Rechargeable Organic Batteries (eBook)

Materials, Mechanisms, and Prospects

Yongzhu Fu, Xiang Li, Shuai Tang, Wei Guo (Autoren)

eBook Download: EPUB

2024 | 1. Auflage
304 Seiten
Wiley-VCH (Verlag)
978-3-527-83912-4 (ISBN)

Infos

A must-have reference on sustainable organic energy storage systems

Organic electrode materials have the potential to overcome the intrinsic limitations of transition metal oxides as cathodes in rechargeable batteries. As promising alternatives to metal-based batteries, organic batteries are renewable, low-cost, and would enable a greener rechargeable world.

Rechargeable Organic Batteries is an up-to-date reference and guide to the next generation of sustainable organic electrodes. Focused exclusively on organic electrode materials for rechargeable batteries, this unique volume provides comprehensive coverage of the structures, advantages, properties, reaction mechanisms, and performance of various types of organic cathodes.

In-depth chapters examine carbonyl-, organosulfur-, radical-, and organometallic complexes, as well as polymer-based active materials for electrochemical energy storage (EES) technologies. Throughout the book, possible application cases and potential challenges are discussed in detail.

• Presents advanced characterization methods for verifying redox mechanisms of organic materials
• Examines recent advances in carbonyl-based small-molecule cathode materials in battery systems including lithium-ion, sodium-ion, and aqueous zinc-ion batteries
• Introduces organosulfide-inorganic composite cathodes with high electrical conductivity and fast reaction kinetics
• Outlines research progress on radical electrode materials, polymer-based organic cathode materials, and the development of all-organic batteries
• Summarizes the synthesis processes, redox mechanisms, and electrochemical performance of different kinds of organic anode materials for metal-ion batteries

Featuring a general introduction to organic batteries, including a discussion of their necessity and advantages, Rechargeable Organic Batteries is essential reading for electrochemists, materials scientists, organic chemists, physical chemists, and solid-state chemists working in the field.

Yongzhu Fu, Professor, FRSC, FIAAM, College of Chemistry, Zhengzhou University, People's Republic of China. Dr. Fu obtained his Ph.D. at the University of Texas at Austin in 2007 in the United States and was an Assistant Professor at Indiana University-Purdue University Indianapolis before he joined Zhengzhou University in 2017. His current research focuses on the development and applications of advanced materials for rechargeable metal, lithium-ion, sodium-ion, and redox flow batteries. He has published more than 180 peer-reviewed papers in scientific journals.

Textauszug

1
Necessity and Advantages of Developing Rechargeable Organic Batteries

1.1 Current Electrochemical Energy Storage Technologies

Li-ion battery (LIB) is well known as one of the electrochemical energy storage (EES) technologies, which can be seen in our daily lives, such as portable equipment and electric vehicles. LIBs have made great progress in the last 30 years, which can be traced back to 1991, when the first reversible LIB was commercialized by Sony Corp. [1]. The battery is based on LiCoO2, graphite, and ester-solvents with LiPF6 [2, 3]. Afterward, a series of ternary LiNixCoyMnzO2 (NCM, x + y + z = 1) and LiFePO4 spring out, considering the aspects of energy density and security [4–11]. Prior to LIBs, actually, lithium metal batteries (LMBs) were commercialized by Moli Energy Corp., based on lithium metal and metal sulfide as negative and positive electrodes, respectively [12]. However, the battery was in a tailspin after several safety incidents due to the lithium dendrites, which are easily generated after cycling [13, 14]. Note that for the discovery and development of LIBs, John B. Goodenough, M. Stanley Whittingham, and Akira Yoshino were awarded the 2019 Nobel Prize in Chemistry.

Similar to LIB, sodium-ion battery (SIB) is also one of the state-of-the-art EES technologies. Actually, SIBs have a longer history compared with LIBs, with the layered oxides discovered toward the end of the 1960s [15, 16]. Considering the limited Li resource, SIB is a suitable alternative EES due to the relatively abundant Na resource (420 times more than Li). It is noted that the oxides NaxMO2 (M = 3d element) have some special structure by regulating deficient sodium [17–20], such as O2, O3, P2, and P3 types, according to the structural packing described by Delmas [17]. Therefore, the electrochemical performance can be modified in Na-based oxides, which has an evident advantage compared with the Li-based oxides used for LIBs. The energy density of SIB could climb to 200 Wh kg−1, as reported by Hu’s group, which is a breakthrough [21]. However, the energy density is still limited with respect to LIBs, which could deliver over 300 Wh kg−1 [22].

The good news is that SIBs have been commercialized by some Chinese companies such as CATL Corp. and HiNa Battery Corp. Given the energy density difference among the typical EES, the different battery systems aim for different market orientation to share the energy pressure. For example, lead-acid batteries, Ni–Cd batteries, and supercapacitors are used for devices with short mileage or low energy density, which are still required by the market. Nonetheless, both LIBs and SIBs cannot satisfy our demand in the long term, considering the resource crisis accompanied by high costs and pollution. Moreover, the traditional batteries are restricted to a sealed system and organic electrolytes (aqueous electrolytes are still facing great difficulties [23, 24]). Herein, we need a new EES without (or with mitigatory) the concerns.

A rechargeable organic battery is a good choice because the active materials are low cost, and the battery has comparable energy density when compared with LIB and SIB [25–31]. Moreover, the properties of organic materials can be controlled by different functional groups, such as the charge/discharge potential, the reaction dynamics, and the structural stability [32–37]. Furthermore, the system is unrestricted which can be used in an aqueous system, typically redox flow batteries (RFBs) [38–42]. Actually, the organic battery has been studied for over 60 years [43]. At the initial stage, the electrochemical performance of the organic material is poor with an ambiguous reaction mechanism, which impedes the development of the battery. In recent years, the corresponding published papers have a manifest rising tendency which can be seen in Figure 1.1, which partially benefits from technological advancements and several outstanding contributions made by Chen’s group and Schubert’s group since 2012 [44–69]. Now, there are many kinds of organics with active centers based on O, N, and S, enriching the family of organic batteries, which could compete with the traditional metal-ion batteries.

Figure 1.1 Published papers per year for the rechargeable organic batteries with keywords such as organic electrode, organic cathode, and organic battery. The time of the statistics is April 2023.

1.2 Rechargeable Organic Batteries

Organic batteries show different mechanisms from the typical LIBs, which mainly include insertion/extraction (LiCoO2, NCM, etc.), alloying (Al, Si, etc.), and conversion mechanism (O, P, S-based composites, etc.) [70–79]. For the organic electrodes, the mechanism usually contains the repeated breaking and bonding of a bond (carbonyl, organosulfide, and radical materials in Chapter 2). A single bond (typically S—S bond) is broken during discharge, after which the broken bond receives an electron and bonds with a metal ion for charge balance. A double bond (typically carbonyl units) shows a similar mechanism. Note that during the reaction, radical materials are usually generated which has been applied in RFBs due to the fast kinetics [80–82]. There seems to be another mechanism not involved in bond breaking, which is based on electron transfer and anion compensation (typically N-containing active materials) [83].

The first investigation of organic materials is carbonyl compounds, which can be traced back to the 1960s [43]. However, the material shows high solubility in aprotic electrolytes, restricting the application although some other carbonyl composites are constructed [32]. Afterward, the direction was turned to conductive polymers in the 1970s because of their less solubility, such as polyacetylene and polypyrrole [83–89]. Unfortunately, these electrodes suffered from limited capacity due to incomplete reaction [88, 89]. A revival emerged when Armand and Tarascon depicted a bright future for organic batteries, attracting more attention [28]. Encouragingly, molecules with popular functional groups (quinones, carboxylates, radical centers, etc.) and other redox-active centers (imines, alkenes, alkynes, azo, etc.) have been investigated [90–97].

Another typical organic material is organosulfide with S as the redox center. Visco et al. initially studied tetraethyl thiuram disulfide (TETD) in 1988 [98]. However, the electrode delivered poor electrochemical performance, which cannot be used in a battery. Actually, the research of organosulfide battery mainly focused on polysulfides from the 1980s to 2015, such as naphtho[1,8-cd][1,2]dithiol and dibenzo[c,e][1,2]dithiin, which have not attracted full attention [99, 100]. The polysulfides have a large specific capacity (over 300 mAh g−1), however, with poor stability due to the rigid framework in which the S—S bonds suffer from breaking and painful bonding, deteriorating the original structure which can be only used for lithium primary battery. Afterward, organosulfide with small molecule was investigated. However, the materials were considered hopeless because they easily dissolved into the electrolyte, leading to a shuttle effect that normally appeared in Li–S batteries. Until 2016, dimethyl trisulfide (DMTS) [101] was successfully applied in organic batteries with a reversible charge/discharge process (with 849 mAh g−1) and cycling performance (50 cycles) with the assistance of a carbon paper which was also proposed for polysulfide in 2013 [102]. The creative idea has opened a broad perspective for the research of small-molecule organosulfur [103–111]. Hereafter, molecules with more sulfur content (–Sn–) were studied to modify the specific capacity [112–116]. The performance of organosulfur can be regulated by heteroatom doping (such as Se, Te), combination with metal sulfides for good conductivity and stability, and the application of RFBs [117–126].

1.3 Goal, Scope, and Organization of this Book

It is obvious that a consequent and growing amount of literature is now easily available on organic batteries after years of silence. There is room for reversible electroactive organic systems in the future EES landscape in view of the application. However, it must be noted that there exists a certain disciplinary boundary between inorganic and organic compounds because the redox chemistry of organics is different from that of typical LIBs, making it challenging for nonspecialist readers when dealing with organic batteries. Therefore, it would be timely to provide a kind of “tutorial”-oriented book for a broader audience. Based on the latest selected and reliable data from both general and specialized scientific literature, this contribution also aims at providing the readers with a better understanding of the consecutive global demand for electrical energy sources and the evolution trends of organic batteries.

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Produkt-Details

• Erscheint lt. Verlag: 14.3.2024
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie
• ISBN-10: 3-527-83912-7 / 3527839127
• ISBN-13: 978-3-527-83912-4 / 9783527839124