CN114824588A - Gel-state chargeable discharge light-assisted iron-air battery and preparation method thereof - Google Patents
Gel-state chargeable discharge light-assisted iron-air battery and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000010410 calcium alginate Nutrition 0.000 claims abstract description 14
- 239000000648 calcium alginate Substances 0.000 claims abstract description 14
- 229960002681 calcium alginate Drugs 0.000 claims abstract description 14
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims abstract description 14
- 239000000017 hydrogel Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 17
- 238000004070 electrodeposition Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 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 compound [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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 6
- 239000011245 gel electrolyte Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
Abstract
The invention relates to a gel-state chargeable discharge light-assisted iron-air battery and a preparation method thereof. Is TiO 2 The iron-air battery comprises a CuO film photoelectrode as an air electrode, an iron sheet as a metal electrode and calcium alginate hydrogel as an electrolyte. TiO prepared by the invention 2 The CuO photo-auxiliary material has excellent photocatalytic activity and stability, and the charging voltage of the iron-air battery is reduced and the discharging voltage of the iron-air battery is improved by introducing sunlight. On the other hand, the invention realizes the conversion among solar energy, chemical energy and electric energy, and opens up a new way for the rechargeable iron-air battery. In addition, water is usedThe gel electrolyte replaces the traditional aqueous solution as electrolyte, solves the problem of leakage of the traditional battery, and provides a new way for the development of electronic equipment.
Description
Technical Field
The invention belongs to the technical field of metal-air batteries, and particularly relates to an iron-air battery based on a semiconductor photoelectrode material and a gel electrolyte.
Background
Energy has been an important subject of human research and development, and batteries have gained wide attention as an important carrier of energy. Among them, the most common battery is a lithium ion battery, which has been widely used due to its characteristics of long cycle life, good low-temperature discharge performance, high specific energy, and the like. However, the lithium ion battery has the defects of high danger, small reserve, high mining difficulty and the like. There is therefore a need for a more efficient and inexpensive battery to replace lithium ion batteries. The metal-air battery just compensates for the deficiency.
On the other hand, with the continuous depletion of fossil fuel derivatives, the development and utilization of abundant, clean renewable energy sources is an urgent need for the development of contemporary energy sources. Among them, solar energy has a wide development prospect as one of the most concerned clean energy. At this time, the photo-assisted metal-air battery based on the photocatalytic technology gradually comes into the field of vision of people. The metal-air battery consists of a metal electrode, an air electrode and an electrolyte solution. The metal-air battery is considered as a new energy technology with great development potential due to the characteristics of high theoretical energy density, environmental friendliness, low cost and the like.
Iron (Fe) is the fourth most abundant element and is a low-price and environment-friendly anode material. Therefore, the iron-air battery is more advantageous in terms of material cost. Moreover, Fe is more corrosion resistant and relatively reduces the self-discharge rate. Therefore, among various metal-air batteries, iron-air batteries have received much attention due to their high energy density, environmental friendliness, abundant content, and excellent safety. Light energy is cited in many electrochemical devices, but its use in a ferro air battery system is rare. Therefore, the light energy is introduced into the iron-air battery, the solar energy can be fully utilized, and the conversion from the solar energy to the electric energy is realized. Meanwhile, a semiconductor photoelectrode material is used for replacing a noble metal electrode, so that the cost of the iron-air battery can be obviously reduced. In addition, the conventional air battery usually selects an aqueous electrolyte, which has the problems of leakage and portability. Further research is required because the gel electrolyte has poor conductivity and the solid electrolyte is easily deteriorated and used when measured for a long time.
Disclosure of Invention
In order to solve the technical problems, the invention prepares TiO with excellent photocatalytic activity by using a hydrothermal method, an electrochemical deposition method and a calcination method 2 -CuO film photoelectrode material and replacing the traditional water system electrolyte with gel electrolyte as the electrolyte of the iron-air battery. The iron-air battery provided by the invention can reduce the charging voltage of the iron-air battery under the illumination condition and improve the discharging voltage of the iron-air battery. The cooperative conversion among solar energy, chemical energy and electric energy is realized.
The technical scheme adopted by the invention is as follows: a gel-state chargeable discharge light-assisted Fe-air battery is a TiO-based rechargeable Fe-air battery 2 The iron-air battery comprises a CuO film photoelectrode as an air electrode, an iron sheet as a metal electrode and calcium alginate hydrogel as an electrolyte.
A preparation method of a gel-state chargeable and dischargeable light-assisted iron-air battery comprises the following steps:
1)TiO 2 -preparation of CuO thin film photoelectrode: performing electrodeposition by electrochemical deposition to deposit cuprous oxide on TiO 2 On the film to obtain TiO 2 -Cu 2 O film, then placing the O film in a muffle furnace for high-temperature calcination, and cooling to obtain TiO 2 -CuO thin film photoelectrode.
Preferably, the TiO is 2 The preparation method of the film comprises the following steps: mixing deionized water, concentrated hydrochloric acid and n-butyl titanate, stirring until the mixture is clear and transparent, placing the obtained mixed solution and a conductive substrate into a high-pressure reaction kettle, reacting for 4 hours at 170 ℃, cooling to room temperature, taking out, washing with deionized water, drying at room temperature, placing into a muffle furnace, calcining for 2 hours at 500 ℃ to obtain the conductive substrate loaded with TiO 2 A film.
Preferably, the volume ratio of the deionized water to the concentrated hydrochloric acid to the n-butyl titanate is 7.5:7.5: 1.
Preferably, step 1) specifically comprises: mixing CuSO 4 ·5H 2 Dissolving O and lactic acid in deionized water, adjusting the pH value to 11-12 by using NaOH solution, taking the obtained solution as a deposition solution, taking a Pt wire as a counter electrode, taking Ag/AgCl as a reference electrode, and loading TiO 2 The conductive substrate of the film is a working electrode, and the electro-deposition is carried out by utilizing an electrochemical deposition method to deposit cuprous oxide on the TiO 2 On the film to obtain TiO 2 -Cu 2 O film, then placing the O film in a muffle furnace, calcining for 2h at 550 ℃, and cooling to obtain TiO 2 -CuO thin film photoelectrode.
Preferably, the mass ratio of CuSO 4 ·5H 2 And (3) O is lactic acid in a ratio of 1: 10-11.
Preferably, the electrodeposition is carried out under the bias of-0.5V for 600-650 s.
2) Preparing the calcium alginate hydrogel: and (3) uniformly mixing the sodium alginate solution and the potassium hydroxide solution, immersing the mixed solution into the calcium chloride solution, and uniformly stirring to form gel, thus obtaining the calcium alginate hydrogel.
Preferably, step 2) specifically comprises: uniformly mixing a sodium alginate solution with the mass percentage concentration of 1% and a potassium hydroxide solution with the concentration of 1M according to the volume ratio of 6:1, and soaking the obtained mixed solution in a calcium chloride solution with the concentration of 0.05g/mL for about 5min to obtain the calcium alginate hydrogel.
3) With TiO 2 And the-CuO film photoelectrode is used as an air electrode, the iron sheet is used as a metal electrode, and the calcium alginate hydrogel is used as an electrolyte to form the iron-air battery.
Compared with the prior art, the invention has the following remarkable advantages:
1. the invention utilizes semiconductor material TiO 2 The CuO film replaces a noble metal material, so that the cost is saved while the battery performance is improved.
2. According to the invention, the metal electrode uses the iron sheet, the iron is low in price and easy to obtain, the energy density and the theoretical voltage of the iron-air battery are larger, and the current iron-air battery is less researched, so that a large research space is provided. In addition, compared with other air batteries, the iron-air battery has the advantages of high safety, long service life and the like.
3. The invention, TiO for air electrode 2 -CuO film, a TiO is prepared 2 And the CuO air semiconductor photoelectrode material reduces the charging voltage of the iron-air battery, improves the discharging voltage of the iron-air battery and fully realizes the conversion between solar energy and electric energy.
4. Compared with the traditional iron-air battery, the invention successfully introduces the gel electrolyte and solar energy into the iron-air battery system, fully utilizes the renewable resource of sunlight, greatly reduces the charging voltage of the battery under the condition of controlling the battery cost, widens the road of green energy sources, and solves the problems of liquid leakage and difficult carrying of the traditional battery. Meanwhile, the photocatalyst is simple to prepare, low in price and good in photoelectric property, and is a photoelectrode material with considerable development prospect.
Drawings
Fig. 1 is a working principle diagram of the iron-air battery based on gel-state chargeable and dischargeable electric assistance in the invention.
FIG. 2 shows TiO in the iron-air battery based on gel-state chargeable/dischargeable electric assistance 2 -test chart of charge and discharge performance of CuO film as air electrode.
FIG. 3 shows TiO in the iron-air battery based on gel-state chargeable/dischargeable electric assistance 2 -alternating current impedance curve of CuO film as air electrode.
Fig. 4 is a schematic structural diagram of the iron-air battery based on gel-state chargeable and dischargeable electric assistance in the invention.
Fig. 5 is a device assembly diagram of the iron-air battery based on gel-state chargeable and dischargeable electric assistance.
FIG. 6 is a diagram of an LED bulb lighted by two serially connected iron-air batteries which can charge and discharge electricity and assist based on gel state under simulated sunlight.
Detailed Description
In order to better illustrate the content of the invention, the invention is further illustrated by the following specific embodiments:
example 1 iron-air cell based on gel-state chargeable discharge light assist
The preparation method comprises the following steps:
1、TiO 2 preparation of films
7.5mL of deionized water, 7.5mL of concentrated hydrochloric acid, and 1mL of n-butyl titanate were mixed and stirred until the mixed solution was clear and transparent. Putting the obtained mixed solution and conductive glass into a high-pressure reaction kettle together, reacting for 4h at 170 ℃, cooling to room temperature, taking out, washing the conductive glass with deionized water, airing at room temperature, putting into a muffle furnace, and calcining for 2h at 500 ℃ to obtain the conductive glass loaded with TiO 2 A film.
2、TiO 2 -preparation of CuO thin film photoelectrode:
1.25g of CuSO 4 ·5H 2 Dissolving O and 13.5g of lactic acid in 50mL of deionized water, adjusting the pH to 11-12 by using a 6M NaOH solution, and taking the obtained solution as a deposition solution.
Carrying out electrodeposition by using an electrochemical deposition method to load TiO 2 The conductive glass of the film is used as a working electrode, Ag/AgCl is used as a reference electrode, a Pt wire is used as a counter electrode, a bias voltage of-0.51V is applied, electrodeposition is carried out for 600s at the temperature of 80 ℃, and cuprous oxide is deposited on TiO 2 On the film to obtain TiO 2 -Cu 2 And (3) O film. Putting the obtained product into a muffle furnace, calcining for 2 hours at 550 ℃, and cooling to room temperature to obtain TiO 2 -CuO thin film photoelectrode.
3. Preparing the calcium alginate hydrogel:
6mL of sodium alginate solution (1% wt) was mixed with 1mL of potassium hydroxide solution (1M) uniformly, and the resulting solution was immersed in calcium chloride solution (0.05g/mL) for about 5min to obtain a calcium alginate hydrogel.
4. Assembly of iron air battery
As shown in FIG. 4, with TiO 2 the-CuO film photoelectrode (1) is an air electrode, the iron sheet (2) is a metal electrode, and the calcium alginate hydrogel (3) is an electrolyte. Fixing the air electrode and the iron sheet by using foam rubber (4) to assemble ironAn air cell. The physical assembly diagram of the components of the iron-air battery is shown in figure 5.
(II) Performance test
1. AC impedance and charging and discharging performance test
The method comprises the following steps: and measuring the alternating current impedance and the charge and discharge performance of the iron-air battery by using an electrochemical workstation under the conditions of illumination and darkness respectively. The results are shown in FIGS. 2 and 3.
As can be seen from fig. 2, the charging voltage under the illumination condition was measured to be 1.45V, and the discharging voltage was measured to be 1.28V; the charging voltage under dark conditions was 2.5V and the discharging voltage was 1.2V.
As can be seen from the electrochemical impedance spectrum of FIG. 3, TiO was observed under light conditions as compared to dark conditions 2 The EIS curve radius of the CuO electrode is small, which shows that the transfer speed of charge carriers under the illumination condition is higher, and the resistance of the whole battery is reduced.
2. Experiment of Battery Performance
Two sections of the gel-state chargeable and dischargeable light-assisted iron-air battery are connected in series and then connected with an LED bulb, and under the irradiation of simulated sunlight, the LED bulb is lighted as shown in figure 6.
Claims (8)
1. A gel-state chargeable and dischargeable light-assisted iron-air battery is characterized in that: is TiO 2 And the iron-air battery comprises a CuO film photoelectrode as an air electrode, an iron sheet as a metal electrode and calcium alginate hydrogel as an electrolyte.
2. The method for preparing a gel-state chargeable discharge light-assisted iron-air battery according to claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
1)TiO 2 -preparation of CuO thin film photoelectrode: performing electrodeposition by electrochemical deposition to deposit cuprous oxide on TiO 2 On the film, TiO is obtained 2 -Cu 2 O film, then placing the O film in a muffle furnace for high-temperature calcination, and cooling to obtain TiO 2 -CuO thin film photoelectrode;
2) preparing the calcium alginate hydrogel: uniformly mixing a sodium alginate solution and a potassium hydroxide solution, and soaking the obtained solution into a calcium chloride solution to obtain a calcium alginate hydrogel;
3) with TiO 2 And the-CuO film photoelectrode is used as an air electrode, the iron sheet is used as a metal electrode, and the calcium alginate hydrogel is used as an electrolyte to form the iron-air battery.
3. The method of claim 2, wherein: step 1), the TiO 2 The preparation method of the film comprises the following steps: mixing deionized water, concentrated hydrochloric acid and n-butyl titanate, stirring until the mixture is clear and transparent, placing the obtained mixed solution and a conductive substrate into a high-pressure reaction kettle, reacting for 4 hours at 170 ℃, cooling to room temperature, taking out, washing with deionized water, drying at room temperature, placing into a muffle furnace, calcining for 2 hours at 500 ℃ to obtain the conductive substrate loaded with TiO 2 A film.
4. The production method according to claim 3, characterized in that: according to the volume ratio, deionized water, concentrated hydrochloric acid and n-butyl titanate are 7.5:7.5: 1.
5. The production method according to claim 3, characterized in that: step 1), specifically: mixing CuSO 4 ·5H 2 Dissolving O and lactic acid in deionized water, adjusting the pH value to 11-12 by using NaOH solution, taking the obtained solution as a deposition solution, taking a Pt wire as a counter electrode, taking Ag/AgCl as a reference electrode, and loading TiO 2 The conductive substrate of the film is a working electrode, and the electro-deposition is carried out by utilizing an electrochemical deposition method to deposit cuprous oxide on the TiO 2 On the film to obtain TiO 2 -Cu 2 O film, then placing the O film in a muffle furnace, calcining for 2h at 550 ℃, and cooling to obtain TiO 2 -CuO thin film photoelectrode.
6. The method of claim 5, wherein: according to the mass ratio of CuSO 4 ·5H 2 And (3) O is lactic acid in a ratio of 1: 10-11.
7. The method of claim 5, wherein: the electrodeposition is carried out under the bias of-0.5V for 600-650 s.
8. The production method according to claim 2, characterized in that: step 2), specifically: uniformly mixing a sodium alginate solution with the mass percentage concentration of 1% and 1M potassium hydroxide according to the volume ratio of 6:1, and immersing the obtained solution into a calcium chloride solution with the concentration of 0.05g/mL to obtain the calcium alginate hydrogel.
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