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CN113838981B - Photoelectric energy storage device and preparation method thereof - Google Patents

Photoelectric energy storage device and preparation method thereof Download PDF

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Publication number
CN113838981B
CN113838981B CN202111082190.2A CN202111082190A CN113838981B CN 113838981 B CN113838981 B CN 113838981B CN 202111082190 A CN202111082190 A CN 202111082190A CN 113838981 B CN113838981 B CN 113838981B
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positive electrode
conductive glass
negative electrode
storage device
energy storage
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CN113838981A (en
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郭丰
杨红新
李子郯
乔齐齐
施泽涛
王鹏飞
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Svolt Energy Technology Maanshan Co Ltd
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Svolt Energy Technology Maanshan Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/46—Accumulators structurally combined with charging apparatus
    • H01M10/465—Accumulators structurally combined with charging apparatus with solar battery as charging system
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The utility model provides a photoelectric energy storage device and a preparation method thereof, wherein the photoelectric energy storage device comprises bottom surface conductive glass, a negative electrode, a glass fiber film, an insulating layer, a positive electrode, a counter electrode, a hole transport layer, a perovskite layer, an electron transport layer and top surface conductive glass which are sequentially stacked, the bottom surface conductive glass and the top surface conductive glass are electrically conducted, an illumination window is arranged on one side of the thickness of the perovskite layer, and a positive electrode lug and a negative electrode lug are respectively led out from one side of the thickness of the counter electrode and one side of the thickness of the bottom surface conductive glass. The utility model comprehensively develops the anode, the cathode and the perovskite solar energy, directly converts the solar energy into electric energy for storage and output, improves the energy utilization rate, has continuous and sustainable energy source, and plays a certain role in promoting the carbon neutralization and carbon peak reaching.

Description

Photoelectric energy storage device and preparation method thereof
Technical Field
The utility model belongs to the technical field of energy storage devices, and relates to a photoelectric energy storage device and a preparation method thereof.
Background
With the continuous consumption of fossil energy, the energy crisis is increasingly prominent, the development of structures capable of generating energy is more and more concerned by people, and the application prospects of wind energy, tidal energy and solar energy are wide, but the reasonable utilization of the renewable energy becomes the continuous challenge focus of researchers. The most reasonable storage device in the current research of lithium ion secondary batteries, however, with the mass production of lithium ion batteries, the production cost of the lithium ion batteries is increasing, as is well known, 30% of the cost of the lithium ion batteries comes from the anode material, and the anode material production cost is gradually increased due to the continuous rising of the price of cobalt on the anode material lithium cobaltate and the ternary anode material in the current market, so that the cobalt-free anode material is more concerned by people, and the cobalt-free anode material has a strong application prospect. On the other hand, at present, solar energy is mostly stored in the solar panel for power generation and transmitted to the battery through a wire, and the process energy consumption is large.
Among various solar cell types, silicon-based solar cells dominate the commercial solar cell industry due to higher photoelectric conversion efficiency and more stable performance, but the production cost thereof is not likely to be greatly reduced due to the necessary silicon wafer thickness. The organic solar cell has low cost, but the stability of the photovoltaic effect is poor. The CIGS solar cell has the advantages of high photoelectric conversion efficiency and no light decay effect, and the production cost of the CIGS solar cell cannot be greatly reduced on the basis of the prior art. The perovskite solar cell is one of the most popular research directions in recent years, the perovskite material used as the light absorption layer has the advantages of proper direct band gap, high absorption coefficient, excellent carrier transport performance, high defect tolerance and the like, the preparation process is simple, the cost is low, the photoelectric conversion efficiency of the perovskite solar cell reported at present reaches 22.1%, and the commercial value potential is huge.
CN109585657A discloses a perovskite solar cell module. The structure of the composite material is a sandwich structure of conductive glass/electronic transmission body// multifunctional nickel screen// electronic transmission body/conductive glass, and specifically comprises upper conductive glass, lower conductive glass, multifunctional nickel screen, upper electronic transmission body, lower electronic transmission body, electrodes and glass adhesive. The structure can ensure that the perovskite absorption layer is fully contacted with the electron transmission body, so that electrons are rapidly led out from the conductive glass on the two sides, and the transmission efficiency of the electrons is greatly improved; the interface contact of the perovskite absorption layer/the hole transport layer can be increased by a net structure, and the hole transport efficiency is promoted. In addition, the battery assembly is tightly packaged, so that the whole perovskite absorption layer is completely in a closed state, and the environmental stability of the whole battery assembly is improved.
CN210805825U discloses a printed wiring board based perovskite electroluminescent device comprising: the solar cell comprises a printed circuit board, a negative electrode, an electron transmission layer, a perovskite luminescent layer, a hole transmission layer, a positive electrode and a glass packaging layer which are sequentially arranged, wherein a luminescent region is reserved on the printed circuit board, the negative electrode, the electron transmission layer, the perovskite luminescent layer, the hole transmission layer and the positive electrode are prepared on the luminescent region, an insulating protective layer and an ultraviolet curing glue layer are wrapped around the luminescent region, and the glass packaging layer is connected with the positive electrode of the printed circuit board. The luminescent device of the utility model adopts the printed circuit board as the substrate of the perovskite electroluminescent device, saves the production cost and has the characteristic of low production cost.
CN109671847A discloses a perovskite solar cell and a preparation method thereof, the perovskite solar cell includes: the organic electroluminescent device comprises a transparent substrate, a negative electrode, a down-conversion luminescent layer, an electron transport layer, a perovskite layer, a hole transport layer, an up-conversion luminescent layer and a positive electrode which are arranged in a stacked mode, wherein the down-conversion luminescent layer is arranged between the negative electrode and the electron transport layer.
Disclosure of Invention
Aiming at the defects in the prior art, the utility model aims to provide a photoelectric energy storage device and a preparation method thereof, wherein the photoelectric energy storage device comprehensively develops the anode, the cathode and perovskite solar energy, directly converts the solar energy into electric energy for storage and output, improves the energy utilization rate, has continuous and sustainable energy source, and plays a certain role in promoting the carbon neutralization and carbon peak reaching.
In order to achieve the purpose, the utility model adopts the following technical scheme:
in a first aspect, the utility model provides a photoelectric energy storage device, which comprises bottom surface conductive glass, a negative electrode, a glass fiber film, an insulating layer, a positive electrode, a counter electrode, a hole transport layer, a perovskite layer, an electron transport layer and top surface conductive glass which are sequentially stacked, wherein the bottom surface conductive glass and the top surface conductive glass are electrically conducted, an illumination window is arranged on one side of the thickness of the perovskite layer, and a positive electrode lug and a negative electrode lug are respectively led out from one side of the thickness of the counter electrode and one side of the thickness of the bottom surface conductive glass.
The utility model provides a photoelectric energy storage device, which comprehensively develops a lithium battery and a perovskite solar battery, converts solar energy into electric energy for storage and output, stores the electric energy under strong light and discharges the electric energy under weak light, improves the energy utilization rate, has continuous and sustainable energy sources, and plays a certain role in promoting the carbon neutralization and carbon peak reaching.
The working principle of the photoelectric energy storage device provided by the utility model comprises the following steps:
under the irradiation of strong light, the perovskite layer absorbs solar photons and is excited to generate exciton separation to generate electrons and holes. Holes are injected into the valence band of the hole transport layer, and as the hole transport layer diffuses to the counter electrode side, the counter electrode excites the positive electrode to ionize into lithium ions and electrons, the electrons are stored in the holes, and the lithium ions migrate to the negative electrode side through the electrolyte. And injecting electrons into a conduction band of the electron transport layer, enriching the electrons, diffusing the electrons to the bottom conductive glass, transmitting the electrons to the negative electrode through the bottom conductive glass, and receiving the electrons by lithium ions transferred to the negative electrode and embedding the lithium ions into graphite to store charges. The discharge is started in an environment without light or weak light.
As a preferred technical scheme of the present invention, side surface conductive glass is disposed between the same edges of the bottom surface conductive glass and the top surface conductive glass, the bottom surface conductive glass and the side surface conductive glass are enclosed to form a U-shaped conductive glass outer frame with one side open, and the bottom surface conductive glass and the top surface conductive glass are electrically connected through the side surface conductive glass.
Preferably, an insulating material is filled between the side of the thickness of the stacked negative electrode, glass fiber membrane, positive electrode, counter electrode, hole transport layer and perovskite layer and the side conductive glass, and the side of the thickness of the electron transport layer is in contact with the side conductive glass.
Preferably, the opening of the conductive glass outer frame with the U-shaped structure is packaged by an aluminum-plastic film, and openings required by an illumination window, a positive electrode lug and a negative electrode lug are reserved on the aluminum-plastic film.
As a preferable technical solution of the present invention, the positive electrode includes a positive electrode material, a conductive agent, and a positive electrode binder.
Preferably, the positive electrode material accounts for 96.5-98.5 wt%, such as 96.5 wt%, 97 wt%, 97.5 wt%, 98 wt% or 98.5wt%, the conductive agent accounts for 2-5 wt%, such as 2.0 wt%, 2.5wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, or 5.0 wt%, and the positive electrode binder accounts for 1-2.5 wt%, such as 1.0 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2.0 wt%, 2.2 wt%, 2.4 wt% or 2.5wt%, based on 100wt% of the mass fraction of the positive electrode, but not limited to the recited values, and other non-recited values in the range are also applicable.
Preferably, the solid content of the cathode binder is 5 to 8wt%, and may be, for example, 5.0 wt%, 5.2 wt%, 5.4 wt%, 5.6 wt%, 5.8 wt%, 6.0 wt%, 6.2 wt%, 6.4 wt%, 6.6 wt%, 6.8 wt%, 7.0 wt%, 7.2 wt%, 7.4 wt%, 7.6 wt%, 7.8 wt%, or 8.0 wt%, but is not limited to the enumerated values, and other non-enumerated values within the range of values are also applicable.
Preferably, the cathode material is a cobalt-free cathode material.
Preferably, the cobalt-free cathode material comprises LixNi1-aMnaO2Or LixNi1-a-bMnaQbO2Wherein Q is selected from any one of Ti, Al, Mg, Zr, Y, Sr, Te or Sb, x is 1 to 1.2, for example, 1.0, 1.02, 1.04, 1.06, 1.08, 1.1, 1.12, 1.14, 1.16, 1.18 or 1.2, a is 0.1 to 0.5, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5, b is 0.05 to 0.2, for exampleBut not limited to the recited values, and other values not recited in this range are equally applicable, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, or 0.2.
Preferably, the negative electrode comprises a negative electrode material and a negative electrode binder.
The mass ratio of the negative electrode material to the negative electrode binder is preferably (90-95): (5-10), and may be, for example, 90:10, 91:9, 92:8, 93:7, 94:6 or 95:5, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the negative electrode material comprises graphite.
Preferably, the solid content of the negative electrode binder is 5 to 8wt%, and may be, for example, 5.0 wt%, 5.5 wt%, 6.0 wt%, 6.5 wt%, 7.0 wt%, 7.5 wt%, or 8.0 wt%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the glass fiber membrane is impregnated with an electrolyte.
Preferably, the counter electrode is a metal simple substance foil or an alloy foil.
Preferably, the metal simple substance used for the metal simple substance foil includes any one of Al, Au, Pt, Ag, Ti, Ir or W.
Preferably, the alloy used for the alloy foil comprises an alloy material composed of at least two of Al, Au, Pt, Ag, Ti, Ir or W.
As a preferred technical solution of the present invention, the material of the electron transport layer includes any one or a combination of at least two of titanium dioxide, tin oxide, zinc oxide, tin dioxide, and tellurium oxide.
Preferably, the material used for the hole transport layer comprises any one of spiro-OMeTAO, P3HT, PTAA or nickel oxide.
The spirol-OMeTAO, P3HT and PTAA are general abbreviations in the field, and the spirol-OMeTAO is called 2, 2', 7, 7' -tetrabromo-9, 9' -spirobi and tri (4-iodobenzene) amine; polymers of P3HT all known as 3-hexylthiophene; the totality of PTAA is known as poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ].
In a second aspect, the present invention provides a method for preparing the optoelectronic energy storage device of the first aspect, the method comprising:
coating negative electrode slurry on the surface of the bottom conductive glass, drying to form a negative electrode, and placing a glass fiber film on the surface of the negative electrode; coating positive electrode slurry on the surface of the counter electrode, drying to form a positive electrode, and attaching the positive electrode to the glass fiber membrane; and sequentially coating the surface of the top surface conductive glass to form an electron transport layer, a perovskite layer and a hole transport layer, and attaching the hole transport layer to the counter electrode to form the photoelectric energy storage device.
As a preferred technical solution of the present invention, the positive electrode slurry includes a positive electrode material, a conductive agent, and a positive electrode binder.
Preferably, the positive electrode material accounts for 96.5-98.5 wt%, such as 96.5 wt%, 97 wt%, 97.5 wt%, 98 wt% or 98.5wt%, the conductive agent accounts for 2-5 wt%, such as 2.0 wt%, 2.5wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, or 5.0 wt%, and the positive electrode binder accounts for 1-2.5 wt%, such as 1.0 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2.0 wt%, 2.2 wt%, 2.4 wt% or 2.5wt%, based on 100wt% of the positive electrode slurry, but is not limited to the recited values, and other non-recited values in the range are also applicable.
Preferably, the solid content of the cathode binder is 5 to 8wt%, and may be, for example, 5.0 wt%, 5.2 wt%, 5.4 wt%, 5.6 wt%, 5.8 wt%, 6.0 wt%, 6.2 wt%, 6.4 wt%, 6.6 wt%, 6.8 wt%, 7.0 wt%, 7.2 wt%, 7.4 wt%, 7.6 wt%, 7.8 wt%, or 8.0 wt%, but is not limited to the enumerated values, and other non-enumerated values within the range of values are also applicable.
Preferably, the cathode material is a cobalt-free cathode material.
Preferably, the cobalt-free cathode material comprises LixNi1-aMnaO2Or LixNi1-a-bMnaQbO2Wherein Q is selected from any one of Ti, Al, Mg, Zr, Y, Sr, Te or Sb, x is 1 to 1.2, for example, 1.0, 1.02, 1.04, 1.06, 1.08, 1.1, 1.12, 1.14, 1.16, 1.18 or 1.2, a is 0.1 to 0.5, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5, b is 0.05 to 0.2, for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19 or 0.2, but the same numerical values are not limited to the same numerical values recited herein.
Preferably, the negative electrode slurry comprises a negative electrode material and a negative electrode binder.
The mass ratio of the negative electrode material to the negative electrode binder is preferably (90-95): (5-10), and may be, for example, 90:10, 91:9, 92:8, 93:7, 94:6 or 95:5, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the negative electrode material comprises graphite.
Preferably, the solid content of the negative electrode binder is 5 to 8wt%, and may be, for example, 5.0 wt%, 5.5 wt%, 6.0 wt%, 6.5 wt%, 7.0 wt%, 7.5 wt%, or 8.0 wt%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical solution of the present invention, the coating process of the electron transport layer includes:
and coating the electron transport material solution on the surface of the top surface conductive glass, and sintering to form the electron transport layer.
Preferably, the coating mode is spin coating.
Preferably, the electron transport material solution includes an electron transport material precursor and a solvent.
Preferably, the volume ratio of the electron transport material precursor to the solvent is 1:1 to 4, and may be, for example, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2.0, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3.0, 1:3.2, 1:3.4, 1:3.6, 1:3.8, or 1:4, but is not limited to the enumerated values, and other non-enumerated values within the range of values are equally applicable.
Preferably, the electron transport material precursor includes any one of titanium dioxide, tin oxide, zinc oxide, tin dioxide or tellurium oxide or a combination of at least two of the two.
Preferably, the solvent comprises isopropanol.
Preferably, the spin coating speed of the electron transport material solution is 2000-5000 rpm, such as 2000rpm, 2500rpm, 3000rpm, 3500rpm, 4000rpm, 4500rpm or 5000rpm, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the spin coating time of the electron transport material solution is 30-60 s, such as 30s, 32s, 34s, 36s, 38s, 40s, 42s, 44s, 46s, 48s, 50s, 52s, 54s, 56s, 58s or 60s, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred technical solution of the present invention, the perovskite coating process comprises:
will PbI2Coating the solution on the surface of the electron transport layer, and dripping CH3NH3And (I) coating the solution, and drying to obtain a perovskite layer.
Preferably, the PbI is2The solvent used in the solution was DMF.
Preferably, said CH3NH3The solvent used in the solution I is isopropanol.
Preferably, the PbI is2The solution was applied by spin coating.
Preferably, the PbI is2The spin coating speed of the solution is 2000 to 5000rpm, and may be, for example, 2000rpm, 2500rpm, 3000rpm, 3500rpm, 4000rpm, 4500rpm or 5000rpm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, said PbI2Spin coating time of solutionFor example, the number of the segments is 30 to 60s, and may be 30s, 32s, 34s, 36s, 38s, 40s, 42s, 44s, 46s, 48s, 50s, 52s, 54s, 56s, 58s or 60s, but the segments are not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
Preferably, said CH3NH3The coating mode of the solution I is spin coating.
Preferably, said CH3NH3The spin coating speed of the solution I is 2000 to 5000rpm, and may be, for example, 2000rpm, 2500rpm, 3000rpm, 3500rpm, 4000rpm, 4500rpm or 5000rpm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, said CH3NH3The spin coating time of the solution I is 60 to 180s, and may be, for example, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, or 180s, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the drying temperature is 150 to 200 ℃, for example, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the drying time is 10 to 24 hours, for example, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical solution of the present invention, the coating method of the hole transport layer is spin coating.
Preferably, the spin coating speed of the hole transport layer is 2000-5000 rpm, such as 2000rpm, 2500rpm, 3000rpm, 3500rpm, 4000rpm, 4500rpm or 5000rpm, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the spin coating time of the hole transport layer is 30-60 s, such as 30s, 35s, 40s, 45s, 50s, 55s or 60s, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Compared with the prior art, the utility model has the beneficial effects that:
the utility model provides a photoelectric energy storage device, which comprehensively develops a lithium battery and a perovskite solar battery, converts solar energy into electric energy for storage and output, stores the electric energy under strong light and discharges the electric energy under weak light, improves the energy utilization rate, has continuous and sustainable energy sources, and plays a certain role in promoting the carbon neutralization and carbon peak reaching.
Drawings
Fig. 1 is a schematic structural diagram of an energy storage device according to an embodiment of the present invention;
fig. 2 is a charging curve of the photoelectric energy storage device prepared in embodiment 1 of the present invention under different illumination;
fig. 3 is a SOC-OCV curve of the optoelectronic energy storage device prepared in example 1 of the present invention.
Wherein, 1-top surface conductive glass; 2-bottom surface conductive glass; 3-an electron transport layer; 4-perovskite layer; 5-a hole transport layer; 6-pair of electrodes; 7-an insulating layer; 8-positive electrode; 9-fiberglass membranes; 10-negative electrode; 11-an insulating material; 12-side conductive glass; 13-positive pole tab; 14-a negative electrode tab; 15-light window.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
In one embodiment, the utility model provides an optoelectronic energy storage device as shown in fig. 1, which comprises a bottom surface conductive glass 2, a negative electrode 10, a glass fiber film 9, an insulating layer 7, a positive electrode 8, a counter electrode 6, a hole transport layer 5, a perovskite layer 4, an electron transport layer 3 and a top surface conductive glass 1 which are sequentially stacked. The bottom surface conductive glass 2 and the top surface conductive glass 1 are electrically conducted, an illumination window 15 is arranged on one side of the thickness of the perovskite layer 4, a positive electrode tab 13 and a negative electrode tab 14 are respectively led out from one side of the thickness of the counter electrode 6 and one side of the thickness of the bottom surface conductive glass 2, and electrolyte is injected into the glass fiber film 9.
Further, a side surface conductive glass 12 is arranged between the same edges of the bottom surface conductive glass 2 and the top surface conductive glass 1, the bottom surface conductive glass 2 and the side surface conductive glass 12 form a U-shaped conductive glass outer frame with an opening on one side after enclosing, and the bottom surface conductive glass 2 and the top surface conductive glass 1 are electrically conducted through the side surface conductive glass 12. An insulating material 11 is filled between the side with the thickness and the side conductive glass 12 after the negative electrode 10, the glass fiber membrane 9, the positive electrode 8, the counter electrode 6, the hole transport layer 5 and the perovskite layer 4 are laminated, and the side with the thickness of the electron transport layer 3 is in contact with the side conductive glass 12.
Furthermore, the opening of the conductive glass outer frame with the U-shaped structure is packaged by an aluminum-plastic film, and openings required by the illumination window 15, the positive electrode tab 13 and the negative electrode tab 14 are reserved on the aluminum-plastic film.
Example 1
The embodiment provides a preparation method of a photoelectric energy storage device, which specifically comprises the following steps:
(1) firstly, taking conductive glass (comprising top surface conductive glass 1, bottom surface conductive glass 2 and side surface conductive glass 12) with a U-shaped structure, spin-coating an electron transport material solution (an isopropanol solution of titanium dioxide, the volume ratio of the titanium dioxide to the isopropanol is 1:1) on the inner side surface of the top surface conductive glass 1, wherein the spin-coating speed is 2000rpm, the spin-coating time is 60s, taking down a pole piece after the spin-coating is finished, putting the pole piece into a box-type atmosphere furnace, and sintering at 200 ℃ in a nitrogen atmosphere to obtain an electron transport layer 3;
(2) PbI configuration 1M2Solution (solute DMF) and 1M CH3NH31mL of PbI solution (solute is isopropanol) is taken firstly2Solution spin coating onto the surface of the electron transport layer 3, PbI2The spin coating speed of the solution was 2000rpm, PbI2The spin coating time of the solution is 60s, and PbI is prepared2Coating, then taking 2mL of CH3NH3The solution I is vertically dropped to PbI2Coating the surface of the coating, and drying at 150 ℃ for 24h after spin coating to obtain a perovskite layer 4, CH3NH3Spin coating of solution ISpeed 2000rpm, CH3NH3The spin coating time of the solution I is 180 s;
(3) spin-coating a hole transport material spiro-OMeTAO on the surface of the perovskite layer 4 at the spin-coating speed of 2000rpm for 100 s;
(4) coating positive electrode slurry on one side surface of an aluminum foil (a counter electrode 6) to leave a positive electrode tab 13, wherein the positive electrode comprises 96.5 wt% of cobalt-free positive electrode material LiNi0.9Mn0.1O23 wt% of conductive agent and 0.5 wt% of positive pole binder PVDF, wherein the solid content of PVDF is 5wt%, and after coating, putting the aluminum foil into a drying oven at 100 ℃ for drying for 12h to form a positive pole 8;
(5) spin-coating negative electrode slurry on the inner surface of the bottom surface conductive glass 2, reserving a negative electrode tab 14, wherein the negative electrode slurry comprises graphite and a negative electrode binder SBR in a mass ratio of 90:10, the solid content of the SBR is 5wt%, and after coating, drying the coated negative electrode slurry in a drying oven at 100 ℃ for 10 hours to obtain a negative electrode 10;
(6) placing the prepared aluminum foil and the glass fiber membrane 9 into conductive glass with a U-shaped structure and separating the conductive glass with an insulating layer to prevent short circuit at two ends;
(7) dropping 1M lithium hexafluorophosphate electrolyte into a glass fiber film 9 in a glove box, cutting openings with proper sizes on an aluminum plastic film to serve as leading-out holes of an illumination window 15, a positive electrode tab 13 and a negative electrode tab 14, packaging the open end of conductive glass by the aluminum plastic film, and fixing the illumination window 15 on one side of an electronic transmission layer 3 by using sealant.
The photoelectric performance of the prepared photoelectric energy storage device is tested, and a charging curve (shown in fig. 2) under different illuminance and an SOC-OCV curve (shown in fig. 3) of the photoelectric energy storage device are obtained. Fig. 2 shows the charging and discharging curves of the battery with different illumination intensities and the calibrated 2Ah capacity, and it can be seen from fig. 2 that the charging time is different under different illumination intensities, which is that the charging speed is accelerated when the light intensity is high due to the difference of the electron migration speed under different illumination intensities. As can be seen from fig. 3, the average discharge voltage of the SOC-OCV of the photovoltaic energy storage device prepared in example 1 is about 3.8V, which is substantially equivalent to that of the current lithium ion battery.
Example 2
The embodiment provides a preparation method of a photoelectric energy storage device, which specifically comprises the following steps:
(1) firstly, taking conductive glass (comprising top surface conductive glass 1, bottom surface conductive glass 2 and side surface conductive glass 12) with a U-shaped structure, spin-coating an electron transport material solution (an isopropanol solution of tin oxide, the volume ratio of the tin oxide to the isopropanol is 1:1.5) on the inner side surface of the top surface conductive glass 1, wherein the spin-coating speed is 3500rpm, the spin-coating time is 54s, taking down a pole piece after the spin-coating, putting the pole piece into a box-type atmosphere furnace, and sintering at 240 ℃ in a nitrogen atmosphere to obtain an electron transport layer 3;
(2) PbI with 1M configuration2Solution (solute DMF) and 1M CH3NH31mL of PbI solution (solute is isopropanol) is taken firstly2Solution spin coating onto the surface of the electron transport layer 3, PbI2The spin coating speed of the solution was 3500rpm, PbI2The spin coating time of the solution is 54s, and PbI is prepared2Coating, then taking 2mL of CH3NH3The solution I is vertically dropped to PbI2Spin coating the surface of the coating, and drying at 160 deg.C for 20h to obtain perovskite layer 4, CH3NH3Spin coating speed of solution I is 3500rpm, CH3NH3The spin coating time of the solution I is 150 s;
(3) spin-coating a hole transport material P3HT on the surface of the perovskite layer 4 at the spin-coating speed of 3500rpm for 92 s;
(4) coating positive electrode slurry on one side surface of the gold foil (counter electrode 6) to leave a positive electrode tab 13, wherein the positive electrode slurry comprises 96.8 wt% of cobalt-free positive electrode material Li1.1Ni0.7Mn0.3O22 wt% of conductive agent and 1.2 wt% of positive pole binder PVDF, wherein the solid content of PVDF is 5.6 wt%, and after coating, the gold foil is put into a drying oven at 100 ℃ to be dried for 12 hours to form a positive pole 8;
(5) spin-coating negative electrode slurry on the inner surface of the bottom surface conductive glass 2, reserving a negative electrode tab 14, wherein the negative electrode slurry comprises graphite and a negative electrode binder SBR in a mass ratio of 91:9, the solid content of the SBR is 5.6 wt%, and after coating, putting the coated negative electrode slurry into a 100 ℃ drying oven for drying for 10 hours to obtain a negative electrode 10;
(6) placing the prepared gold foil and the glass fiber film 9 into conductive glass with a U-shaped structure and separating the conductive glass with the insulating layer to prevent short circuit at two ends;
(7) dropping 1M lithium hexafluorophosphate electrolyte into a glass fiber film 9 in a glove box, cutting openings with proper sizes on an aluminum plastic film to serve as leading-out holes of an illumination window 15, a positive electrode tab 13 and a negative electrode tab 14, packaging the open end of conductive glass by the aluminum plastic film, and fixing the illumination window 15 on one side of an electronic transmission layer 3 by using sealant.
Example 3
The embodiment provides a preparation method of a photoelectric energy storage device, which specifically comprises the following steps:
(1) firstly, taking conductive glass (comprising top surface conductive glass 1, bottom surface conductive glass 2 and side surface conductive glass 12) with a U-shaped structure, spin-coating an electron transport material solution (an isopropanol solution of zinc oxide, the volume ratio of the zinc oxide to the isopropanol is 1:2) on the inner side surface of the top surface conductive glass 1, wherein the spin-coating speed is 4000rpm, the spin-coating time is 48s, taking down a pole piece after the spin-coating, putting the pole piece into a box-type atmosphere furnace, and sintering at 280 ℃ in a nitrogen atmosphere to obtain an electron transport layer 3;
(2) PbI configuration 1M2Solution (solute DMF) and 1M CH3NH31mL of PbI solution (solute is isopropanol) is taken firstly2Solution spin-coating onto the surface of the electron transport layer 3, PbI2The spin coating speed of the solution was 4000rpm, PbI2The spin coating time of the solution is 48s, and PbI is prepared2Coating, then taking 2mL of CH3NH3The solution I is vertically dropped to PbI2Spin coating the surface of the coating, and drying at 170 deg.C for 18h to obtain perovskite layer 4, CH3NH3Spin coating speed of solution I was 4000rpm, CH3NH3The spin coating time of the solution I is 130 s;
(3) spin-coating a hole transport material PTAA on the surface of the perovskite layer 4 at the spin-coating speed of 4000rpm for 84 s;
(4) coating positive electrode slurry on one side surface of platinum foil (counter electrode 6) to leave a positive electrodeA tab 13, the positive electrode slurry comprises 97 wt% of cobalt-free positive electrode material Li1.2Ni0.5Mn0.5O22.5wt% of conductive agent and 0.5 wt% of positive pole binder PVDF, wherein the solid content of PVDF is 6.2 wt%, and after coating, the platinum foil is put into a drying oven at 100 ℃ to be dried for 12h to form a positive pole 8;
(5) spin-coating negative electrode slurry on the inner surface of the bottom surface conductive glass 2, reserving a negative electrode tab 14, wherein the negative electrode slurry comprises graphite and a negative electrode binder SBR in a mass ratio of 92:8, the solid content of the SBR is 6.2 wt%, and after coating, putting the coated negative electrode slurry into a 100 ℃ oven to dry for 10 hours to obtain a negative electrode 10;
(6) putting the prepared platinum foil and the glass fiber membrane 9 into conductive glass with a U-shaped structure, and separating the platinum foil and the glass fiber membrane by using an insulating layer to prevent short circuit at two ends;
(7) dropping 1M lithium hexafluorophosphate electrolyte into a glass fiber film 9 in a glove box, cutting openings with proper sizes on an aluminum plastic film to serve as leading-out holes of an illumination window 15, a positive electrode tab 13 and a negative electrode tab 14, packaging the open end of conductive glass by the aluminum plastic film, and fixing the illumination window 15 on one side of an electronic transmission layer 3 by using sealant.
Example 4
The embodiment provides a preparation method of a photoelectric energy storage device, which specifically comprises the following steps:
(1) firstly, taking U-shaped conductive glass (comprising top surface conductive glass 1, bottom surface conductive glass 2 and side surface conductive glass 12), spin-coating an electron transport material solution (an isopropanol solution of tin dioxide, the volume ratio of tin dioxide to isopropanol is 1:2.5) on the inner side surface of the top surface conductive glass 1, wherein the spin-coating speed is 4200rpm, the spin-coating time is 42s, taking down a pole piece after the spin-coating is finished, putting the pole piece into a box-type atmosphere furnace, and sintering at 320 ℃ in a nitrogen atmosphere to obtain an electron transport layer 3;
(2) PbI configuration 1M2Solution (solute DMF) and 1M CH3NH31mL of PbI solution (solute is isopropanol) is taken2Solution spin coating onto the surface of the electron transport layer 3, PbI2The spin coating speed of the solution was 4200rpm, PbI2Of solutionsThe spin coating time is 42s, and PbI is prepared2Coating, then taking 2mL of CH3NH3The solution I is vertically dropped to PbI2Spin-coating the surface of the coating, and drying at 180 deg.C for 15h to obtain perovskite layer 4, CH3NH3The spin coating speed of the solution I is 4200rpm, CH3NH3The spin coating time of the solution I is 100 s;
(3) spin-coating a hole transport material nickel oxide on the surface of the perovskite layer 4 at the spin-coating speed of 4200rpm for 76 s;
(4) coating positive electrode slurry on one side surface of the silver foil (the counter electrode 6) to leave a positive electrode tab 13, wherein the positive electrode slurry comprises 97.2 wt% of cobalt-free positive electrode material LiNi0.7Mn0.1Ti0.2O22 wt% of conductive agent and 0.8 wt% of positive pole binder PVDF, wherein the solid content of PVDF is 6.8 wt%, and after coating, putting the silver foil into a drying oven at 100 ℃ to dry for 12h to form a positive pole 8;
(5) spin-coating negative electrode slurry on the inner surface of the bottom surface conductive glass 2, reserving a negative electrode tab 14, wherein the negative electrode slurry comprises graphite and a negative electrode binder SBR with a mass ratio of 93:7, the solid content of the SBR is 6.8 wt%, and after coating, putting the coated negative electrode slurry into a 100 ℃ oven to dry for 10 hours to obtain a negative electrode 10;
(6) putting the prepared silver foil and the glass fiber film 9 into conductive glass with a U-shaped structure, and separating the conductive glass with the insulating layer to prevent short circuit at two ends;
(7) dropping 1M lithium hexafluorophosphate electrolyte into a glass fiber film 9 in a glove box, cutting openings with proper sizes on an aluminum plastic film to serve as leading-out holes of an illumination window 15, a positive electrode tab 13 and a negative electrode tab 14, packaging the open end of conductive glass by the aluminum plastic film, and fixing the illumination window 15 on one side of an electronic transmission layer 3 by using sealant.
Example 5
The embodiment provides a preparation method of a photoelectric energy storage device, which specifically comprises the following steps:
(1) firstly, taking conductive glass (comprising top surface conductive glass 1, bottom surface conductive glass 2 and side surface conductive glass 12) with a U-shaped structure, spin-coating an electron transport material solution (an isopropanol solution of tellurium oxide, wherein the volume ratio of tellurium oxide to isopropanol is 1:3.5) on the inner side surface of the top surface conductive glass 1, wherein the spin-coating speed is 4500rpm, the spin-coating time is 36s, taking down a pole piece after the spin-coating, putting the pole piece into a box-type atmosphere furnace, and sintering at 360 ℃ in a nitrogen atmosphere to obtain an electron transport layer 3;
(2) PbI configuration 1M2Solution (solute DMF) and 1M CH3NH31mL of PbI solution (solute is isopropanol) is taken firstly2Solution spin coating onto the surface of the electron transport layer 3, PbI2The spin coating speed of the solution was 4500rpm, PbI2The spin coating time of the solution is 36s, and PbI is prepared2Coating, then taking 2mL of CH3NH3The solution I is vertically dropped to PbI2Spin coating the surface of the coating, and drying at 190 deg.C for 12h to obtain perovskite layer 4, CH3NH3Spin coating speed of solution I was 4500rpm, CH3NH3The spin coating time of the solution I is 85 s;
(3) spin-coating a hole transport material spiro-OMeTAO on the surface of the perovskite layer 4 at the spin-coating speed of 4500rpm for 68 s;
(4) coating positive electrode slurry on one side surface of the aluminum-titanium alloy foil (the counter electrode 6) to leave a positive electrode tab 13, wherein the positive electrode slurry comprises 97.5 wt% of cobalt-free positive electrode material Li1.1Ni0.6Mn0.3Zr0.1O22 wt% of conductive agent and 0.5 wt% of positive pole binder PVDF, wherein the solid content of PVDF is 7.4 wt%, after coating, the aluminum-titanium alloy foil is put into a drying oven at 100 ℃ for drying for 12h to form a positive pole 8;
(5) spin-coating negative electrode slurry on the inner surface of the bottom surface conductive glass 2, reserving a negative electrode tab 14, wherein the negative electrode slurry comprises graphite and a negative electrode binder SBR with a mass ratio of 94:6, the solid content of the SBR is 7.4 wt%, and after coating, putting the coated negative electrode slurry into a 100 ℃ drying oven for drying for 10 hours to obtain a negative electrode 10;
(6) placing the prepared aluminum-titanium alloy foil and the glass fiber film 9 into conductive glass with a U-shaped structure and separating the conductive glass with the insulating layer to prevent short circuit at two ends;
(7) dropping 1M lithium hexafluorophosphate electrolyte into a glass fiber film 9 in a glove box, cutting openings with proper sizes on an aluminum plastic film to serve as leading-out holes of an illumination window 15, a positive electrode tab 13 and a negative electrode tab 14, packaging the open end of conductive glass by the aluminum plastic film, and fixing the illumination window 15 on one side of an electronic transmission layer 3 by using sealant.
Example 6
The embodiment provides a preparation method of a photoelectric energy storage device, which specifically comprises the following steps:
(1) firstly, taking U-shaped conductive glass (comprising top conductive glass 1, bottom conductive glass 2 and side conductive glass 12), spin-coating an electron transmission material solution (an isopropanol solution of titanium dioxide, wherein the volume ratio of the titanium dioxide to the isopropanol is 1:4) on the inner side surface of the top conductive glass 1, wherein the spin-coating speed is 5000rpm, the spin-coating time is 30s, taking down a pole piece after the spin-coating is finished, putting the pole piece into a box-type atmosphere furnace, and sintering at 400 ℃ in a nitrogen atmosphere to obtain an electron transmission layer 3;
(2) PbI configuration 1M2Solution (solute DMF) and 1M CH3NH31mL of PbI solution (solute is isopropanol) is taken2Solution spin-coating onto the surface of the electron transport layer 3, PbI2The spin coating speed of the solution was 5000rpm, PbI2The spin coating time of the solution is 30s, and PbI is prepared2Coating, then taking 2mL of CH3NH3The solution I is vertically dropped to PbI2Spin coating the surface of the coating, and drying at 200 deg.C for 10h to obtain perovskite layer 4, CH3NH3Spin coating speed of solution I was 5000rpm, CH3NH3The spin coating time of the solution I is 60 s;
(3) spin-coating a hole transport material P3HT on the surface of the perovskite layer 4 at the spin-coating speed of 5000rpm for 60 s;
(4) coating positive electrode slurry on one side surface of a gold-silver alloy foil (counter electrode 6) to leave a positive electrode tab 13, wherein the positive electrode slurry comprises 98 wt% of cobalt-free positive electrode material Li1.2Ni0.4Mn0.55Sr0.05O21 wt% of conductive agent and 1 wt% of positive pole binder PVDF, wherein the solid content of PVDF is 8wt%, after coating, putting the gold-silver alloy foil into a drying oven at 100 ℃ for dryingDrying for 12h to form a positive electrode 8;
(5) spin-coating negative electrode slurry on the inner surface of the bottom surface conductive glass 2, reserving a negative electrode tab 14, wherein the negative electrode slurry comprises graphite and a negative electrode binder SBR with a mass ratio of 95:5, the solid content of the SBR is 8wt%, and after coating, drying the coated negative electrode slurry in a drying oven at 100 ℃ for 10 hours to obtain a negative electrode 10;
(6) placing the prepared gold-silver alloy foil and the glass fiber film 9 into conductive glass with a U-shaped structure and separating the conductive glass with the insulating layer to prevent short circuit at two ends;
(7) dropping 1M lithium hexafluorophosphate electrolyte into a glass fiber film 9 in a glove box, cutting openings with proper sizes on an aluminum plastic film to serve as leading-out holes of an illumination window 15, a positive electrode tab 13 and a negative electrode tab 14, packaging the open end of conductive glass by the aluminum plastic film, and fixing the illumination window 15 on one side of an electronic transmission layer 3 by using sealant.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.

Claims (48)

1. The photoelectric energy storage device is characterized by comprising bottom surface conductive glass, a negative electrode, a glass fiber film, an insulating layer, a positive electrode, a counter electrode, a hole transport layer, a perovskite layer, an electron transport layer and top surface conductive glass which are sequentially stacked, wherein the bottom surface conductive glass and the top surface conductive glass are electrically conducted, an illumination window is arranged on one side of the thickness of the perovskite layer, and a positive electrode lug and a negative electrode lug are respectively led out from one side of the thickness of the counter electrode and one side of the thickness of the bottom surface conductive glass;
the side conductive glass is arranged between the edges of the bottom conductive glass and the top conductive glass, the bottom conductive glass and the side conductive glass are enclosed to form a U-shaped conductive glass outer frame with an opening on one side, and the bottom conductive glass and the top conductive glass are electrically conducted through the side conductive glass;
insulating materials are filled between the side with the thickness and the side face conductive glass after the negative electrode, the glass fiber membrane, the positive electrode, the counter electrode, the hole transport layer and the perovskite layer are laminated, and the side with the thickness of the electron transport layer is in contact with the side face conductive glass;
the glass fiber membrane is injected with electrolyte.
2. The photoelectric energy storage device of claim 1, wherein the opening of the outer frame of the U-shaped conductive glass is encapsulated by an aluminum-plastic film, and openings required for an illumination window, a positive electrode tab and a negative electrode tab are reserved on the aluminum-plastic film.
3. The optoelectronic energy storage device of claim 1, wherein the positive electrode comprises a positive electrode material, a conductive agent, and a positive electrode binder.
4. The photoelectric energy storage device according to claim 3, wherein the positive electrode material accounts for 96.5-98.5 wt%, the conductive agent accounts for 2-5 wt%, and the positive electrode binder accounts for 1-2.5 wt%, based on 100wt% of the positive electrode.
5. The optoelectronic energy storage device of claim 3, wherein the solid content of the positive electrode binder is 5-8 wt%.
6. The optoelectronic energy storage device of claim 3, wherein the positive electrode material is a cobalt-free positive electrode material.
7. The optoelectronic energy storage device of claim 6, wherein said cobalt-free positive electrode material comprises LixNi1- aMnaO2Or LixNi1-a-bMnaQbO2Wherein Q is selected from Ti, Al, Mg, Zr, Y, Sr, Ti, Mg, Zr, Y, Sr, or Ti, Al, Mg, Zr, Sr, or Ti, or Mg, or Zr, or Sr, or Ti, or Mg, or Sr, or Ti, or Mg, or Zr, or Sr, or Ti, or Mg, or Ti, or Mg, or Zr, or Y, or Sr, or Ti, or Mg, or Zr, or Y, or Sr, or Ti, or Mg, or Zr, or Sr, or a combination thereof,Any one of Te and Sb, x is 1 to 1.2, a is 0.1 to 0.5, and b is 0.05 to 0.2.
8. The optoelectronic energy storage device of claim 1, wherein the negative electrode comprises a negative electrode material and a negative electrode binder.
9. The optoelectronic energy storage device as claimed in claim 8, wherein the mass ratio of the negative electrode material to the negative electrode binder is (90-95): 5-10.
10. The optoelectronic energy storage device of claim 8, wherein the negative electrode material comprises graphite.
11. The photovoltaic energy storage device according to claim 8, wherein the solid content of the negative electrode binder is 5 to 8 wt%.
12. The optoelectronic energy storage device of claim 1, wherein the counter electrode is a metal foil or an alloy foil.
13. The optoelectronic energy storage device of claim 12, wherein the elemental metal foil employs elemental metal comprising any one of Al, Au, Pt, Ag, Ti, Ir, or W.
14. The optoelectronic energy storage device of claim 12, wherein the alloy foil is made of an alloy material comprising at least two of Al, Au, Pt, Ag, Ti, Ir, or W.
15. The optoelectronic energy storage device of claim 1, wherein the material of the electron transport layer comprises any one of or a combination of at least two of titanium dioxide, tin oxide, zinc oxide, tin dioxide and tellurium oxide.
16. The optoelectronic energy storage device of claim 1, wherein the hole transport layer is made of a material selected from the group consisting of spiro-OMeTAO, P3HT, PTAA, and nickel oxide.
17. A method of fabricating an optoelectronic energy storage device according to any one of claims 1 to 16, wherein the method comprises:
sequentially coating the surface of the top surface conductive glass to form an electron transport layer, a perovskite layer and a hole transport layer; coating negative electrode slurry on the surface of the bottom surface conductive glass, and drying to form a negative electrode; coating positive electrode slurry on the surface of the counter electrode, and drying to form a positive electrode; and sequentially laminating a counter electrode, a positive electrode, an insulating layer and a glass fiber film, then placing the laminated counter electrode, the positive electrode, the insulating layer and the glass fiber film between the hole transport layer and the negative electrode, laminating the counter electrode and the hole transport layer, and laminating the glass fiber film and the negative electrode to form the photoelectric energy storage device.
18. The method according to claim 17, wherein the positive electrode slurry comprises a positive electrode material, a conductive agent and a positive electrode binder.
19. The preparation method of claim 18, wherein the mass fraction of the positive electrode is 100wt%, the positive electrode material is 96.5-98.5 wt%, the conductive agent is 2-5 wt%, and the positive electrode binder is 1-2.5 wt%.
20. The preparation method of claim 18, wherein the solid content of the positive electrode binder is 5-8 wt%.
21. The method according to claim 18, wherein the positive electrode material is a cobalt-free positive electrode material.
22. The method of claim 21, wherein the cobalt-free cathode material comprises LixNi1- aMnaO2Or LixNi1-a-bMnaQbO2Wherein Q is selected from any one of Ti, Al, Mg, Zr, Y, Sr, Te or Sb, x is 1-1.2, a is 0.1-0.5, and b is 0.05-0.2.
23. The method according to claim 17, wherein the negative electrode slurry comprises a negative electrode material and a negative electrode binder.
24. The method according to claim 23, wherein the mass ratio of the negative electrode material to the negative electrode binder is (90-95): 5-10.
25. The method of claim 23, wherein the negative electrode material comprises graphite.
26. The preparation method according to claim 23, wherein the solid content of the negative electrode binder is 5 to 8 wt%.
27. The method according to claim 17, wherein the coating process of the electron transport layer comprises:
and coating the electron transport material solution on the surface of the top surface conductive glass, and sintering to form the electron transport layer.
28. The method according to claim 27, wherein the coating is spin coating.
29. The method according to claim 27, wherein the electron transport material solution comprises an electron transport material precursor and a solvent.
30. The preparation method according to claim 29, wherein the volume ratio of the electron transport material precursor to the solvent is 1 (1-4).
31. The method of claim 30, wherein the electron transport material precursor comprises any one of titanium dioxide, tin oxide, zinc oxide, tin dioxide, or tellurium oxide, or a combination of at least two thereof.
32. The method of claim 30, wherein the solvent comprises isopropyl alcohol.
33. The method according to claim 28, wherein the spin coating speed of the electron transporting material solution is 2000 to 5000 rpm.
34. The method of claim 28, wherein the spin coating time of the electron transport material solution is 30-60 s.
35. The method of claim 17, wherein the perovskite coating process comprises:
will PbI2Coating the solution on the surface of the electron transport layer, and dripping CH3NH3And (I) coating the solution, and drying to obtain a perovskite layer.
36. The method according to claim 35, wherein the PbI is prepared by a method comprising2The solvent used in the solution was DMF.
37. The method of claim 35, wherein the CH is3NH3The solvent used in the solution I is isopropanol.
38. The method according to claim 35, wherein the PbI is prepared by a method comprising2The solution was applied by spin coating.
39. The method according to claim 38, wherein the PbI is prepared by a method comprising2The spin coating speed of the solution is 2000-5000 rpm.
40. The method according to claim 38, wherein the PbI is prepared by2The spin coating time of the solution is 30-60 s.
41. The method of claim 35, wherein the CH is3NH3The coating mode of the solution I is spin coating.
42. The method of claim 41, wherein said CH is3NH3The spin coating speed of the solution I is 2000-5000 rpm.
43. The method of claim 41, wherein said CH is3NH3The spin coating time of the solution I is 60-180 s.
44. The method according to claim 35, wherein the drying temperature is 150 to 200 ℃.
45. The method as claimed in claim 35, wherein the drying time is 10-24 hours.
46. The method according to claim 17, wherein the hole transport layer is applied by spin coating.
47. The method of claim 46, wherein the spin coating speed of the hole transport layer is 2000-5000 rpm.
48. The method of claim 46, wherein the spin coating time of the hole transport layer is 30-60 s.
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