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Lifetime and Degradation Science Of LIFETIME AND DEGRADATION SCIENCE OF POLYMERIC ENCAPSULANT IN PHOTOVOLTAIC SYSTEMS: INVESTIGATING THE ROLE OF ETHYLENE VINYL ACETATE IN PHOTOVOLTAIC MODULE PERFORMANCE LOSS WITH SEMI-GSEM ANALYTICS by NICHOLAS R. WHEELER Submitted in partial fulfillment of the requirements For the degree of Doctor of Philosophy Department of Macromolecular Science and Engineering CASE WESTERN RESERVE UNIVERSITY January, 2017 Case Western Reserve University We hereby approve the thesis document1 of NICHOLAS R. WHEELER for the degree of Doctor of Philosophy Dr. Roger H. French Committee Chair, Adviser Date Department of Materials Science and Engineering Dr. Ozan Akkus Committee Member, Faculty Date Department of Mechanical and Aerospace Engineering Dr. Michael Hore Committee Member, Faculty Date Department of Macromolecular Science and Engineering Dr. Timothy J. Peshek Committee Member, Faculty Date Department of Materials Science and Engineering Dr. Laura S. Bruckman Committee Member, Faculty Date Department of Materials Science and Engineering Defense Date: August 25, 2016 1We certify that written approval has been obtained for any proprietary material contained therein. Table of Contents List of Figuresv Acknowledgements ix Acknowledgements ix x Abstractx Chapter 1. Introduction1 World Energy Demands1 Lifetime and Degradation Science for PV2 Chapter 2. Literature Review4 Carrisa Plains Disaster4 Subsequent PV Studies6 Modern PV Module Degradation Perspective7 Confocal Raman Spectroscopy for PV Materials9 EL Images for Localized PV Performance 11 I-V Curves for System Level PV Performance 13 Chapter 3. Experimental Methods 15 Mini-Module Samples 15 Exposure Equipment and Procedures 18 Evaluation Equipment and Procedures 19 Data Analytics & Environment 24 Statistical Methods 32 iii Chapter 4. Experimental Results 36 UL PV Module Study - Degradation Pathway Modeling 36 SDLE Mini-Modules Pilot Study 43 Screen Printed Silver (SP-Ag) Corrosion L&DS Dataset 45 Chapter 5. Discussion & semi-gSEM Modeling 52 Hypothetical Degradation Mechanisms 52 Interpretation of Variable Trends 54 Exploratory Data Analysis - Pairwise Plotting 66 Semi-gSEM Modeling of Degradation Pathways 72 Domain Knowledge - Observed Causal Mechanisms 82 Sample Construction Geometry Comparison 85 PV Module Change Point Phenomenon 86 Chapter 6. Conclusions 88 Chapter 7. Future Research 90 Appendix A. CV 92 0. Presentations 92 0. Publications - Proceedings 93 0. Publications - Refereed 94 Appendix B. Free and Open Source Software Tools 95 Analytical software packages 95 Preparation of this document 96 Appendix. Complete References 97 iv List of Figures 1.1 Comparative Nameplate Capacity Chart from DOE Report2 1.2 Mesoscopic Evolution Model3 2.1 Carrisa Plains Power Plant Performance Degradation5 2.2 Raman Spectroscopy of EVA in Literature9 2.3 Test Figure for EL Images 11 2.4 Test Figure for I-V Curves 13 3.1 SDLE Mini-Module Construction 16 3.2 DPVS Mini-Module Gridline Geometry 17 3.3 Environmental Test Chambers 18 3.4 Confocal Raman SNR Study 19 3.5 Confocal Raman Procedure 20 3.6 Gage R&R 21 3.7 EL Imaging Procedure 22 3.8 I-V Curve Tracing Procedure 23 3.9 Computational Environment - FOSS Tools 24 3.10 Confocal Raman Analytics 25 3.11 EL Image Processing 26 3.12 EL Image Quantification 27 3.13 I-V Curve Tracing Analytics 28 3.14 I-V Curve Calibration 29 v 3.15 Delta Format 30 3.16 Data Pipeline 31 3.17 Pairwise Plotting 32 4.1 L&DS Model Needs and SEM Technique 36 4.2 UL PV Module Dataset Experimental Summary 38 4.3 UL Study Changepoint 39 4.4 UL PV Module Dataset Semi-gSEM Results 41 4.5 Confocal Raman Pilot Study 43 4.6 EL & I-V Pilot Study 44 4.7 Confocal Raman Cell Edge CHb/CO Peak Ratio 46 4.8 Confocal Raman Cell Center CHb/CO Peak Ratio 46 4.9 Confocal Raman Cell Edge Degradation Peak Ratios 47 4.10 Confocal Raman Cell Center Degradation Peak Ratios 47 4.11 EL Image Pixel Sums 48 4.12 EL Mean Threshold Sum Ratios 48 4.13 EL Mean Threshold Count Ratios 49 4.14 EL Area Ratios 49 4.15 I-V PMax Results 50 4.16 I-V Fill Factor Results 50 4.17 I-V Corrected PMax Results 51 5.1 Spectral Shape Discussion 54 vi 5.2 EVA CO Peak Discussion 55 5.3 Degradation Feature Discussion 56 5.4 Polymer Luminescence Discussion 57 5.5 Glass Peak Discussion 58 5.6 Glass Peak Discussion 59 5.7 Edge vs Center and Agg vs NAgg Comparison 60 5.8 Image Pixel Sum Discussion 61 5.9 Image Threshhold Variables Discussion 62 5.10 Area Sum Ratio Discussion 63 5.11 EL Gridline Geometry Discussion 63 5.12 PMax Discussion 64 5.13 Fill Factor Discussion 65 5.14 Confocal Raman CHb/CO Ratios Pairwise Correlaton 66 5.15 Confocal Raman Degradation Ratios Pairwise Correlaton 67 5.16 EL Pairwise Correlaton 68 5.17 I-V Pairwise Correlation 69 5.18 I-V Pairwise Correlation Revised 69 5.19 Aggressive Geometry Pairwise Functional Forms 70 5.20 Non-Aggressive Geometry Pairwise Functional Forms 71 5.21 Aggressive semi-gSEM Model 72 5.22 Aggressive semi-gSEM Degradation Path 74 5.23 Aggressive semi-gSEM Model Predictions 75 vii 5.24 Aggressive semi-gSEM Model Error 76 5.25 Non-Aggressive semi-gSEM Model 77 5.26 Non-Aggressive semi-gSEM Degradation Path 79 5.27 Non-Aggressive semi-gSEM Model Predictions 80 5.28 Non-Aggressive semi-gSEM Model Error 81 viii Acknowledgements 0.1 Acknowledgements Thanks to fellow SDLE researchers Junheng Ma, Abdulkerim Gok, Mohammad Hos- sain, Yang Hu, Ian Kidd, Pei Zhao, Yifan Xu, Wenyu Du, Mohamed Elsaeiti, Heather Lemire, Luke Revitsky, Maria Kim, and Reena Patel, for cooperation and coordinated efforts during this work. Special thanks and much gratitude to SDLE researchers Nikhil Goel and Davis Zabiyaka, for their loyal and sustained help and support with IV and EL data collection, and to Justin Fada for his hard work and dedication to creating and developing the democratized EL camera setup utilized extensively in these experiments. Thanks to industrial collaborators Carl Wang and Ethan Wang (from Underwrit- ers Laboratories) for facilitating access to the dataset from their comprehensive PV module degradation experiments, and Andreas Meisel, Thomas Dang, Christopher Alcantara, and Mason Terry (from Dupont Photovoltaic Systems / Silicon Valley Technology Center) for providing high quality PV Mini-Module samples for the stud- ies featured in this work. And special thanks to my thesis adviser, Roger French, and additional thesis committee members, Timothy Peshek, Laura Bruckman, Ozan Akkus, and Michael Hore, many of whom have played a role in influencing and advancing this research directly. ix Lifetime and Degradation Science of Polymeric Encapsulant in Photovoltaic Systems: Investigating the Role of Ethylene Vinyl Acetate in Photovoltaic Module Performance Loss with Semi-gSEM Analytics Abstract by NICHOLAS R. WHEELER 0.2 Abstract The lifetime performance and degradation behavior of photovoltaic (PV) modules is of the utmost importance for the success and growth of solar energy as a major resource for fulfilling growing worldwide energy needs. While PV reliability has been a concern for some time, existing qualification testing methods do not reflect a cohesive picture of the science behind module degradation, and are not capable of accurately predicting module lifetime performance. Towards these goals, a statistical methodology, semi- gSEM, was developed and applied to investigate the response of full sized PV modules to accelerated stress conditions. The results of this initial study indicated that a correlation exists between system level power loss and the buildup of acetic acid resulting from the hydrolytic degra- dation of ethylene-vinyl acetate (EVA) polymer encapsulant. To further explore this proposed mechanistic pathway, a study was designed and conducted to characterize x the degradation of mini-module samples under damp heat accelerated stress condi- tions. Mini-module samples featured two construction geometries that differed in the thicknesses of screen-printed silver conductive lines (SP-Ag) to assess the impact of gridline size on damp heat induced degradation. Samples were measured non-destructively at many points along their degradation pathway, using techniques that gathered both chemical and electrical information. The semi-gSEM analytical method was applied to this dataset to highlight degra- dation pathways and mechanisms observed in the experimental results. An EVA encapsulant spectroscopic degradation feature was found to be statistically related to quantified degradation features of simultaneously measured EL images. In turn, the EL image degradation was found to be statistically related to I-V curve parameters describing system level power loss. The degradation pathway observed was attributed to EVA encapsulant degra- dation leading to metallization corrosion and ultimately system level power loss in the PV mini-module samples. Mini-module samples with thinner SP-Ag conduc- tive lines were observed to be more severely damaged by the metallization corrosion process. This represents a valuable step in exploring the often misunderstood role of EVA degradation in PV module performance loss under damp heat conditions, and demonstrates novel methodologies for building a more integrated picture of PV module degradation as a whole. xi 1 1 Introduction Predicting the lifetime performance and reliability of photovoltaic (PV) power systems is an important and growing global need that this work seeks to contribute to. Lifetime and degradation science1 is a scientific perspective and approach to investigating these concerns in long-lived (30+ years) systems, and it is especially applicable to PV technologies. 1.1 World Energy Demands A recent report from the US Department of Energy Office of Basic Energy Sciences was released with the goal of identifying priority research directions for accelerating the development and growth of clean energy technology.2 This report features a wide and comprehensive overview of many scientific challenges and basic research needs facing the advancement of energy sciences and technologies worldwide.
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