With the demand growing for more sustainable forms of energy in replacement of fossil fuels, a major obstacle arises in the end-of life solar modules that are disposed of in landfills. Aside from the hazardous materials, silicon solar modules contain valuable and scarce materials such as silver. Silver is used in many industries and many applications therefore the recycling and recovering of it is financially beneficial. The purpose of this research was to achieve high purity and recovery of silver using hydrofluoric acid. The following work presents the feasibility of silver recovery through the process of leaching and electrowinning by examining the percent recovery and cathodic coulombic efficiency, followed by a chemical analysis to determine the purity. Varying conditions in leaching and electrowinning parameters are conducted in a synthetic solution to determine the effect on silver recovery and cathodic coulombic efficiency. It was determined that the silver recovery was dependent on the applied potential, system configuration and time. The system is capable of recovery rates of over 95% at -1 V. The system is further tested on solar cells to prove that silver can be recovered. There was over 99% purity from the experiments conducted in synthetic solution and from solar cells. Additionally, a circular chemistry is proposed that allows the reuse of hydrofluoric acid for leaching and electrowinning.

The silicon-based solar cell has been extensively deployed in photovoltaic industry and plays an important role in renewable energy industries. A more energy-efficient, environment-harmless and eco-friendly silicon production technique is required for price-competitive solar energy harvesting. Silicon electrorefining in molten salt is promising for the ultrapure solar-grade Si production. To avoid using highly corrosive fluoride salt, CaCl2-based salt is widely employed for silicon electroreduction. For Si electroreduction in CaCl2-based salt, CaO is usually added to enhance the solubility of SiO2. However, the existence of oxygen in molten salt could result in system corrosion, anode passivation and the co-deposition of secondary phases such as CaSiO3 and SiO2 at the cathode. This research focuses on the development of reusable oxygen-free CaCl2-based molten salt for solar-grade silicon electrorefining. A new multi-potential electropurification process has been proposed and proven to be more effective in impurities removal. The as-received salt and the salt after electrorefining have been electropurified. The inductively-coupled plasma mass spectrometry and cyclic voltammetry have been utilized to determine the impurities removal of electropurification. The salt after silicon electrorefining has been regenerated to its original purity level before by the multi-potential electropurification process, demonstrating the feasibility of a reusable salt by electropurification. In an oxygen-free CaCl2-based salt without silicon precursor, the silicon dissolved from the silicon anode can be successfully deposited at the cathode. The silicon anode has been operated for more than 50 hours without passivation in the oxygen-free system. Silicon ions start to be deposited after 0.17 g of silicon has been dissolved into the salt from the silicon anode. A 180 µm deposit with a silver-luster surface was obtained at the cathode. The main impurities in the silicon anode such as aluminum, iron and titanium were not found in the silicon deposits. No oxygen-containing secondary phases are detected in the silicon deposits. These results confirm the feasibility of silicon electrorefining in the oxygen-free CaCl2-based salt.

A general review of film growth with various mechanisms is given. Additives and their potential effects on film properties are also discussed. Experimental light-induced aluminum (Al) plating tool design is discussed. Light-induced electroplating of Al as the front electrode on the n-type emitter of silicon (Si) solar cells is proposed as a substitute for screen-printed Silver (Ag). The advantages and disadvantages of Al over copper (Cu) as a suitable Ag replacement are examined. Optimization of the power given to a green laser for silicon nitride (SiNx) anitreflection coating patterning is performed. Laser damage and contamination removal conditions on post-patterned cell surfaces are identified. Plating and post-annealing temperature effects on Al morphology and film resistivity are explored. Morphology and resistivity improvement of the Al film are also investigated through several plating additives. The lowest resistivity of 3.1 µΩ-cm is given by nicotinic acid. Laser induced damage to the cell emitter experimentally limits the contact resistivity between light-induced Al and Si to approximately 69 mΩ-cm2. Phosphorus pentachloride (PCl5) is introduced into the plating bath and improved the the contact resistivity between light induced Al and Si to a range of 0.1-1 mΩ-cm2. Secondary ion mass spectroscopy (SIMS) was performed on a film deposited with PCl5 and showed a phosphorus peak, indicating emitter phosphorus concentration may be the reason for the low contact resistivity between light-induced Al and Si. SEM also shows that PCl5 improves Al film density and plating throwing power. Post plating annealing performed at a temperature of 500°C allows Al to spike through the thin n-type emitter causing cell failure. Atmospheric moisture causes poor process reproducibility.

This paper presents the electrolytic application of a load-matching PV system to produce green hydrogen. The system has proven its viability with purely resistive loads, and a static analysis has shown the performance potential of the system for electrolytic applications. This paper focuses on dynamic simulation of the load-matching PV system for green hydrogen production in SIMULINK. It is shown that an over 99% energy transfer efficiency from the PV array’s available energy to the electrolytic loads can be achieved under dynamic conditions for the system. The design parameters to optimize include the number of hydrogen cells per stack, the stack resistance, and the number of available stacks in the system. This system provides a simple but efficient approach for large-scale photovoltaic hydrogen production.

Nearly all solar photovoltaic (PV) systems are designed with maximum power point tracking (MPPT) functionality to maximize the utilization of available power from the PV array throughout the day. In conventional PV systems, the MPPT function is handled by a power electronic device, like a DC-AC inverter. However, given that most PV systems are designed to be grid-connected, there are several challenges for designing PV systems for DC-powered applications and off-grid applications. The first challenge is that all power electronic devices introduce some degree of power loss. Beyond the cost of the lost power, the upfront cost of power electronics also increases with the required power rating. Second, there are very few commercially available options for DC-DC converters that include MPPT functionality, and nearly all PV inverters are designed as “grid-following” devices, as opposed to “grid-forming” devices, meaning they cannot be used in off-grid applications.

To address the challenges of designing PV systems for high-power DC and off-grid applications, a load-managing photovoltaic (LMPV) system topology has been proposed. Instead of using power electronics, the LMPV system performs maximum power point tracking through load management. By implementing a load-management approach, the upfront costs and the power losses associated with the power electronics are avoided, both of which improve the economic viability of the PV system. This work introduces the concept of an LMPV system, provides in-depth analyses through both simulation and experimental validation, and explores several potential applications of the system, such as solar-powered commercial-scale electrolyzers for the production of hydrogen fuel or the production and purification of raw materials like caustic soda, copper, and zinc.

As Energy needs grow and photovoltaics expand to meet humanity’s demand for electricity, waste modules will start building up. Tao et. al. propose a recycling process to recover all precious solar cell materials, a process estimated to generate a potential $15 billion in revenue by 2050. A key part of this process is metal recovery, and specifically, silver recovery. Silver recovery via electrowinning was studied using a hydrofluoric acid leachate/electrolyte. Bulk electrolysis trials were performed at varied voltages using a silver working electrode, silver pseudo-reference electrode and a graphite counter-electrode. The highest mass recovery achieved was 98.8% which occurred at 0.65 volts. Product purity was below 90% for all trials and coulombic efficiency never reached above 20%. The average energy consumption per gram of reduced silver was 2.16kWh/kg. Bulk electrolysis indicates that parasitic reactions are drawing power from the potentiostat and limiting the mass recovery of the system. In order to develop this process to the practical use stage, parasitic reactions must be eliminated, and product purity and power efficiency must improve. The system should be run in a vacuum environment and the reduction peaks in the cell should be characterized using cyclic voltammetry.

Lithium metal is a promising anode for the next generation lithium batteries owing to its high capacity (3860 mAh g-1) and the lowest negative reduction potential (-3.04 V). Commercial produced lithium anodes have a native rough surface which deteriorates the cycling performance of the battery. Here, an attempt has been made to deposit lithium on copper from an electrolytic cell consisting of simple electrolyte of pyridine and lithium chloride at room temperature. Water is known to react aggressively with the lithium metal, however in the electrochemical plating process, it has a significant beneficial effect in catalyzing the electrochemical reactions. The effect of trace amounts of water was investigated in air as well as in controlled atmosphere of argon, nitrogen, breathing grade dry air and ultra-zero dry air. The electrochemical products examined by Fourier transform infrared spectroscopy revealed the deposition might require the reduction of pyridine to facilitate the reduction of the lithium salt. Purity of the lithium film was determined by inductively coupled plasma mass spectrometry.

Photovoltaics (PV) is one of the promising options for maintaining sustainable energy supply because it is environmentally friendly, a non-polluting and low-maintenance energy source. Despite the many advantages of PV, solar energy currently accounts for only 1% of the global energy portfolio for electricity generation. This is because the cost of electricity from PV remains about a factor of two higher than the fossil fuel (10¢/kWh). Widely-used commercial methods employed to generate PV energy, such as silicon or thin film-based technologies, are still expensive as they are processed through vacuum-based techniques. Therefore, it is desirable to find an alternative method that is open-air and continuous process for the mass production of solar cells.

The objective of the research in this thesis is to develop low-cost spray pyrolysis technique to synthesize oxides thin films for applications in solar cells. Chapter 4 and 5 discuss spray-deposited dielectric oxides for their applications in Si solar cells. In Chapter 4, a successful deposition of Al2O3 is demonstrated using water as the solvent which ensures a lower cost and safer process environment. Optical, electrical, and structural properties of spray-deposited Al2O3 are investigated and compared to the industrial standard Atomic Layer Deposition (ALD) Al2O3/Plasma Enhanced Chemical Vapor Deposition (PECVD) SiNx stack, to reveal the suitability of spray-deposited Al2O3 for rear passivation and optical trapping in p-type Si Passivated Emitter and Rear Cell (PERC) solar cells. In Chapter 5, The possibility of using low-cost spray-deposited ZrO2 as the antireflection coating for Si solar cells is investigated. Optical, electrical and structural properties of spray-deposited ZrO2 films are studied and compared to the industrial standard antireflection coating PECVD SiNx. In Chapter 6, spray-deposited hematite Fe2O3 and sol-gel prepared anatase TiO2 thin films are sulfurized by annealing in H2S to investigate the band gap narrowing by sulfur doping and explore the possibility of using ternary semiconductors for their application as solar absorbers.

A major obstacle to sustainable solar technologies is end-of-life solar modules. In this thesis, a recycling process is proposed for crystalline-Si solar modules. It is a three-step process to break down Si modules and recover various materials. Over 95% of a module by weight can be recovered with this process. Two new technologies are demonstrated to enable the proposed recycling process. One is sequential electrowinning which allows multiple metals to be recovered one by one from Si modules, Ag, Pb, Sn and Cu. The other is sheet resistance monitoring by the 4-point probe which maximizes the amount of solar-grade Si recovered from Si modules with high throughput. The purity of the recovered metals is above 99% and the recovery rate can achieve between 70~80%. The recovered Si meets the specifications for solar-grade Si and at least 91% of Si from c-Si solar cells can be recovered. The recovered Si and metals are new feedstocks to the solar industry and generate over $12/module in revenue. This revenue enables a profitable recycling business for Si modules without any government support. The chemicals for recycling are carefully selected to minimize their environmental impact and also the cost. A network for collecting end-of-life solar modules is proposed based on the current distribution network for solar modules to contain the collection cost. As a result, the proposed recycling process for c-Si modules is technically, environmentally and financially sustainable.

In this thesis, the methods of aluminum electroplating in an ionic liquid for silicon solar cell front side metallization were studied. It focused on replacing the current silver screen printing with an alternative metallization technology using a low-cost Earth-abundant metal for mass production, due to the high cost and limited availability of silver. A conventional aluminum electroplating method was employed for silicon solar cells fabrication on both p-type and n-type substrates. The highest efficiency of 17.9% was achieved in the n-type solar cell with a rear junction, which is comparable to that of the same structure cell with screen printed silver electrodes from industrial production lines. It also showed better spiking resistant performance than the common structure p-type solar cell. Further efforts were put on the development of a novel light-induced plating of aluminum technique. The aluminum was deposited directly on a silicon substrate without the assistance of a conductive seed layer, thus simplified and reduced the process cost. The plated aluminum has good adhesion to the silicon surface with the resistivity as low as 4×10–6 -cm. A new demo tool was designed and set up for the light-induced plating experiment, aiming to utilize this technique in large-size solar cells fabrication and mass production. Besides the metallization methods, a comprehensive sensitivity analysis for the efficiency dispersion in the production of crystalline-Si solar cells was presented based on numerical simulations. Temperature variation in the diffusion furnace was the most significant cause of the efficiency dispersion. It was concluded that a narrow efficiency range of ±0.5% absolute is achievable if the emitter diffusion temperature is confined to a 13˚C window, while other cell parameters vary within their normal windows. Possible methods to minimize temperature variation in emitter diffusion were proposed.