All-solid-state light and energy storage integrated device and preparation method thereof

Abstract

The application belongs to the technical field of energy conversion and storage devices, and discloses a full-solid-state light energy storage integrated device and a preparation method thereof. The full-solid-state light energy storage integrated device comprises, from bottom to top, an energy storage electrode, an energy storage gel electrolyte, a compatible electrode, a photoelectric conversion gel electrolyte and a photoanode; the energy storage electrode, the energy storage gel electrolyte and the compatible electrode constitute a supercapacitor module; the compatible electrode, the photoelectric conversion gel electrolyte and the photoanode constitute a dye-sensitized solar cell module; components of the photoelectric conversion gel electrolyte include polyvinylidene fluoride-hexafluoropropylene and 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid; components of the energy storage gel electrolyte include polyvinylidene fluoride-hexafluoropropylene, 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and tetrabutylammonium tetrafluoroborate. The application adopts double gel electrolytes to replace liquid electrolytes, and has good energy conversion efficiency and cycle stability.

Description

Technical Field

[0001] This invention belongs to the field of energy conversion and storage device technology, and specifically relates to an all-solid-state integrated optical energy storage device and its preparation method. Background Technology

[0002] To fully utilize solar energy and meet the need for converting and storing solar light, integrated photovoltaic energy storage devices have become a current research hotspot. The electrolyte is a key factor affecting the performance of these devices. Traditional integrated photovoltaic energy storage devices mostly use liquid electrolytes. However, liquid electrolytes are prone to evaporation and leakage during device assembly. Furthermore, in integrated devices assembled with liquid electrolytes, the dye in the dye-sensitized solar cell section is prone to desorption, resulting in poor cycle stability; typically, the device can only stably cycle 20-50 times. Summary of the Invention

[0003] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes an all-solid-state integrated photovoltaic energy storage device with good energy conversion efficiency and cycle stability.

[0004] A first aspect of the present invention provides an all-solid-state photovoltaic energy storage integrated device, wherein the all-solid-state photovoltaic energy storage integrated device comprises, from bottom to top, an energy storage electrode, an energy storage gel electrolyte, a compatible electrode, a photoelectric conversion gel electrolyte, and a photoanode; the energy storage electrode, the energy storage gel electrolyte, and the compatible electrode constitute a supercapacitor module; the compatible electrode, the photoelectric conversion gel electrolyte, and the photoanode constitute a dye-sensitized solar cell module; the components of the photoelectric conversion gel electrolyte include: polyvinylidene fluoride-hexafluoropropylene and 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid; the components of the energy storage gel electrolyte include: polyvinylidene fluoride-hexafluoropropylene, 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid, and tetrabutylammonium tetrafluoroborate.

[0005] Preferably, the components of the photoelectric conversion gel electrolyte further include: elemental iodine and lithium iodide.

[0006] Preferably, in the photoelectric conversion gel electrolyte, the molar ratio of elemental iodine, lithium iodide and 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid is 1:(5-10):(3-5).

[0007] Preferably, in the energy storage gel electrolyte, the mass ratio of the polyvinylidene fluoride-hexafluoropropylene and the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid is 1:(2-5).

[0008] Preferably, in the energy storage gel electrolyte, the mass ratio of the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid to the tetrabutyltetrafluoroborate ammonium is (0.5-5):1.

[0009] Preferably, the energy storage electrode comprises a graphite sheet and polypyrrole / graphene oxide electrodeposited on one side of the graphite sheet. The energy storage electrode of the present invention serves as an electrode in a supercapacitor module, wherein the graphite sheet acts as a current collector and the polypyrrole / graphene oxide acts as the electrode material.

[0010] Preferably, the compatible electrode comprises a graphite sheet and polypyrrole / graphene oxide electrodeposited on both sides of the graphite sheet. The compatible electrode of the present invention serves as both an electrode for a supercapacitor module and a counter electrode for a dye-sensitized solar cell module, wherein the graphite sheet acts as a current collector and the polypyrrole / graphene oxide acts as the electrode material.

[0011] A second aspect of the present invention provides a method for fabricating the all-solid-state integrated optical energy storage device of the present invention, comprising the following steps:

[0012] The energy storage electrode, the energy storage gel electrolyte, the compatible electrode, the photoelectric conversion gel electrolyte, and the photoanode are stacked sequentially from bottom to top to assemble the all-solid-state integrated photovoltaic energy storage device.

[0013] Preferably, the preparation method of the energy storage gel electrolyte includes the following steps:

[0014] The components of the energy storage gel electrolyte are mixed and dissolved with a solvent, and then dried to obtain the energy storage gel electrolyte.

[0015] Preferably, the preparation method of the energy storage gel electrolyte includes the following steps:

[0016] Polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and solvent were mixed and stirred at 60-80℃ for 2-4 hours. Then, 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (BMIMBF4 ionic liquid) was added and stirred for 1-3 hours. Then, tetrabutylammonium tetrafluoroborate (TBABF4) was added and stirred for 1-3 hours. Finally, the mixture was dried at 60-80℃ for 4-6 hours to obtain the energy storage gel electrolyte (PVDF-HFP / BMIMBF4 / TBABF4).

[0017] Preferably, the preparation method of the photoelectric conversion gel electrolyte includes the following steps:

[0018] The components of the photoelectric conversion gel electrolyte are mixed and dissolved with a solvent, and then dried to obtain the photoelectric conversion gel electrolyte.

[0019] Preferably, the preparation method of the photoelectric conversion gel electrolyte includes the following steps:

[0020] Lithium iodide, iodine, and solvent were mixed, and then 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid was added and mixed evenly. Then polyvinylidene fluoride-hexafluoropropylene was added, and the mixture was stirred at 50-70℃ for 1-3 hours. Finally, it was dried at 50-70℃ for 2-4 hours to obtain the photoelectric conversion gel electrolyte (PVDF-HFP / BMIMBF4 / LiI / I2).

[0021] Preferably, the solvent is an organic solvent such as N,N-dimethylformamide (DMF).

[0022] Preferably, the mass-to-volume ratio of the polyvinylidene fluoride-hexafluoropropylene and the solvent is 1 g:(10-20) mL.

[0023] Preferably, the photoanode is a dye-sensitized titanium dioxide photoanode. The dye-sensitized titanium dioxide photoanode is prepared by a conventional method, including the steps of spin-coating titanium dioxide slurry onto an FTO or ITO conductive glass substrate and then immersing it in a dye-sensitization solution.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] (1) The all-solid-state photovoltaic energy storage integrated device of the present invention includes an energy storage gel electrolyte and a photoelectric conversion gel electrolyte, that is, a dual gel electrolyte is used to replace the traditional liquid electrolyte. The all-solid-state photovoltaic energy storage integrated device is assembled from a dye-sensitized solar cell module and a supercapacitor module, which improves the cycle stability. The dye-sensitized solar cell module and the supercapacitor module both use ionic liquid gel electrolyte based on PVDF-HFP / BMIMBF4, which has good compatibility. Since the ionic liquid is not easily volatilized, the long-term stability of the all-solid-state photovoltaic energy storage integrated device is improved. The all-solid-state photovoltaic energy storage integrated device can stably cycle for more than 150 cycles. In addition, the addition of tetrabutylammonium tetrafluoroborate (TBABF4) to the energy storage gel electrolyte has a high ionic conductivity, which is beneficial to improving the conductivity of the all-solid-state photovoltaic energy storage integrated device.

[0026] (2) The all-solid-state photovoltaic energy storage integrated device of the present invention is based on a three-electrode system assembled with a dual-gel electrolyte. It is different from the previous photovoltaic supercapacitors assembled with liquid electrolyte. Instead, it uses a dual-gel electrolyte based on PVDF-HFP / BMIMBF4 and graphite sheets as current collectors. The double-sided deposition of polypyrrole / graphene composite material is used as a compatible electrode material to prepare an all-solid-state photovoltaic energy storage integrated device. It realizes a highly integrated dual-function integrated device of photoelectric conversion and energy storage. No internal connecting wires are required, and it has a high energy conversion efficiency. At the same time, the addition of TBABF4 helps to improve the conductivity of the integrated device. Attached Figure Description

[0027] Figure 1 These are LSV curves of the dye-sensitized solar cell modules prepared in Example 1 and the control group;

[0028] Figure 2 These are LSV curves of the dye-sensitized solar cell modules prepared in Example 1 and Comparative Example 1.

[0029] Figure 3 Here is a SEM image of the energy storage gel electrolyte obtained in Example 2;

[0030] Figure 4 This is a SEM image of the energy storage gel electrolyte obtained in Comparative Example 2;

[0031] Figure 5 These are the ionic conductivity test graphs of the energy storage gel electrolytes obtained in Example 2 and Comparative Example 2;

[0032] Figure 6 These are the CV curves of the supercapacitor modules prepared in Example 2 and Comparative Example 2 at a scan rate of 100 mV / s;

[0033] Figure 7 These are GCD curves of the supercapacitor modules prepared in Example 2 and Comparative Example 2 at a charge / discharge current density of 1 A / g;

[0034] Figure 8 These are EIS curves of the supercapacitor modules prepared in Example 2 and Comparative Example 2;

[0035] Figure 9 These are the CV curves of the supercapacitor modules prepared in Example 2 and Comparative Example 3 at a scan rate of 100 mV / s;

[0036] Figure 10 These are GCD curves of the supercapacitor modules prepared in Example 2 and Comparative Example 3 at a charge / discharge current density of 1 A / g.

[0037] Figure 11These are EIS curves of the supercapacitor modules prepared in Example 2 and Comparative Example 3;

[0038] Figure 12 This is a structural diagram of the all-solid-state integrated optical energy storage device of Example 3;

[0039] Figure 13 This is a charge-discharge curve of the all-solid-state photovoltaic energy storage integrated device obtained in Example 3 under different discharge current densities;

[0040] Figure 14 This is a cycle stability curve of the all-solid-state photovoltaic energy storage integrated device obtained in Example 3;

[0041] Figure 15 This is a demonstration diagram of the integrated photovoltaic energy storage device obtained in Example 4 lighting up a light-emitting diode.

[0042] Figure 12 In the middle, 100-graphite sheet, 200-polypyrrole / graphene oxide, 300-energy storage gel electrolyte, 400-photoelectric conversion gel electrolyte, 500-photoanode. Detailed Implementation

[0043] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0044] Example 1

[0045] The fabrication method of a dye-sensitized solar cell module includes the following steps:

[0046] S1. Dissolve 0.67g lithium iodide and 0.127g elemental iodine in 10mL N,N-dimethylformamide organic solvent, then add 0.33g 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (BMIMBF4 ionic liquid), mix well, then add 1g polyvinylidene fluoride-hexafluoropropylene, stir at 70℃ for 2h, and finally dry at 50℃ to obtain photoelectric conversion gel electrolyte (PVDF-HFP / BMIMBF4 / LiI / I2);

[0047] S2. Polypyrrole / graphene oxide is electrodeposited on one side of a graphite sheet as a counter electrode;

[0048] S3. TiO2 slurry is coated onto FTO conductive glass by spin coating and sintered at 450℃ for 350 min. Then it is immersed in dye solution for 24 h and the residual solution on the surface is cleaned with ethanol to obtain photoanode.

[0049] S4. The counter electrode, photoelectric conversion gel electrolyte and photoanode are stacked from bottom to top to assemble the dye-sensitized solar cell module.

[0050] Control group (using a conventional platinum counter electrode)

[0051] The fabrication method of a dye-sensitized solar cell module includes the following steps:

[0052] S1. Dissolve 0.67g lithium iodide and 0.127g elemental iodine in 10mL N,N-dimethylformamide organic solvent, then add 0.33g 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (BMIMBF4 ionic liquid), mix well, then add 1g polyvinylidene fluoride-hexafluoropropylene, stir at 70℃ for 2h, and finally dry at 50℃ to obtain photoelectric conversion gel electrolyte (PVDF-HFP / BMIMBF4 / LiI / I2);

[0053] S2. Spin-coat an isopropanol solution containing chloroplatinic acid onto FTO conductive glass and sinter at 450°C for 30 min. Use the prepared platinum electrode as the counter electrode.

[0054] S3. TiO2 slurry is coated onto FTO conductive glass by spin coating and sintered at 450℃ for 350 min. Then it is immersed in dye solution for 24 h and the residual solution on the surface is cleaned with ethanol to obtain photoanode.

[0055] S4. The counter electrode, photoelectric conversion gel electrolyte and photoanode are stacked from bottom to top to assemble the dye-sensitized solar cell module.

[0056] Comparative Example 1 (The difference from Example 1 is that the BMIMBF4 ionic liquid was replaced with the BMIMTFSI ionic liquid)

[0057] The fabrication method of a dye-sensitized solar cell module includes the following steps:

[0058] S1. Dissolve 0.67g lithium iodide and 0.127g elemental iodine in 10mL N,N-dimethylformamide organic solvent, then add 0.63g 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt ionic liquid (BMIMTFSI ionic liquid), mix well, then add 1g polyvinylidene fluoride-hexafluoropropylene, stir at 70℃ for 2h, and finally dry at 50℃ to obtain photoelectric conversion gel electrolyte (PVDF-HFP / BMIMTFSI / LiI / I2);

[0059] S2. Polypyrrole / graphene oxide is electrodeposited on one side of a graphite sheet as a counter electrode;

[0060] S3. TiO2 slurry is coated onto FTO conductive glass by spin coating and sintered at 450℃ for 350 min. Then it is immersed in dye solution for 24 h and the residual solution on the surface is cleaned with ethanol to obtain photoanode.

[0061] S4. The counter electrode, photoelectric conversion gel electrolyte and photoanode are stacked from bottom to top to assemble the dye-sensitized solar cell module.

[0062] The dye-sensitized solar cell modules prepared in Example 1 and the control group were subjected to LSV (linear sweep voltammetry) testing. The test results are as follows: Figure 1 As shown, the photoelectric conversion efficiency of the dye-sensitized solar cell module prepared in Example 1 was calculated to be 4.22%, while the photoelectric conversion efficiency of the dye-sensitized solar cell module prepared in the control group was 7.25%, with little difference between the two. Therefore, it can be seen that the present invention, by using polypyrrole / graphene oxide electrodeposition on a single side of a graphite sheet as the counter electrode of the dye-sensitized solar cell module, can achieve a high photoelectric conversion efficiency. When used in the all-solid-state photovoltaic energy storage integrated device of the present invention, the integrated device also possesses a high photoelectric conversion efficiency.

[0063] The dye-sensitized solar cell modules prepared in Example 1 and Comparative Example 1 were subjected to LSV (linear sweep voltammetry) testing, and the test results are as follows: Figure 2 As shown, the photoelectric conversion efficiency of the dye-sensitized solar cell module prepared in Example 1 was calculated to be 4.22%, while the photoelectric conversion efficiency of the dye-sensitized solar cell module prepared in Comparative Example 1 was 2.95%. Therefore, it can be seen that the BMIMBF4 ionic liquid used in this invention achieves a higher photoelectric conversion efficiency compared to other ionic liquids such as BMIMTFSI ionic liquid.

[0064] The above Figure 1 , Figure 2 The vertical axis “Current Density” represents current density, and the horizontal axis “Voltage” represents voltage.

[0065] Example 2

[0066] The fabrication method of the supercapacitor module includes the following steps:

[0067] S1. Dissolve 1g of polyvinylidene fluoride-hexafluoropropylene in 10mL of N,N-dimethylformamide organic solvent, heat and stir at 60℃ for 4h, then add 4g of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid, and continue stirring at 60℃ for 2h to obtain a mixture.

[0068] S2. Dissolve 1g of tetrabutylammonium tetrafluoroborate in 1mL of N,N-dimethylformamide organic solvent, add it to the above mixture, stir at 60℃ for 3h, and let it dry naturally at room temperature to obtain the energy storage gel electrolyte (PVDF-HFP / BMIMBF4 / TBABF4).

[0069] S3. Polypyrrole / graphene oxide is electrodeposited on one side of a graphite sheet to serve as an energy storage electrode.

[0070] S4. Stack the energy storage electrode, energy storage gel electrolyte and energy storage electrode from bottom to top to assemble a "sandwich structure" supercapacitor module.

[0071] Comparative Example 2 (the difference from Example 2 is that tetrabutylammonium tetrafluoroborate was not added)

[0072] The fabrication method of the supercapacitor module includes the following steps:

[0073] S1. Dissolve 1g of polyvinylidene fluoride-hexafluoropropylene in 10mL of N,N-dimethylformamide organic solvent, heat and stir at 60℃ for 4h, then add 4g of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid, continue stirring at 60℃ for 2h, and let it dry naturally at room temperature to obtain energy storage gel electrolyte (PVDF-HFP / BMIMBF4).

[0074] S2. Polypyrrole / graphene oxide is electrodeposited on one side of a graphite sheet to serve as an energy storage electrode.

[0075] S3. Stack the energy storage electrode, energy storage gel electrolyte, and energy storage electrode from bottom to top to assemble a "sandwich structure" supercapacitor module.

[0076] Figure 3 The image shows a scanning electron microscope (SEM) image of the energy storage gel electrolyte (PVDF-HFP / BMIMBF4 / TBABF4) obtained in Example 2. Figure 4 The image shows a SEM image of the energy storage gel electrolyte (PVDF-HFP / BMIMBF4) obtained in Comparative Example 2; compared to Figure 4 , Figure 3 Because TBABF4 was added in Example 2, it has a distinct porous structure; the porous structure is beneficial for ion transport.

[0077] The ionic conductivity of the energy storage gel electrolytes obtained in Example 2 and Comparative Example 2 were tested respectively, and the test results are as follows: Figure 5 As shown; from Figure 5 The ionic conductivity of Example 2 can be calculated to be 14.03 mS / cm, while that of Comparative Example 2 is 6.68 mS / cm. Figure 5In the diagram, the vertical coordinate “Z” / ohm” represents the imaginary part, and the horizontal coordinate “Z’ / ohm” represents the real part.

[0078] The supercapacitor modules prepared in Example 2 and Comparative Example 2 were subjected to cyclic voltammetry (CV), constant current charge-discharge (CP), and electrostatic impedance (EIS) tests, respectively. The test results are shown below. Figure 6 , 7 As shown in Figures 8 and 9, it can be seen that adding TBABF4 in Example 2 can improve the specific capacitance of the supercapacitor, thereby improving the conductivity of the integrated device. Figure 6 The vertical axis “CurrentDensity” represents current density, and the horizontal axis “Potential” represents electric potential. Figure 7 The vertical axis “Potential” represents electric potential, and the horizontal axis “Time” represents time. Figure 8 In the diagram, the vertical coordinate “Z” / ohm” represents the imaginary part, and the horizontal coordinate “Z’ / ohm” represents the real part.

[0079] Comparative Example 3 (The difference from Example 2 is that the BMIMBF4 ionic liquid was replaced with the BMIMTFSI ionic liquid)

[0080] The fabrication method of the supercapacitor module includes the following steps:

[0081] S1. Dissolve 1g of polyvinylidene fluoride-hexafluoropropylene in 10mL of N,N-dimethylformamide organic solvent, heat and stir at 60℃ for 4h, then add 7.42g of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt ionic liquid (BMIMTFSI ionic liquid), and continue stirring at 60℃ for 2h to obtain a mixture.

[0082] S2. Dissolve 1g of tetrabutylammonium tetrafluoroborate in 1mL of N,N-dimethylformamide organic solvent, add it to the above mixture, stir at 60℃ for 3h, and let it dry naturally at room temperature to obtain the energy storage gel electrolyte (PVDF-HFP / BMIMTFSI / TBABF4).

[0083] S3. Polypyrrole / graphene oxide is electrodeposited on the surface of a graphite sheet as an energy storage electrode;

[0084] S4. Stack the energy storage electrode, energy storage gel electrolyte and energy storage electrode from bottom to top to assemble a "sandwich structure" supercapacitor module.

[0085] The supercapacitor modules prepared in Example 2 and Comparative Example 3 were subjected to cyclic voltammetry (CV), constant current charge-discharge (CP), and electrostatic impedance (EIS) tests, respectively. The test results are shown below. Figure 9 , 10As shown in Figures 1 and 11, it can be seen that the BMIMBF4 ionic liquid used in Example 2 has better performance. At the same time, BMIMBF4 is well compatible when applied to dye-sensitized solar cell modules and supercapacitor modules.

[0086] Example 3

[0087] like Figure 12 As shown, an all-solid-state photovoltaic energy storage integrated device includes, from bottom to top, an energy storage electrode, an energy storage gel electrolyte 300, a compatible electrode, a photoelectric conversion gel electrolyte 400, and a photoanode 500; the energy storage electrode, the energy storage gel electrolyte 300, and the compatible electrode constitute a supercapacitor module; the compatible electrode, the photoelectric conversion gel electrolyte 400, and the photoanode 500 constitute a dye-sensitized solar cell module; the energy storage electrode includes a graphite sheet 100 and polypyrrole / graphene oxide 200 electrodeposited on one side of the graphite sheet 100; the compatible electrode includes a graphite sheet 100 and polypyrrole / graphene oxide 200 electrodeposited on both sides of the graphite sheet 100.

[0088] The fabrication method of this all-solid-state integrated photovoltaic energy storage device includes the following steps:

[0089] S1. Dissolve 0.67g lithium iodide and 0.127g elemental iodine in 10mL N,N-dimethylformamide organic solvent, then add 0.33g 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (BMIMBF4 ionic liquid), mix well, then add 1g polyvinylidene fluoride-hexafluoropropylene, stir at 70℃ for 2h, and finally dry at 50℃ to obtain photoelectric conversion gel electrolyte (PVDF-HFP / BMIMBF4 / LiI / I2);

[0090] S2. Polypyrrole / graphene oxide is electrodeposited on both sides of a graphite sheet as a compatible electrode;

[0091] S3. TiO2 slurry is coated onto FTO conductive glass by spin coating and sintered at 450℃ for 350 min. Then it is immersed in dye solution for 24 h and the residual solution on the surface is cleaned with ethanol to obtain photoanode.

[0092] S4. Dissolve 1g of polyvinylidene fluoride-hexafluoropropylene in 10mL of N,N-dimethylformamide organic solvent, heat and stir at 60℃ for 4h, then add 4g of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid, and continue stirring at 60℃ for 2h to obtain a mixture.

[0093] S5. Dissolve 1g of tetrabutylammonium tetrafluoroborate in 1mL of N,N-dimethylformamide organic solvent, and add it to the mixture obtained in S4. Stir at 60℃ for 3h, and let it dry naturally at room temperature to obtain the energy storage gel electrolyte (PVDF-HFP / BMIMBF4 / TBABF4).

[0094] S6. Polypyrrole / graphene oxide is electrodeposited on one side of a graphite sheet to serve as an energy storage electrode.

[0095] S7. The energy storage electrode, energy storage gel electrolyte, compatible electrode, photoelectric conversion gel electrolyte and photoanode are stacked from bottom to top to assemble an all-solid-state integrated photovoltaic energy storage device.

[0096] The charge-discharge curves of the all-solid-state photovoltaic energy storage integrated device obtained in Example 3 under different discharge current densities are shown below. Figure 13 As shown, an integrated total conversion efficiency of 4.05% was obtained at a discharge current of 1 A / g; the cycle stability curve of the all-solid-state photovoltaic energy storage integrated device obtained in Example 3 at a charge / discharge current density of 1 A / g is shown in the figure. Figure 14 As shown, the all-solid-state photovoltaic energy storage integrated device assembled by the present invention can stably cycle 150 times.

[0097] Example 4

[0098] The fabrication method of a series-connected integrated photovoltaic energy storage device includes the following steps:

[0099] S1. Preparation of photoanode: TiO2 slurry was coated onto FTO conductive glass using spin coating and sintered at 450℃ for 350 min. Then, it was immersed in dye solution for 24 h and the residual solution on the surface was cleaned with ethanol to obtain photoanode.

[0100] S2. Preparation of compatible electrodes: Polypyrrole / graphene oxide (PPy / GO) is electrodeposited on both sides of a graphite sheet to serve as compatible electrodes;

[0101] S3. Preparation of counter electrode: Polypyrrole / graphene oxide (PPy / GO) is electrodeposited on one side of a graphite sheet to serve as the counter electrode;

[0102] S4. Preparation of energy storage electrode: Polypyrrole / graphene oxide (PPy / GO) is electrodeposited on one side of a graphite sheet to serve as an energy storage electrode;

[0103] S5. Assemble four sets of dye-sensitized solar cell modules in series: Using a 6×1.8cm first FTO conductive glass and a 4.5×1.8cm second FTO conductive glass as substrates, clean them three times sequentially with acetone, ethanol, and water. Divide one side of the first FTO conductive glass into four equal parts (A, B, C, D) from left to right. Fabricate the counter electrode, photoanode, counter electrode, and photoanode sequentially in parts A, B, C, and D respectively. Simultaneously, chemically etch between part B (photoanode) and part C (counter electrode). Divide one side of the second FTO conductive glass into three equal parts (A', B', C') from left to right. Fabricate the counter electrode, photoanode, counter electrode, and photoanode sequentially in parts A, B, C, and D respectively. The photoanode, counter electrode, and photoanode are sequentially fabricated in parts A' (photoanode) and B' (counter electrode). Chemical etching is used between parts A' (photoanode) and B' (counter electrode). The first FTO conductive glass and the second FTO conductive glass are joined (A, B, and C correspond to A', B', and C', respectively). Photoelectric conversion gel electrolyte prepared in Example 1 is placed between the photoanode and the counter electrode (between A and A', B and B', and C and C'). An energy storage electrode is added to the right end of the second FTO conductive glass, corresponding to part D (photoanode) of the first FTO conductive glass, thus realizing the series connection of four dye-sensitized solar cell modules.

[0104] S6. Assemble the series-connected integrated photovoltaic energy storage device: Between the energy storage electrode in step S5 and the D part (photoanode) of the first FTO conductive glass, the energy storage gel electrolyte prepared in Example 2 (connected to the energy storage electrode), the compatible electrode, and the photoelectric conversion gel electrolyte prepared in Example 1 (connected to the photoanode) are sequentially arranged to obtain the series-connected integrated photovoltaic energy storage device.

[0105] Example 4 shows the tandem optical energy storage integrated device used to light up a light-emitting diode (LED). Figure 15 As shown, in Figure 15 In (a), closing the switch connects the circuit. Under illumination from both light sources, the series-connected integrated photoelectric energy storage device can convert and store photogenerated electrons. At this time, the LED marked "STU" is in an emitting state. Figure 15 In (b), when the switch is turned off to disconnect the circuit, the light sources on both sides are not lit. Under dark conditions (no light), the energy stored in the series-connected photoelectric energy storage device can light up the LED marked "STU".

[0106] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention, and these equivalent modifications or substitutions are all included within the scope defined by the claims of this application.

Claims

1. An all-solid-state integrated photovoltaic energy storage device, characterized in that, The all-solid-state photovoltaic energy storage integrated device comprises, from bottom to top, an energy storage electrode, an energy storage gel electrolyte, a compatible electrode, a photoelectric conversion gel electrolyte, and a photoanode; the energy storage electrode, the energy storage gel electrolyte, and the compatible electrode constitute a supercapacitor module; The compatible electrode, the photoelectric conversion gel electrolyte, and the photoanode constitute a dye-sensitized solar cell module; The components of the photoelectric conversion gel electrolyte include: polyvinylidene fluoride-hexafluoropropylene and 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid; the components of the energy storage gel electrolyte include: polyvinylidene fluoride-hexafluoropropylene, 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and tetrabutylammonium tetrafluoroborate. The energy storage electrode comprises a graphite sheet and polypyrrole / graphene oxide electrodeposited on one side of the graphite sheet; The compatible electrode comprises a graphite sheet and polypyrrole / graphene oxide electrodeposited on both sides of the graphite sheet.

2. The all-solid-state photovoltaic energy storage integrated device according to claim 1, characterized in that, The components of the photoelectric conversion gel electrolyte also include: elemental iodine and lithium iodide.

3. The all-solid-state photovoltaic energy storage integrated device according to claim 2, characterized in that, In the photoelectric conversion gel electrolyte, the molar ratio of elemental iodine, lithium iodide and 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid is 1:(5-10):(3-5).

4. The all-solid-state photovoltaic energy storage integrated device according to claim 1, characterized in that, In the energy storage gel electrolyte, the mass ratio of the polyvinylidene fluoride-hexafluoropropylene and the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid is 1:(2-5).

5. The all-solid-state photovoltaic energy storage integrated device according to claim 1, characterized in that, In the energy storage gel electrolyte, the mass ratio of the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid to the tetrabutyltetrafluoroborate ammonium is (0.5-5):

1.

6. The method for fabricating the all-solid-state integrated photovoltaic energy storage device according to any one of claims 1-5, characterized in that, Includes the following steps: The energy storage electrode, the energy storage gel electrolyte, the compatible electrode, the photoelectric conversion gel electrolyte, and the photoanode are stacked sequentially from bottom to top to assemble the all-solid-state integrated photovoltaic energy storage device.

7. The preparation method according to claim 6, characterized in that, The preparation method of the energy storage gel electrolyte includes the following steps: The components of the energy storage gel electrolyte are mixed and dissolved with a solvent, and then dried to obtain the energy storage gel electrolyte.

8. The preparation method according to claim 6, characterized in that, The preparation method of the photoelectric conversion gel electrolyte includes the following steps: The components of the photoelectric conversion gel electrolyte are mixed and dissolved with a solvent, and then dried to obtain the photoelectric conversion gel electrolyte.

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