High‐Performance SOFC Cathodes Prepared by Infiltration

Improved cathodes are required for low‐temperature operation of solid‐oxide fuel cells (SOFCs). Recent work has shown that electrode fabrication and modification by infiltration of active components into a porous scaffold can result in outstanding electrochemical performance. In this paper we review the literature on this new approach for cathode preparation and discuss the insights that this work has provided for understanding the relationships between the materials properties, electrochemical performance, and electrode stability.     

Carbon‐Nanotube–Polymer Nanocomposites for Field‐Emission Cathodes

The electron field‐emission (FE) characteristics of functionalized single‐walled carbon‐nanotube (CNT)–polymer composites produced by solution processing are reported. It is shown that excellent electron emission can be obtained by using as little as 0.7% volume fraction of nanotubes in the composite. Furthermore by tailoring the nanotube concentration and type of polymer, improvements in the charge transfer through the composite can be obtained. The synthesis of well‐dispersed randomly oriented nanotube–polymer composites by solution processing allows the development of CNT‐based large area cathodes produced using a scalable technology. The relative insensitivity of the cathode's FE characteristics to the electrical conductivity of the composite is also discussed.     

Self‐Activating,Capacitive Anion Intercalation Enables High‐Power Graphite Cathodes

Developing high‐power cathodes is crucial to construct next‐generation quick‐charge batteries for electric transportation and grid applications. However, this mainly relies on nanoengineering strategies at the expense of low scalability and high battery cost. Another option is provided herein to build high‐power cathodes by exploiting inexpensive bulk graphite as the active electrode material, where anion intercalation is involved. With the assistance of a strong alginate binder, the disintegration problem of graphite cathodes due to the large volume variation of >130% is well suppressed, making it possible to investigate the intrinsic electrochemical behavior and to elucidate the charge storage kinetics of graphite cathodes. Ultrahigh power capability up to 42.9 kW kg^?1 at the energy density of >300 Wh kg^?1 (based on graphite mass) and long cycling life over 10 000 cycles are achieved, much higher than those of conventional cathode materials for Li‐ion batteries. A self‐activating and capacitive anion intercalation into graphite is discovered for the first time, making graphite a new intrinsic intercalation‐pseudocapacitance cathode material. The finding highlights the kinetical difference of anion intercalation (as cathode) from cation intercalation (as anode) into graphitic carbon materials, and new high‐power energy storage devices will be inspired.     

Robust,Ultra‐Tough Flexible Cathodes for High‐Energy Li–S Batteries

Sulfur cathodes have become appealing for rechargeable batteries because of their high theoretical capacity (1675 mA h g^?1). However, the conventional cathode configuration borrowed from lithium‐ion batteries may not allow the pure sulfur cathode to put its unique materials chemistry to good use. The solid_(sulfur)–liquid_{(polysulfides)}–solid_(sulfides) phase transitions generate polysulfide intermediates that are soluble in the commonly used organic solvents in Li–S cells. The resulting severe polysulfide diffusion and the irreversible active‐material loss have been hampering the development of Li–S batteries for years. The present study presents a robust, ultra‐tough, flexible cathode with the active‐material fillings encapsulated between two buckypapers (B), designated as buckypaper/sulfur/buckypaper (B/S/B) cathodes, that suppresses the irreversible polysulfide diffusion to the anode and offers excellent electrochemical reversibility with a low capacity fade rate of 0.06% per cycle after 400 cycles. Engineering enhancements demonstrate that the B/S/B cathodes represent a facile approach for the development of high‐performance sulfur electrodes with a high areal capacity of 5.1 mA h cm^?2, which increases further to approach 7 mA h cm^?2 on coupling with carbon‐coated separators.     

Bioinspired Redox‐Active Catechol‐Bearing Polymers as Ultrarobust Organic Cathodes for Lithium Storage

Redox‐active catechols are bioinspired precursors for ortho ‐quinones that are characterized by higher discharge potentials than para ‐quinones, the latter being extensively used as organic cathode materials for lithium ion batteries (LIBs). Here, this study demonstrates that the rational molecular design of copolymers bearing catechol‐ and Li⁺ ion‐conducting anionic pendants endow redox‐active polymers (RAPs) with ultrarobust electrochemical energy storage features when combined to carbon nanotubes as a flexible, binder‐, and metal current collector‐free buckypaper electrode. The importance of the structure and functionality of the RAPs on the battery performances in LIBs is discussed. The structure‐optimized RAPs can store high‐capacities of 360 mA h g^?1 at 5C and 320 mA h g^?1 at 30C in LIBs. The high ion and electron mobilities within the buckypaper also enable to register 96 mA h g^?1 (24% capacity retention) at an extreme C‐rate of 600C (6 s for total discharge). Moreover, excellent cyclability is noted with a capacity retention of 98% over 3400 cycles at 30C. The high capacity, superior active‐material utilization, ultralong cyclability, and excellent rate performances of RAPs‐based electrode clearly rival most of the state‐of‐the‐art Li⁺ ion organic cathodes, and opens up new horizons for large‐scalable fabrication of electrode materials for ultrarobust Li storage.     

Recent Progress of Layered Transition Metal Oxide Cathodes for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) are attracting increasing attention and considered to be a low‐cost complement or an alternative to lithium‐ion batteries (LIBs), especially for large‐scale energy storage. Their application, however, is limited because of the lack of suitable host materials to reversibly intercalate Na⁺ ions. Layered transition metal oxides (Na_xMO₂, M = Fe, Mn, Ni, Co, Cr, Ti, V, and their combinations) appear to be promising cathode candidates for SIBs due to their simple structure, ease of synthesis, high operating potential, and feasibility for commercial production. In the present work, the structural evolution, electrochemical performance, and recent progress of Na_xMO₂ as cathode materials for SIBs are reviewed and summarized. Moreover, the existing drawbacks are discussed and several strategies are proposed to help alleviate these issues. In addition, the exploration of full cells based on Na_xMO₂ cathodes and future perspectives are discussed to provide guidance for the future commercialization of such systems.     

金刚石薄膜阴极电子发射特性研究

宽带隙半导体材料金刚石的负电子亲合势特性使其在电子场发射应用方面备受瞩目。材料的功函数对其热电子发射或场电子发射都有决定性的影响。本文从热电子发射的角度出发 ,对钨基金刚石薄膜阴极有效功函数进行了测量。文章阐述了实验方法、装置及结果 ,测得金刚石涂层阴极的有效功函数为 0 70eV ,并对实验结果进行了理论分析     

Role of Redox‐Inactive Transition‐Metals in the Behavior of Cation‐Disordered Rocksalt Cathodes

Owing to the capacity boost from oxygen redox activities, Li‐rich cation‐disordered rocksalts (LRCDRS) represent a new class of promising high‐energy Li‐ion battery cathode materials. Redox‐inactive transition‐metal (TM) cations, typically d⁰ TM, are essential in the formation of rocksalt phases, however, their role in electrochemical performance and cathode stability is largely unknown. In the present study, the effect of two d⁰ TM (Nb⁵⁺ and Ti⁴⁺) is systematically compared on the redox chemistry of Mn‐based model LRCDRS cathodes, namely Li_1.3Nb_0.3Mn_0.4O₂ (LNMO), Li_1.25Nb_0.15Ti_0.2Mn_0.4O₂ (LNTMO), and Li_1.2Ti_0.4Mn_0.4O₂ (LTMO). Although electrochemically inactive, d⁰ TM serves as a modulator for oxygen redox, with Nb⁵⁺ significantly enhancing initial charge storage contribution from oxygen redox. Further studies using differential electrochemical mass spectroscopy and resonant inelastic X‐ray scattering reveal that Ti⁴⁺ is better in stabilizing the oxidized oxygen anions (O^n?, 0 < n < 2), leading to a more reversible O redox process with less oxygen gas release. As a result, much improved chemical, structural and cycling stabilities are achieved on LTMO. Detailed evaluation on the effect of d⁰ TM on degradation mechanism further suggests that proper design of redox‐inactive TM cations provides an important avenue to balanced capacity and stability in this newer class of cathode materials.