There is an urgent global need for electrochemical energy storage that includes materials that can provide simultaneous high power and high energy density One strategy to achieve this goal is with pseudocapacitive materials that take advantage of reversible surface or near-surface Faradaic reactions to store charge This allows them to surpass the capacity limitations of electrical double-layer capacitors and the mass transfer limitations of batteries The past decade has seen tremendous growth in the understanding of pseudocapacitance as well as materials that exhibit this phenomenon The purpose of this Review is to examine the fundamental development of the concept of pseudocapacitance and how it came to prominence in electrochemical energy storage as well as to describe new classes of materials whose electrochemical energy storage behavior can be described as pseudocapacitive

Pseudocapacitance: From Fundamental Understanding to High Power Energy Storage Materials

The exponential increase in research focused on two-dimensional (2D) metal oxides has offered an unprecedented opportunity for their use in energy conversion and storage devices, especially for promising next-generation rechargeable batteries, such as lithium-ion batteries (LIBs) and sodium-ion batteries (NIBs), as well as some post-lithium batteries, including lithium–sulfur batteries, lithium–air batteries, etc. The introduction of well-designed 2D metal oxide nanomaterials into next-generation rechargeable batteries has significantly enhanced the performance of these energy-storage devices by providing higher chemically active interfaces, shortened ion-diffusion lengths, and improved in-plane carrier-/charge-transport kinetics, which have greatly promoted the development of nanotechnology and the practical application of rechargeable batteries. Here, the recent progress in the application of 2D metal oxide nanomaterials in a series of rechargeable LIBs, NIBs, and other post lithium-ion batteries is reviewed relatively comprehensively. Current opportunities and future challenges for the application of 2D nanomaterials in energy-storage devices to achieve high energy density, high power density, stable cyclability, etc. are summarized and outlined. It is believed that the integration of 2D metal oxide nanomaterials in these clean energy devices offers great opportunities to address challenges driven by increasing global energy demands.

Two-Dimensional Metal Oxide Nanomaterials for Next-Generation Rechargeable Batteries.

Owing to the excellent abundance and availability of sodium reserves, sodium ion batteries (NIBs) show great promise for meeting the material supply and cost demands of large-scale energy storage systems (ESSs) used for the application of renewable energy sources and smart grids. However, the cost advantages of stationary NIBs alone are not enough to ensure their commercial success. In this review, we summarize the emerging attractive characteristics of stationary NIBs, such as high-rate capability, all-climate operation, and full-battery recyclability. Together with inherent cost advantages, these merits have resulted in an excellent compatibility between stationary NIBs and large-scale ESSs that dictates their validity in practical applications. Representative electrode materials are highlighted to illustrate advances in corresponding features. The insights presented in this review can inspire further research interest into NIB design and serve as a guide for the application of NIBs in large-scale stationary energy storage.

Exploring competitive features of stationary sodium ion batteries for electrochemical energy storage

Electrochemical capacitors (ECs) that store charge based on the pseudocapacitive mechanism combine high energy densities with high power densities and rate capabilities. 2D transition metal carbides (MXenes) have been recently introduced as high-rate pseudocapacitive materials with ultrahigh areal and volumetric capacitances. So far, 20 different MXene compositions have been synthesized and many more are theoretically predicted. However, since most MXenes are chemically unstable in their 2D forms, to date only one MXene composition, Ti3 C2 Tx , has shown stable pseudocapacitive charge storage. Here, a cation-driven assembly process is demonstrated to fabricate highly stable and flexible multilayered films of V2 CTx and Ti2 CTx MXenes from their chemically unstable delaminated single-layer flakes. The electrochemical performance of electrodes fabricated using assembled V2 CTx flakes surpasses Ti3 C2 Tx in various aqueous electrolytes. These electrodes show specific capacitances as high as 1315 F cm-3 and retain ≈77% of their initial capacitance after one million charge/discharge cycles, an unprecedented performance for pseudocapacitive materials. This work opens a new venue for future development of high-performance supercapacitor electrodes using a variety of 2D materials as building blocks.

Assembling 2D MXenes into Highly Stable Pseudocapacitive Electrodes with High Power and Energy Densities.

Inactive lithium (more frequently called dead lithium) in the forms of solid–electrolyte interphase and electrically isolated metallic lithium is principally responsible for the performance decay commonly observed in lithium metal batteries. A fundamental solution of recovering dead lithium is urgently needed to stabilize lithium metal batteries. Here we quantify the solid–electrolyte interphase components, and determine their relation with the formation of electrically isolated dead lithium metal. We present a lithium restoration method based on a series of iodine redox reactions mainly involving I3−/I−. Using a biochar capsule host for iodine, we show that the I3−/I− redox takes place spontaneously, effectively rejuvenating dead lithium to compensate the lithium loss. Through this design, a full-cell using a very limited lithium metal anode exhibits an excellent lifespan of 1,000 cycles with a high Coulombic efficiency of 99.9%. We also demonstrate the design with a commercial cathode in pouch cells. Cycling lithium batteries often results in inactive lithium that no longer participates in redox reactions, leading to performance deterioration. Here the authors use an iodic species to react with inactive lithium, bringing it back to life and thus making batteries last longer.

Rejuvenating dead lithium supply in lithium metal anodes by iodine redox

Graphitic carbons have been used as conductive supports for developing rechargeable batteries. However, the classic ion intercalation in graphitic carbon has yet to be coupled with extrinsic redox reactions to develop rechargeable batteries. Herein, we demonstrate the preparation of a free-standing, flexible nitrogen and phosphorus co-doped hierarchically porous graphitic carbon for iodine loading by pyrolysis of polyaniline coated cellulose wiper. We find that heteroatoms could provide additional defect sites for encapsulating iodine while the porous carbon skeleton facilitates redox reactions of iodine and ion intercalation. The combination of ion intercalation with redox reactions of iodine allows for developing rechargeable iodine–carbon batteries free from the unsafe lithium/sodium metals, and hence eliminates the long-standing safety issue. The unique architecture of the hierarchically porous graphitic carbon with heteroatom doping not only provides suitable spaces for both iodine encapsulation and cation intercalation but also generates efficient electronic and ionic transport pathways, thus leading to enhanced performance. Carbon-based electrodes able to intercalate Li+ and Na+ ions have been exploited for high performing energy storage devices. Here, the authors combine the ion intercalation properties of porous graphitic carbons with the redox chemistry of iodine to produce iodine–carbon batteries with high reversible capacities.

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A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry

Lithium metal is considered as the most promising anode material due to its high theoretical specific capacity and the low electrochemical reduction potential. However, severe dendrite problems have to be addressed for fabricating stable and rechargeable batteries (e.g., lithium-iodine batteries). To fabricate a high-performance lithium-iodine (Li-I2 ) battery, a 3D stable lithium metal anode is prepared by loading of molten lithium on carbon cloth doped with nitrogen and phosphorous. Experimental observations and theoretical calculation reveal that the N,P codoping greatly improves the lithiophilicity of the carbon cloth, which not only enables the uniform loading of molten lithium but also facilitates reversible lithium stripping and plating. Dendrites formation can thus be significantly suppressed at a 3D lithium electrode, leading to stable voltage profiles over 600 h at a current density of 3 mA cm-2 . A fuel cell with such an electrode and a lithium-iodine cathode shows impressive long-term stability with a capacity retention of around 100% over 4000 cycles and enhanced high-rate capability. These results demonstrate the promising applications of 3D stable lithium metal anodes in next-generation rechargeable batteries.

A 3D and Stable Lithium Anode for High-Performance Lithium-Iodine Batteries.

The rapid development of advanced energy-storage devices requires significant improvements of the electrode performance and a detailed understanding of the fundamental energy-storage processes. In this work, the self-assembly of two-dimensional manganese oxide nanosheets with various metal cations is introduced as a general and effective method for the incorporation of different guest cations and the formation of sandwich structures with tunable interlayer distances, leading to the formation of 3D Mx MnO2 (M=Li, Na, K, Co, and Mg) cathodes. For sodium and lithium storage, these electrode materials exhibited different capacities and cycling stabilities. The efficiency of the storage process is influenced not only by the interlayer spacing but also by the interaction between the host cations and shutter ions, confirming the crucial role of the cations. These results provide promising ideas for the rational design of advanced electrodes for Li and Na storage.

Ziyu Hu

Papers

A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry

A 3D and Stable Lithium Anode for High-Performance Lithium-Iodine Batteries.

Cation Intercalation in Manganese Oxide Nanosheets: Effects on Lithium and Sodium Storage.