Electrochemistry represents one of the most intimate ways of interacting with molecules. This review discusses advances in synthetic organic electrochemistry since 2000. Enabling methods and synthetic applications are analyzed alongside innate advantages as well as future challenges of electroorganic chemistry.

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

As an alternative to conventional inorganic intercalation electrode materials, organic electrode materials are promising candidates for the next generation of sustainable and versatile energy storage devices. In this paper we provide an overview of organic electrode materials, including their fundamental knowledge, development history and perspective applications. Based on different organics including n-type, p-type and bipolar, we firstly analyzed their working principles, reaction mechanisms, electrochemical performances, advantages and challenges. To understand the development history and trends in organic electrode materials, we elaborate in detail various organics with different structures, including conducting polymers, organodisulfides, thioethers, nitroxyl radical polymers and conjugated carbonyl compounds. The high electrochemical performance, in addition with the unique features of organics such as flexibility, processability and structure diversity, provide them great perspective in various energy storage devices, including rechargeable Li/Na batteries, supercapacitors, thin film batteries, aqueous rechargeable batteries, redox flow batteries and even all-organic batteries. It is expected that organic electrode materials will show their talents in the “post Li-ion battery” era, towards cheap, green, sustainable and versatile energy storage devices.

Towards sustainable and versatile energy storage devices: an overview of organic electrode materials

4.2. Solid-Supported Electrolytes 2280 4.3. Solid-Supported Mediators 2282 4.4. Supported Substrate-Product Capture 2283 4.5. A Unique Electrolyte/Solvent System 2285 5. Reaction Conditions 2285 5.1. Supercritical Fluids 2285 5.1.1. Electrochemical Properties of scCO2 2285 5.1.2. Electroreductive Carboxylation in scCO2 2286 5.1.3. Electrochemical Polymerization in scCO2 2286 5.2. The Cation-Pool Method 2286 5.2.1. Generation of N-Acyliminium Ion Pools 2286 5.2.2. Generation of Alkoxycarbenium Ion Pools 2287 5.2.3. Generation of Diarylcarbenium Ion Pools 2288 5.2.4. Generation of Other Cation Pools 2289 6. Electrochemical Devices 2289 6.1. Electrode Materials 2289 6.2. Ultrasound and Centrifugal Fields 2290 6.3. Electrochemical Microflow Systems 2290 7. Combinatorial Electrochemical Synthesis 2292 7.1. Parallel Electrolysis Using a Macrosystem 2292 7.2. Parallel Electrolysis Using a Microsystem 2293 7.3. Serial Electrolysis Using a Microsystem 2294 8. Conclusions 2294 9. Acknowledgments 2294 10. References 2294

Modern Strategies in Electroorganic Synthesis

Sodium-ion batteries (SIBs) receive significant attention for electrochemical energy storage and conversion owing to their wide availability and the low cost of Na resources. However, SIBs face challenges of low specific energy, short cycling life, and insufficient specific power, owing to the heavy mass and large radius of Na(+) ions. As an important component of SIBs, cathode materials have a significant effect on the SIB electrochemical performance. The most recent advances and prospects of inorganic and organic cathode materials are summarized here. Among current cathode materials, layered transition-metal oxides achieve high specific energies around 600 mW h g(-1) owing to their high specific capacities of 180-220 mA h g(-1) and their moderate operating potentials of 2.7-3.2 V (vs Na(+) /Na). Porous Na3 V2 (PO4 )3 /C nanomaterials exhibit excellent cycling performance with almost 100% retention over 1000 cycles owing to their robust structural framework. Recent emerging cathode materials, such as amorphous NaFePO4 and pteridine derivatives show interesting electrochemical properties and attractive prospects for application in SIBs. Future work should focus on strategies to enhance the overall performance of cathode materials in terms of specific energy, cycling life, and rate capability with cationic doping, anionic substitution, morphology fabrication, and electrolyte matching.

Recent Advances and Prospects of Cathode Materials for Sodium‐Ion Batteries

The storage of electric energy is of ever growing importance for our modern, technology-based society, and novel battery systems are in the focus of research. The substitution of conventional metals as redox-active material by organic materials offers a promising alternative for the next generation of rechargeable batteries since these organic batteries are excelling in charging speed and cycling stability. This review provides a comprehensive overview of these systems and discusses the numerous classes of organic, polymer-based active materials as well as auxiliary components of the battery, like additives or electrolytes. Moreover, a definition of important cell characteristics and an introduction to selected characterization techniques is provided, completed by the discussion of potential socio-economic impacts.

Polymer-Based Organic Batteries

Organic rechargeable batteries have received significant research interest from the viewpoints of structural diversity and sustainability of electrode materials. We designed core structures of organic cathode materials for lithium-ion (Li-ion) batteries based on density functional theory (DFT) calculations, which indicated that six-membered cyclic 1,2-diketones serve as excellent core structures because of the high redox energy change resulting from favorable coordination of the oxygen atoms to Li and the aromaticity of the reduced form. Here, we show that the Li-ion battery composed of pyrene-4,5,9,10-tetraone (PYT), which has two six-membered cyclic 1,2-diketone units, bound to polymethacrylate exhibits remarkable charge–discharge properties with a high specific capacity of 231 mAh/g, excellent rechargeability (83% of the capacity retained after 500 cycles), and charge–discharge ability (90% of the capacity at 30 C as compared to 1 C) in the LiNTf2/tetraglyme ionic-liquid system.

Polymer-bound pyrene-4,5,9,10-tetraone for fast-charge and -discharge lithium-ion batteries with high capacity.

Glycosyl triflates, which serve as important intermediates in glycosylation reactions, were generated and accumulated by the low-temperature electrochemical oxidation of thioglycosides such as thioglucosides, thiogalactosides, and thiomannosides in the presence of tetrabutylammonium triflate (Bu4NOTf) as a supporting electrolyte. Thus-obtained solutions of glycosyl triflates (glycosyl triflate pools) were characterized by low-temperature NMR measurements. The thermal stability of glycosyl triflates and their reactions with glycosyl acceptors were also examined.

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Electrochemical generation of glycosyl triflate pools.

An iterative method for molecular assembly has been developed based on the cation-pool method using (trimethylsilyl)diphenylmethane as a building block. The silyl group works as both an activating group of the benzene ring in the Friedel−Crafts type reaction and an electroauxiliary in the subsequent low temperature anodic oxidation to generate dendritic diarylcarbenium ions, which were well characterized by low-temperature NMR spectroscopy. The convergent synthesis of dendritic molecules has been achieved by repeating the sequence.

Iterative Molecular Assembly Based on the Cation-Pool Method. Convergent Synthesis of Dendritic Molecules

We have found that tetrabutylammonium triflate (Bu4NOTf) serves as an effective electrolyte for electrochemical glycosylation using thioglycosides. Based on this method, a one-pot electrochemical g...

Hiroaki Tsuyama

Papers

Polymer-bound pyrene-4,5,9,10-tetraone for fast-charge and -discharge lithium-ion batteries with high capacity.

Electrochemical generation of glycosyl triflate pools.

Iterative Molecular Assembly Based on the Cation-Pool Method. Convergent Synthesis of Dendritic Molecules

Oligosaccharide Synthesis Based on a One-pot Electrochemical Glycosylation–Fmoc Deprotection Sequence