Perovskite photovoltaic enclosures for automotive keys, methods of making the same, and self-charging automotive keys

Abstract

This invention provides a perovskite photovoltaic housing for car keys, its fabrication method, and a self-charging car key, relating to the technical field of automotive electronic devices and photovoltaic charging devices. The perovskite photovoltaic housing for car keys comprises a first substrate, a conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, a metal electrode layer, and a second substrate, sequentially stacked. This invention uses the first and second substrates directly as the structural body of the car key housing, and sets a functional layer between the first and second substrates to form an integrated housing structure with power generation capabilities. The overall structure ensures a thin profile while enabling the housing itself to possess stable light energy conversion capabilities. This solves the problems of traditional car keys relying on disposable batteries, requiring periodic replacement and lacking self-sustaining operation, as well as the difficulty in reliably integrating existing photovoltaic solutions into a compact housing due to structural separation and excessive thickness.

Description

Technical Field

[0001] This invention relates to the field of automotive electronic equipment and photovoltaic charging devices, and in particular to a perovskite photovoltaic housing for car keys, its preparation method, and a self-charging car key. Background Technology

[0002] Traditional car remote keys generally use CR2032 disposable button batteries for power, which have problems such as being non-rechargeable, requiring regular manual replacement, users easily forgetting to replace the batteries leading to key malfunction, and heavy metal pollution from discarded disposable batteries. Although there have been attempts at self-powered systems such as piezoelectric power generation (e.g., CN104481211B) and wireless charging (e.g., CN117261821A), they are limited by poor structural reliability, weak adaptability to different scenarios, and the lack of an environmental closed-loop system, respectively, and have failed to fundamentally solve the need for long-term self-powered power. Existing photovoltaic solutions mostly use crystalline silicon cells, which have low efficiency in low light, large thickness, and poor flexibility, making them difficult to integrate into the compact shell structure of car keys, and cannot achieve continuous power supply around the clock. In addition, the conventional car key shell is a separate structure, and photovoltaic components are usually introduced as additional patches, resulting in overall thickness, sealing difficulties, and failing to meet the comprehensive requirements of car keys for long-term power supply, compact structure, and safety. Summary of the Invention

[0003] One of the objectives of this invention is to provide a perovskite photovoltaic housing for car keys, so as to at least solve one of the technical problems existing in the prior art.

[0004] The second objective of this invention is to provide a method for preparing a perovskite photovoltaic casing for car keys.

[0005] The third objective of this invention is to provide a self-charging car key.

[0006] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted: In a first aspect, the present invention provides a perovskite photovoltaic housing for a car key, comprising: a first substrate, a conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, a metal electrode layer, and a second substrate, which are sequentially stacked.

[0007] Furthermore, the thickness of the first substrate is 0.5mm-2mm; Preferably, the thickness of the conductive layer is 150-250 nm; Preferably, the thickness of the electron transport layer is 20-40 nm; Preferably, the thickness of the perovskite active layer is 450-550 nm; Preferably, the thickness of the hole transport layer is 100-200 nm; Preferably, the thickness of the metal electrode layer is 100-150 nm; Preferably, the thickness of the second substrate is 0.5 mm to 2 mm; Preferably, the second substrate is in contact with the edge of the first substrate, and the contact area is a blank area of ​​the substrate, the width of which is not less than 2 cm.

[0008] Furthermore, the first substrate and / or the second substrate are thermoplastic materials; the thermoplastic materials include one or more of PET, PC, and PMMA; Preferably, the perovskite photovoltaic housing further includes a scratch-resistant coating stacked on the second substrate; the scratch-resistant coating is made of polymethyl methacrylate and / or silicon dioxide. Preferably, the thickness of the anti-scratch coating is 0.03 mm to 0.05 mm.

[0009] Furthermore, the perovskite photovoltaic housing is the front and / or back housing of a car key; Preferably, the perovskite photovoltaic shell is a curved shell.

[0010] Secondly, the present invention provides a method for preparing a perovskite photovoltaic casing for an automobile key, comprising the following steps: (a) A conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer and a metal electrode layer are sequentially stacked on a first substrate; (b) Cover the surface of the metal electrode layer with a second substrate to obtain a laminated preform; (c) The laminated preform is hot-stamped to obtain the perovskite photovoltaic shell for car keys.

[0011] Furthermore, the preparation process of the conductive layer includes: using a mixture of In2O3 and SnO2 as the target material, the conductive layer is prepared by magnetron sputtering; the mass ratio of In2O3 to SnO2 is 85-95:10; Preferably, the preparation process of the electron transport layer includes: using SnO2 nano-dispersion as a precursor, coating it, and then annealing it to obtain the electron transport layer; the concentration of the SnO2 nano-dispersion is 2-3 wt%; the coating speed is 0.5-1 m / min; the annealing temperature is 120-180℃, and the time is 20-40 minutes. Preferably, the preparation process of the perovskite active layer includes: preparing a precursor solution containing cesium, formamidinium, methylamine and lead-iodine complex, then adding a thermoplastic polyurethane toughening agent to the precursor solution, then coating the resulting mixed solution onto the surface of the electron transport layer, and then performing induced crystallization and annealing to obtain the perovskite active layer; Preferably, the precursor solution is prepared in a ratio of Cs. 0.03-0.07 FA 0.8-0.9 MA 0.05-0.15 PbI3; the concentration of the precursor solution is 1.0 mol / L-1.5 mol / L, and the solvent is a mixture of N,N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 3:1-5:1; the mass percentage of the thermoplastic polyurethane toughening agent in the precursor solution is 1.0 wt%-3.0 wt%; during the coating process, the temperature is 50-70℃, and the coating speed is 0.3-0.8 m / min; chlorobenzene is used as the anti-solvent for the induced crystallization; the annealing temperature is 90-110℃, and the time is 5-15 minutes; Preferably, the grain size of the perovskite active layer is 200-500 nm; Preferably, the hole transport layer is prepared by coating a mixture of Spiro-OMeTAD solution, 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonylimide) as coating material to obtain the hole transport layer; the coating speed is 1-1.5 m / min. Preferably, the preparation process of the metal electrode layer includes: preparing comb-shaped silver electrodes using a mask thermal evaporation process; the evaporation rate is 0.05-0.15 Å / s; Preferably, step (b) further includes: vacuum hot-pressing the second substrate with a substrate carrying the first substrate and each functional layer; the vacuum hot-pressing temperature is 100-120°C, the pressure is 0.1-0.5 MPa, the vacuum degree is <10Pa, and the time is 10-20 minutes.

[0012] Furthermore, both the first substrate and the second substrate are subjected to plasma cleaning treatment; Preferably, a mixture of O2 and N2 gas is used, and the treatment is carried out for 1 min to 5 min at a radio frequency power of 150-250 W.

[0013] Furthermore, the hot stamping process includes: performing a three-stage hot pressing process on the laminated preform, wherein the three-stage hot pressing process includes a preheating and softening stage, a precision forming stage, and a cooling and shaping stage; Preferably, the preheating and softening section has a processing temperature of 80-90℃, a pressure of 0.5-1 MPa, and a pressure holding time of 35-45 seconds; Preferably, the processing temperature of the precision forming section is 95-105℃, the pressure is 1-1.8 MPa, and the holding time is 10-15 seconds; Preferably, the pressure in the cooling and shaping section is 0.4-0.6 MPa, and the temperature is cooled to below 35-45°C at a rate of 5-10°C / min; Preferably, the preparation method further includes: preparing a scratch-resistant coating on the outer surface of the perovskite photovoltaic shell; the scratch-resistant coating has a double-layer structure, including a bottom layer and a top layer stacked sequentially; the bottom layer includes silicon dioxide; the top layer includes diamond-like carbon and / or PMMA.

[0014] Thirdly, the present invention provides a self-charging car key, comprising the perovskite photovoltaic shell for car keys or the perovskite photovoltaic shell prepared by the preparation method described above.

[0015] Furthermore, this also includes rechargeable lithium-ion batteries; The perovskite photovoltaic housing has a pad area on its inner side, which forms a charging circuit with the rechargeable lithium-ion battery through an electrical connection.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The perovskite photovoltaic housing for car keys provided by this invention uses a first substrate and a second substrate as the structural body of the car key housing, and sets a conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, and a metal electrode layer between the first and second substrates to form an integrated housing structure with power generation function. The dual substrates provide both high light transmittance and mechanical support; the conductive layer, electron transport layer, and hole transport layer synergistically promote the directional separation and transport of photogenerated carriers; the perovskite active layer endows the housing with excellent weak light response characteristics; and the metal electrode layer enables low-resistance collection of photogenerated current. The overall structure ensures a thin profile while enabling the housing itself to possess stable light energy conversion capabilities, thus solving the problems of traditional car keys relying on disposable batteries, requiring periodic replacement and lacking self-sustaining operation, and the difficulty of reliably integrating existing photovoltaic solutions into a compact housing due to structural separation and excessive thickness. Attached Figure Description

[0017] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0018] Figure 1 A schematic diagram of the cross-sectional structure of the perovskite photovoltaic shell provided by the present invention; Figure 2 A schematic diagram of the planar structure of the perovskite photovoltaic thin film provided by the present invention; Figure 3 A schematic diagram of the front structure of the self-charging car key provided by the present invention; Figure 4 A schematic diagram of the back structure of the self-charging car key provided by the present invention; Figure 5 An exploded view of the self-charging car key provided by the present invention; Figure 6 This is a three-dimensional structural diagram of the self-charging car key provided by the present invention.

[0019] Icons: 1-First blank area; 2-Second blank area; 3-Button area; 4-Connector; 5-Front power generation window area; 6-First rear power generation window area; 7-Second rear power generation window area; 8-LIR2032 battery; 9-FPC circuit board. Detailed Implementation

[0020] Unless otherwise defined herein, the scientific and technical terms used in conjunction with this invention shall have the meanings commonly understood by one of ordinary skill in the art. The meaning and scope of terms shall be clear; however, in any case of potential ambiguity, the definitions provided herein shall prevail over any dictionary or foreign definitions. In this application, unless otherwise stated, the use of "or" means "and / or". Furthermore, the use of the term "comprising" and other forms is non-limiting.

[0021] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] like Figure 1 As shown, the first aspect of the present invention provides a perovskite photovoltaic shell for a car key, comprising: a first substrate, a conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, a metal electrode layer, and a second substrate, which are sequentially stacked.

[0023] In this invention, the perovskite photovoltaic thin film composed of a first substrate, a conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, a metal electrode layer, and a second substrate has advantages such as high power generation efficiency in low light, thin thickness, good flexibility, low preparation cost, and strong weather resistance. Its power generation performance under indoor natural light and artificial light sources far exceeds that of traditional crystalline silicon cells.

[0024] Wherein, the first substrate and / or the second substrate are selected from thermoplastic materials such as PET, PC, or PMMA, and the first substrate and / or the second substrate are transparent substrate layers; the thickness of the first substrate is 0.5mm-2mm, for example, it can be 0.5mm, 1mm, 1.5mm, 2mm, etc., and more preferably 1.0 ± 0.05 mm; the thickness of the second substrate is 0.5mm-2mm, for example, it can be 0.5mm, 1mm, 1.5mm, 2mm, etc., and more preferably 1.0 ± 0.05 mm; the total thickness of the double-layer substrate composite is 1mm-4mm, the light transmittance is ≥90%, and the impact strength is ≥5 kJ / m 2 It can be directly used as an outer shell structural component.

[0025] The thickness of the conductive layer is 150-250 nm, for example, 150 nm, 200 nm, 250 nm, etc., and more preferably 180 ± 20 nm; the thickness of the electron transport layer is 20-40 nm, for example, 20 nm, 30 nm, 40 nm, etc., and more preferably 30 ± 5 nm; the thickness of the perovskite active layer is 450-550 nm, for example, 450 nm, 500 nm, 550 nm, etc., and more preferably 500 ± 30 nm; the thickness of the hole transport layer is 100-200 nm, for example, 100 nm, 150 nm, 200 nm, etc., and more preferably 150 ± 10 nm; the thickness of the metal electrode layer is 100-150 nm, for example, 100 nm, 125 nm, 150 nm, etc., and more preferably 120 ± 10 nm.

[0026] Preferably, the second substrate contacts the edge of the first substrate, and the contact area is a blank area of ​​the substrate, the width of which is not less than 2 cm. Figure 3 and Figure 4 As shown, Figure 3 The blank area on the substrate of the front shell is designated as the first blank area 1. Figure 4 The blank area on the back shell is the second blank area 2.

[0027] Specifically, the blank area of ​​the substrate is located at the edge of the perovskite photovoltaic shell, covering the edge area where the first substrate and the second substrate are in contact. No functional layer, such as conductive layer, electron transport layer, perovskite active layer, hole transport layer and metal electrode layer, is set in the blank area of ​​the substrate. This allows the functional layers such as the perovskite active layer to be set only in the middle area of ​​the overlapping part of the first substrate and the second substrate (i.e., the battery module area), which is surrounded by the blank area of ​​the substrate. The width of not less than 2 cm can meet the engineering requirements of edge sealing, bending resistance and assembly tolerance of car key shells in hot stamping and daily use.

[0028] Preferably, the perovskite photovoltaic shell further includes a scratch-resistant coating stacked on the second substrate; the scratch-resistant coating is a transparent scratch-resistant coating, the material of which includes polymethyl methacrylate and / or silicon dioxide; the thickness of the scratch-resistant coating is 0.03mm-0.05mm; the pencil hardness of the scratch-resistant coating is ≥2H, and it works stably in an environment of -20℃-60℃.

[0029] In some preferred embodiments, the perovskite photovoltaic housing is the front and / or back housing of a car key.

[0030] A second aspect of the present invention provides a method for preparing a perovskite photovoltaic casing for an automobile key, comprising the following steps: (a) A conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer and a metal electrode layer are sequentially stacked on a first substrate; (b) Cover the surface of the metal electrode layer with a second substrate to obtain a laminated preform; (c) The laminated preform is hot-stamped and cooled to obtain a curved shell with built-in photovoltaic function.

[0031] The present invention provides a method for preparing a perovskite photovoltaic shell for car keys. By hot stamping a laminated preform, the laminated preform simultaneously completes surface shaping and interlayer interface strengthening. This not only gives the shell geometric adaptability to match the three-dimensional contour of the car key, but also avoids the debonding, blistering, and power generation attenuation caused by adhesive layer aging and thermal expansion and contraction in traditional surface-mount photovoltaic modules. The preparation method enables the photovoltaic functional layer and the shell structure to achieve physical and functional integration, significantly improving integration reliability and long-term environmental tolerance.

[0032] The specific fabrication process of each functional layer is as follows: (1) The preparation process of the conductive layer includes: using a mixture of In2O3 and SnO2 as the target material, the conductive layer is prepared by magnetron sputtering; the mass ratio of In2O3 to SnO2 is 85-95:10, for example, it can be 85:10, 90:10, 95:10, etc.

[0033] (2) The preparation process of the electron transport layer includes: using SnO2 nano-dispersion as a precursor, coating it, and then annealing it to obtain the electron transport layer.

[0034] The concentration of the SnO2 nano-dispersion is 2-3 wt%, for example, it can be 2 wt%, 2.5 wt%, 3 wt%, etc.; the coating speed is 0.5-1 m / min, for example, it can be 0.5 m / min, 0.6 m / min, 0.7 m / min, 0.8 m / min, 0.9 m / min, 1 m / min, etc.; the annealing temperature is 120-180℃, for example, it can be 120℃, 140℃, 160℃, 180℃, etc., and the time is 20-40 minutes, for example, it can be 20 minutes, 30 minutes, 40 minutes, etc.

[0035] (3) The preparation process of the perovskite active layer includes: preparing a precursor solution containing cesium, formamidine, methylamine and lead-iodine complex, then adding a thermoplastic polyurethane toughening agent to the precursor solution to ensure that the film layer does not crack during the stamping process, then coating the resulting mixed solution onto the surface of the electron transport layer, and then inducing crystallization and annealing to obtain the perovskite active layer.

[0036] The precursor solution is prepared in the following proportion: Cs 0.03-0.07 FA 0.8-0.9 MA 0.05-0.15 PbI3; the concentration of the precursor solution is 1.0 mol / L-1.5 mol / L, for example, 1.0 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L, 1.5 mol / L, etc., and the solvent is a mixture of N,N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 3:1-5:1, preferably 4:1; the mass percentage of the thermoplastic polyurethane toughening agent in the precursor solution is 1.0 wt%-3.0 wt%, for example, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, etc.; during the coating process, the temperature is 50-70℃, for example, 50℃, 60℃, 70℃, etc., and the coating speed is 0.3-0.8 m / min, for example, 0.3 m / min, 0.4 m / min, 0.5 m / min, etc. The annealing speeds are 0.6 m / min, 0.7 m / min, 0.8 m / min, etc.; chlorobenzene is used as the antisolvent for the induced crystallization; the annealing temperature is 90-110℃, for example, 90℃, 100℃, 110℃, etc., and the time is 5-15 minutes, for example, 5 minutes, 10 minutes, 15 minutes, etc.

[0037] Preferably, the grain size of the perovskite active layer is 200-500 nm.

[0038] (4) The preparation process of the hole transport layer includes: coating with a mixture of Spiro-OMeTAD solution, 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonylimide) as coating material to obtain the hole transport layer; the coating speed is 1-1.5 m / min, for example, it can be 1 m / min, 1.1 m / min, 1.2 m / min, 1.3 m / min, 1.4 m / min, 1.5 m / min, etc.

[0039] (5) The preparation process of the metal electrode layer includes: using a mask thermal evaporation process to prepare comb-shaped silver electrodes; the evaporation rate is 0.05-0.15 Å / s, for example, it can be 0.05 Å / s, 0.1 Å / s, 0.15 Å / s, etc.

[0040] In some preferred embodiments, step (b) further includes: vacuum thermopressing the second substrate with a substrate carrying the first substrate and each functional layer; the vacuum thermopressing temperature is 100-120°C, for example, 100°C, 110°C, 120°C, etc., the pressure is 0.1-0.5 MPa, for example, 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, etc., the vacuum degree is <10 Pa, and the time is 10-20 minutes, for example, 10 minutes, 15 minutes, 20 minutes, etc.

[0041] In some preferred embodiments, both the first substrate and the second substrate are subjected to plasma cleaning: a mixed gas of O2 and N2 is used, and the treatment is carried out for 1 min to 5 min under the condition of 150-250 W radio frequency power, for example, 1 min, 2 min, 3 min, 4 min, 5 min, etc.

[0042] In some preferred embodiments, the hot stamping process includes: performing a three-stage hot pressing process on the laminated preform, wherein the three-stage hot pressing process adopts a step-by-step temperature-controlled pressure forming process, the forming mold is precisely matched with the curved surface of the target key shell, and the three-stage hot pressing process specifically includes a preheating and softening section, a precision forming section, and a cooling and shaping section. (1) The processing temperature of the preheating and softening section is 80-90℃, for example, 80℃, 85℃, 90℃, etc., the pressure is 0.5-1 MPa, for example, 0.5 MPa, 0.75 MPa, 1 MPa, etc., and the pressure holding time is 35-45 seconds, for example, 35 seconds, 40 seconds, 45 seconds, etc.

[0043] (2) The processing temperature of the precision forming section is 90-105℃, for example, 90℃, 95℃, 100℃, 105℃, etc., the pressure is 1-1.6 MPa, for example, 1 MPa, 1.3 MPa, 1.6 MPa, etc., and the holding time is 10-15 seconds, for example, 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds, 15 seconds, etc.

[0044] (3) The pressure of the cooling and shaping section is 0.4-0.6 MPa, for example, 0.4 MPa, 0.5 MPa, 0.6 MPa, etc., and it is cooled to below 35-45℃ (for example, 35℃, 40℃, 45℃, etc.) at a rate of 5-10℃ / min (for example, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, 10℃ / min, etc.).

[0045] Preferably, the preparation method further includes: preparing a scratch-resistant coating on the outer surface of the perovskite photovoltaic shell; the scratch-resistant coating has a double-layer structure, including a bottom layer and a top layer stacked sequentially; the bottom layer includes silicon dioxide; the top layer includes diamond-like carbon and / or PMMA.

[0046] Specifically, a magnetron sputtering double-layer composite coating is applied to the surface of the key shell: the bottom layer is preferably 10-micron SiO2 as a transition layer to improve adhesion (reaching level 0 in cross-cut test); the top layer is preferably 40-micron diamond-like carbon (DLC) coating or sol-gel PMMA coating (hardness 3H), with an elastic modulus >5GPa, pencil hardness ≥2H, and water contact angle >110° as measured by nanoindentation test, and has self-cleaning function.

[0047] A third aspect of the present invention provides a self-charging car key, comprising a perovskite photovoltaic shell for the car key or a perovskite photovoltaic shell prepared by the aforementioned preparation method. The front or back shell of the car key is directly formed by hot stamping of a perovskite photovoltaic module (i.e., a perovskite photovoltaic thin film composed of a first substrate, a conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer, a metal electrode layer, and a second substrate).

[0048] The self-charging car key provided by this invention is a self-charging car key integrating a curved perovskite photovoltaic module. It is particularly suitable for smart car keys that require long-term self-powered operation and low maintenance frequency. It can achieve long-term self-charging and has a compact, adaptable, safe, and durable structure. By integrating a perovskite photovoltaic thin film into the car key shell, combined with a rechargeable lithium-ion battery and an intelligent charging control module, the car key achieves continuous self-powered operation, completely solving the technical pain points of traditional car keys such as the need to replace batteries when they run out, poor adaptability to curved surfaces, easy wear and tear of integrated structures, and lack of safety protection during charging. At the same time, it ensures a compact structure, strong compatibility, good weather resistance, improved user experience, and reduced environmental pollution.

[0049] In some preferred embodiments, the self-charging car key also includes a rechargeable lithium-ion battery. The inner side of the perovskite photovoltaic housing has a solder pad area, which forms a charging circuit with the rechargeable lithium-ion battery via electrical connection.

[0050] The power generation window region is defined as the functional area in the perovskite photovoltaic shell that is not blocked, allows light to enter, and excites the perovskite active layer to generate photogenerated carriers. It corresponds to the middle region of the first and second substrates, where the conductive layer, electron transport layer, perovskite active layer, hole transport layer, and metal electrode layer are stacked and completely overlapped.

[0051] Optionally, the front casing structure includes a button area 3 (without a perovskite functional layer) and a front power generation window area 5. The front power generation window area 5 is a continuous light-transmitting power generation surface located below the button area 3 and belonging to the battery module area. The back casing structure includes a first back power generation window area 6 and a second back power generation window area 7, which together constitute the back power generation surface. The light transmittance of each of the above power generation window areas remains not less than 88% after hot stamping. The first blank area 1 and the second blank area 2 are blank areas of the substrate, which form the casing frame structure after hot stamping.

[0052] Optionally, in the self-charging car key of the present invention, the front perovskite photovoltaic shell and the back perovskite photovoltaic shell are joined by a connector snap-fit ​​and a sealant, with the seam filled with waterproof adhesive, and the overall protection level reaches IP67 or above. The energy storage unit uses an LIR2032 type rechargeable lithium-ion battery with a rated voltage of 3.6 V, a nominal capacity of not less than 50 mAh, and a cycle life of not less than 500 cycles. The input terminal of the charging control module is electrically connected to the solder pad area provided on the inner side of the perovskite photovoltaic shell, and the output terminal is connected to the rechargeable lithium-ion battery and the core circuit of the car key respectively; the module has overcharge protection (trigger threshold of 4.2 V ± 0.05 V), over-discharge protection (trigger threshold of 2.75 V ± 0.05 V), short circuit protection, and voltage regulation output function, and the static operating current is not higher than 10 μA, thereby ensuring charging safety, battery life and low power consumption operation of the whole device.

[0053] The self-charging car key provided by this invention utilizes perovskite photovoltaic thin-film technology, providing continuous power generation in all indoor and outdoor scenarios (direct sunlight / diffused light / artificial light sources). Combined with a rechargeable lithium-ion battery with a cycle life of ≥500 cycles, it forms a self-circulating "photovoltaic-electrical energy" system, completely eliminating the pain point of traditional car keys requiring periodic replacement of CR2032 button batteries, achieving zero-maintenance power supply throughout its entire lifecycle. Through the perovskite self-charging system and the recyclable rechargeable lithium-ion battery, zero battery replacement is achieved within an 8-year cycle under effective sunlight, saving costs compared to traditional CR2032 solutions. Furthermore, it completely replaces disposable CR2032 button batteries, reducing heavy metal pollution and aligning with global green and low-carbon development trends. In addition, the integrated charging control module with multiple protection functions uses intelligent algorithms to achieve precise charge and discharge management: avoiding overcharging / over-discharging damage to the battery, ensuring constant voltage power supply to the car key's core circuitry (no voltage fluctuations), eliminating malfunctions caused by unstable power supply, and significantly improving reliability and user experience.

[0054] In addition, in terms of durability and reliability, the self-charging car key provided by this invention has passed 50,000 presses, 10,000 bends and harsh environmental tests, meeting the automotive-grade AEC-Q100 standard.

[0055] The present invention will be further illustrated below by way of examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.

[0056] Example 1 This embodiment provides a self-charging car key, the preparation process of which is as follows: Step 1: Material pretreatment and preparation of functional layer substrate The transparent substrate is made of PC board with a thickness of 1.0 mm, light transmittance ≥91%, and impact strength ≥7 kJ / m. 2 Both the first and second substrates were subjected to plasma cleaning treatment, using a mixture of O2 and N2 gas and 200 W RF power for 3 minutes, to increase the surface energy to ≥40 dyn / cm and ensure the adhesion of subsequent functional layers. The transparent conductive layer (ITO) was prepared by magnetron sputtering with a target material of In2O3 and SnO2 in a mass ratio of 90:10. The resulting film had a thickness of 180 nm, a sheet resistance of ≤8 Ω / □, and a transmittance of >85% at a wavelength of 550 nm.

[0057] Step 2: Fabrication of planar perovskite photovoltaic modules: Functional layers are sequentially deposited on the first substrate in a cleanroom using a roll-to-roll slot coating process. Step 2.1, Preparation of electron transport layer: SnO2 nanoparticles with a particle size of 8 nm were dispersed in deionized water to prepare a 2.5 wt% dispersion. After filtration through a 0.22 μm filter, the dispersion was deposited at a coating speed of 0.8 m / min and a coating gap of 80 μm. Subsequently, it was heat-annealed at 150℃ for 30 minutes to form a dense film with a final thickness of 30 nm. Step 2.2, Preparation of the perovskite active layer: Prepare a precursor solution with the composition Cs 0.05 FA 0.85 MA 0.1 PbI3 (concentration 1.2 mol / L) was coated using a mixture of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 4:1. A thermoplastic polyurethane toughening agent of 1.5 wt% was added to this precursor solution. The substrate temperature was controlled at 60°C, the coating speed at 0.5 m / min, and the wet film thickness approximately 8 μm. The substrate was then placed in a glove box with a humidity <20%RH, and chlorobenzene was used as the antisolvent (100 μL / cm²). 2 The crystals were induced to crystallize, and then annealed at 100℃ for 10 min to obtain a polycrystalline thin film with a grain size of 200-500 nm and a thickness of 500 nm. Step 2.3: Preparation of hole transport layer: Using a mixture of Spiro-OMeTAD solution, 4-tert-butylpyridine (tBP) and lithium bis(trifluoromethanesulfonylimide) (Li-TFSI) as coating material, the coating speed is 1.2 m / min, and a film with a thickness of 150 nm is obtained. Step 2.4: Fabrication of metal electrode layer: Comb-shaped silver electrodes were fabricated using a mask thermal evaporation process with a deposition rate of 0.1 Å / s. The thickness of the metal electrode layer was 120 nm, the linewidth was 50 μm, the spacing was 200 μm, and the electrode coverage area was optimized to 80%, maximizing the light transmission area while ensuring carrier collection efficiency. Step 2.5, Lamination and Encapsulation: After completing the above functional layer deposition, the second substrate (also a PC board, 1.0 mm thick, with a light transmittance ≥91% and an impact strength ≥7 kJ / m) is laminated and encapsulated. 2 The substrate is covered on the surface of the metal electrode layer to form a laminated preform; then it is hot-pressed in a vacuum laminator (Baccini LDE 1.2) with the following process parameters: temperature 105 ℃, pressure 0.3 MPa, vacuum degree <10Pa, time 15 min, to form a "substrate-functional layer-substrate" sandwich structure with an edge blank width ≥2cm.

[0058] Step 3: Curved surface hot stamping forming to prepare the perovskite photovoltaic shell: The above-mentioned planar perovskite photovoltaic preform is placed in a mold for three-stage forming: Step 3.1, Preheating and softening section: temperature 85±2℃, pressure 0.6±0.05 MPa, pressure holding time 40 s, heating rate 5 ℃ / min; Step 3.2, Precision forming section: temperature 102±1℃, pressure 1.5±0.1 MPa, holding time 12 s; Step 3.3, Cooling and Shaping Section: Maintain pressure of 0.5±0.05 MPa, cool to below 40 ℃ at a rate of 8℃ / min, and then demold; The mold is made of stainless steel SUS304 mirror mold, and the cavity is precisely matched with the three-dimensional model of the target car key shell. It is coated with diamond-like coating with a hardness >2000HV and a roughness Ra≤0.02μm, and sprayed with polytetrafluoroethylene release agent to ensure smooth demolding.

[0059] After hot stamping, a front shell and a back shell matching the three-dimensional contour of the car key are obtained; both are made of independently prepared perovskite photovoltaic thin film by hot stamping and both integrate photovoltaic functions.

[0060] Step 4, Multifunctional surface protection treatment: Prepare a scratch-resistant coating on the outer surface of the perovskite photovoltaic shell after hot stamping: Sequentially deposit a bottom layer of SiO2 (10 micrometers thick) and a top layer of diamond-like carbon (DLC) coating (40 micrometers thick) using magnetron sputtering.

[0061] Step 5: Overall assembly and electrical integration of the car key: like Figure 5 and Figure 6 As shown, the FPC circuit board 9 is fixed to the inside of the front shell by the positioning post, then the LIR2032 battery 8 is installed into the battery compartment, then the back shell is fastened by the connector 4, and then sealed with sealant to complete the assembly of the car key.

[0062] Example 2 This embodiment provides a self-charging car key, which differs from Embodiment 1 in that: the thickness of the conductive layer is 150 nm, the thickness of the electron transport layer is 40 nm, the thickness of the perovskite active layer is 450 nm, the thickness of the hole transport layer is 200 nm, and the thickness of the metal electrode layer is 100 nm.

[0063] Example 3 This embodiment provides a self-charging car key, which differs from Embodiment 1 in that: the thickness of the conductive layer is 250 nm, the thickness of the electron transport layer is 20 nm, the thickness of the perovskite active layer is 550 nm, the thickness of the hole transport layer is 100 nm, and the thickness of the metal electrode layer is 150 nm.

[0064] Example 4 This embodiment provides a self-charging car key, which differs from Embodiment 1 in that: The preheating and softening section has a processing temperature of 80℃ and a holding time of 15 seconds. The precision forming section has a processing temperature of 105℃ and a holding time of 10 seconds.

[0065] Example 5 This embodiment provides a self-charging car key, which differs from Embodiment 1 in that: The preheating and softening section has a processing temperature of 90℃ and a holding time of 10 seconds. The precision forming section has a processing temperature of 95℃ and a holding time of 15 seconds.

[0066] Example 6 This embodiment provides a self-charging car key, which differs from Embodiment 1 in that: The preheating and softening section has a processing temperature of 75℃; the precision forming section has a processing temperature of 90℃.

[0067] Example 7 This embodiment provides a self-charging car key, which differs from Embodiment 1 in that: The preheating and softening section has a processing temperature of 95℃; the precision forming section has a processing temperature of 110℃.

[0068] Example 8 This embodiment provides a self-charging car key, which differs from Embodiment 1 in that it does not undergo preheating and softening.

[0069] Example 9 This embodiment provides a self-charging car key, which differs from Embodiment 1 in that: in step 2.2, no thermoplastic polyurethane toughening agent is added to the precursor solution.

[0070] Comparative Example 1 This comparative example provides a self-charging car key, which differs from Example 1 in that it is a single-substrate package (i.e., a second substrate is provided), only the first substrate and each functional layer are provided, the surface is covered with transparent protective adhesive, and there is no blank area left on the substrate.

[0071] Comparative Example 2 This comparative example provides a crystalline silicon patch car key, which uses a monocrystalline silicon solar cell and is bonded to the surface of a PC casing with UV adhesive.

[0072] Test case The self-charging car keys prepared in Examples 1-9 and the car keys in Comparative Examples 1-2 were used as samples for testing.

[0073] Test method: Photovoltaic performance test: The test was conducted in accordance with IEC 61215-2:2021 standard under an AAA-level solar simulator (Sciencetech SF300A, AM1.5G).

[0074] The test results are shown in Tables 1-4.

[0075] Table 1

[0076] Table 2

[0077] Table 3

[0078] Table 4

[0079] As shown in Tables 1-4, Comparative Example 1 (single substrate with no blank space) and Comparative Example 2 (crystalline silicon patch) have inherent shortcomings in structural integration and weak light response. The car key prepared using the perovskite photovoltaic shell of this invention exhibits significantly better overall photoelectric performance than Comparative Example 1 and Comparative Example 2. The parameters selected in Examples 1-5 are within the preferred range defined by this invention, thus exhibiting superior photovoltaic output performance under various lighting conditions (direct sunlight, cloudy outdoor, natural light near a window, and LED light source). In contrast, Examples 6-7, due to exceeding the preferred temperature control window, resulted in interfacial stress mismatch in the film layer or a decrease in perovskite crystal quality, further weakening the performance; Examples 8-9 lacked key processes or components such as preheating softening or toughening agents, resulting in a significant degradation in power generation capacity. Therefore, this invention achieves photoelectric functional integration of the car key shell under miniaturization and curved surface design, while also taking into account the advantages of long-term self-powering capability.

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A perovskite photovoltaic housing for car keys, characterized in that, include: The first substrate, conductive layer, electron transport layer, perovskite active layer, hole transport layer, metal electrode layer and second substrate are stacked sequentially.

2. The perovskite photovoltaic housing for car keys according to claim 1, characterized in that, The thickness of the first substrate is 0.5mm-2mm; Preferably, the thickness of the conductive layer is 150-250 nm; Preferably, the thickness of the electron transport layer is 20-40 nm; Preferably, the thickness of the perovskite active layer is 450-550 nm; Preferably, the thickness of the hole transport layer is 100-200 nm; Preferably, the thickness of the metal electrode layer is 100-150 nm; Preferably, the thickness of the second substrate is 0.5 mm to 2 mm; Preferably, the second substrate is in contact with the edge of the first substrate, and the contact area is a blank area of ​​the substrate, the width of which is not less than 2 cm.

3. The perovskite photovoltaic housing for car keys according to claim 1, characterized in that, The first substrate and / or the second substrate are thermoplastic materials; the thermoplastic materials include one or more of PET, PC and PMMA; Preferably, the perovskite photovoltaic housing further includes a scratch-resistant coating stacked on the second substrate; the scratch-resistant coating is made of polymethyl methacrylate and / or silicon dioxide. Preferably, the thickness of the anti-scratch coating is 0.03 mm to 0.05 mm.

4. The perovskite photovoltaic housing for car keys according to claim 1, characterized in that, The perovskite photovoltaic casing is the front and / or back casing of a car key; Preferably, the perovskite photovoltaic shell is a curved shell.

5. The method for preparing a perovskite photovoltaic casing for an automobile key according to any one of claims 1-4, characterized in that, Includes the following steps: (a) A conductive layer, an electron transport layer, a perovskite active layer, a hole transport layer and a metal electrode layer are sequentially stacked on a first substrate; (b) Cover the surface of the metal electrode layer with a second substrate to obtain a laminated preform; (c) The laminated preform is hot-stamped to obtain the perovskite photovoltaic shell for car keys.

6. The preparation method according to claim 5, characterized in that, The preparation process of the conductive layer includes: using a mixture of In2O3 and SnO2 as the target material, the conductive layer is prepared by magnetron sputtering; the mass ratio of In2O3 to SnO2 is 85-95:

10. Preferably, the preparation process of the electron transport layer includes: using SnO2 nano-dispersion as a precursor, coating it, and then annealing it to obtain the electron transport layer; the concentration of the SnO2 nano-dispersion is 2-3 wt%; the coating speed is 0.5-1 m / min; the annealing temperature is 120-180℃, and the time is 20-40 minutes. Preferably, the preparation process of the perovskite active layer includes: preparing a precursor solution containing cesium, formamidinium, methylamine and lead-iodine complex, then adding a thermoplastic polyurethane toughening agent to the precursor solution, then coating the resulting mixed solution onto the surface of the electron transport layer, and then performing induced crystallization and annealing to obtain the perovskite active layer; Preferably, the precursor solution is prepared in a ratio of Cs. 0.03-0.07 FA 0.8-0.9 MA 0.05-0.15 PbI3; the concentration of the precursor solution is 1.0 mol / L-1.5 mol / L, and the solvent is a mixture of N,N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 3:1-5:1; the mass percentage of the thermoplastic polyurethane toughening agent in the precursor solution is 1.0 wt%-3.0 wt%; during the coating process, the temperature is 50-70℃, and the coating speed is 0.3-0.8 m / min; chlorobenzene is used as the anti-solvent for the induced crystallization; the annealing temperature is 90-110℃, and the time is 5-15 minutes; Preferably, the grain size of the perovskite active layer is 200-500 nm; Preferably, the hole transport layer is prepared by coating a mixture of Spiro-OMeTAD solution, 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonylimide) as coating material to obtain the hole transport layer; the coating speed is 1-1.5 m / min. Preferably, the preparation process of the metal electrode layer includes: preparing a comb-shaped silver electrode using a mask thermal evaporation process; the evaporation rate is 0.05-0.15 Å / s; Preferably, step (b) further includes: vacuum hot-pressing the second substrate with a substrate carrying the first substrate and each functional layer; the vacuum hot-pressing temperature is 100-120°C, the pressure is 0.1-0.5 MPa, the vacuum degree is <10Pa, and the time is 10-20 minutes.

7. The preparation method according to claim 5, characterized in that, Both the first substrate and the second substrate were subjected to plasma cleaning treatment; Preferably, a mixture of O2 and N2 gas is used, and the treatment is carried out for 1 min to 5 min at a radio frequency power of 150-250 W.

8. The preparation method according to claim 5, characterized in that, The hot stamping process includes: performing a three-stage hot pressing process on the laminated preform, the three-stage hot pressing process including a preheating and softening stage, a precision forming stage and a cooling and shaping stage; Preferably, the preheating and softening section has a processing temperature of 80-90℃, a pressure of 0.5-1 MPa, and a pressure holding time of 35-45 seconds; Preferably, the processing temperature of the precision forming section is 95-105℃, the pressure is 1-1.8 MPa, and the holding time is 10-15 seconds; Preferably, the pressure in the cooling and shaping section is 0.4-0.6 MPa, and the temperature is cooled to below 35-45°C at a rate of 5-10°C / min; Preferably, the preparation method further includes: preparing a scratch-resistant coating on the outer surface of the perovskite photovoltaic shell; the scratch-resistant coating has a double-layer structure, including a bottom layer and a top layer stacked sequentially; the bottom layer includes silicon dioxide; the top layer includes diamond-like carbon and / or PMMA.

9. A self-charging car key, characterized in that, Includes the perovskite photovoltaic housing for car keys as described in any one of claims 1-4, or the perovskite photovoltaic housing prepared by the preparation method described in any one of claims 5-8.

10. The self-charging car key according to claim 9, characterized in that, It also includes rechargeable lithium-ion batteries; The perovskite photovoltaic housing has a pad area on its inner side, which forms a charging circuit with the rechargeable lithium-ion battery through an electrical connection.

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