Corrosion and Degradation in Fuel Cells, Supercapacitors and Batteries

Inhaltsverzeichnis

1. Frontmatter

2. Electrochemical Energy Storage and Conversion

   1. Frontmatter

   2. Chapter 1. Electrochemical Energy Storage and Conversion Devices—Types and Importance

      Rudolf Holze

      Abstract

      Using electric energy on all scales is practically impossible without devices for storing and converting this energy into other storable forms. This applies to many mobile and portable applications, grid-related stationary applications, and the growing integration of renewable energies. Fundamentals of electric energy storage and conversion are outlined, and related thermodynamics are sketched. Classification of devices and their combination and typical applications are outlined.

   3. Chapter 2. Materials Degradation in Electrochemical Energy Storage and Conversion Devices—An Overview

      Viswanathan S. Saji

      Abstract

      Electrochemical energy storage and conversion (EESC) devices typically suffer from various corrosion and degradation issues, including bipolar plate corrosion and carbon corrosion of polymer electrolyte membrane (PEM) fuel cells, corrosion of current collectors in metal-ion batteries and supercapacitors, and anode corrosion in metal-air batteries. Various associated degradation issues of active materials, electrolytes or membranes, solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI) formation, and galvanic corrosion are also accompanied. Several mitigation strategies were explored to tackle these degradation types. This chapter overviews research progress in this area.

3. Fuel Cells

   1. Frontmatter

   2. Chapter 3. Corrosion and Its Mitigation Approaches of Metallic Bipolar Plates

      Avinash Vijay Ingle

      Abstract

      In recent years, considerable attention has been directed toward proton exchange membrane fuel cells (PEMFCs) owing to their notable energy efficiency and environmentally friendly byproducts. Bipolar plates (BPPs), as pivotal components of PEMFCs, assume critical functions in gas isolation, flow field distribution, electron collection, and heat conduction. Metal BPPs exhibit commendable manufacturing attributes, cost-effectiveness, and mechanical strength, rendering them a compelling alternative to conventional graphite BPPs. The surface modification of metal BPPs becomes imperative for their effective integration into PEMFCs. This chapter provides a comprehensive account on corrosion and its mitigation approaches of metallic BPPs in PEMFCs. Metallic coatings such as metal nitrides and carbides focusing on corrosion resistance, conductivity, and contact angle considerations specific to metal BPPs within PEMFC environments are analyzed. The analysis delves into the strengths and limitations of various surface modification methods, while also contemplating future trends in commercialization.

   3. Chapter 4. Carbon Corrosion in Fuel Cells-Fundamentals and Mitigation Approaches

      Zhengkai Tu, Junjie Zhao

      Abstract

      At present, Pt nanoparticles (NPs), supported on a high specific surface area carbon are widely used as proton exchange membrane fuel cell (PEMFC) catalysts. However, carbon is not thermodynamically stable under the operating conditions in PEMFCs, and the electrochemical oxidation of carbon is accelerated at elevated temperature and potential. The performance degradation is mainly caused by Pt detaching or agglomerating due to the weakened interaction between Pt and the carbon support, which leads to the loss of Pt surface area. Therefore, carbon corrosion in the catalyst is one of the main reasons that limit the lifetime of the PEMFC and there are three main conditions that cause carbon corrosion, including startup and shutdown, water flooding, and long-term aging. This chapter presents an overview of the causes and consequences of the carbon corrosion mechanism and summarizes the corresponding mitigation strategies for various operating conditions.

   4. Chapter 5. Platinum Dissolution and Ionomer Redistribution/Degradation in Fuel Cells—An Evaluation

      Zhengkai Tu, Yang Liu

      Abstract

      Catalyst has a significant influence on the performance, lifetime, and efficiency of proton exchange membrane fuel cell (PEMFC). Platinum (Pt) has been wildly used for its rapid oxygen reduction reaction, but the cost and durability become one of the main challenges for Pt-based electrocatalysts. In this chapter, the degradation characteristics of PEMFCs with Pt black and Pt/C catalyst after continuous operation have been elucidated via electrochemical techniques and morphological characterization methods. To explore the performance degradation of the fuel cells operating in dual recirculation mode for both the anode and cathode, the dynamic characteristics of gas purging of the PEMFC was studied and the effects of the electrolyte and gas management strategy of the fuel cell on performance degradation were detailed.

   5. Chapter 6. Performance Degradation of PEM Fuel Cells During Startup–Shutdown Cycles: A Case Study

      Zhengkai Tu, Junjie Zhao

      Abstract

      As a catalyst carrier material, the oxidation of carbon materials is considered one of the main factors affecting the performance degradation of proton-exchange membrane fuel cells (PEMFCs) during startup and shutdown and must be alleviated to achieve acceptable durability. This chapter first addresses the effect of cathode exhaust conditions on the degradation behaviors of fuel cells using two single cells named the open-ended and closed cells. Then, the effect of shutoff sequences of hydrogen and air on the degradation behaviors of PEMFCs is explored with two different shutdown procedures. Meanwhile, electrochemical techniques, including the measurement of polarization curves, cyclic voltammetry, and cross-sectional scanning electron microscopy of membrane electrode assemblies and transmission electron microscopy of Pt/C catalyst, are employed to discuss the performance degradation of PEMFCs.

4. Supercapacitors

   1. Frontmatter

   2. Chapter 7. Corrosion and Degradation in Supercapacitors and Mitigation Approaches

      Xuecheng Chen, Yuping Wu, Rudolf Holze

      Abstract

      Corrosion of metals and carbon in its numerous forms and of different functional materials like metal oxides used as active masses in supercapacitor electrodes contribute to the ageing and degradation of supercapacitors of the various established types. Examples, symptoms, and mechanisms of the degradation of material/electrode and the device level are presented and discussed. Remedies and suggestions are indicated to avoid this unwanted contribution to device failure and ageing.

   3. Chapter 8. Carbon Corrosion in Supercapacitors

      Montree Sawangphruk

      Abstract

      In this chapter, we delve into carbon corrosion in supercapacitors, a critical challenge impacting their durability and efficiency. Highlighting the degradation of carbon electrodes at high voltages, especially at the positive-electrode side, we explore the factors contributing to this corrosion, including electrolyte interactions and operational conditions. The chapter outlines innovative mitigation strategies, focusing on advanced carbon materials and electrolyte modifications. This comprehensive analysis aims to enhance the understanding of carbon corrosion mechanisms, contributing significantly to the development of more resilient and efficient supercapacitors for sustainable energy technologies.

5. Batteries

   1. Frontmatter

   2. Chapter 9. Corrosion in Pb-Acid Batteries—Recent Developments

      Marco Cattelan, Marco Mazzucato, Christian Durante

      Abstract

      Battery-based energy storage systems with high power/energy densities and excellent cycle efficiency are expected to play a key role in our everyday lives. Even though Lead-Acid Batteries (LABs) are the oldest electrochemical energy storage technology, they still attract a lot of interest thanks to their properties: stability, reliability, recyclability, and low cost of the raw materials. Precisely for these reasons, LAB technology will retain its strong position at least until 2030 and remain very competitive, but ongoing investments are needed to improve production and performance. The main weak points of LABs are the limited charge efficiency and cyclability, mostly due to the degradation of electrodes during the charging/discharging process. Corrosion, in particular, represents a severe problem for LABs and has been the subject of many studies. Although LABs inevitably corrode to a certain extent throughout life, runaway corrosion of the positive grid will ultimately lead to failure. This phenomenon results in capacity degradation, often termed “Premature Capacity Loss” (PCL) or in electrical shorts. This chapter, after having given a general overview of LABs, describing their different types, their chemistry, and their failure modes, focuses specifically on the problem of corrosion of the grids stressing the causes of this phenomenon and the different strategies to evaluate and reduce it.

   3. Chapter 10. Corrosion in Nickel-Metal Hydride (Ni-MH) Batteries—Recent Developments

      Judith Monnier, Junxian Zhang, Valérie Paul-Boncour, Fermin Cuevas

      Abstract

      Ni-MH batteries are a family of alkaline storage batteries featuring a positive nickel hydroxide electrode and a negative electrode based on an intermetallic compound able to reversibly absorb hydrogen at ambient conditions of pressure and temperature. This chapter focuses on the corrosion encountered for negative electrode materials. First, the different intermetallic families able to be used as negative electrode materials are presented, then for each case the corrosion mechanisms are described. It is evidenced that the corrosion mechanisms are mainly driven by the anodic oxidation of the elements more electropositive than nickel—such as rare earth (RE) but also vanadium or titanium—which are strongly oxidized by the KOH solution and form hydroxides or oxides at the surface, their morphology depending on their chemical composition. Nickel and partially substituting late transition metals form on the cathodic side a catalytic layer that promotes water reduction. To conclude, main prospects to overcome corrosion issues are presented.

   4. Chapter 11. Corrosion of Current Collectors in Metal-Ion Batteries

      Svetlozar Ivanov

      Abstract

      Effective control over the ageing of metal-ion rechargeable batteries is of fundamental importance for the realization of a fast global energy transition, where the improvement of key concepts like electromobility and stationary energy storage is particularly envisaged. Among the multiple factors that have impact on this complex phenomenon, the deeper understanding and prevention of current collector (CC) corrosion play leading roles. It turned out that CC corrosion is a major challenge for the development of both conventional and next-generation highly efficient electrochemical storage technologies. This chapter introduces the reader to the basics of the anodic behaviour and electrochemical corrosion of the CCs in rechargeable metal-ion batteries (MIBs). Details on corrosion mechanisms and most important factors controlling the stability of CCs are reviewed for Li-ion batteries. Additionally, overview of the CC performance in the next-generation aqueous and non-aqueous metal-ion rechargeable batteries is presented. The work can serve as a general guideline for academic scientists and industrial product engineers in their endeavours to fight against degradation of battery CCs.

   5. Chapter 12. Novel Corrosion-Resistant Nonmetallic Current Collectors for Aqueous Batteries

      Futoshi Matsumoto, Mika Fukunishi

      Abstract

      Current collectors (CCs) that hold the anode and cathode active material layers and collect the current flowing in the active material layers play an important role in maintaining the performance of the anodes and cathodes. In safe and inexpensive aqueous batteries, corrosion of CCs is unavoidable, so nonmetallic CCs have recently been investigated. This chapter introduces the results of recent studies on noncorrosive carbon-based CCs as nonmetallic CCs. Carbon coatings on metal-based CCs, carbon-based CCs, CC films made by combining active materials and carbon-based materials, etc., will be introduced. The results of the examination of carbon-based CCs in various aqueous secondary batteries that have been recently developed will be described.

   6. Chapter 13. CEI and SEI Formation in Li-Ion Batteries

      Jijian Xu

      Abstract

      In the broader context of global efforts toward carbon neutrality, there is a growing imperative for high-energy battery technologies. This chapter offers a historical and technical exploration of the solid-electrolyte-interphase (SEI) and cathode-electrolyte-interphase (CEI) in lithium-ion batteries, crucial components for enhancing battery performance and longevity. Starting with electrolyte design strategies for regulating interfacial reactions. Followed by revisiting the SEI and CEI concept’s inception and their evolution, respectively. This chapter encompasses an in-depth analysis of SEI and CEI composition and formation, enriched by the latest advancements in characterization and modeling. Addressing the challenge of stability in high-capacity anodes and high-voltage cathodes, it highlights strategies for forming inorganic-rich interphases, pivotal in advancing lithium-ion battery technology.

   7. Chapter 14. Corrosion and Degradation in Aqueous Zn-based Batteries

      Yi Yuan, Zixuan Li, Shengda D. Pu

      Abstract

      Aqueous zinc-based batteries have emerged as promising contenders in the realm of energy storage owing to their high safety, low cost and environmental friendliness. However, their practical implementation faces substantial challenges stemming from corrosion and related degradation issues that impact their performance and longevity. The inherent thermodynamic instability of the Zn metal in aqueous electrolytes initiates detrimental side reactions at the electrode/electrolyte interface, leading to reduced Zn anode reversibility and continuous performance deterioration. This chapter offers an in-depth exploration of the corrosion mechanisms affecting Zn metal anodes in both alkaline and mild/acidic electrolytes, elucidating the adverse effects and ensuing issues. Additionally, comprehensive insights into recent advancements in mitigating corrosion are provided, encompassing multifaceted strategies such as electrode modifications, electrolyte innovations and interface enhancements. Finally, some perspectives on challenges and concerns in future research are presented.

   8. Chapter 15. Novel Electrolytes and Electrolyte Additives for Metal-Ion and Metal-Air Batteries: A Case Study of Acetonitrile and LiCTFSI

      Naoki Matsuoka

      Abstract

      Acetonitrile (AN) as an electrolyte solvent enhances ionic conductivity, and its unique cation solvation affects the transfer kinetics. This chapter provides an exploration of AN’s role, emphasizing its impact on electrolyte functionality. A significant aspect highlighted is the meticulous selection of electrode protection additives in AN-based electrolytes, a critical determinant for their usability. These additives are strategically chosen to undergo reductive decomposition on the negative electrode in metal-ion batteries, effectively preventing repetitive electrolyte decomposition. The chapter further investigates the durability of AN-containing electrolytes featuring low or moderate concentrations of lithium salt using electrochemical methods. This investigation serves to illustrate the enhanced battery performance resulting from the heightened ionic conductivity of the electrolyte.

      Lithium 4,4,5,5-tetrafluoro-1,3,2-dithiazolidine-1,1,3,3-tetraoxide (LiCTFSI), is a promising lithium salt for usage in lithium-ion battery electrolytes because it does not cause corrosion (anodic dissolution) of the aluminum current collector below 5.0 V vs. Li/Li⁺. This chapter also provides an overview of LiCTFSI, delving into its unique characteristics and properties. Additionally, the chapter explores the synthetic conditions of LiCTFSI and examines the impact of impurities present in LiCTFSI on battery performance.

   9. Chapter 16. Degradation in Metal–Air Batteries—Recent Developments

      Xiangwen Gao, Chuan Tan, Max Jenkins

      Abstract

      Research into metal–air batteries is spurred by the promise of high energy densities, often surpassing those of lithium-ion batteries. Despite this promise, the development of practical metal–air batteries is hampered by their poor reversibility. Current research has indicated that the mechanisms causing battery degradation typically involve multiple aspects: 1. Whether the limiting factor in the formation/decomposition of the discharge production (such as Li₂O₂, in Li–O2 batteries) is e⁻ or Li⁺, i.e. does the interface occur at the Li₂O₂/electrolyte or the electrode/Li₂O₂? 2. The continuous formation of production during discharge clogs the electrode pores, reducing the effective area of the cathode material and thereby diminishing the capacity of the metal-air battery. 3. The generation of intermediate active species at the cathode, such as superoxides, peroxides, and singlet oxygen (¹O₂), leads to corrosion of critical battery components, including the electrolyte and electrodes. This corrosion leads to the formation of numerous decomposition products that are challenging to decompose, further exacerbating battery degradation. This chapter will briefly introduce the basic mechanisms of metal–air batteries and give an overview of the causes of battery degradation. Strategies to mitigate degradation will be explored along with suggested research directions.

   10. Chapter 17. Anode Corrosion and Its Mitigation in Metal–Air Batteries—I (Li/Na/Al/Mg-Air)

       Sahriah Basri, Nurul Shahzira Hazri, Siti Kartom Kamarudin

       Abstract

       Metal–air batteries, often called metal–air fuel cells, have emerged as a promising energy storage technology due to their high energy density and environmental sustainability. Nevertheless, the problem of anode corrosion poses a significant danger to their practical implementation. This chapter discusses the fundamentals of anode corrosion in air batteries, its mitigation approaches, and existing challenges, intending to gain a deeper understanding and find effective strategies to address this issue. The implications pertain to the formulation of techniques for reducing anode corrosion, which involve choosing materials resistant to corrosion such as applying protective coatings and making design adjustments can improve the dependability and effectiveness of air battery technology, thereby aiding the progress of sustainable energy storage options.

   11. Chapter 18. Anode Corrosion and Mitigation in Metal–Air Batteries—II (Zn–Air)

       Ramin Khezri, Shiva Rezaei Motlagh, Mohammad Etesami, Ahmad Azmin Mohamad, Soorathep Kheawhom

       Abstract

       This chapter explores the intricate area of zinc–air batteries (ZABs), positioning them as promising candidates for sustainable energy storage. A central theme of the discussion revolves around the critical need to comprehend and alleviate anode corrosion—a pivotal factor that significantly impacts the durability, efficiency, and overall performance of these batteries. The examination within an alkaline medium unravels the complexities of anode corrosion, laying the foundation for a thorough investigation of potential countermeasures. The chapter systematically delves into the underlying mechanisms of anode corrosion in ZABs, containing the hydrogen evolution reaction (HER) and various strategies made to combat the self-corrosion of ZABs. Surface coatings, protective layers, zinc alloys, and composite electrodes emerge as distinct contributions to the arsenal against anode corrosion. Furthermore, the significant impact of electrolyte additives, structural modifications of electrodes, and the profound implications of anode corrosion on battery performance are explained in detail. Mitigating zinc anode corrosion in ZABs is acknowledged as a complex yet imperative endeavor. The insights conveyed throughout this chapter provide a comprehensive toolkit for addressing and limiting this compelling issue in the field of energy storage. As the pursuit of efficient and sustainable energy storage progresses, expertise in managing anode corrosion in ZABs and the ability to mitigate its effects stand out as influential factors in realizing the full potential of these energy reservoirs.

   12. Chapter 19. Electrolyte Additives/Corrosion Inhibitors for Anode Corrosion in Metal–Air Batteries

       M. A. Deyab

       Abstract

       In metal–air batteries, the anode corrosion can be a significant issue that affects the overall performance and lifespan of the battery. To mitigate anode corrosion, electrolyte additives or corrosion inhibitors can be employed. This chapter shows commonly used additives for anode corrosion control in metal–air batteries. It’s important to note that the selection and effectiveness of these additives can vary depending on the specific metal–air battery system and operating conditions. Extensive research and testing are typically conducted to evaluate the performance and compatibility of different additives with the battery components. Furthermore, the concentration, compatibility, and stability of the additives should be carefully considered to avoid any adverse effects on battery performance or other electrochemical processes within the system.

   13. Chapter 20. Approaches to Construct High-Performance Mg–Air Batteries

       Hongxing Liang, Wenhui Yao, Wenbo Du, Liang Wu

       Abstract

       Achieving higher discharge performance in Mg–air batteries has been a persistent challenge. This quest is hindered by issues such as low anodic efficiency and discharge voltage. These challenges arise from the rapid self-corrosion at the anode and the sluggish oxygen reduction reaction at the cathode. This study offers a comprehensive exploration of strategies aimed at enhancing the discharge performance of Mg–air batteries through optimization of both the anode and cathode components. Furthermore, traditional trial-and-error approaches, commonly employed in previous research, are recognized for their inefficiency and time-consuming nature. As a result, this study provides a concise overview of innovative design methodologies, encompassing density-functional theory and machine learning. By gaining a comprehensive understanding of the strengths and weaknesses of these strategies, researchers can more effectively design high-performance anodes and cathodes, thereby expediting the discovery process.

   14. Chapter 21. Corrosion and Its Control in Redox-Flow Batteries

       Xuecheng Chen, Yuping Wu, Rudolf Holze

       Abstract

       Corrosion of metals and carbon in their numerous forms used as functional and auxiliary materials in redox flow batteries is an unwelcome cause of performance degradation, malfunction, and even failure of these devices. The high chemical reactivities of employed redox systems add to the problems. Reported observations, causes of corrosion, and options to control and avoid corrosion are presented in this chapter.

6. Backmatter