1.1. The role of practicable artificial photosynthesis to achieve self-sufficiency in energy security and to solve the CO2 associated global warming problem and the social cost of carbon
Today, the development of a simple, inexpensive and efficient process for producing electricity from sunlight, and use of that electricity to convert the waste-steam greenhouse CO
2 gas into energy rich solar-fuels, and to split water into H
2 and O
2 gases, which is popularly called as an “
Artificial Photosynthesis (AP)” [
1], have been considered as one of the top-most research priorities across the globe as these processes can solve the problems related to i) securing the self-sufficiency in energy production by each and every country, ii) the CO
2 associated global warming, and the resultant social cost of carbon, iii) the storing of renewable (and surplus) energy in an high-energy-density carbon-neutral liquid-fuels such as, methanol so that they can be directly employed in place of diesel and petrol in the present existing energy distribution infrastructure (i.e., in the
internal combustion (IC) engines) so that there would not be any severe economic consequences while transforming from fossil fuel energy dependency to non-fossil fuel, renewable and solar energy dependency, and iv) depletion of fossil fuels mainly the crude oil, which is an important resource of several commodity chemicals required for the future generations [1-25]. Efficient sunlight-to-electricity conversion technology can eliminate up to 8-15% power transmission losses that are associated with the grid-connected electricity produced at remote places far from the densely populated cities by burning fossil fuels (i.e., coal, natural gas and crude oil) at thermal power plants. In fact, as on today, the synthesis of liquid-fuels from CO
2, and, splitting of water into H
2 and O
2 gases using electricity derived from sunlight in electrochemical cells can be considered as one of the most effective, and economic way of storing energy to circumvent the daily and seasonal intermittency of solar energy as the energy stored in H
2 and O
2 gases or CO gas can be taken back again as and when required on a demand basis using fuel cells [
1,
10,
12,
26]. In fact, today, the fossil fuels are the main energy resource supplying to meet >85% of the primary energy requirement of all most all developed and developing countries except very few countries including France and Germany, and their usage has been found to be responsible for raising the concentrations of CO
2 in the atmosphere and for the resultant global warming as well as for the social cost of carbon problems [1,27-37].
It is a well-known fact that nature stores solar energy to feed not only 8 billion people but also the entire life living today on our planet in the natural photosynthesis (NP) process by using CO
2 and water as energy storing materials [1,4,8,38-47]. In fact, the NP process is nothing but the storing of solar energy by using CO
2 and water as energy storing materials by following a natural photosynthesis process in the form of food materials and bio-mass to feed human beings and animals. The solar energy stored in the form of food materials (i.e., grains) can be preserved and used as and when required on a demand basis. The natured stored solar energy in the form of food materials need not have to be used immediately like the electricity produced from sunlight by using SPVC solar panels needs to be used. Furthermore, the amount of solar energy stored by plant leaves in the form of food material and bio-mass in the NP process cannot be stored in any of the manmade existing energy storing devices including the most advanced lithium ion batteries and capacitors as it would be prohibitively expensive [
1,
10,
12]. Nature clearly suggests that any amount of energy can be stored by using CO
2 and water as energy storing materials while beneficially contributing to the environment. In fact, the fossil fuels are nothing but solar energy stored by the nature. The fuel chemicals synthesized in AP by using electricity derived from sunlight are called as solar fuels, which are exactly similar to fossil fuels. The only difference between the fossil and solar fuels is the former ones are created by the nature from bio-mass in which the solar energy was stored by plant leaves using CO
2 and water as energy storing materials at the rate of 0.2%, whereas, the solar-fuels, have to be synthesized by following manmade technologies by electrochemically reducing CO
2 and splitting water using electricity derived from sunlight to meet all the energy needs of the society with a minimum (conversion) efficiency >10% so that these processes can be practiced at industry with economic viability. Hence, the entire energy distribution infrastructure available today to use fossil fuels can also be used for solar fuels formed in AP process as well. Thus, the renewable liquid-fuel chemicals produced from CO
2 gas in AP process can indeed replace the fossil fuels in all their current uses such as, powering industrial processes, machinery and transportation, etc.. In fact, the AP process can establish a closed-loop CO
2 cycle that turns the conventional fuels into the “green energy vectors”. Furthermore, the energy density of electricity storing batteries is far too low for most of the power-intensive applications (about 1-2%) in comparison to those can be stored in carbon-based fuels (50 MJ/kg with methane, methanol, diesel and gasoline) [
1,
10,
12]. In fact, the e-batteries such as Li-ion batteries are best suitable and opt for low-energy required portable devices such as, mobile phones, laptops, etc., but not for high-energy intensive applications such as, heavy duty vehicles, buses, lorries, trucks, aero planes, etc.. Furthermore, batteries also have certain limitations with respect to their cost, service life, recharging time, involvement of hazardous and polluting materials, etc..
Once a suitable and inexpensive method for converting sunlight into electricity is developed, and thus, obtained electricity is suitably utilized to convert the waste-stream greenhouse CO
2 gas into CO, and the water into H
2 and O
2 gases, all most all countries can use solar energy to meet all their energy requirements without depending on foreign countries to import the fossil fuels while meeting all the deadlines imposed by
Intergovernmental Panel on Climate Change (IPCC) and
United Nations Framework Convention on Climate Change (UNFCCC) as far as environmental safety and release of CO
2 gas into the atmosphere are concerned [1,18-22,24]. Upon implementing such an AP process worldwide, in about 10 to 15 years period, a lot of fossil fuels burned so far to meet the energy requirement of the society can be restored in the form of natural gas at all the sea shores across the globe as no CO
2 is freshly released into the atmosphere in large quantities as CO
2 present in the atmosphere is consumed by the plant leaves so that its concentration will come down to those levels (i.e., about 280 ppm) present in the atmosphere prior to the industrial revolution started during period of around 1750 to early 1800 century. Once, this target is reached, the unseasonal and un-expected heavy rains and floods that are occurring these days can be minimized, which are disturbing the functioning of society for several days together in certain cities like those recently occurred in Chennai city in the year 2015 [
48], and Kerala in the year 2018 [
49].
In view of the above reasons, the development of a simple, easy to fabricate, and inexpensive method to produce electricity from sunlight, and using thus obtained electricity to drive the reactions of AP are of utmost important to solve both energy and environment related problems. For example, today, India alone has 118 thermal power plants, 220 cement industries, 650 steel plants (including those small scale industries), and 18 public sector refineries and 5 refineries in the private sector/or as a joint venture, the largest refineries being RIL Jamnagar (Gujarat), NEL Vadinar (Gujarat) and IOC Panipat (Haryana). All these industries together everyday generate several million tons of CO2 gas by burning fossil fuels such as, oil, coal, and natural gas to meet the energy needs of the society, and all thus generated CO2 gas is released into the atmosphere. Once, an inexpensive and simple to fabricate solar panels to produce electricity from sunlight are developed to drive the reactions of AP efficiently at lower processing cost, then by following that process all the CO2 generated at major outlets across the globe can be converted into CO gas initially, and then into methanol, diesel and synthetic petrol [1,18-22,24]. The IPCC and UNFCCC are responsible for pledging 197 countries (as on December 2015) to take the responsibility to stabilize the greenhouse CO2 gas concentration in the atmosphere at a level that would prevent dangerous anthropogenic interference with the climatic system. Furthermore, for example, according to IPCC and UNFCCC by 2030, the European Union (EU) has to meet ≥27% of their primary energy requirement from the renewable energy resources, which ensures up to 40% reduction in greenhouse gas (GHGs) emissions in comparison to 1990 levels [1,50-54]. Today, EU gets about 50% of its primary energy from the imported fossil fuels. In EU, the buildings are the leading consumers of energy (40%), ahead of transportation (32%), industry (27%) and agriculture (2%). Heating is at top of the consumption list accounting for 65% of domestic energy use. As a result, 33% of the total CO2 emissions in EU come from fossil fuels used for heating purposes only. Only ~17% of the total energy requirement is met by the electricity and out of which about 11.7% is met from hydroelectric power.
There are two ways to control the CO
2 associated global warming problem. One is to replace the fossil fuels usage with renewable energy vectors such as, solar energy [
1,
10,
12], and the other one is to find out the solutions to solve the CO
2 associated global warming problem [1,55-61]. Today, the readily available technology to solve the CO
2 associated global warming problem is the “
CO2 sequestration”, which is also known as the “
carbon capture and storage (CCS)” process. This latter process is not only expensive but also quite cumbersome. As a part of the CCS process, the CO
2 captured at various outlets such as, thermal power plants, cement industry, steel factories, gas refineries, etc., is transported and pumped mainly into the deep seawater below 3500 meters [
55]. At 3500 meters deep in the sea, a pressure of >350 bar and a temperature of ~3°C exist. When CO
2 is exposed to these conditions, it turns into CO
2 clathrate, which is a snow-like crystalline substance, composed of H
2O ice and CO
2. Nevertheless, its long term stability is still a debatable subject. It is also a known fact that the CO
2 capturing sites are most often far away from those sites normally used for CO
2 sequestration. In certain places like those in Europe, CO
2 transportation in pipelines to the storage sites is quite difficult, and it will increase the cost of the process by at least 15-20%, which is considered to be unacceptable [
1,
10,
12]. The
Department of Energy (DoE), USA, suggests that the transportation of CO
2 in tankers on road is not acceptable if the distance is more than 100 km. In the total CCS process, about 35-40% is the transportation and storage costs. This cost would be between 35 and 50 €/ton for early commercial phase and between 60 and 90 €/ton during demonstration phase, when transportation of CO
2 is made by pipelines for distances not over 200-300 km [
10,
12]. This cost would be further increased if the transportation is made by road (for example, in certain European countries). Recently, a new CO
2 sequestration process was reported, in which when a mixture of water and CO
2 was pumped 540 meters deep into the Iceland rocks, this acidic solution causes the leaching of the Mg and Ca metals out of the basalt rocks and converts them into MgCO
3 and CaCO
3 rocks [
62]. These latter rocks have been found to be stable for more than two-year period. The cost of this new CO
2 sequestration process has been estimated to be about 18 USD for disposing off a ton CO
2 gas. Thus, the CO
2 sequestration processes are not only expensive and laborious, they also irreversibly blocks the important C
1 carbon resource in the form of CO
2 cletherate in deep seawater, which cannot be used for any of the beneficial activities of the human beings. In fact, the CO
2 shall be participated in the natural carbon cycle that is required for the sustainability of the life on earth [
47,
63].
Alternatively, CO
2 can be converted into several value added chemicals and fuels in a process called “
carbon capture and utilization (CCU)” with the same expenditure that can be incurred for the CCS process [1-3,64]. Sometimes, the value of the product(s) formed in the CCU process can become a bonus as the cost of the products can offset the processing cost to some extent. It is also a known fact that CO
2 conversion into fuel chemicals needs thermodynamic energy input apart from those required for overcoming the activation energy barrier. In fact, the high thermodynamic stability of CO
2 is responsible for its ability to store the external energy in the form of fuel chemicals synthesized out of it [
1,
65]. In fact, the energy spent for overcoming the activation energy barrier is a waste of energy; whereas, the energy spent for overcoming the thermodynamic energy barrier is energy storage. Thus, more amounts of thermodynamic energy requirement means more amount of energy storage in the form of chemical products formed in a particular endothermic reaction. That is the reason why always researchers look for the best catalytic systems to perform a particular reaction to occur
via a path that is associated with the least activation energy barrier. Lower the activation energy barrier means lower the amount of energy wastage while driving that particular thermodynamically favorable reaction. The high thermodynamic stability of water (ΔE° = −1.23 V vs. NHE or 1.23 eV) is also responsible for its ability to store 1.23 eV energy in the form of H
2 and ½O
2 gases formed in electrolysis of water. This same 1.23 eV equivalent electrical energy comes out again when these two gases are reacted in a fuel cell [
1,
10,
12].
Even by replacing the usage of the
liquefied petroleum gas (LPG) utilized for cooking with the electric stoves driven by electricity derived from sunlight, a significant amount of CO
2 gas generation can be avoided. Not only that now-a-days, even the cost of LPG gas has been increasing exorbitantly, and without the government aid or subsidy, it has become an unbearable cost for a common man living in India. In
Telangana state of India, a 14.2 kg LPG gas cylinder costs about Rs. 1500/- without the Government subsidy, and with subsidy, it is about Rs. 950/- [
66]. Even the petrol and diesel costs are being increased now-a-days in India very exorbitantly. If all the CO
2 gas generated at all its major outlets in India is converted into synthetic petrol using electricity derived from sunlight, and used in place of petrol and diesel utilized today to meet the energy requirements, there would be a lot of reduction in the importing of fossil fuels from foreign countries [1,39-46]. In fact, an inexpensive way of producing electricity from sunlight and using it for converting CO
2 gas produced at all its major outlets into fuel chemicals, and for splitting water into H
2 and O
2 gases can even change the global energy economy and energy dynamics of the world as well [1,18-22,24]. In view of the these and to solve the CO
2 associated global warming problem, at the outset, a simple, easy and highly economical method to produce electricity from sunlight is highly essential [
10,
12]. Furthermore, to continuously supply the intermittently available solar energy to the society without any back-up from fossil fuels, it is also required to be stored in a well usable form of energy. Fortunately, sunlight is abundant, clean, and free, and, all the world's population living areas also receive the required insolation levels (i.e., 150–300 watts/m
2 or 3.5–7.0 kWh/m
2 per day) [
67]. With this insolation capacity, the required amount of electrical energy can be generated to meet all the needs of the society for buildings using a suitable sunlight to electricity generation technology.
1.4. Theoretical setbacks associated with SPVC solar panels
As with any renewable energy resource, the main limitation of SPVC solar panels is also the discontinuity between the solar radiation and power consumption during a day, year and geographical location. In addition to these, the theoretical maximum efficiency of a SPVC panel is <20%, and they convert >70% of the absorbed sunlight into the waste heat energy, which is dissipated into the atmosphere [83-88]. The various other limitations/setbacks associated with these SPVC panels are listed in
Table 1 [
1,
89]. About 10% incident light is reflected back into the atmosphere from the front cover solar glass of SPVC solar panels. Up to about 8% of the incident light on SPVC panels is blocked by the grid and bus-bar lines printed on SPV cells. With a band-gap energy of about 1.1 eV, whose corresponding wavelength is ~1127 nm, the semiconducting Si material used in SPVC solar panels does not absorb sunlight reaching the earth surface with a wavelength range starting from 1127 nm to 2400 nm, which is accounted for about 30% of the sunlight reaching the earth surface. The percentage of sunlight reaching the earth surface with various wavelength ranges is given in
Table 2 [
1,
89]. This sunlight energy data confirms that with 1.1 eV band-gap energy, the Si semiconductor in SPVC solar panels considers only around 70% of the sunlight reaching the earth surface for converting it into the electricity, and the remaining 30% incident sunlight is not absorbed or considered by these SPVC solar panels.
Apart from the above, the SPVC solar panels also suffer from several other limitations as summarized in
Table 1 [
1]. They are associated with high fabrication cost and cumbersome manufacturing procedure, hence, electricity generated by these SPVC solar panels is relatively expensive when compared with the one produced at thermal power plants by burning fossil fuels. They generate DC current instead of AC current as converting of DC into AC is also consumes some energy. The maximum voltage that can be generated by a single Si semiconductor cell in each SPVC solar panel is only about 0.5 to 0.6 V (Fig. 1) [
1,
90], and to obtain the required high voltage several of such single SPVCs needs to be connected in series, which generate considerable amounts of Ohmic loss. The sunlight-to-electricity (STE) conversion efficiency of SPVC solar panels decreases with the increasing operating (ambient) temperature at a rate of 0.5 V/°C or K (Fig. 2) [
1,
91,
92]. They contain toxic heavy Sn-Pb solder metals coated over Cu stripe, which is used as grid and bus-bar lines, and as interconnecting wire to transport the generated electricity from one individual SPVC to other cell. The after use disposal is a great concern for SPVC solar panels, and the recycling of these panels has been found to be a no profitable venture. They create local heat island effect when deployed in large areas (Fig. 3) [
1,
93]. They are not reusable, recyclable, and are not physically very robust (i.e., they become redundant when they are accidentally hit with a physical object). Because of only <20% efficiency, SPVC panels need relatively large areas of land to generate the required amount of electricity [1,83-88]. Furthermore, when the operating temperature of SPVC panels is reached to a certain higher level, which normally happens in peak summer period, they permanently and irreversibly lose their electricity generating capability [
94]. The Qatari utility companies stopped using SPVC solar energy because the drop in the efficiency has been noted to be as high as 60%. Because of the combination of the latter country’s extreme heat and dust accumulation on the solar panels, the fall in the efficiency has been noted to be up to 60%. In the case of SPVC solar panels, there’s an irony in the fact that the locations best suited for solar energy generation are also limited by those same conditions in several central Asian countries such as, Saudi Arabia [
95].
Figure 1.
I-V and P-V characteristics of a silicon solar cell [
1,
90].
Figure 1.
I-V and P-V characteristics of a silicon solar cell [
1,
90].
Figure 2.
IV curves of a solar PV module under different operating temperatures [
1,
91,
92].
Figure 2.
IV curves of a solar PV module under different operating temperatures [
1,
91,
92].
Figure 3.
Illustration of midday energy exchange. Assuming equal rates of incoming energy from the sun, a transition from (A) a vegetated ecosystem to (B) a photovoltaic (PV) power plant installation will significantly alter the energy flux dynamics of the area. Within natural ecosystems, vegetation reduces heat capture and storage in soils (orange arrows), and infiltrated water and vegetation release heat-dissipating latent energy fluxes in the transition of water-to-water vapor to the atmosphere through evapotranspiration (blue arrows). These latent heat fluxes are dramatically reduced in typical PV installations, leading to greater sensible heat fluxes (red arrows). Energy re-radiation from PV panels (brown arrows) and energy transferred to electricity (purple arrows) are also shown [
1,
93].
Figure 3.
Illustration of midday energy exchange. Assuming equal rates of incoming energy from the sun, a transition from (A) a vegetated ecosystem to (B) a photovoltaic (PV) power plant installation will significantly alter the energy flux dynamics of the area. Within natural ecosystems, vegetation reduces heat capture and storage in soils (orange arrows), and infiltrated water and vegetation release heat-dissipating latent energy fluxes in the transition of water-to-water vapor to the atmosphere through evapotranspiration (blue arrows). These latent heat fluxes are dramatically reduced in typical PV installations, leading to greater sensible heat fluxes (red arrows). Energy re-radiation from PV panels (brown arrows) and energy transferred to electricity (purple arrows) are also shown [
1,
93].
Another major limitation of SPVC solar panels is that they are needed to be placed in a direction facing the south side with some angle of inclination so that while sun is travelling from east to west, it can strike the surface of these SPVC solar panels with the straight and direct light radiation. Similar to SPVC solar panels, the plant leaves also need sunlight to capture and store the solar energy in the form of food materials and bio-mass by using CO
2 and water as energy storing materials to feed the human beings and animals [
22]. However, a closer look at those plant leaves reveal that they do not face only south direction but all the directions to receive solar energy during the entire day. It has been found that the water (a liquid substance) present in the plant leaves is responsible for receiving the sunlight from all the directions and during the entire day time. Thus, the plant leaves suggest that the liquid containing surfaces receive more amount of sunlight from all directions without causing much of reflection back into the atmosphere [
96]. It has also been established that the solid surfaces reflect more sunlight than those reflected by the liquid surfaces (Figs. 4 & 5) [
1]. Furthermore, the SPVC panels also become quite hot during daytime [
93].
Figure 4.
(A) Schematic illustrating characteristic experiment (left) where a dense solution of nanoparticles contained in a cuvette is illuminated with 808 nm laser light; multiparticle optical interactions in such nanofluids (right) where photons are scattered and/or absorbed. (B) Experimentally obtained (left) and Monte Carlo (MC) simulated (right) scattered light as viewed from the side of cuvettes containing nanoshell solutions of the indicated concentrations. Integration times are not the same for all three experiments [
1,
96].
Figure 4.
(A) Schematic illustrating characteristic experiment (left) where a dense solution of nanoparticles contained in a cuvette is illuminated with 808 nm laser light; multiparticle optical interactions in such nanofluids (right) where photons are scattered and/or absorbed. (B) Experimentally obtained (left) and Monte Carlo (MC) simulated (right) scattered light as viewed from the side of cuvettes containing nanoshell solutions of the indicated concentrations. Integration times are not the same for all three experiments [
1,
96].
Figure 5.
Digital photos showing decolourization of aqueous MB solution in the presence of TiO
2 nano-powder photocatalyst under the irradiation of a simulated solar light; (a) – pure aqueous 0.01 mM MB solution; (b) – aqueous 0.01 mM MB solution dispersed with TiO
2 nano-powder; (c & d) – aqueous 0.01 mM MB solution dispersed withTiO
2 nano-powder being irradiated with light having a wavelength range of (300–700 nm at 44 mW/cm
2 power density (rare & side views, respectively); & (e) slurry after exposing to the light irradiation. No light was detected backside of the reactor as the light passed into the reaction mixture solution was completely absorbed by the contents in it. Considerable amount of light reflection from the front face (wall) of the quartz-glass reactor can be seen from (d) photograph. The reflected light was determined to be about 6% [
1,
89].
Figure 5.
Digital photos showing decolourization of aqueous MB solution in the presence of TiO
2 nano-powder photocatalyst under the irradiation of a simulated solar light; (a) – pure aqueous 0.01 mM MB solution; (b) – aqueous 0.01 mM MB solution dispersed with TiO
2 nano-powder; (c & d) – aqueous 0.01 mM MB solution dispersed withTiO
2 nano-powder being irradiated with light having a wavelength range of (300–700 nm at 44 mW/cm
2 power density (rare & side views, respectively); & (e) slurry after exposing to the light irradiation. No light was detected backside of the reactor as the light passed into the reaction mixture solution was completely absorbed by the contents in it. Considerable amount of light reflection from the front face (wall) of the quartz-glass reactor can be seen from (d) photograph. The reflected light was determined to be about 6% [
1,
89].
In SPVCs, the
n-type Si semiconductor doped with phosphorous and antimony (top layer) and
p-type Si doped with boron (bottom layer) are deposited by following a
chemical vapor deposition (CVD) technique to form a two layered thin film Si p-n junction cell with a band-gap energy of ~1.1 eV. Its top surface up to 8 to 10%, and the complete bottom surface are covered with an electrically conducting thin layer of Ag or Al to serve as grid and bus-bar lines, and as light reflecting bottom surface, respectively. In a one meter by two meters SPVC solar panel, 72 numbers of individual SPVCs are interconnected in a series using a copper thin stripe (coated with Sn-Pb layers to facilitate the soldering process while joining the individual cells together). Finally, these interconnected cells are placed in between two thin layers of ethylene vinyl acetate (EVA) sheets (5 × 10
−4 m), which are in turn placed in between a top layer of fully tempered low-iron containing transparent solar glass (3.2 mm thick) sheet and a bottom polyurethane plastic (few mm thickness) sheet, and then all these parts are together hot compacted under vacuum so that no air-bubbles are trapped in the inter layers of the SPVC solar panel [
67,
88,
97]. On the top surface of a SPVC, a very thin (about few hundred nanometer thick) layer of Si
3N
4 anti-reflection coating is given by following the same
CVD technique. This latter layer also avoids to some extent the unforeseen oxidation of
c-Si upon exposure to light irradiation in oxidizing environment, and to arrest the light reflection from SPVCs to some extent (Fig. 6) [
1,
98]. If SPVCs are not sealed in between two-EVA layers under vacuum properly, Si undergoes oxidation into SiO
2 with a band-gap energy of ~9.0 eV upon irradiation with sunlight in presence of air/moisture atmosphere. Once Si is converted into SiO
2, it loses its ability to capture sunlight and to turn it into electricity or heat energy as the sunlight reaching the SPVC solar panel do not possess the band-gap energy higher than 3.2 eV. The sunlight with 3.2 eV energy cannot excite the
valance-band (VB) (i.e., the
highest occupied molecular orbital (HOMO) electrons of SiO
2 into its
conduction band (CB) (i.e., into the
lowest unoccupied molecular orbital (LUMO)) as its band-gap energy is ~9.0 eV to create the electron-hole pairs. When Si undergoes ionization upon irradiation with sunlight (i.e., light with <1125 nm wavelength) having energy higher than that of its band-gap (i.e., 1.1 eV) by exciting its VB electrons into CB, there is a creation of electron-hole pairs with definite oxidation and reduction potentials [
80]. These Si oxidation potentials can pull electrons from water molecule when it comes into contact with the ionized Si
4+ ions and oxidizes it to form O
2 and H
2 gases. Furthermore, if any air or moisture is present between the EVA layer and SPVC after hot-compaction into SPVC solar panel, the entrapped air/moisture undergoes volumetric expansion when it receives the heat generated by
c-Si cells and creates considerable amount of strain capable of breaking the very-thin and highly brittle
c-Si cells. Thus it can cause a very serious damage to the SPVC cells and decreases the overall STE generating efficiency of these solar panels. The thin Si
3N
4 layer present on
c-Si cells cannot confer sufficient strength to withstand the strain and to prevent SPVCs from breakage. Furthermore, when the amount of heat dissipated by EVA, glass-sheet, and polyurethane bottom protective plastic sheet, and by thin strips of electrically conducting Sn-Pb coated Cu interconnecting material printed on top and bottom surfaces of SPVCs not enough, the generated heat can also cause the irreversible loss of electricity generating ability of p-n junctions of these SPVCs. Fortunately, in most locations, solar panels are operated within the comfortable temperature range; hence, not much efficiency is lost as there is the decrease of only 0.5 V per every degree temperature rise [
80]. Furthermore, the voltage generation is inversely proportional to the current generating ability of
c-Si, which increases with the increase of operating temperature.
Figure 6.
Silicon photovoltaic cell (SPVC) solar panel components [
1,
98].
Figure 6.
Silicon photovoltaic cell (SPVC) solar panel components [
1,
98].
In order to have the continuous performance of SPVC solar panels even after exposure to the increased temperatures, their laminating materials have to withstand 85°C in thermal cycling and damp heat tests according to the
International Electrotechnical Commission (IEC) 61215 [
99]. So far several efforts were made to reduce the operating temperature of SPVC solar panels, and as a part of these developments,
photovoltaic thermal (PV/T) systems have been introduced to increase the STE conversion efficiency as they take off the
in situ generated heat energy from the SPVC solar panels by a coolant liquid (mostly water), and thus collected heat energy in the form of hot-water is utilized for house-hold applications [1,81,91,92,96,100-108]. Apart from SPVCs, other semiconducting materials were also investigated for collecting solar energy in the form of heat energy for hot-water applications (a Japanese patent - JP2016145653). In PV/T systems, the heat carrying working fluid (WF) is not directly coming into contact with the heat generating SPVCs. Furthermore, in these latter systems, the SPVCs and the WF are separated by either EVA layer or by heat absorbing metal sheet followed by Cu tube. Besides that in order to avoid the oxidation of Si in SPVCs, they do not allow coming directly in contact with the WF. In fact, when the light energy absorbing SPVCs are fully immersed in a liquid solution, the
in situ generated heat energy is absorbed by the liquid immediately and there will not be any associated heat losses during the transmission from one material to the another material. The thermal conductance of the layer between SPVCs and the metal plate used in the PV/T systems can be determined using Eq. (1) [
109].
The specific conductivity of an EVA layer used in SPVC solar panels to protect the semiconducting Si from oxidation is k
EVA = 0.35 W/m.K, and the thickness EVA lamination layer (t
EVA) commonly used is 5 × 10
−4 m. This corresponds to a thermal conductance (h
PV-metal) of about 700 W/m
2.K [
81]. Stagnation, although infrequent, is a possible occurrence in forced circulated solar PV/T thermal systems [
1,
92,
107,
108], and is caused by low thermal demand (fully charged thermal storage tank), power outages (no electricity available to run the pumps) and other problems leading to a no-flow condition (plugged pipes, leaks, broken pumps, etc.). In these situations, the collector temperatures only depend on the idle heat losses and on the insolation heat dissipating capability.
Consequently, stagnation temperatures sometimes reach up to 220-350ºC for evacuated tube collectors, 170-210ºC for flat-plate collectors with selective absorbers and 115-150ºC for flat-plate collectors with non-selective absorbers [
77]. Although, the SPVCs can withstand temperatures up to 220ºC, the EVA encapsulate loses its mechanical properties at 130-140ºC and undergo delamination [
1,
77]. The occurrence of such high collector temperatures can cause the accelerated ageing of temperature sensitive components leading to their eventual failure, safety hazards for humans, uncomfortable acoustic emissions due to condensation pressure shocks (measured up to a maximum pressure of 6 bar for 60% water + 40% propylene glycol solution), enhanced vulnerability to hot spots resulting from manufacturing imperfections and the vaporization of common heat carrier fluids, and their potential release into the atmosphere from the loop
via safety valves. Owing to these problems, although the overall STE conversion efficiency of PV/T systems has been found to be higher than those of pure SPVC solar panels, their usage has been very limited. Nevertheless, the components used in the fabrication of SPVC solar panels such as low iron containing top solar glass, and the EVA polymer layer ensure that maximum amount of
in situ generated heat energy is dissipated as soon as possible, which is the reason behind the normally absorbed local heat island effect when a large number of SPVC solar panels are deployed [
80]. Furthermore, the SPVC solar panels also get detached in very windy conditions, and consequently can cause damage to property and persons. In addition to these technological limitations, another disadvantage of SPVC solar panels is it is often required to get the permission of the planning commission in certain jurisdictions in order to install SPVC solar panels as they can have a visual impact in areas where architectural integrity is required.
1.5. The environmental concerns of the retired SPVC solar panels
It is a known fact that the SPVC solar panels do not generate power forever. The industry standard life span of these solar panels is about 25 to 30 years, and the panels installed at the early end of the current boom (i.e., at the beginning of 1990s) are not long from being retired. For each and every passing year, more and more panels will be retired from the service; it will soon start adding up to millions, and then tens of millions of metric tons of material. According to a recent survey, by the end of the year 2020 in Japan, the solar panel waste will exceed 10,000 tons, it will reach 1,00,000 tons by 2031, it will be reaching 3,00,000 tons by 2034, and between 2034 and 2040, it will be between 7,00,000 to 8,00,000 tons annually [
1,
110]. The projected 8 lakh tons is equivalent to 40.5 million panels. To dispose of that amount in a year would mean getting rid of 1,10,000 panels per day. In response to this waste management,
M/s. Toshiba Environmental Solutions, Japan, says that recycling of SPVC solar panels do not provide any profit as the expenditure incurred for recycling process is higher than the cost of the materials recovered from the recycled SPVC solar panels [
110]. Furthermore, the current price of these solar panels in the market is considered to be below their manufacturing cost, and consequently, are unsustainable, in large part because several leading non-Chinese firms in the industry have recently announced losses cutbacks or massive write-downs or filed for bankruptcy. Furthermore, a new study by Environmental Progress warns that the toxic waste generated from used SPVC solar panels pose a global environmental threat [
111]. A Berkeley-based group found that SPVC solar panels create 300 times more toxic waste per unit of energy generated when compared with the one exhibited nuclear-power plants. Discarded SPVC solar panels, which contain dangerous elements such as lead, chromium, and cadmium, are piling up around the world, and no techniques found so far to mitigate their potential danger to the environment [
111]. A lot is talked about the dangers of nuclear waste, but that nuclear waste can be carefully monitored, regulated, and disposed of. But there is no idea about an enormous amount of SPVC panels that could cause so much ecological damage. SPVC solar panels are considered a form of toxic, hazardous electronic or "e-waste". The e-waste is burned in order to salvage the valuable copper wires for resale. Since, this process requires burning off EVA and polyurethane plastics, the resulting smoke contains toxic fumes that are carcinogenic and teratogenic (birth defect-causing) when inhaled [
111].
In fact, today, the cost of SPPV solar panel installations is dominated by packaging and systems integration, which are fixed costs [
22]. These trends indicate that reducing the SPVC solar panels manufacturing cost is no longer sufficient to improve its competitiveness. Furthermore, manufacturing of SPVC solar panels can also have consequences for workers and for environment throughout their life cycle (from raw material extraction and procurement to manufacturing, disposal, and/or recycling) [
1,
112]. Since, the SPVCs manufacturing has roots in the electronics industry, many of the chemicals found in e-waste are also found in SPVCs, including Pb, Br flame retardants, Cd, and Cr. The manufacturing of SPVCs involves several toxic, flammable and explosive chemicals. Many of those components suppose a health hazard to workers involved in the manufacturing of these SPVC solar panels [
113]. Today, the disposal of electronic products has been found to be an escalating environmental and health problem in many countries.
1.6. Is it possible to fully depend on SPVC solar panels to meet all the energy needs of the society without any backup from fossil fuels?
The major economic failure of SPVC solar panels can be seen from the Germany’s
Energiewende program [1,114-116]. The main achievement of
Energiewende program has been the increase of renewable energy from solar, wind and biomass in the overall consumed electricity from 3.4 % in the 1990s to almost 40 % today in the Germany. It can be appreciated that
Energiewende program successful in making everybody a part of this program by installing their own renewable energy generating systems. This really made up the success of the energy transformation and brought acceptance that people are relying on it [
1]. However, the first failure of this program has been the requirement of the massive government subsidies from taxpayers’ money to operate, and the Germany accelerated the program without much of planning, so it is no surprise that
$100 billion was wasted on the installation of roof top solar panels [
1,
116]. In fact, the two major objectives of Germany’s
Energiewende program are complete elimination of nuclear energy usage and complete minimization of CO
2 release into the atmosphere [
1]. However, none of these two objectives were completely met [
1]. The major obstacle for not achieving these objectives is due to the fact that the sun does not shine in the winter so the most solar energy is generated when the least electricity is needed period that is summer. Often it is thought that impressive amounts of solar energy being generated and used in the country, but those figures come from the summer season. In the case of wind, it is usually a daily stat taken when the wind was blowing strongest that day. In reality, only about 10% of energy throughout the year is renewable [
1]. The next failure is that wind and solar power are intermittent – the sun does not shine always and the wind does not blow always [
1]. Renewable energy gets access to the grid when it is available, essentially pushing thermal energy from coal offline. Thermal plants are designed to run all day, every day and now they are only marginally profitable because this energy is still required when intermittent solar and wind energy are not available. The main reason for its failure is due to the non-availability of the facilities to store the surplus electricity generated during summer period. About 60% of electricity is still produced by burning coal and natural gas, which are imported fossil fuels from other countries. As there is also no viable storage mechanism for wind and solar energies – it has to be used when it is produced. That means back-up is required, which in Germany’s case is the coal. The country started the
Energiewende program with a goal to eliminate the nuclear energy by the year 2000, which provides as much as 25 per cent of power. As a result of phasing out nuclear energy and due to the using of coal as the back-up for renewables, GHGs have risen in the country, exactly the opposite of what they implemented the energy program to do [
1]. There is a reason only 2 per cent of global energy is produced today by solar and wind together – they are not viable. They are intermittent sources that cannot be stored. Furthermore, it takes a lot of work to concentrate these types of energies for actual usage. Until humans find a way to capture and store solar and wind energies to be used in a free standing facility without back-up, renewable energy plans are just an expensive and faulty government experiments funded by the public [1,114-116].
In view of the above, to build a society fully supplied by the vast but intermittently available solar energy, it is also required to develop a practical self-sustainable energy package capable of directly supplying a dispatchable and most usable form of energy vector to the society. For this purpose, the successful development of both the inexpensive, highly efficient, and highly stable STE production method, and effective
AP process are needed [1,18-22,24,25]. It is known that the electrochemical conversion of CO
2 into fuel chemicals requires voltages in the range of 2-3 V to overcome the thermodynamic energy requirements together with the activation energy barriers. So, with conventional SPVC solar panels, at least 5 series-connected SPVCs are required to drive such reactions, which imply significant Ohmic and current mismatch losses in the cells’ interconnections. In view of these, it is difficult to completely depend on expensive SPVC solar panels for renewable energy production. Hence, another inexpensive, simple, and easy to fabricate technology to generate electricity from sunlight is needed to be developed with commercial viability [
1].
1.7. Semiconductor assisted photothermal effect (SAPE)
It is a known fact that all the semiconducting materials including Si (amorphous, single- and poly-crystalline), TiO
2, MgB
2, ZnO, FeO, Fe
2O
3, Fe
3O
4, Co
2O
3, Co
3O
4, Cu
2O, NiO, WO
3, CdS, PbS, PbSe, PbTe, PbS, InN, Ge, GeSb, SiC, Si
3N
4, InSb, InAs, GaP, GaSb, GaAs, GaN, CIGS, cadmium telluride, copper indium sulphide, etc., either in pure form or after doping them with any other single metal or non-metal or a combination of elements in elemental form or in compound form, and all organic dye materials (including those employed so far in all the dye-sensitized solar cells (DSSCs) and Perovskite solar cells (PSCs)), and low energy band-gap polymers absorb light energy upon their exposure to the sunlight [
1]. Semiconducting materials upon exposure to light energy higher than that of their band-gap energy excite their valance band (VB) (i.e., HOMO) electrons into their corresponding conduction band (CB) (i.e., into LUMO), and create holes having positive charge in their in the VB orbitals. When the excited electrons are recombined again with their corresponding hole-vacancies in the VB owing to their equal and opposite charges, the absorbed energy is released back again as light energy, which is manifested in the form of photoluminescence (PL). The released light energy is quantized and is the characteristic signal of that semiconducting material. The PL is two types, i) fluorescence and ii) phosphorescence. The kind of PL generation is decided by the type of band-gap (direct or indirect) present in that particular semiconducting material. In fact, in SPVC solar panels with
p-n junctions generate electricity upon irradiation with sunlight that cause excitation of electrons from VB to CB of
c-Si semiconducting material. However, when the semiconducting materials are irradiated with light energy much higher than that of the band-gap energy (for example Si having a band-gap energy of 1.1 eV is irradiated with 3.0 eV light), then light energy equivalent to its band-gap energy is converted into the PL or electricity generation in SPVC solar panel, and the remaining excess energy (for example 1.9 eV = 3.0 eV – 1.1 eV) is converted into the heat energy [
1,
117]. It is also a known fact that every photon (E = hν) causes excitation of only one electron from the valance orbital of a Si atom. Furthermore, when the SPVC solar panels are operated under the open-circuit (OC) voltage and short-circuit (SC) current conditions, the complete light energy absorbed by SPVCs is converted into only heat energy without generating any electricity [
1,
76,
88,
97,
118,
119]. In such OC voltage and SC current conditions, about >90% of the incident light gets converted into heat energy by SPVC solar panels. The process of heat generation by a semiconducting material upon exposure to a light energy is referred to as the “
Semiconductor Assisted Photothermal Effect (SAPE)” [
1].
The SAPE is also responsible for generating well-known sensitive spectral information in methods such as,
thermal lensing (TL),
photoacoustic spectroscopy (PAS), and
photothermal deflection spectroscopy (PDS) [
1,
120]. Furthermore, the SAPE can also be correlated very well with the heat generation by the resistive heating elements upon supplying with a suitable electrical energy, and with the heat generated by the electrodes used in electrochemical reactions. The resistive heating elements such as, MoSi
2, graphite, zirconia with fluorite structure, nichrome (nichrome 80/20; 80% nickel, 20% chromium), Kanthal (a trademark for a family of iron-chromium-aluminium, FeCrAl) alloys, Cupronickel (copper-nickel, CuNi, is an alloy of copper that contains nickel and strengthening elements, such as iron and manganese), etc., convert electrical energy into heat energy according to the
Joule’s law (W = I2R) [
1,
121]. Similarly, for example, when water is electrolyzed in 30 wt.% aqueous KOH solution by immersing an anode made of Ni or stainless steel (SS), and a cathode made of Ni connected to a 12 V or 16 V battery (
DC current), out of which only 2 V energy is consumed for splitting of water into H
2 and O
2 gases, and the remaining 10 V or 14 V is consumed in the generation of heat by those electrodes resulting into the generation of steam instead of H
2 and O
2 gases. To avoid the generation of steam in the electrolyzers that use 12 V or 16 V DC batteries, the concept of using electrolyzer stack has been introduced [
1,
122]. The stacks in both alkaline or
PEM (polymer or proton exchange membrane) electrolyzers ensure supply of only 2 V electricity between any two adjacent electrodes, which act as anode and cathode, by introducing suitable number of neutral (bipolar) plates between the end plates of anode and cathode connected to a battery. When 16 V battery is connected, then seven (7) neutral plates are placed between anode and cathode connected to the battery terminals so that there will be total eight (8) pairs of anodes and cathodes (i.e., cells); where each pair can draw only 2 V electricity from the battery. Based on these findings, it can be concluded that when certain semiconductor materials are supplied with energy not bearable by them, they generate heat energy.
In a recent patented process, a method and a device were employed to turn sunlight into heat energy (A Japanese patent - JP2016145653) [
1]. This device consists of a metallic tube through which the heat carrying working fluid (WF) is flown. The STE generating materials coating given on metallic tube consists of a STE conversion layer made of manganese silicide sandwiched in between two layers of infrared reflecting material (i.e., between metallic tube and manganese silicide) and a antireflection material coating on top of the manganese silicide. In this method, the heat generating material, i.e., manganese silicide, does not directly come into contact with the heat carrying working fluid, which flows inside the metal copper tube, whereas, the layers of the light absorbing materials are given on the outer surface of the metallic copper tube. The drawback of this method and device is the low STE generating efficiency [
1].
1.9. Semiconductor and liquid assisted photothermal effect (SLAPE)
Since, neither the SPVC solar panels, nor SAPE or NAPE phenomenon absorb the complete sunlight reaching the earth surface to convert it into electricity, it is required to have a new method or system to completely absorb the sunlight reaching the earth surface in the wavelength range of about 250 nm and 2400 nm, of course, with varying intensity [
1]. It is known that silicon semiconductor absorbs light having wavelength <1127 nm, whereas, the liquid solutions absorb infrared radiation from 1100 nm to 2400 nm. To capture the complete sunlight reaching the earth surface, for the first time, the SLAPE concept was employed in this investigation to generate initially heat energy from sunlight, and then electricity from that
in situ generated heat energy with the help of an electric generator and the reciprocally moved steam engine [
1,
126]. When semiconducting materials including
Si (amorphous, single- or poly-crystalline), black silicon wafers, etc., are suspended in electrochemically quite stable organic solvents such as, γ-butyrolactone (γ-BL), γ-valerolactone (GVL), methoxyacetonitrile (MAN), acetonitrile (AN), trimethyl phosphate (TMP), propylene carbonate (PC), 1,2-butylene carbonate (BC), 3-methoxypropionitrile (MPN), etc., which are referred to as non-working fluid (NWF), and exposed to the sunlight, none of the semiconducting materials identified so far can either oxidize or reduce these NWFs as their oxidation and reduction potentials are much higher than those of the semiconducting materials (
Table 3) [1,127-129]. Thus, the required characteristics of these NWFs should be i) a very high electrochemical stability window of about 7 V, ii) high-boiling point (up to 200°C), and iii) fully dried solvents without the presence of any trace of moisture. If water is present in these NWFs, when semiconducting materials suspended in them are exposed to sunlight, they undergo oxidation. Except, pure TiO
2, and ZnO, all other semiconducting materials lose their light absorbing capabilities when they are exposed to sunlight in the presence of water as water undergoes oxidation into H
2 and ½ O
2 gases [
1]. Not only water, if any other organic solvent or matter with lower oxidation and reduction potentials is exposed to sunlight together with any of the semiconducting material, those organic matter undergo oxidation into CO
2 and to other stable molecules, which is nothing but a photocatalytic reaction. This process can be clearly seen from the contents of Fig. 5 [
1,
89], where the methylene blue organic dye completely underwent de-colorization or decomposed in the presence of B-doped TiO
2 and water upon exposure to a light energy. The heat-energy generated from sunlight can be used to boil a low-boiling-temperature solvent such as, dichloromethane (DCM), hydro-fluoro-ethers (HFEs) including HFE-7000 and HFE7100, etc., as working fluids (WF) to generate enough pressure in them to rotate the electric generator (dynamo) connected to a reciprocally moved steam engine (RSE) that turns heat-energy into rotational mechanical to generate both AC or DC electricity [
1]. The major required characteristics for WFs are i) a low-boiling point, ii) higher latent heat of vaporization, iii) higher density and higher molecular weight than those of water along with iv) non-flammable and v) non-corrosive characteristics. Furthermore, they should be compatible with stainless steel, copper, aluminum, polypropylene, polyethylene and nylon. In addition to these, it shall be a dry fluid with a positively slopped saturation vapor curve so that it can be in a dry vapor state when it is in the steam engine and shall not contain any liquid droplets, otherwise, those liquid droplets can damage the moving parts within the system having the capability to turn the heat energy into a mechanical energy. If a wet (negatively slopped saturation vapor curve) WF is used, it would be needed to be superheated before pumping it into such system. The WFs shall also be environmentally friendly and possess zero ozone depletion potential (ODP), and they should not cause any threat to the human health or to the environment [
1,
130].
In SLAPE, the semiconducting materials in conjunction with an electrochemically stable organic solvent (NWF) such as, γ-butyrolactone are employed to capture the complete sunlight reaching the earth surface (infrared portion of the sunlight is captured by the γ-butyrolactone and the remaining portion of the sunlight) is captured by the semiconducting material such as Si in SPVCs and black silicon wafers, when they are together exposed to the sunlight [
1]. This latter method of capturing sunlight by semiconducting material in conjunction with organic solvent is referred to as the “SLAPE”. When the semiconducting materials of either inorganic or organic type with band-gap energies in the range of 0.5-3.2 eV are fully immersed in γ-butyrolactone and exposed to the sunlight, they can together absorb more than >80% of the sunlight falling on them. If the semiconducting particles are suspended in γ-butyrolactone are exposed to the sunlight, they can absorb the maximum light energy as they can be packed with 100% packing factor like liquid crystal display (LCD) screen. In such a case, all the three concepts viz.: SLAPE, NAPE and SAPE are operative together in synchronization [
1]. In order to realize such a combined effect to capture the sunlight to generate heat-energy, in this study, the multicrystalline SPVCs in conjunction with γ-butyrolactone as non-working fluid (NWF) were employed to capture the sunlight and to generate heat energy to boil DCM working fluid (WF) present in a copper tube conduit. Thus
in situ generated heat-energy from the captured sunlight upon exposure of the SLAPE solar panels fabricated in this study was converted into electricity using custom made electric generator and commercially available laboratory scale reciprocally moved steam engine [
1]. Thus obtained results obtained in these experiments are presented and discussed in this article.