A preparation method of an MPc-VOH high-efficiency bifunctional photoelectric cathode material based on a p-n type heterojunction

Abstract

The application provides a preparation method of an MPc-VOH high-efficiency bifunctional photoelectric cathode material based on a p-n type heterostructure, which comprises the following steps: dispersing vanadium pentoxide in deionized water to obtain a vanadium pentoxide solution, then adding hydrogen peroxide solution drop by drop, carrying out a hydrothermal reaction with a porous carbon material as a substrate to obtain a VOH / C precursor; dissolving a p-type semiconductor in a solvent, then mixing the p-type semiconductor with the VOH / C precursor, carrying out a reaction under heating, and drying; taking out the dried material after cooling to room temperature, then washing, drying and annealing to obtain a fan-shaped nanosheet-shaped composite material MPc-VOH / C. The cathode material has not only a suitable structure and higher light absorption capacity, but also can accelerate the separation of photo-generated electron-hole pairs, and exhibits good photoelectrochemical performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of light-assisted zinc ion batteries, and particularly relates to a preparation method of an MPc-VOH high-efficiency bifunctional photoelectric cathode material based on a p-n type heterojunction. BACKGROUND

[0002] The explosive growth of portable electronic devices and electric vehicles has put forward urgent demands for long service life and high energy density of energy storage systems, and the energy density of mainstream metal ion batteries has approached the theoretical limit, which is difficult to meet the demands. Under this background, the electrochemical energy storage-solar photovoltaic integrated system combining secondary batteries and solar technologies has become a breakthrough direction, and the light-assisted rechargeable zinc ion battery provides a feasible path for solving the above problems by directly converting and storing solar energy.

[0003] Vanadium pentoxide hydrate is a common and stable layered vanadium-based material, which has a high theoretical capacity of zinc ion storage (589 mAh·g -1 ), and as a visible light responsive semiconductor, its band gap energy (2.2 eV) is suitable for collecting the visible light spectrum, the energy band spans the electrochemical redox potential, and the photocharge can be realized by photoexcited electron-hole, which is an ideal bifunctional photoelectric cathode material for light-assisted zinc ion batteries. However, the electrochemical and photocatalytic performance of single material still has a large space for improvement, and therefore, the development of a bifunctional photoelectrode with high catalytic activity and excellent energy storage capacity is an urgent demand to promote the development of this field. The metal phthalocyanine (MPC) family exhibits enhanced light response and charge separation performance due to its unique electrical and optical properties, and it may become one of the candidate materials for bifunctional photoelectric cathodes. However, most bifunctional light active materials have the problem of mismatch between rapid charge recombination and slow redox reaction, resulting in low light conversion efficiency, and the insufficient utilization of photo-generated carriers will exacerbate the efficiency decay during the cycle process. SUMMARY

[0004] Therefore, the present application aims to overcome the defects in the prior art and provides a preparation method of an MPc-VOH high-efficiency bifunctional photoelectric cathode material based on a p-n type heterojunction and its application in light-assisted zinc ion batteries.

[0005] To achieve the above-mentioned purpose, the technical scheme of the present application is as follows:

[0006] In a first aspect, the present application provides a preparation method of an MPc-VOH high-efficiency bifunctional photoelectric cathode material based on a p-n type heterojunction, which comprises the following steps:

[0007] Step one: dispersing vanadium pentoxide in deionized water to obtain a vanadium pentoxide solution, then adding H2O2 solution drop by drop, and performing hydrothermal reaction on a porous carbon material as a substrate to obtain a VOH / C precursor;

[0008] Step two, after dissolving the p-type semiconductor in the solvent, the reaction is carried out under the condition of mixing and heating with the VOH / C precursor, and the MPc-VOH / C composite material is obtained after drying;

[0009] Step three, after cooling the dried MPc-VOH / C composite material to room temperature, it is taken out, washed, dried and annealed to obtain a fan-shaped nanosheet composite material MPc-VOH / C. The composite material MPc-VOH / C is a fan-shaped nanosheet material in the shape of "ginkgo leaf".

[0010] Preferably, the raw material in step one is anhydrous vanadium pentoxide.

[0011] Preferably, the concentration of the vanadium pentoxide solution in step one is 0.2-0.6 mol / L.

[0012] Preferably, the hydrogen peroxide solution is a hydrogen peroxide solution with a mass fraction of 30%.

[0013] Preferably, the amount of hydrogen peroxide solution added dropwise in step one is 2-6 ml.

[0014] Preferably, the hydrothermal reaction temperature in step one is 170-190℃, and the reaction time is 6-10 hours.

[0015] Preferably, the porous carbon material in step one is selected from one or a mixture of several of carbonized cotton fibers, carbon fibers, carbon nanotubes, and carbon nanofibers.

[0016] Preferably, the p-type semiconductor in step two is selected from one or a mixture of several of zinc phthalocyanine, iron phthalocyanine, copper phthalocyanine, and cobalt phthalocyanine in the phthalocyanine family.

[0017] Preferably, the mass ratio of the p-type semiconductor to vanadium pentoxide in step two is 0.05-0.15.

[0018] Preferably, the molar mass of the p-type semiconductor in step two is 0.03-0.1 mmol.

[0019] Preferably, the solvent in step two is ethanol, and the amount of ethanol used is 30-50 ml.

[0020] Preferably, the heating temperature in step two is 110-130℃, and the reaction time is 10-14 hours.

[0021] Preferably, the drying temperature in step three is 60-80℃, and the time is 10-14h. The annealing temperature is 290-310℃, and the time is 1-3 hours.

[0022] In a second aspect, the application provides a high-efficiency bifunctional photoelectrode material for a light-assisted zinc ion battery, which is prepared by the above preparation method.

[0023] In a third aspect, the application provides an application of the above-mentioned cathode material in the preparation of a light-assisted zinc ion battery.

[0024] In a fourth aspect, the application provides a light-assisted zinc ion battery, which comprises a photoelectrode, an anode, a diaphragm and an electrolyte, and the photoelectrode material used is the above-mentioned high-efficiency bifunctional photoelectrode material for a light-assisted zinc ion battery.

[0025] Preferably, the anode is a zinc sheet, the diaphragm is a Whatman GF / D glass fiber filter paper, and the electrolyte is a zinc trifluoromethane sulfonate aqueous solution with a concentration of 2-3 mol / L.

[0026] The application can adjust the band gap to widen the visible light response range, improve the solar energy utilization rate, promote charge separation and transmission, and enhance the photoelectrochemical performance of the light-assisted zinc ion battery by coupling the band gap levels of different visible light response semiconductors.

[0027] Compared with the prior art, the application has the following advantages:

[0028] (1) The application first proposes a p-n type heterojunction MPc-VOH high-efficiency bifunctional photoelectrode material. The material not only has a suitable band structure and higher light absorption capacity, but also can accelerate the separation of photo-generated electron-hole pairs, and exhibits good photoelectrochemical performance, thereby laying a foundation for the future development of bifunctional photoelectrode design.

[0029] (2) The "ginkgo leaf-shaped" fan-shaped nanosheet material prepared by the application has a uniform structure distribution, can significantly improve the storage kinetics of zinc ions, not only improves the electrochemical performance of the vanadium-based cathode zinc ion battery, but also enhances the material structure stability and capacity retention rate, thereby providing a new path for the optimization of zinc ion battery electrode materials. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 is a scanning electron microscope (SEM) image of the material obtained in Example 1~Comparative Example 3;

[0031] Figure 2 is an electrochemical short cycle performance diagram of the material obtained in Example 1~Comparative Example 3 under the conditions of no light (A) and one sunlight (B);

[0032] Figure 3 is an ultraviolet-visible light absorption spectrum (UV-Vis) diagram of the material obtained in Example 1 and Comparative Example 1;

[0033] Figure 4is a plot of the photoluminescence (PL) spectrum of the material obtained in Example 1 and Comparative Example 1 ;

[0034] Figure 5 is a plot of the current-time response (I-T) of the material obtained in Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0035] The embodiments of the present application are described in detail below. The embodiments described below are examples only and are not intended to limit the present application, as defined by the appended claims.

[0036] In the present text, unless otherwise defined, all the technical and scientific terms used have the same meaning as that normally understood by a person of the ordinary skill in the art to which the present application belongs.

[0037] In the present text, where values are described as ranges, it is to be understood that the disclosure includes disclosure of all possible sub-ranges within the range, and of the specific numerical values falling within the range, regardless of whether the specific numerical values or the specific sub-ranges are explicitly indicated.

[0038] In the present text, reference to "a plurality of" or the like, unless otherwise specified, means greater than or equal to two or equal to two. For example, "one or more" means one or more than two.

[0039] In the present text, reference to "preferably", "more preferably" is only for describing embodiments or examples with better effects, and it is understood that it does not constitute a limitation on the scope of protection of the present application.

[0040] In the present text, reference to "further" or the like is for the purpose of description, indicating a difference in content, but should not be understood as a limitation on the scope of protection of the present application.

[0041] In the present text, the term "and / or" is a description of the association between objects, indicating that there can be three relationships. For example, A and / or B, means: A or B, or A and B, the three relationships.

[0042] In the present text, the term "about" means + / - 10% of the specified value, preferably + / - 5%, more preferably + / - 1%.

[0043] In the present text, "comprising", "including", "having", "containing", and the like, are all open terms, i.e. meaning including but not limited to.

[0044] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. Although preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application.

[0045] The application will be described in detail below with reference to examples.

[0046] Example 1

[0047] First step, preparation of VOH / CCFs precursor material;

[0048] First, the cotton carbon fiber (CCFs) substrate (3 x 4 cm 2 ) was pre-carbonized to preserve its natural hollow structure, which acts as a scaffold for the active material. 0.364 g of V2O5 was dispersed in 50 ml of deionized water, followed by dropwise addition of 4 mL of H2O2 (30 wt%). The mixture was stirred for 1 hour to form a clear orange-red solution. The hydrothermal reaction was carried out at 180°C for 8 hours. After hydrothermal treatment, the sample was taken out after the autoclave was naturally cooled to room temperature, washed with ethanol and deionized water three times respectively, and then dried in a 60°C oven for 12 h to obtain the VOH / CCFs precursor material.

[0049] Second step, preparation of ZnPc 0.1 -VOH / CCFs composite material;

[0050] 0.0364 g of ZnPc was dissolved in 40 mL of ethanol, and the mass ratio of ZnPc to V2O5 was controlled to be 0.1. After ultrasonic treatment for 30 min and continuous stirring for 1 h, the above solution was added to the VOH / CCFs precursor material and continuously stirred for 30 min. The mixture was transferred to a 100 mL autoclave, sealed and heated at 120°C for 12 h. After cooling to room temperature, it was washed with ethanol and deionized water three times respectively and then dried in a 60°C oven for 12 h to obtain the ZnPc 0.1 -VOH / CCFs composite material.

[0051] Third step, preparation of ZnPc 0.1 -VOH / CCFs composite material;

[0052] After the ZnPc 0.1 -VOH / CCFs composite material prepared in the second step was cooled to room temperature, it was taken out, washed with ethanol and distilled water three times respectively, and then dried in a 60°C oven for 12 h. Finally, the completely dried sample was annealed at 300°C for 2 h to obtain the ZnPc 0.1 -VOH / CCFs composite material, the SEM image of which is shown in Figure 1 .

[0053] Fourth step, assembly of light-assisted button cell;

[0054] To achieve illumination, a 8 mm diameter hole was drilled on the top of the CR2032 coin cell housing, and then ITO film was firmly attached on top of the hole using epoxy glue. The photoelectrode was then placed on the side of the cell with the optical window, ensuring its alignment for photo-driven electrochemical measurements.

[0055] ZnPc 0.1 VOH / CCFs composite was used as the cathode, zinc metal as the anode, Whatman GF / D glass fiber filter paper as the separator, and 2.5 mol / L zinc trifluoromethanesulfonate aqueous solution as the electrolyte to assemble CR2032 type photo-assisted zinc ion batteries in air atmosphere.

[0056] Example 2

[0057] First step, preparation of VOH / CCFs precursor material;

[0058] The same as the first step in Example 1.

[0059] Second step, preparation of ZnPc 0.05 VOH / CCFs composite;

[0060] The same as Example 1, except that 0.0182 g of ZnPc was dissolved in 40 mL of ethanol, and the mass ratio of ZnPc to V2O5 was controlled at 0.05. The above solution was added to the VOH / CCFs precursor material, and continuous stirring was performed for 30 min. The mixture was transferred to a 100 mL autoclave, sealed and heated at 120°C for 12 h. After cooling to room temperature, it was washed with ethanol and deionized water three times respectively, and then dried in a 60°C oven for 12 h to obtain ZnPc 0.05 VOH / CCFs composite.

[0061] Third step, preparation of ZnPc 0.05 VOH / CCFs composite;

[0062] The same as the third step in Example 1, ZnPc 0.05 VOH / CCFs composite was prepared. Figure 1

[0063] Fourth step, assembly of photo-assisted coin cell;

[0064] The same as the fourth step in Example 1.

[0065] Example 3

[0066] First step, preparation of VOH / CCFs precursor material;

[0067] ​The first step in Example 1.

[0068] The second step, preparation of ZnPc 0.15 -VOH / CCFs composite material.

[0069] The same as Example 1, except that 0.0546 g of ZnPc was dissolved in 40 mL of ethanol, and the mass ratio of ZnPc to V2O5 was controlled at 0.15, and the above solution was added to the VOH / CCFs precursor material, and continuously stirred for 30 min. The mixture was transferred to a 100 mL autoclave, sealed and heated at 120°C for 12 h. After cooling to room temperature, it was washed with ethanol and deionized water three times respectively and then dried in a 60°C oven for 12 h to obtain ZnPc 0.15 -VOH / CCFs composite material.

[0070] The third step, preparation of ZnPc 0.15 -VOH / CCFs composite material.

[0071] The third step in Example 1, to obtain ZnPc 0.15 -VOH / CCFs composite material, the SEM image of which is shown in Figure 1 .

[0072] The fourth step, assembly of a light-assisted button cell.

[0073] The fourth step in Example 1.

[0074] Example 4

[0075] The first step, preparation of a VOH / CCFs precursor material.

[0076] The first step in Example 1.

[0077] The second step, preparation of FePc 0.1 -VOH / CCFs composite material.

[0078] The same as Example 1, except that ZnPc was replaced by FePc, to obtain FePc 0.1 -VOH / CCFs composite material.

[0079] The third step, preparation of FePc 0.1 -VOH / CCFs composite material.

[0080] The third step in Example 1, to obtain FePc 0.1 -VOH / CCFs composite material.

[0081] The fourth step, assembly of a light-assisted button cell.

[0082] Step 4, Assemble the light-assisted button cell.

[0083] Example 5

[0084] Step 1, Prepare VOH / CCFs precursor material.

[0085] Step 1, As in Example 1.

[0086] Step 2, Prepare CuPc 0.1 -VOH / CCFs composite material.

[0087] As in Example 1, except that ZnPc is replaced with CuPc to give CuPc 0.1 -VOH / CCFs composite material.

[0088] Step 3, Prepare CuPc 0.1 -VOH / CCFs composite material.

[0089] Step 3, As in Example 1, to give CuPc 0.1 -VOH / CCFs composite material.

[0090] Step 4, Assemble the light-assisted button cell.

[0091] Step 4, As in Example 1.

[0092] Example 6

[0093] Step 1, Prepare VOH / CCFs precursor material.

[0094] Step 1, As in Example 1.

[0095] Step 2, Prepare CoPc 0.1 -VOH / CCFs composite material.

[0096] As in Example 1, except that ZnPc is replaced with CoPc to give CoPc 0.1 -VOH / CCFs composite material.

[0097] Step 3, Prepare CoPc 0.1 -VOH / CCFs composite material.

[0098] Step 3, As in Example 1, to give CoPc 0.1 -VOH / CCFs composite material.

[0099] Step 4, Assemble the light-assisted button cell.

[0100] Step 4, As in Example 1.

[0101] Comparative Example 1

[0102] First step, preparation of VOH / CCFs precursor material;

[0103] Same as the first step in Example 1.

[0104] Second step, preparation of VOH / CCFs nanosheet material;

[0105] The completely dried sample was annealed at 300°C for 2h. VOH / CCFs composite material was obtained, which was different from Example 1 in that no zinc phthalocyanine was added, and the SEM image of the VOH / CCFs composite material is shown in Figure 1

[0106] Third step, assembly of light-assisted button cell;

[0107] Same as the fourth step in Example 1.

[0108] Comparative Example 2

[0109] First step, preparation of VOH / CCFs precursor material;

[0110] Same as the first step in Example 1.

[0111] Second step, preparation of PANI 0.1 -VOH / CCFs composite material;

[0112] 0.0364g of PANI was dissolved in 40mL of ethanol, and the mass ratio of PANI to V2O5 was controlled to be 0.1. The above solution was added to the VOH / CCFs precursor material, and continuous stirring was performed for 30min. The mixture was transferred to a 100mL autoclave, sealed and heated at 120°C for 12h. After cooling to room temperature, it was washed with ethanol and deionized water three times respectively and then placed in a 60°C oven for drying for 12h to obtain a PANI 0.1 -VOH / CCFs composite material.

[0113] Third step, preparation of PANI 0.1 -VOH / CCFs nanowire composite material;

[0114] Same as the third step in Example 1, a PANI 0.1 -VOH / CCFs composite material was obtained, and the SEM image thereof is shown in Figure 1

[0115] Fourth step, assembly of light-assisted button cell;

[0116] Same as the fourth step in Example 1.

[0117] Comparative Example 3

[0118] First step, preparation of VOH / CCFs precursor material;​​

[0119] The first step was the same as in Example 1.

[0120] The second step, preparation of ZnPc 0.2 -VOH / CCFs composite material;

[0121] The same as in Example 1, except that 0.0728 g of ZnPc was dissolved in 40 mL of ethanol, and the mass ratio of ZnPc to V2O5 was controlled at 0.2, and the above solution was added to the VOH / CCFs precursor material, and continuously stirred for 30 min. The mixture was transferred to a 100 mL autoclave, sealed and heated at 120°C for 12 h. After cooling to room temperature, it was washed with ethanol and deionized water three times respectively and then placed in a 60°C oven for drying for 12 h to obtain ZnPc 0.2 -VOH / CCFs composite material.

[0122] The third step, preparation of ZnPc 0.2 -VOH / CCFs composite material;

[0123] The third step in Example 1 to obtain ZnPc 0.2 -VOH / CCFs composite material, the SEM image of which is shown in Figure 1 .

[0124] The fourth step, assembly of a light-assisted button cell;

[0125] The fourth step in Example 1.

[0126] Test Example: Photoelectrochemical performance test:

[0127] (1) Constant current charge and discharge test:

[0128] The CR2032 type light-assisted button cells assembled in Example 1 to Comparative Example 3 were tested for performance under no light conditions and under one sun light conditions (xenon lamp as a solar light source, light intensity of 100 mW cm -2 ), and constant current charge and discharge tests were carried out at a current density of 500 mAh·g -1 , as shown in Figure 2 .

[0129] Under no light conditions, after 100 cycles, the capacity of Example 1 was 392.4 mAh·g -1 , the capacity of Example 2 was 342.8 mAh·g -1 , the capacity of Example 3 was 311.3 mAh·g -1 , the capacity of Comparative Example 1 was 200.1 mAh·g -1 , and the capacity of Comparative Example 2 was 180.5 mAh·g -1The capacity of Comparative Example 3 was 276 mAh.g -1 ; the capacity of Example 1 increased to 461.1 mAh.g after 100 cycles under the condition of sunlight -1 , the capacity of Example 2 increased to 383.2 mAh.g -1 , the capacity of Example 3 increased to 351.5 mAh.g -1 , the capacity of Comparative Example 1 increased to 233.2 mAh.g -1 , the capacity of Comparative Example 2 increased to 210.2 mAh.g -1 , the capacity of Comparative Example 3 increased to 320.9 mAh.g -1 .

[0130] (2) Absorbance test:

[0131] The UV diffuse reflectance spectra of Example 1 and Comparative Example 1 are shown in Figure 3 , both of which have strong absorption in the range of 200-800 nm, while ZnPc 0.1 -VOH has higher absorption in the range of 200-800 nm than VOH material, which indicates that the p-n heterojunction ZnPc-VOH material significantly improves the absorption of light.

[0132] (3) Test of separation efficiency of photo-generated electron-hole pairs:

[0133] The fluorescence (PL) spectra of Example 1 and Comparative Example 1 are shown in Figure 4 , the low PL intensity indicates that the photo-generated electron-hole pairs are easily separated. As can be seen from the figure, the PL emission peak of Comparative Example 1 is much stronger than that of Example 1, indicating that there is serious electron-hole recombination. The fluorescence emission of ZnPc 0.1 -VOH is significantly lower than that of VOH, indicating that the p-n heterojunction ZnPc-VOH material accelerates the separation of photo-generated electron-hole pairs, thereby improving the photoelectrochemical performance.

[0134] (4) Test of transient photocurrent response:

[0135] The transient photocurrent responses of Example 1 and Comparative Example 1 are shown in Figure 5 . The current response (I-T) of the photoelectrode was tested under the condition of controlling the light shielding time interval to be 30 s. The photocurrent response of Example 1 was significantly enhanced compared with Comparative Example 1, almost twice that of Comparative Example 1. This result clearly indicates that the p-n heterojunction ZnPc-VOH material has a higher response ability to light.

[0136] The above merely provides the preferred embodiment of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a high-efficiency bifunctional photocathode material based on a pn-type heterostructure, characterized in that: The method comprises the following steps: Step one, dispersing vanadium pentoxide in deionized water to obtain a vanadium pentoxide solution, then adding hydrogen peroxide solution drop by drop, and performing hydrothermal reaction with a porous carbon material as a substrate to obtain a VOH / C precursor; Step two, dissolving a p-type semiconductor in a solvent, mixing the p-type semiconductor with the VOH / C precursor, and performing reaction under heating to obtain a MPc-VOH / C composite material after drying, wherein the p-type semiconductor is selected from one or a mixture of several of zinc phthalocyanine, iron phthalocyanine, copper phthalocyanine and cobalt phthalocyanine in a phthalocyanine family; Step three, taking out the dried MPc-VOH / C composite material after cooling to room temperature, and washing, drying and annealing to obtain a fan-shaped nanosheet composite material MPc-VOH / C.

2. The preparation method of the p-n type heterostructure-based MPc-VOH high-efficiency bifunctional photocathode material according to claim 1, characterized in that: In the step one, the raw material is anhydrous vanadium pentoxide; and the concentration of the vanadium pentoxide solution in the step one is 0.2-0.6 mol / L.

3. The preparation method of the p-n type heterostructure-based MPc-VOH high-efficiency bifunctional photocathode material according to claim 1, characterized in that: In the step two, the mass ratio of the p-type semiconductor to vanadium pentoxide is 0.05-0.

15.

4. The preparation method of the p-n type heterostructure-based MPc-VOH high-efficiency bifunctional photocathode material according to claim 1, characterized in that: In the step two, the solvent is ethanol, and the amount of ethanol is 30-50 ml.

5. The preparation method of the p-n type heterostructure-based MPc-VOH high-efficiency bifunctional photocathode material according to claim 1, characterized in that: The hydrogen peroxide solution is a hydrogen peroxide solution with a mass fraction of 30%; and the amount of the hydrogen peroxide solution added dropwise in the step one is 2-6 ml.

6. The preparation method of the p-n type heterostructure-based MPc-VOH high-efficiency bifunctional photocathode material according to claim 1, characterized in that: In the step one, the porous carbon material is selected from one or a mixture of several of carbonized cotton fibers, carbon fibers and carbon nanotubes.

7. The preparation method of the p-n type heterostructure-based MPc-VOH high-efficiency bifunctional photocathode material according to claim 1, characterized in that: In the step two, the heating temperature is 110-130 DEG C, and the reaction time is 10-14 hours; in the step three, the drying temperature is 60-80 DEG C, the drying time is 10-14 hours, the annealing temperature is 290-310 DEG C, and the annealing time is 1-3 hours.

8. The light-assisted zinc ion battery high-efficiency bifunctional photoelectric cathode material prepared by the preparation method in any one of claims 1-7.

9. The application of the light-assisted zinc ion battery high-efficiency bifunctional photoelectric cathode material in claim 8 in the preparation of a light-assisted zinc ion battery.

10. A light-assisted zinc ion battery comprising a photoelectric cathode, an anode, a diaphragm and an electrolyte, wherein the photoelectric cathode material used is the light-assisted zinc ion battery high-efficiency bifunctional photoelectric cathode material in claim 8; the anode is a zinc sheet; the diaphragm is a glass fiber filter paper; and the electrolyte is a zinc trifluoromethane sulfonate aqueous solution with a concentration of 2-3 mol / L.

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