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Hybrid Energy Harvesting Solar Cells―From Principles to Applications

Qiyao Guo , Jialong Duan , Yuanyuan Zhao , Qingwei Zhou , Qunwei Tang

Progress in Chemistry ›› 2023, Vol. 35 ›› Issue (2) : 318 -329.

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Progress in Chemistry ›› 2023, Vol. 35 ›› Issue (2) : 318-329 DOI: 10.7536/PC220706
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Hybrid Energy Harvesting Solar Cells―From Principles to Applications
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Abstract

Photovoltaics are one of the strategic solutions to solve energy and environmental problems. The state-of-the-art solar cells always photo-induce electrons and generate electricity by the photovoltaic effect under the illumination of sunlight or indoor light, but the power output is still extremely low in dark-light or nonluminous conditions such as rainfall and night. The hybrid energy harvesting solar cells that can persistently output electricity in multiple weather are expected to further increase total power output and generating time. This perspective focuses on discussing the coupling principles of photovoltaic effect with hydrovoltaic effect, triboelectric effect, light storing-emitting effect, piezoelectric effect and thermoelectric effect in hybrid energy harvesting solar cells and summarizing the recent advances of these novel solar cells as well as analyzing the future development of this field.

Contents

1 Introduction

2 Hybrid energy harvesting solar cells for harvesting raindrop energy

2.1 Hydrovoltaic effect

2.2 Triboelectric effect

3 Hybrid energy harvesting solar cells based on solar energy storing-emitting effect

4 Hybrid energy harvesting solar cells based on piezoelectric and thermoelectric effects

5 Conclusions and outlook

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solar cells / energy integration / energy conversion / photovoltaics / carbon neutrality

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Qiyao Guo, Jialong Duan, Yuanyuan Zhao, Qingwei Zhou, Qunwei Tang. Hybrid Energy Harvesting Solar Cells―From Principles to Applications. Progress in Chemistry, 2023, 35(2): 318-329 DOI:10.7536/PC220706

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1 Introduction

Carbon peaking and carbon neutrality are strategic choices to achieve sustainable economic and social development, and the development of renewable clean energy is a key technical means to change the world's energy pattern and initiate carbon neutrality actions in various countries. The energy radiated from the sun to the earth is as high as 612,000 terajoules per hour, which is much higher than the total energy consumed by the world every year. At the same time, solar energy is an inexhaustible clean energy. Therefore, the development and efficient utilization of solar energy has become the core of the energy development strategy of all countries in the world. Compared with photothermal, photochemical, photobiological and other solar energy utilization methods, photoelectric conversion technology, which converts solar energy into electric energy, is one of the most direct and effective ways to utilize solar energy. In order to enhance the competitiveness with traditional fossil energy, solar cells with high efficiency, low cost, long life and diversified application environments have always been the goal pursued by people[1⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~13]. According to the statistics of the International Renewable Energy Agency, by the end of 2020, the global photovoltaic power generation capacity has reached 692 GW, meeting about 16% of the electricity demand, and it is predicted that the new installed capacity will reach 270 GW in 2030, with a total installed capacity of 2.84 TW, and it is expected to increase to 372 GW/year by 2050.The total installed capacity will reach 8.5 TW, and the global carbon dioxide emissions will be reduced by 4.9 GT, accounting for 22% of the total emission reduction in the energy industry. Therefore, many developed countries, such as the United States, Japan, the European Union and Australia, are vigorously developing new materials and technologies to continuously improve the efficiency of solar cells and reduce the cost of photovoltaic power generation. Solar cells have been developed for three generations, and the second generation of thin film solar cells (gallium arsenide, cadmium telluride, copper indium gallium selenide, etc.) And the third generation of new solar cells have certain advantages in low cost and flexibility.However, there are also some problems such as toxic raw materials (arsenic, cadmium, etc.), scarcity (gallium, tellurium, indium, etc.), light decay of devices (such as amorphous silicon solar cells) and insufficient stability (such as dye-sensitized solar cells, perovskite solar cells, etc). At present, the mainstream cell in the market is still the first generation of monocrystalline silicon solar cells. In the past 25 years, its photoelectric conversion efficiency has entered a development plateau and reached 26.7%, which is close to its Shockley-Queisser limit efficiency of 29.4%[10]. Despite the high photoelectric conversion efficiency of monocrystalline silicon solar cells, there is limited room for future growth[11⇓~13]. It is mainly attributed to the following two reasons: (I) Complex silicon purification and material treatment processes are usually used to continuously improve the photoelectric conversion efficiency of crystalline silicon solar cells, but there are still many problems in the control of impurities and defects in the production process of silicon semiconductors, and the effect of this method has gradually approached the limit. (ii) The response range of monocrystalline silicon solar cells to the solar spectrum is limited, which restricts the further improvement of their photoelectric conversion efficiency. At present, the developed solar cells need to achieve energy conversion under sunlight, but in the weak or dark environment such as rain and night, the photogenerated built-in electric field strength is low, which can not effectively extract photogenerated carriers, resulting in serious electron-hole pair recombination. Therefore, it is a long-standing industry problem for solar cells to fundamentally adjust the differences in materials and device structures, greatly improve the output power, prolong the power generation time and realize the diversification of application environments.
The developed solar cells with conventional structures all convert solar energy into electric energy by photovoltaic effect under direct sunlight irradiation, but it is difficult to effectively extract photogenerated carriers in rainy days with low light intensity (usually lower than 10 mW/cm2), resulting in low photoelectric conversion efficiency or even failure to generate electricity normally. South China, South America, Central America, Southeast Asia and other regions have abundant rainfall resources and long rainfall cycles, which seriously restrict the popularization and application of solar photovoltaic power generation technology. Meteorological data show that the average illumination time in China is about 3000 hours per year, accounting for 34.6% of the total annual time, that is, the carrier extraction efficiency of solar cells is low due to the weak built-in electric field intensity of photogeneration under 65.4% of weak or no light conditions, which is also the fundamental reason for intermittent power generation of solar cells. In view of the intermittent characteristics of solar cells, on the one hand, the photoelectric conversion efficiency is further improved by optimizing cell materials and innovating preparation technologies; On the other hand, other energy conversion principles are used to collect natural energy and integrate with solar cells to design "hybrid energy collection solar cells", which not only improves the total output power, but also realizes the diversification of application environment. Wind-solar complementation is a hybrid energy harvesting technology: wind and solar energy have natural complementary advantages, that is, strong sunshine in the daytime, more wind at night, good sunshine and weak wind in summer, and strong wind and weak sunshine in winter and spring. The reasonable combination of photovoltaic and wind power is expected to achieve uninterrupted power generation. In addition, under normal operating conditions, the temperature of solar cells will increase sharply, especially in hot summer, usually reaching more than 60 ℃, resulting in a significant decline in the performance of solar cells, especially monocrystalline silicon solar cells or carbon-based solar cells.The main reason is that photogenerated hot carriers will relax to the bottom of the band by emitting phonons extremely quickly, and this process will generate heat energy that cannot be effectively utilized, thus theoretically limiting the highest photoelectric conversion efficiency of solar cells to about 31%. Through the study of high-energy hot carrier generation and extraction of monolayer molybdenum disulfide and other transition metal chalcogenides, it is found that if they can be effectively applied to photovoltaic devices,It will slow down the cooling process of hot carriers, so that they can be extracted before relaxing to the bottom of the energy band, which is expected to further improve the photoelectric conversion efficiency of solar cells[14,15].
In recent years, the development of new energy conversion materials and technologies with hydrovoltaic effect, triboelectric effect, light storage-luminescence effect, piezoelectric effect and thermoelectric effect has brought new opportunities for the innovation of solar cells[16⇓⇓⇓~20][21⇓⇓~24][25⇓⇓~28][29⇓⇓~32][33⇓~35]. Hybrid energy harvesting solar cells are expected to fundamentally solve the core problems that restrict the design of new cell materials, cell assembly and device structure optimization. On the one hand, they can reveal the relevant energy conversion mechanism and improve the photoelectric conversion efficiency of solar cells. On the other hand, it can also realize the application of solar cells in weak or dark weather such as rain and night, realize multi-energy integration and improve its total output power. Based on the principle of power generation, this review discusses the research status of hybrid energy harvesting solar cells fabricated by coupling photovoltaic effect with hydrovoltaic effect, triboelectric effect, light storage-luminescence effect, piezoelectric effect and thermoelectric effect.On this basis, the application and technical difficulties in solar cells are emphatically introduced. Finally, the development direction of hybrid energy harvesting solar cells is prospected.

2 Hybrid Energy Harvesting Solar Cell Converting Water Kinetic Energy of Raindrop

Water covers about 71% of the earth's surface. It absorbs 70% of the energy of solar radiation reaching the surface to form the water cycle. The water cycle not only stores huge energy resources that have not yet been exploited and utilized, but also transfers other energy, which can evolve into evaporation energy, raindrop water kinetic energy, flow energy, wave kinetic energy and other forms in the process of water cycle. It is estimated that the annual average power of energy absorbed and released by water dynamics on the earth is as high as 60 trillion kilowatts, of which the annual average power of raindrop kinetic energy alone is tens of trillion kilowatts. Eastern China and South China, Southeast Asia, South America, Central Africa and other countries along the "Belt and Road" and "South-South Cooperation" are rich in rainfall resources, and the output power of solar cells is obviously insufficient.Through the integrated application of solar energy → electric energy and raindrop water kinetic energy → electric energy conversion, the hybrid energy harvesting solar photovoltaic power generation technology is developed, which can fundamentally adjust the structural differences, prolong the power generation time and realize the diversification of application environment. In general, there are two main conversion mechanisms for the kinetic energy of raindrop water: the first is the hydrovoltaic effect, the main principle of which is that when an aqueous droplet containing ions contacts with a surface electron-rich material, the cations in the droplet adsorb on the electrons on the surface of the material to form an electric double layer pseudocapacitance; When the droplet moves, the front part of the droplet is continuously adsorbed to form an electric double layer to charge the pseudocapacitance, and the tail part of the droplet is continuously desorbed to discharge the pseudocapacitance, so that the current and voltage pulses are generated during the charging and discharging of the pseudocatacitor, wherein the voltage is generally microvolt to millivolt, and the power is only nanowatt[20]; The second type is triboelectric effect, whose main principle is to convert the kinetic energy of water droplets into electric energy by using the induced potential difference between electrodes through the coupling of triboelectric effect and electrostatic induction effect between droplets and high electronegative dielectric materials. The output voltage can reach several volts or even tens of volts, and the power can also be increased to microwatt level[36,37]. We will discuss in detail the conversion principle of these two types of raindrop water kinetic energy harvesting and the research progress of their application in solar cells.

2.1 Hydrometric effect

In 2014, Guo Wanlin et al. Of Nanjing University of Aeronautics and Astronautics first discovered that water droplets containing Na+ ions can generate electrical signals when they move on the surface of monolayer graphene, and the phenomenon that carbon nanomaterials can stably output electrical energy through interaction with water is called "water volt effect"[20]. As shown in Figure 1A, when a droplet of NaCl aqueous solution with a concentration of 0. 6 mol/L slides on the surface of single-layer graphene, an open-circuit voltage of up to 0. 15 mV can be output, and if the sliding direction is changed, a voltage signal in the opposite direction can be output, while a stationary droplet cannot generate a streaming potential. Based on the above experimental phenomena and the calculation results of density functional theory, they further proposed the theory of electric double layer pseudocapacitance: when a NaCl aqueous droplet is in contact with a single layer of graphene,The Na+ in the droplet is enriched on the graphene surface due to the 2 eV adsorption energy between the Na+ and the conjugated electrons on the graphene surface.With the increase of the concentration of the adsorbed Na+, a positive electric layer is formed.In order to maintain electrical neutrality, the conjugated electrons are aggregated on the surface of graphene to form a negative electron layer, thus forming an electric double layer pseudocapacitance. When the droplet is stationary, the charge distribution at the graphene/droplet interface is balanced, and there is no potential difference between the solid/liquid interface. When the droplet moves on the surface of the single-layer graphene, the Na+ in the droplet at the front end of the displacement direction continuously adsorbs free electrons on the surface of the graphene to charge the pseudocapacitance and generate a high potential; On the contrary, the Na+ at the rear end of the droplet continuously desorbs from the electrons and makes the electrons adsorbed on the surface of graphene return to their original position, which makes the pseudocapacitance discharge and produce a low potential, and the streaming potential generated at the front and back ends of the droplet is the fundamental reason for the conversion of "drag energy" into electrical energy. This work pioneered the discovery of the phenomenon of ion droplets sliding on the surface of two-dimensional carbon materials to output electric energy, which broadened people's understanding of the water potential generated by carbon nanomaterials. At the same time, the advantage of increasing current and potential through series-parallel circuit design provides a new idea for capturing energy contained in liquid water such as rainwater and seawater in a large area, and also opens the prelude to the research of "graphene + water = electricity"[38⇓⇓~41]. Inspired by this work, our group designed and fabricated reduced graphene oxide electrodes using hot pressed film technology and integrated them with flexible dye-sensitized solar cells to construct the first prototype hybrid energy harvesting solar cell device that simultaneously converts solar energy and raindrop water kinetic energy.A photoelectric conversion efficiency of 6.53% was obtained under AM 1.5G standard solar illumination, and an open-circuit voltage of 150 μV/drop and a short-circuit current of 0.5 μA/drop were output under simulated rainfall conditions (Figure 1b)[39]. The results show that the cation/electron double layer pseudocapacitance is formed by the adsorption of the delocalized electrons in the π-conjugated structure of graphene and the cations in the raindrop. At the same time, the graphene film has a certain hydrophobicity, and the process of spreading and shrinking occurs after the raindrop falls on the surface of the graphene film. The cations at the solid/liquid/gas interface continuously adsorb with free electrons to form pseudocapacitance when the raindrop spreads, and desorb with electrons when the raindrop shrinks, thus outputting pulsed current and voltage. Cyclic voltammetry detected that the simulated raindrop formed a closed quasi-rectangular cyclic voltammetry curve during the spreading/shrinking process (as shown in Figure 1C), and the rectangular area and pseudocapacitive capacity increased linearly with the spreading area, which provided an experimental basis for the nature of the electric double layer pseudocapacitive[40]. It is further found that the raindrop falling time interval, falling speed and cation concentration have important effects on the electrical signal output: (1) The conjugated electrons of graphene are not reset before the raindrop completes the contraction process, and the subsequent raindrop falling at this stage will reduce the pseudocapacitance intensity of the electric double layer, thereby weakening the electrical properties; (2) The higher the speed of raindrops falling on the surface of graphene film, the faster the spreading and contraction of raindrops, which will produce higher streaming potential; (3) High concentration of cations can adsorb with more free electrons to form strong pseudocapacitance, which further improves the electrical output. This pioneering work lays the foundation for the construction of hybrid energy harvesting solar cells based on the hydrovoltaic and photovoltaic coupling effects. Subsequently, our group also found similar experimental results in the study of hybrid energy harvesting solar cells based on graphene-carbon black/polytetrafluoroethylene (G-CB/PTFE) composite electrodes, and the current and voltage reached the peak when the G-CB content was 95 wt%, as shown in Figure 1 d[41]. The reason is that the conductive polymer composite can be prepared by doping conductive G-CB into PTFE insulating matrix, and the conductivity of the composite is discontinuous in a certain range of G-CB concentration. When the concentration of G-CB reaches a certain value, the conductivity will change suddenly, indicating that the dispersion state of G-CB nanoparticles in the PTFE matrix changes suddenly, that is, G-CB forms a continuous conductive percolation network in PTFE. Therefore, 95wt% G-CB has formed a complete percolation network, which is conducive to electron conduction (Fig. 1e).
In addition to carbon materials, our group has further enriched the scope of hydrophoric materials. The basic principle of water potential effect is to use the electric double layer between water and electrons to produce streaming potential, and its essence is the interaction between water droplets (or water molecules) and electron-rich materials. Similar to carbon materials such as graphene, platinum alloys and conductive polymers are also electron-rich materials, which can produce water effect with water. In 2016, we developed a series of platinum alloy materials such as PtFe, PtCo, PtNi, PtCu and PtMo. Because the electronegativity of transition metals such as Fe (1.83), Co (1.88), Ni (1.92), Cu (1.90) and Mo (2.16) is lower than that of Pt (2.28), the outer electron cloud of transition metal atoms is biased to Pt atoms and produces an electron-rich surface during alloying[42]. In addition, in 2017, we further found that intrinsic conducting polymers such as polyaniline, polypyrrole and polythiophene have electron enrichment characteristics due to a large number of conjugated long chain structures in their molecular skeletons, and delocalized π electrons can migrate on the molecular chains[43]. Therefore, platinum alloys and conductive polymer materials can also be used to construct dye-sensitized solar cell-based hybrid energy harvesting solar cells.
Polyoxometalates (POMs) are a class of molecular-based nanomaterials with nanometer size, which are molecular-based inorganic semiconductor materials. Because of their unique electronic structure diversity, POMs can be used as electron acceptors to convert the kinetic energy of raindrops. Wang Enbo and Chen Weilin of Northeast Normal University found that POMs can form an electric double layer with raindrop cations through electrostatic interaction, thus generating electrical signals, and obtain continuous current in the process of charging and discharging with the continuous dripping of raindrops[44,45].
In 2017, Guo Wanlin et al. Further found that when water vapor flows along the pores of the film constructed by carbon black sheets, a streaming potential of about 1 V will be generated, and the output voltage will be increased to 4.8 V by series connection, as shown in Figure 2a, which indicates that the flow of water vapor can also output electricity[46]. The reason is that the electric double layer is formed by the adsorption of water molecules and carbon atomic layers, and the flow of water molecules between the nanocarbon layers during evaporation induces a streaming potential, which drives the ionic solution through the slit or porous medium under the pressure gradient to produce a potential difference between the two sides. Water evaporation is an important part of the water cycle, and it is also a common natural phenomenon in life. Water absorbs heat energy from the surrounding environment and transforms from liquid to gas. Solar photovoltaic power plants are usually built on the ground, pastures, aquaculture farms, forests, farmland and other areas, where there is continuous water evaporation. If the evaporation energy can be further collected and integrated with solar energy, it is expected to greatly improve the output power of solar cells. To this end, our research group designed and fabricated an all-inorganic CsPbBr3 perovskite solar cell with a FTO/TiO2/CsPbBr3/Cstructure that can simultaneously convert solar energy and evaporation energy, as shown in Figure 2B[45]. Under sunlight, the carbon electrode extracts photo-generated holes generated by the CsPbBr3 to realize the effective separation of electron-hole pairs; In the high humidity environment, the carbon electrode generates a streaming potential between the carbon electrode and the water vapor to output additional voltage and current, so as to realize water vapor induced power generation. By optimizing the energy level structure of the cell and the surface structure of the carbon electrode, the all-inorganic perovskite solar cell achieves a photoelectric conversion efficiency of 9. 43% under standard solar illumination conditions, and can obtain a voltage of 0. 35 V and a current of 0. 45 μA at a relative humidity of 80%. It can be seen that the coupling of photovoltaic effect and photovoltaic effect is also one of the effective ways to increase the output power by using external energy.
At present, there are relatively few studies on the construction of hybrid energy harvesting solar cells using the water photovoltaic effect. On the one hand, the poor light transmission performance of water photovoltaic materials hinders the excitation of photogenerated carriers by sunlight through water photovoltaic materials. On the other hand, the current and voltage generated by the water volt effect are still lower than those of solar cells, and the improvement of the comprehensive performance of solar cells is limited.

2.2 Triboelectric effect

When any two objects of different materials rub together, electrons are transferred from one object to the other, so that the two objects are charged with equal and opposite charges. This phenomenon is called triboelectric effect. Triboelectric phenomenon can occur at solid-solid, solid-liquid, or solid-gas interfaces. In 2014, Wang Zhonglin of the Georgia Institute of Technology in the United States pioneered the construction of a friction nanogenerator (TENG)/silicon wafer tandem cell for simultaneous conversion of solar energy and raindrop water kinetic energy, as shown in Figure 3A[48]. Commercial crystalline silicon solar cells are usually packaged with glass and polyvinyl chloride backplane. In this work, transparent polytetrafluoroethylene (PTFE)/transparent conductive layer ITO/polyethylene terephthalate (PET) TENG with single electrode structure is used to replace glass. On the one hand, sunlight irradiates crystalline silicon solar cells through transparent TENG to achieve photoelectric conversion; On the other hand, the single-electrode TENG converts the raindrop water kinetic energy through the solid-liquid friction interface. However, the upper transparent TENG and the lower crystalline silicon solar cell are in physical contact, that is, there is no interaction between them during the operation of the cell, such as charge induction and transmission. The results show that under the standard sunlight of 100 mW/cm2, the open-circuit voltage of the new solar cell is 0. 6 V, the short-circuit current density is 350 A/m2, and the photoelectric conversion efficiency is 14%, while the photoelectric conversion efficiency of the conventional crystalline silicon solar cell is 16%.The attenuation of the photoelectric conversion efficiency is mainly due to the fact that the transmittance of the friction nanogenerator in the visible region is lower than that of glass, although it is stimulated by raindrops to produce an open-circuit voltage of 30 V/drop and a short-circuit current density of 4.2 mA/m2 (that is, an output power of 16.31 mW/m2) in a simulated rainfall environment. However, the total output power of the solar cell is still reduced by 12.42%. Subsequently, in 2015, they further constructed solid-liquid and solid-solid coupling TENGs, as shown in Figure 3B. On the one hand, the direct interaction between raindrops and the upper dielectric film is used to generate electrostatic charges.On the other hand, the friction between the bottom dielectric films is further accumulated by the vibration of raindrops, so that the instantaneous power of the friction nanogenerator is increased to 170 mW/m2, but the output power is still three orders of magnitude lower than that of the solar cell 160 W/m2[49].
Cheng Gang et al. Of Henan University deposited ITO transparent conductive electrode and polydimethylsiloxane (PDMS) dielectric film on the surface of silicon solar cell in turn, and improved the utilization rate of sunlight by constructing wrinkled surface. The hybrid energy harvesting solar cell prepared by this method achieved a photoelectric conversion efficiency of 13.57%.Compared with the cell based on the planar PDMS film (12.92%), the efficiency is improved by 5%, and the maximum instantaneous power under raindrop stimulation is only about 1 μW/drop (about 2.2 W/m2), as shown in Figure 3C[50]. In this cell, although the PDMS friction layer is tightly bonded to the silicon wafer through the ITO electrode, there is still no charge transfer between them, and the improvement of its efficiency is due to the light trapping effect of the wrinkled PDMS. Sun Baoquan et al. Of Soochow University also found that when TENG and silicon cell shared PEDOT: PSS electrode, the photoelectric conversion efficiency of tandem cell increased from 12.0% to 13.6%, which was mainly caused by the high transmittance of the surface friction layer rather than the additional energy generated by raindrop stimulation (short-circuit current was 33.0 nA, open-circuit voltage was 2.14 V)[51]. It can be seen that if TENG is physically stacked with crystalline silicon solar cells (that is, there is no charge transfer between them), the increase of total output power is very limited.Moreover, the performance characterization mainly focuses on the output of TENG stimulated by raindrops, while the deep-seated mechanisms such as charge generation, transport, and the coupling of triboelectric effect and photovoltaic effect in solar cells are not well understood, so it is urgent to develop new cell structures to greatly improve the output power and improve the characterization system.
In 2020, our research group took the lead in developing hybrid energy harvesting solar cells with field effect enhancement, as shown in Figure 4A, by scraping PDMS precursor on the surface of monocrystalline silicon solar cells, after curing, a layer of high electronegative dielectric film with a transmittance of more than 97% in the visible region was prepared, and Ag2 gate electrodes were deposited on its surface.A novel three-electrode hybrid energy harvesting solar cell was constructed, in which the Ag2 gate electrode, the Ag1 gate electrode on the surface of the crystalline silicon solar cell, and the Al electrode on the back of the crystalline silicon solar cell were used as the three electrodes of the hybrid energy harvesting solar cell, respectively[52]. It is found that when the crystalline silicon solar cell is used as the friction layer, the electrostatic field generated by the friction nanogenerator has a significant enhancement effect on the photogenerated built-in electric field inside the crystalline silicon solar cell (Figure 4B); That is to say, in rainy weather, the electrostatic field generated by the action of raindrops on the friction nano-generator can significantly enhance the photoelectric conversion efficiency, open-circuit voltage and short-circuit current density of crystalline silicon solar cells. By optimizing the thickness of the PDMS film, the photoelectric conversion efficiency of the solar cell was finally increased from 18.41% to 22.04%, an increase of about 20% (Figure 4C); At the same time, the electrical output performance of 7. 59 μA/drop and 37. 19 V/drop was obtained in the simulated rainfall environment, and the instantaneous power was up to 140 μW/drop (62 W/m2), and the total output power of the device was 53. 2% higher than that of the crystalline silicon solar cell, reaching the 282 W/m2. It can be seen that the three-electrode TENG and crystalline silicon solar cells can be efficiently coupled and the performance and stability of the cells can be greatly improved by constructing hybrid energy solar cells with field enhancement effect, which has guiding significance for further optimizing material preparation, cell structure and improving characterization methods. Subsequently, Xu Xiaofeng and Li Xiaoyi of Ocean University of China and Pan Caofeng of Chinese Academy of Sciences proposed a kinetic energy calculation and current integration (KECCI) method, which significantly improved the understanding of the mechanical-electrical energy conversion process.On this basis, a multi-layer hybrid energy harvesting system composed of perovskite solar cells and TENG is designed to achieve all-weather energy harvesting (Figure 4D)[53]. On sunny days, the hybrid energy harvesting system quickly charges the capacitor to 3 V. If it starts to rain, the capacitor will continue to charge to 65 V, demonstrating the advantages of all-weather energy harvesting (Figure 4 e). This high-performance hybrid energy harvesting system provides a new strategy for harvesting energy from multiple natural resources, thus promoting the industrialization of TENG technology.

3 Hybrid energy harvesting solar cell based on light-storage-luminescence effect

At present, the developed light-absorbing materials are very sensitive to visible light, but they make little use of ultraviolet light or infrared and near-infrared light, which account for up to 52% of the total energy of sunlight. Therefore, the efficient use of sunlight is an important technical way to greatly improve the output power of solar cells: on the one hand, new light absorbers are developed to broaden the spectral response range, but the photovoltaic curve of solar cells in the absence of light still passes through the origin of coordinates, indicating that there is no power output at this time (as shown in Figure 5A); On the other hand, the light-storage-luminescence material is used to store the unabsorbed sunlight and convert it into available visible light through the upper and lower conversion effects. Long afterglow phosphors (LPP) generate free electrons (or holes) and store them in trapped energy States when they are irradiated by broad-spectrum sunlight with a wavelength of 200 nm ~ 1500 nm. After the irradiation is stopped, the trapped electrons (or holes) are released again by thermal disturbance at room temperature and recombine with the luminescent center to emit monochromatic afterglow for several hours or even days. Our research group prepared a N719-TiO2/LPP composite photoanode with light storage and persistent luminescence properties as shown in Figure 5B by using the light storage-luminescence properties of LPP, and constructed a novel dye-sensitized solar cell (DSSCs) with I-/ I 3 - redox electrolyte and Pt counter electrode[54]. As shown in Figure 5C, after being illuminated by sunlight for 1 min and removing the light source, the composite photoanode (square area in the middle) is black, while the surrounding area without N719 dye emits purple light, blue light, cyan light, green light, red light and white light respectively according to the properties of the LPP material.This fully shows that LPP has stored ultraviolet light and infrared light that are not absorbed by N719 and emitted visible light of 425 ~ 625 nm (as shown in Figure 5d), which is reabsorbed and utilized by N719 dye. The DSSC prepared by the light-storage-luminescence effect showed typical photovoltaic characteristics (open circuit voltage 0.35 V, short-circuit current density 0.25 mA/cm2) in the dark environment, as shown in Fig. 5e, the photoelectric conversion efficiency of the DSSC based on LPP nanocrystals also increased from 8.08% to 10.08% under 1standard solar irradiation, an increase of 24.8%. In addition, considering that the surface glass of the solar panel has a certain reflection effect on the incident light, a part of the incident light is scattered to the back of the front row of panels by the glass, the solar cell can receive up to 50% additional light by using the double-sided light harvesting technology, and the photoelectric conversion efficiency can be increased by 20% -35%. Our research group further prepared a counter electrode with a Pt/Ti/Pt symmetrical structure by electrodepositing a Pt catalyst layer on the surface of a Ti foil substrate and constructed a double-sided DSSC as shown in Figure 5F, and its working principle is shown in Figure 5g[55]. Due to the light storage-luminescence property of LPP nanocrystals, the TiO2/LPP anode can absorb visible and near-infrared light in the wavelength range of 600 – 950 nm and excite monochromatic light at 516 nm, which is very close to the characteristic absorption peak of N719 photosensitizer at 526 nm, as shown in Fig. 5 H. Its double-sided DSSC can not only continuously output current and voltage in dark and dark environment, but also increase the current density from the 15.01 mA/cm2 of single-sided cell to the 28.59 mA/cm2 of double-sided cell. The above studies illustrate that the coupling of light storage-luminescence effect and photovoltaic effect not only greatly improves the photoelectric conversion efficiency of solar cells, especially the third generation of new solar cells under light, but also realizes continuous power generation in dark and dark environment, forming all-weather DSSCs.
As a typical representative of the current third-generation photovoltaic technology, the long-term stability of perovskite solar cells (PSCs) is usually affected by humidity and illumination, which has become a technical problem for their commercial application. Through the development of new passivator materials and encapsulation technologies, the long-term stability of PSCs in humid environments has been continuously improved, and the research on photostability has gradually increased[7,8][56,57]. In order to improve the decomposition of perovskite materials induced by UV irradiation and reduce the device performance, Dai Qilin et al. Of Jackson State University and Song Hongwei et al. Of Jilin University applied the LPP material SrAl2O4:Eu2+,Dy3+(SAED) as a mesoscopic skeleton layer to PSC, as shown in Figure 6A[56]. On the one hand, SrAl2O4:Eu2+,Dy3+ can convert ultraviolet photons into low-energy photons, thereby reducing the degradation effect of ultraviolet light on perovskite photosensitive materials; On the other hand, due to the down-conversion property of the SrAl2O4:Eu2+,Dy3+, the photons emitted in the green band can be effectively absorbed by the perovskite material, thereby enhancing the light storage capacity of the perovskite (as shown in fig. 6B). By optimizing the thickness of the SAED layer, the photoelectric conversion efficiency reached 17. 8%, which was 6% higher than that of the control group, and the initial efficiency of 92% could be maintained after 100 H of continuous UV irradiation, while the control group could only maintain 40%. In addition, due to the long afterglow of SAED, the device can still output current for 3 hours in a dark environment (Figure 6 C). However, due to the poor conductivity and low energy level matching of SAED, the series resistance of the device is high, resulting in limited improvement of the open circuit voltage and fill factor of the device. Subsequently, Song Hongwei et al. Further developed Y2O2S:Eu3+,Ti4+,Mg2+(YOS, as shown in Figure 6 d), which was inserted into PSCs as a bridge between the photoactive layer and the electron transport layer to improve the light storage capacity and ultraviolet stability of the device[57]. In addition, as an n-type semiconductor, YOS has a narrow band gap and a suitable conduction band position, which can reduce the carrier trap States and optimize the energy level alignment, improve the carrier extraction ability of PSCs and reduce the degree of hysteresis, as shown in Figure 6E. After YOS thickness optimization, the device achieved a conversion efficiency of 20.9%, and the hysteresis factor was reduced from 8.9% to 1.7% (Figure 6 f), and maintained 91% and 83% of the initial efficiency after 120 H of full-spectrum standard light and 100 H of ultraviolet light irradiation. The above studies show that LPP can be used to improve the energy level alignment, light storage capacity and UV stability of PSCs.
To sum up, it is feasible to prepare hybrid energy harvesting solar cells that can continuously generate electricity in low-light or no-light environment through the coupling of light-storage-luminescence effect and photovoltaic effect, especially by using the characteristics of third-generation solar cells such as DSSCs and PSCs, which are insensitive to impurities but extremely sensitive to interfaces. By studying the basic problems of photon, carrier transmission and conversion mechanism in mesoscopic space, the assembly and integration of nano-device units and the synthesis of related materials in the process of macro-device module construction are explored.Design a cell structure with high efficiency, low cost and diversified power generation environment, develop hybrid energy harvesting solar cell technology and new cell module construction methods that can generate electricity under light and at night, and establish a perfect new device characterization system.

4 Hybrid Energy Harvesting Solar Cell Based on Piezoelectric and Thermoelectric Effects

In 2010, Wang Zhonglin et al. Of Georgia Institute of Technology proposed the concept of "piezoelectric photoelectric effect".That is to say, the piezoelectric potential generated by strain in piezoelectric semiconductor materials is used to control the generation, transmission and separation of carriers at metal-semiconductor contacts or p-n junctions, so as to improve the performance of optoelectronic devices such as photon detectors, solar cells and light-emitting diodes[58]. The piezoelectric photoelectron effect generated by piezoelectric semiconductor nanowire arrays with typical lead-zincite structure has been proved to be able to effectively enhance the separation of photoinduced electron-hole pairs and suppress non-radiative recombination, which can significantly improve the photovoltaic performance of solar cells. Before that, the piezoelectric optoelectronic effect of single nanowires has been widely used to improve the photovoltaic performance of battery devices. The main principle is that the single nanowires with lead-zincite structure have non-centrosymmetric crystal structure,Piezoelectric polarization charge will generate a piezoelectric potential at the nanowire heterojunction or interface, which is used as a "gate" potential to adjust the heterojunction band structure, regulate the separation, transmission and recombination of charges in the photoelectric process, and ultimately lead to the change of photocurrent[59]. Zinc oxide (ZnO) nanowire is a commonly used piezoelectric semiconductor material. When a compressive stress is applied to the nanowire to bend it, a potential will be generated on both sides. Due to the relative movement of oxygen ions and zinc ions, the compression region shows a negative charge and the tension region shows a positive charge. They used this phenomenon to prepare a silicon-based nano-heterojunction solar cell with a p+-Si/p-Si/n+-Si(n-Si)/n-ZnO nanowire structure as shown in Figure 7A, through the piezoelectric optoelectronic effect generated by the ZnO nanowire array.Piezoelectric charges are generated at the n-type doped Si/ZnO interface, thereby reducing the corresponding energy band structure in the n+-Si/n-ZnO nanowire heterojunction (as shown in fig. 7B), which is helpful to improve the extraction efficiency of carriers[60]. Under static compressive stress, the photoelectric conversion efficiency of the solar cell increases from 8.97% to 9.51%, as shown in Figure 7c. The photogenerated built-in electric field intensity of solar cells is low in rain, fog, overcast and other low-light weather, resulting in serious recombination of photogenerated carriers. This work proposes a new idea of using piezoelectric optoelectronic effect to prepare high-efficiency silicon-based nano-heterojunction photovoltaic devices, which provides a reference for improving the power output of solar cells in low-light environment. In addition, ZnO is also a good electron transport layer for perovskite battery devices. To this end, Wang Zhonglin et al. Joined several teams, such as Meng Qingbo et al., Pan Caofeng et al., Chinese Academy of Sciences, and Dong Lin of Zhengzhou University, to grow ZnO nanowire arrays on flexible plastic substrates as electron transport layers for flexible perovskite solar cells[61]. Thanks to the piezoelectric polarization charge optimization of the ZnO/perovskite interface band structure (Fig. 7d), the photoelectric conversion efficiency of the flexible device is increased by about 40% from 9.3% to 12.8% under a static mechanical strain of 1.88% (Fig. 7e and Fig. 7f), and the material and device structure are not changed. It shows that the piezoelectric photoelectric effect can first optimize the band structure of the p-n or metal-semiconductor junction interface. Secondly, it can also control the separation, transport and recombination processes of photogenerated carriers, and become a universal strategy to improve the performance of flexible perovskite batteries without destroying their basic structure.
With the rise of perovskite solar cells, the coupling of photovoltaic effect and thermoelectric effect has gradually attracted attention, as shown in Figure 8 a, although organic-inorganic hybrid perovskite materials have strong photoelectric conversion characteristics (EQE > 90%) in the visible region (λ = 400 nm ~ 800 nm).The infrared light, which accounts for 52% of the total energy, is released in the form of heat energy and causes the device temperature to rise, which not only causes the peak power to decrease with the increase of temperature (that is, the peak power loss rate of the solar cell is about 0.41% when the temperature rises by 1 ℃), but also causes the decomposition of the organic-inorganic hybrid perovskite material due to high temperature[62⇓⇓~65]. At present, there are two main technical means for the coupling of photovoltaic effect and thermoelectric effect: the first is to use thermoelectric materials in solar cells, and the second is to couple photovoltaic cells with thermoelectric elements through stacks. For example, Guozhong Cao et al. at the University of Washington used electrospinning technology to prepare NaCo2O4/TiO2 nanowires with thermoelectric effect and further assembled organic-inorganic hybrid perovskite solar cells as shown in Fig.Under solar irradiation, the temperature gradient formed by the cell device makes the NaCo2O4/TiO2 nanowire generate thermal electromotive force, which improves the power transmission process of photogenerated electrons to the anode. The J-V curve shown in Fig. 8C also confirms that the short-circuit current density increases from 19.71 mA/cm2 to 22.37 mA/cm2, which finally improves the photoelectric conversion efficiency of the cell from 13.59% to 14.96%[62].
In terms of photovoltaic/thermoelectric stack, Han Hongwei et al. Of Huazhong University of Science and Technology further stacked bismuth telluride (Bi2Te3) thermoelectric elements on the back electrode of carbon-based organic-inorganic hybrid perovskite solar cells to assemble the prototype, as shown in Fig. 8D. Because the carbon electrode can fully absorb infrared light and convert it into heat energy, the cell device can reach up to 70 ℃ and form a temperature difference of 25 ℃ with the surrounding environment to generate thermoelectric potential. The hot-end electrons of the bismuth telluride element flow to the FTO driven by the thermoelectric potential and form a thermal current through the external circuit. Therefore, the photovoltaic/thermoelectric tandem cell is equivalent to a photovoltaic cell in series with a thermoelectric device (as shown in Figure 8e)[63]. It can be seen from Figure 8 f that the short-circuit current density of the stacked cell does not change with the number of thermoelectric elements, but the open-circuit voltage increases from 0.87 V to 1.29 V when 10 thermoelectric elements are stacked, and the photoelectric conversion efficiency increases from 13.69% of the original device to 20.3%, an increase of 48.3%. For example, Lin Hong of Tsinghua University used the same technology to increase the efficiency of perovskite solar cells to 25.0%[64]. Recently, our group also integrated the Bi2Te3 thermoelectric module into the all-inorganic CsPbBr3 concentrator cell, using the harmful heat generated by the light absorption of the carbon electrode to play the role of refrigerant under the concentrating condition, and finally achieved a photoelectric conversion efficiency of 12.46% and an ultra-high open-circuit voltage of 2.114 V by using the photovoltaic-thermoelectric principle[65].
To sum up, infrared light accounts for half of the total solar energy, but the known semiconductor light absorbers can not efficiently use infrared light, resulting in energy loss. The integration of thermoelectric materials or thermoelectric elements with solar cells, especially the third generation perovskite solar cells, not only reduces the temperature of the cells, but also greatly improves the photoelectric conversion efficiency of the cells, which is considered to be the most promising hybrid energy harvesting solar cells.

5 Conclusion and prospect

The realization of high-performance solar cells largely depends on energy conversion materials (light absorber), charge transport materials (electron transport materials, hole transport materials), surface/interface modification materials (passivator, electrode materials, etc.), advanced preparation technology and device structure.However, the optical band gap and band structure of the light absorber determine the spectral response range of the cell, and the photoelectric conversion efficiency of all kinds of solar cells is close to their theoretical efficiency, so there is limited room for further improvement of the efficiency of traditional solar cells. Therefore, it is of great significance to further study the basic principle, material preparation and cell structure of hybrid energy harvesting solar cells for further improving the output power of solar cells, prolonging the power generation time and realizing the diversification of application environment. This review focuses on the coupling mechanisms of solar photovoltaic effect with hydrovoltaic effect, triboelectric effect, light-storage-luminescence effect, piezoelectric effect and thermoelectric effect, as well as the design and performance of cell devices. Although some important progress has been made, there are still many problems to be solved in material preparation and device structure from basic research to practical application: (1) there is still a lack of full understanding of the coupling mechanism between photovoltaic effect and other effects, so more in-depth basic theoretical research is needed; (2) How to greatly improve the electrical performance of the water volt effect regardless of its low current and voltage output? It is necessary to deepen the understanding of the physical and chemical processes of electron-rich materials and ionic liquids. (3) The triboelectric effect has been well applied to solar cells, but the characterization methods are relatively single, and the cell testing and characterization systems need to be further enriched; (4) The luminescence intensity and time of storage-luminescence materials are still unable to meet the design requirements of high-performance solar cells, so it is necessary to understand the luminescence mechanism from the physical point of view and develop new long afterglow materials with optimal crystal traps; (5) Piezoelectric optoelectronic effect can be theoretically applied to solar cells. How to seek application scenarios in real environment? (6) Thermoelectric effect has shown a wide range of application prospects in solar cells. How much room is there to improve the conversion efficiency of solar cells in the future? This still requires further exploration of new thermoelectric materials, new preparation technologies and optimal design of batteries. Although there are still many challenges, the basic principle and application research of hybrid energy harvesting solar cells with high photoelectric conversion efficiency and diversified application environments are of great significance for reducing the cost of photovoltaic power generation and helping to achieve the goal of "carbon peak and carbon neutralization".

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Funding

National Key Research and Development Program of China(2021YFE0111000)

National Natural Science Foundation of China(U1802257)

National Natural Science Foundation of China(22179051)

National Natural Science Foundation of China(61774139)

Natural Science Foundation of Guangdong Province(2019B151502061)

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