Kinetics Of Redox Reactions Research Articles

Alternating 3rd- to 2nd-Order Charge Reaction Kinetics on Bismuth Vanadate Photoanodes with Ultrathin Bismuth Metal-Organic-Frameworks.

The most challenging obstacle for photocatalysts to efficiently harvest solar energy is the sluggish surface redox reaction (e. g., oxygen evolution reaction, OER) kinetics, which is believed to originate from interface catalysis rather than the semiconductor photophysics. In this work, we developed a light-modulated transient photocurrent (LMTPC) method for investigating surface charge accumulation and reaction on the W-doped bismuth vanadate (W : BiVO4) photoanodes during photoelectrochemical water oxidation. Under illuminating conditions, the steady photocurrent corresponds to the charge transfer rate/kinetics, while the integration of photocurrent (I~t) spikes during the dark period is regarded as the charge density under illumination. Quantitative analysis of the surface hole densities and photocurrents at 0.6 V vs. reversible hydrogen electrode results in an interesting rate-law kinetics switch: a 3rd-order charge reaction behavior appeared on W : BiVO4, but a 2nd-order charge reaction occurred on W : BiVO4 surface modified with ultrathin Bi metal-organic-framework (Bi-MOF). Consequently, the photocurrent for water oxidation on W : BiVO4/Bi-MOF displayed a 50 % increment. The reaction kinetics alternation with new interface reconstruction is proposed for new mechanism understanding and/or high-performance photocatalytic applications.

Highly Conductive Quasi‐1D Hexagonal Chalcogenide Perovskite Sr8Ti7S21 with Efficient Polysulfide Regulation in Lithium‐Sulfur Batteries

AbstractLithium‐sulfur batteries (LSBs) are regarded as one of the most promising candidates for next‐generation energy storage systems. However, the commercialization of LSBs is still hindered by several technical issues, including the notorious polysulfide migration from the cathode to the anode and the sluggish sulfur conversion kinetics. Herein, a quasi‐1D hexagonal chalcogenide perovskite, Sr8Ti7S21, is demonstrated as an efficient sulfur host able to overcome these limitations. Experimental results and density functional theory calculations show Sr8Ti7S21 to offer strong lithium polysulfides (LiPS) binding through multiple bond formation. Besides, Sr8Ti7S21 effectively facilitates the kinetics of the LiPS redox reaction. As a result, S@Sr8Ti7S21‐based cathodes exhibit excellent initial capacities up to 1315 mAh g−1 at 0.2C, impressive cycling stability with an average capacity decay rate of 0.08% per cycle over 400 cycles at 1C, and a high areal capacity of 6.58 mAh cm−2 under a high sulfur loading of 6.5 mg cm−2. This work reveals the potential capabilities and promising prospects of chalcogenide perovskites in advancing LSBs technology.

A Highly Effective Polysulfide-Trapping Approach for the Development of High Energy Density, Scalable Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are identified as one of the most promising next-generation battery technologies owing to their high theoretical specific energy, sustainability, and affordability. However, the commercialization of Li-S batteries has been hindered by severe technical challenges, including the lithium polysulfide (PS) dissolution/shuttling effect, a major cause of fast capacity degradation over cycling. We demonstrated that, for the first time, nanolayer polymer coated high surface area porous carbons (NPCs) were coated directly on sulfur electrodes (NPC-S), which led to a high specific capacity of ∼1,600 mAh g−1 approaching the theoretical specific capacity limit in the NPC-S based Li-S batteries. The NPC-S based Li-S batteries maintained their large initial specific capacity gain compared with the Baseline-S based Li-S batteries (control) over extended cycles. A follow-on study indicated that the NPC-S approach is a necessary and critical step to boost the near-theoretical specific capacity while being stabilized over long cycles with a synergistic strategy. Our experimental and computational results suggest that NPC coated on sulfur electrodes provides not only an effective and strong PS-trapping power but also an increased redox reaction kinetics for sulfur ↔ PS’s conversions during battery charge and discharge, rendering the realization of near-theoretical discharge specific capacity in the NPC-S based Li-S batteries. The findings presented in this study may inspire a new, simple, low-cost, and commercially scalable approach, without adding any appreciable dead weight or volume to the batteries, in the effort to tackle the technical challenges facing SOA Li-S batteries.

Mn and N-doped RGO as a sulfur hosting accelerate electron transfer and redox reactions for Li–S batteries

The notorious polysulfides shuttling and slow redox reaction kinetics largely limit the Li–S battery commercial application as an effective energy storage system. In this report, Mn/N catalysts were co-doped on a high specific surface area reduced graphene oxide (RGO) scaffold by a simple formamide media-assisted method to develop the sulfur holding material for Li–S battery. The N-doped RGO with conductive layer structure not only facilitates the ion and electron transfer, but also provides superb reservoir space for sulfur volume expansion and intermediate polysulfides. Moreover, the introduction of Mn metal catalysts both paly the roles of chemical trappers and electrocatalysts to chemically anchor the polysulfides and accelerate the redox kinetics. It is a promising holding material to improve the reutilization of the polysulfides and suppression of the shuttle effect in lithium-sulfur batteries. As a result, the high initial discharge capacity for the Mn-NG modified Li–S battery is about 1124.7 mAh g−1 at 0.2 C, which can still reach to 914.3 mAh g−1 after 100 cycles, with a retention rate up to 81%. We believe that our method offers a significant approach to prepare multi-functional sulfur hosts for high performance Li–S batteries.

Rational Design of Naphthol Groups Functionalized Bipolar Polymer Cathodes for High Performance Alkali-Ion Batteries.

Redox-active organic compounds gather significant attention for their potential application as electrodes in alkali ion batteries, owing to the structural versatility, environmental friendliness, and cost-effectiveness. However, their practical applications of such compounds are impeded by insufficient active sites with limited capacity, dissolution in electrolytes, and sluggish kinetics. To address these issues, a naphthol group-containing triarylamine polymer, namely poly[6,6'-(phenylazanediyl)bis(naphthol)] (poly(DNap-OH)) is rationally designed and synthesized, via oxidative coupling polymerization. It is capable of endowing favorable steric structures that facilitate fast ion diffusion, excellent chemical stability in organic electrolytes, and additional redox-active sites that enable a bipolar redox reaction. By exploiting these advantages, poly(DNap-OH) cathodes demonstrate remarkable cycling stability in both lithium-ion batteries (LIBs) and potassium-ion batteries (PIBs), showcasing enhanced specific capacity and redox reaction kinetics in comparison to the conventional poly(4-methyltriphenylamine) cathodes. Overall, this work offers insights into molecular design strategies for the development of high-performance organic cathodes in alkali-ion batteries.

Construction of binary metal sulfide nanoparticles to boost catalytic activity for lithium-sulfur batteries

Lithium-sulfur batteries (LSBs) are considered viable options for the next generation of energy storage devices owing to their remarkable theoretical advantages.However, the further practical implementation the LSBs is hindered by certain challenges, including the shuttle effect and the slow reaction kinetics associated with soluble lithium polysulfides (LiPSs). Herein, Co9S8–MoS2/PC nanoparticles with a polyhedral structure are designed as effective host materials to tackle these challenges.The electrocatalysis activity of Co9S8–MoS2/PC nanoparticles can be maximized via tuning the ratio of metal ions in the precursor. The experimental results reveal that Co9S8–MoS2/PC nanoparticles could enhance the transfer of electrons and ions, reinforce the interaction with LiPSs, and accelerate the redox reaction kinetics of LiPSs. The LSBs with optimal S@Co9S8–MoS2/PC(5:1) cathode achieve an enhanced rate capability, a high specific capacity, and long cycle life with a capacity decay of 0.059 % per cycle over 500 cycles at 0.5C. This work demonstrates the great potential of binary metal sulfide nanoparticles for the effective conversion of LiPSs in LSBs.

Preparation and application of NiS2/NiSe2 heterostructure as a sulfur host in lithium-sulfur batteries

The introduction of heterostructure in the cathode material of Li-S battery is an effective method to improve the redox reaction kinetics and suppress the shuttle effect of polysulfide. A metal sulfide/metal selenide (NiS2/NiSe2) heterostructure with hollow tetrahedral structure is prepared as a sulfur host of lithium-sulfur batteries. The prepared NiS2/NiSe2 heterostructure exhibits efficient charge transfer at the heterojunction interface, thereby enhancing catalytic activity for redox reactions of polysulfides and facilitating their rapid conversion. Moreover, the unique hollow tetrahedral structure, along with abundant surface pores, enables high sulfur loading capacity, providing abundant electrochemical reaction sites to enhance sulfur utilization efficiency. The results demonstrate that the NiS2/NiSe2 heterostructure material exhibits a remarkable initial capacity of 1338.9 mAh/g at 0.2 C, along with exceptional cycling stability (maintaining a capacity of 517.6 mAh/g after 200 cycles at 0.2 C, with only a negligible decay rate of 0.3% per cycle, retaining a capacity of 462.6 mAh/g after 500 cycles at 1 C, with an insignificant decay rate of merely 0.12% per cycle). The facile preparation of this NiS2/NiSe2 heterostructure not only enables the realization of lithium-sulfur batteries with exceptional capacity, but also opens up broader avenues for exploring high-performance heterogeneous materials.

Boosted charge separation via Ce2S3 over dual Z-scheme ZnO–Ce2S3–MnO2 core double-shell nanocomposite for the degradation of diverse dye pollutants

Herein, core double-shell direct dual Z-scheme ZnO–Ce2S3–MnO2 nanocomposite was synthesized via a hydrothermal route along with pure ZnO, Ce2S3, MnO2, and characterized by numerous characterization tools for application in synthetic dyes degradation. The XRD, Raman, and FTIR analyses have confirmed the nanocomposite formation. TEM images exhibited the core double-shell morphology with an average particle diameter of 81 nm and stacking of ZnO, Ce2S3, and MnO2. EDX confirmed the existence of desired elements in the grown composition. The varied oxidation states, presence of defects, and fast charge transfer were also revealed from XPS, PL, and EIS. The ZnO–Ce2S3–MnO2 nanocomposite has an optical energy bandgap of 2.84 eV, capable of decomposing harmful dyes with excellent efficiency, 99.81% MB, 97.62% MO, 88.5% MR, and 58.9% EY in 40 min sunlight exposure. The effect of several operating parameters is also observed and obtained results showed the optimal catalyst dose was 20 mg, pH of 8, and dye concentration of 10 ppm. The scavenger's experiment suggests that •O2− and •OH are the main active radicals in the photodegradation reaction which is also evident in the dual Z-scheme formation. The MnO2 and ZnO layers covered the Ce2S3 (core) and dual Z-scheme formation allows rapid kinetics of redox reaction and provides plenteous channels for transfer of photo-generated charge carriers during photocatalysis. Thus, core double-shell direct dual Z-scheme photocatalysts having inorganic components could be an excellent choice for photocatalysis at the industrial level, particularly for water purification.

A green and cost-effective zinc-biphenol hybrid flow battery with eutectic electrolyte

Eutectic electrolytes have been widely used in redox flow batteries (RFBs) due to their unique features such as abundant availability, biodegradability, and low cost, as well as their excellent dissolution ability for redox-active substances. Despite these advantages, eutectic electrolytes still have some limitations in important aspects such as reaction kinetics, mass transport and ionic conductivity due to their relatively high intrinsic viscosity. In this work, we explore a green and cost-effective zinc-based eutectic electrolyte containing small molecules additives, which not only has elevated ionic conductivity, but also can dissolve organic cathode materials 3,3′,5,5′-tetramethylaminemethylene-4,4′-biphenol (TABP) at high concentrations. In this zinc-based eutectic electrolyte, TABP exhibits a highly positive redox potential (1.50 V versus Zn/Zn2+), quasi-reversible redox reaction kinetics and good redox stability. When operated in a practical hybrid flow battery, the Zn-TABP cell based on this eutectic electrolyte exhibits excellent rate performance, high capacity utilization, and low capacity decay rate (0.119 % per cycle). Post-analysis for the TABP catholyte suggests that the Michael side reaction rate of TABP in electrochemical cycling appears to depend upon its concentration.

Accelerating redox kinetics of sulfurized polyacrylonitrile nanosheets by trace doping of element

“Solid-solid” conversion mechanism of sulfurized polyacrylonitrile (SPAN) could eliminate the “shuttle effect” of polysulfides intermediate in LiS batteries, but it leads to poor redox reaction kinetics. Herein, traces of high conductivity elements Se and Te are doped in two-dimensional SPAN nanosheets (NS) by co-heating method. This synergistic effect enhances the conductivity of SPAN while affording a larger contact area with the electrolyte and shortening the electron/ion transport path. As a result, both the energy barrier for redox reaction and polarization for battery are decreased. At a high current density of 3 A g−1, Te0.052S0.948PAN NS and Se0.071S0.929PAN NS exhibit significantly enhanced discharge capacities of 485 mA h g−1composite and 457 mA h g−1composite, respectively, while SPAN nanoparticles (NP) only delivers a capacity of 417 mA h g−1composite. At 0.2 A g−1 current density, the capacity retention rates of Te0.052S0.948PAN NS and Se0.071S0.929PAN NS are 92.20 % and 56.10 % after 200 cycles, respectively, both higher than the 40.10 % of SPAN NP. When the loading amount is further increased, Te0.052S0.948PAN NS and Se0.071S0.929PAN NS still maintain excellent electrochemical performance. In-situ Raman and XPS analysis confirms the reversible breaking and formation of CS/SS bonds during the first cycle. Additionally, XPS and SEM analysis after 100 cycles demonstrate the stable nanostructure and molecular structure of Se0.071S0.929PAN NS and Te0.052S0.948PAN NS throughout the cycling process. These results herald a new approach to high redox kinetics of SPAN by the synergistic effect of elements doping and nanoscale modulation.

Cobalt-iron layered double hydroxides/CNTs composite modified separator enabling high-performance lithium–sulfur batteries

The active material loss and capacity degeneration resulted from severe shuttle effect and sluggish redox reaction kinetics of lithium polysulfides (LiPSs) have greatly hindered the further development of high-performance lithium–sulfur batteries (LiSBs). Herein, the functional polymer separator consisting of cobalt-iron layered double hydroxides (CoFe LDH)/carbon nanotubes (CNTs) modified polymer separator is developed. This CoFe LDH/CNTs composite combines the advantages of enhanced chemical bonding between CoFe LDH and LiPSs and improved conductivity, which can significantly suppress the shuttling effect of LiPSs and accelerate the redox reaction kinetics. Therefore, LiSBs assembled by CoFe LDH/CNT-modified separators exhibit superior electrochemical performance with high initial capacity (961.4 mAh g−1) and excellent cycling stability during 200 cycles at 0.5 C rate. The results demonstrate that the Co-Fe LDH/CNTs composites are efficient functional separators for for high-performance LiSBs.

Anion-Involved Solvation Structure of Lithium Polysulfides in Lithium-Sulfur Batteries.

Lithium polysulfides (LiPSs) are pivotal intermediates involved in all the cathodic reactions in lithium-sulfur (Li-S) batteries. Elucidating the solvation structure of LiPSs is the first step for rational design of electrolyte and improving Li-S battery performances. Herein, we investigate the solvation structure of LiPSs and find that Li salt anions tend to enter the first solvation sheath of LiPSs and form contact ion pairs in electrolyte. The anion-involved solvation structure of LiPSs significantly influences the intrinsic kinetics of the sulfur redox reactions. In particular, the LiPS solvation structure modified by lithium bis(fluorosulfonyl)imide endows Li-S batteries with reduced polarization and enhanced rate performances under high sulfur areal loading and lean electrolyte volume conditions. This work updates the fundamental understanding of the solvation chemistry of LiPSs and highlights electrolyte engineering for promoting the performances of Li-S batteries.

Anion‐Involved Solvation Structure of Lithium Polysulfides in Lithium–Sulfur Batteries

AbstractLithium polysulfides (LiPSs) are pivotal intermediates involved in all the cathodic reactions in lithium–sulfur (Li−S) batteries. Elucidating the solvation structure of LiPSs is the first step for rational design of electrolyte and improving Li−S battery performances. Herein, we investigate the solvation structure of LiPSs and find that Li salt anions tend to enter the first solvation sheath of LiPSs and form contact ion pairs in electrolyte. The anion‐involved solvation structure of LiPSs significantly influences the intrinsic kinetics of the sulfur redox reactions. In particular, the LiPS solvation structure modified by lithium bis(fluorosulfonyl)imide endows Li−S batteries with reduced polarization and enhanced rate performances under high sulfur areal loading and lean electrolyte volume conditions. This work updates the fundamental understanding of the solvation chemistry of LiPSs and highlights electrolyte engineering for promoting the performances of Li−S batteries.

Ion/Electron Co-Conductive Triple-Phase Interface Enabling Fast Redox Reaction Kinetics in Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) are promising next-generation energy storage systems because of their high energy densities and high theoretical specific capacities. However, most catalysts in the LSBs are based on carbon materials, which can only improve the conductivity and are unable to accelerate lithium-ion transport. Therefore, it would be worthwhile to develop a catalytic electrode exhibiting both ion and electron conductivity. Herein, a triple-phase interface using lithium lanthanum titanate/carbon (LLTO/C) nanofibers to construct ion/electron co-conductive materials was used to afford enhanced adsorption of lithium polysulfides (LiPSs), high conductivity, and fast ion transport in working LSBs. The triple-phase interface accelerates the kinetics of the soluble LiPSs and promotes uniform Li2S precipitation/dissolution. Additionally, the LLTO/C nanofibers decrease the reaction barrier of the LiPSs, significantly improving the conversion of LiPSs to Li2S and promoting rapid conversion. Specifically, the LLTO promotes ion transport owing to its high ionic conductivity, and the carbon enhances the conductivity to improve the utilization rate of sulfur. Therefore, the LSBs with LLTO/C functional separators deliver stable life cycles, high rates, and good electrocatalytic activities. This strategy is greatly important for designing ion/electron conductivity and interface engineering, providing novel insight for the development of the LSBs.

Heteroatom surface engineering with distinct doping ways and valence state regulation: Boosting electrocatalysis performance of Ni-doped MoS2/rGO host for excellent lithium sulfur batteries

Sulfur host materials are crucial to the electrochemical performances of lithium sulfur batteries (LSBs). Two-dimensional (2D) nanomaterials with close atomic thickness and large specific surface area are considered as excellent sulfur hosts in lithium sulfur batteries due to their extraordinary physical properties and special structures, which play a key role in improving the redox reaction kinetics of sulfur/Li2S. The heteroatom doping, which is usually applied in surface engineering, can not only adjust surface coordination environment but also form surface functional groups. Herein, the surface structures and properties of 2D Ni-doped MoS2/rGO composite are regulated via two surface engineering strategies. One is that nickel atoms are doped into 2D MoS2 nanosheets by two distinct hydrothermal techniques, which would result in notable differences of surface heteroatom content, and another is that the valence state of surface heteroatom nickel is changed by the thermal reduction technology. The content and valence state of surface heteroatom nickel can significantly influence the electrocatalysis activities of host materials during the redox reaction processes of sulfur/Li2S, which would substantially alter the electrochemical performances of LSBs. When the S@3%Ni-MoS2/rGO-IIRe is used as sulfur host, the lithium‑sulfur cell has an initial discharge capacity of 936.4 mA h g−1 and a low capacity attenuation of only 0.027 % each cycle with the high capacity of 819.7 mA h g−1 after 450 cycles at 1C, exhibiting an excellent coulombic efficiency and outstanding cycle stability. This study would provide some inspiration for improving the electrochemical performance of advanced lithium‑sulfur batteries through the rational regulation of surface atomic structures and electronic states of sulfur hosts.

Enhanced electrocatalytic conversion of tellurium with MnO hollow nanospheres modified hierarchical n-doped carbon nanosheets in high-performance aqueous Zn-Te battery

Rechargeable aqueous zinc batteries (AZBs) are increasingly recognized as an alternative to conventional energy storage systems due to their environmentally safe nature, abundant zinc resources, and high theoretical capacity. However, the intercalation or surface redox mechanisms limit the development of AZBs cathode materials due to low specific capacity and energy density. The tellurium-based (Te) materials with conversion mechanisms are promising cathode materials for AZBs. Nevertheless, the slow kinetics are detrimental to the increase in specific capacity and energy density for Zn-Te battery. Therefore, a hierarchical structure of manganese oxide (MnO) hollow nanospheres loaded on nitrogen-doped carbon nanosheets (MnO@NC) was rationally designed and used as Te hosts (Te/MnO@NC) for Zn-Te battery. This hierarchical structure facilitates the loading of more Te species. Meanwhile, the MnO hollow nanospheres can expose more active sites, which can promote the kinetics of Te redox reactions thereby lowering the reaction energy barrier. The Te/MnO@NC cathode exhibits high specific capacity and high energy density (429 mAh g−1 and 407 Wh Kg−1 at 0.1 A g−1). Additionally, the conversion mechanism was investigated by systematic characterization and density functional theory (DFT) calculations. This study presents a new design platform for developing AZBs with high specific capacity and energy density.

Rational design of hollow flower-like MoS2/Mo2C heterostructures in N-doped carbon substrate for synergistically accelerating adsorption-electrocatalysis of polysulfides in lithium sulfur batteries

Lithium–sulfur (Li–S) batteries have been garnered significant attention in the energy storage field due to their high theoretical specific capacity and low cost. However, Li–S batteries suffer from issues like the shuttle effect, poor conductivity, and sluggish chemical reaction kinetics, which hinder their practical development. Herein, a novel hollow flower-like architecture composed of MoS2/Mo2C heterostructures in N-doped carbon substrate (H-Mo2S/Mo2C/NC NFs), which were well designed and prepared through a calcination-vulcanization method, were used as high-efficiency catalyst to propel polysulfide redox kinetics. Ex situ electrochemical impedance spectroscopy verify that the abundant heterojunctions could facilitate electron and ion transfer, revealed the excellent interface solid–liquid–solid conversion reaction. The adsorption test of Li2S6 showed that Mo2S and Mo2C formed heterostructure generate the binding of polysulfide could be enhanced. And cyclic voltammetry test indicate boost the polysulfide redox reaction kinetics and ion transfer of H-Mo2S/Mo2C/NC/S NFs cathode. Benefiting from the state-of-the-art design, the H-Mo2S/Mo2C/NC/S NFs cathode demonstrates remarkable rate performance with a specific capacity of 1351.9 mAh g−1 at 0.2 C, when the current density was elevated to 2 C and subsequently reverted to 0.2 C, the H-Mo2S/Mo2C/NC/S NFs cathode retained a capacity of 1150.4 mAh g−1, and it maintains exceptional long cycling stability (840 mA h g−1 at 2 C after 500 cycles) a low capacity decay of 0.0073% per cycle. This work presents an effective approach to rapidly fabricating multifunctional heterostructures as an effective sulfur host in improving the polysulfide redox kinetics for lithium sulfur batteries.

Enhanced Spin-Polarized Electric Field Modulating p-Band Center on Ni-Doped CdS for Boosting Photocatalytic Hydrogen Evolution.

It is a challenge to regulate charge separation dynamics and redox reaction kinetics at the atomic level to synergistically boost photocatalytic hydrogen (H2) evolution. Herein, a robust Ni-doped CdS (Ni-CdS) photocatalyst is synthesized by incorporating highly dispersed Ni atoms into the CdS lattice in substitution for Cd atoms. Combined characterizations with theoretical analysis indicate that local lattice distortion and S-vacancy of Ni-CdS induced by Ni incorporation lead to an increased dipole moment and enhanced spin-polarized electric field, which promotes the separation and transfer of photoinduced carriers. In this contribution, charge redistribution caused by enhanced internal electric field results in the downshift of the S p-band center, which is conducive to the desorption of intermediate H* for boosting the H2 evolution reaction. Accordingly, the Ni-CdS photocatalyst shows a remarkably improved photocatalytic performance with an H2 evolution rate of 20.28mmolg-1h-1 under visible-light irradiation, which is 5.58 times higher than that of pristine CdS. This work supplied an insightful understanding that the enhanced polarization electric field governs the p-band center for efficient photocatalytic H2 evolution activity.

Opportunities and Challenges of Phosphorus‐based Anodes for Practical Battery Application

AbstractPhosphorus‐based anode materials have attracted considerable attention due to their high theoretical capacity, safe operational potential, and favorable redox chemistry for diverse alkali metal‐ion storage applications. Their excellent performance in lithium storage makes them promising candidates for fast‐charging batteries. However, challenges such as complex redox reactions, substantial volume expansion during lithiation, vulnerability to oxidation, and the lack of a mature mass production process hinder their further development. Current research predominantly focuses on establishing multilevel nanostructures or robust solid electrolyte interphases (SEI) to mitigate volume expansion. Nonetheless, a consensus within the academic community on the maximum degree of volume expansion for practical electrode application in cells is yet to be established. Furthermore, investigations into the kinetics of redox reactions, side reactions in the presence of air or electrolyte, and mass production processes for phosphorus‐based anodes are relatively limited. This comprehensive review meticulously examines these challenges, providing nuanced insights. Additionally, the review offers perspectives on potential advancements in phosphorus‐based anode development, contributing to the ongoing discourse on the future trajectory of research in this domain.

Multifunctional radical polymers-enabled rapid charge/discharge and high capacity for flexible self-standing LiFePO4/PETM/SWNT hybrid electrodes

The combination of high output and high energy storage performance at the same time is a long-standing and formidable challenge in electrode technology. Herein, a multifunctional radical polymer binder, poly (ethylene-alt-TEMPO maleate) (PETM) is first introduced to construct flexible self-standing organic/inorganic hybrid electrodes, PETM/lithium iron phosphate (LFP)/single-walled carbon nanotubes (SWNT). Notably, PETM plays multifunctional roles in the PETM/LFP/SWNT electrodes as a polymer binder, electrochemical mediator, and auxiliary active material. First, PETM provides strong adhesive strength to generate robust structural integrity, allowing a three-dimensional hierarchical consecutive structure. Second, together with the electrochemical mediation of PETM, the hybrid structure greatly expedites electron/ion transportation, thus bringing fast redox reaction kinetics and high output. Third, PETM offer additional energy storage owing to the electro-activeness of radical groups. Coupled with the self-supporting property of the electrode without any redundant electro-inactive components, the electrode energy density can be substantially improved. Profiting from those advantages, the formed electrode achieves exceptional rate performance (97.5 mA h/g at 20 C), extraordinary specific/areal capacity (173 mA h g−1/8.2 mA h cm−2 at 0.1 C), and ultralong-life cycle under ultrahigh rate (over 2000 cycles at 20 C). More importantly, the electrode can be utilized as a flexible cathode in flexible batteries.