrode thin film and application thereof in photoelectrochemical water decomposition | |
| CN113293404B (en) | Heterojunction photo-anode material and preparation method and application thereof | |
| CN113502513A (en) | Method for directly depositing copper metal by utilizing solar energy | |
| CN106876144A (en) | A kind of DSSC of utilization eggshell film preparation is to electrode material and method | |
| JP2008243754A (en) | Photoelectric conversion electrode, manufacturing method of the same, and dye-sensitized solar cell | |
| CN110408954B (en) | Preparation method of photoelectrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201215 |