Multicore–Shell Bi@N‐doped Carbon Nanospheres for High Power Density and Long Cycle Life Sodium‐ and Potassium‐Ion Anodes

Bismuth (Bi) is an attractive material as anodes for both sodium‐ion batteries (NIBs) and potassium‐ion batteries (KIBs), because it has a high theoretical gravimetric capacity (386 mAh g^?1) and high volumetric capacity (3800 mAh L^?1). The main challenges associated with Bi anodes are structural degradation and instability of the solid electrolyte interphase (SEI) resulting from the huge volume change during charge/discharge. Here, a multicore–shell structured Bi@N‐doped carbon (Bi@N‐C) anode is designed that addresses these issues. The nanosized Bi spheres are encapsulated by a conductive porous N‐doped carbon shell that not only prevents the volume expansion during charge/discharge but also constructs a stable SEI during cycling. The Bi@N‐C exhibits unprecedented rate capability and long cycle life for both NIBs (235 mAh g^?1 after 2000 cycles at 10 A g^?1) and KIBs (152 mAh g^?1 at 100 A g^?1). The kinetic analysis reveals the outstanding electrochemical performance can be attributed to significant pseudocapacitance behavior upon cycling.     

Potassium Prussian Blue Nanoparticles: A Low‐Cost Cathode Material for Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) in organic electrolytes hold great promise as an electrochemical energy storage technology owing to the abundance of potassium, close redox potential to lithium, and similar electrochemistry with lithium system. Although carbon materials have been studied as KIB anodes, investigations on KIB cathodes have been scarcely reported. A comprehensive study on potassium Prussian blue K_0.220Fe[Fe(CN)₆]_0.805?4.01H₂O nanoparticles as a potential cathode material is for the first time reported. The cathode exhibits a high discharge voltage of 3.1–3.4 V, a high reversible capacity of 73.2 mAh g^?1, and great cyclability at both low and high rates with a very small capacity decay rate of ≈0.09% per cycle. Electrochemical reaction mechanism analysis identifies the carbon‐coordinated Fe^III/Fe^II couple as redox‐active site and proves structural stability of the cathode during charge/discharge. Furthermore, for the first time, a KIB full‐cell is presented by coupling the nanoparticles with commercial carbon materials. The full‐cell delivers a capacity of 68.5 mAh g^?1 at 100 mA g^?1 and retains 93.4% of the capacity after 50 cycles. Considering the low cost and material sustainability as well as the great electrochemical performances, this work may pave the way toward more studies on KIB cathodes and trigger future attention on rechargeable KIBs.     

Trifluoropropylene Carbonate‐Driven Interface Regulation Enabling Greatly Enhanced Lithium Storage Durability of Silicon‐Based Anodes

The extremely high specific capacity of Si anodes is a double‐edged sword, bringing both high energy density and poor lifespan to Li‐ion batteries (LIBs). Despite recent advances in constructing nanostructured/composite‐Si anodes with an alleviated volume change and improved cycle life, daunting challenges still remain for Si anodes to suppress the irreversible capacity loss associated with the repeated rupture/reconstruction of the solid electrolyte interphase (SEI) layer. Herein, an electrolyte‐based optimization strategy is devised to in situ construct a thin, continuous, and mechanically stable SEI film on Si surface by using a trifluoropropylene carbonate (TFPC) cosolvent, targeting highly stable Si‐based anodes for LIBs. TFPC is featured with its low unoccupied molecular orbital energy, high reduction potential and outstanding film‐forming capability, outperforming those of the state‐of‐the‐art fluoroethylene carbonate additive. More importantly, TFPC plays a key role in regulating the structure and component of SEI layer. As such, 10 wt% TFPC addition promotes the formation of an optimal SEI film with appropriate amounts of polyolefins and LiF, endowing the SEI layer with enhanced rigidity and toughness as well as high ionic conductivity. Both the Si nanoparticle‐based and Si/C composite electrodes deliver a greatly enhanced cycling stability, rate capability, and overall structural integrity in such optimized electrolyte.     

Engineering Solid Electrolyte Interphase for Pseudocapacitive Anatase TiO2 Anodes in Sodium‐Ion Batteries

Anatase TiO₂ is considered as one of the promising anodes for sodium‐ion batteries because of its large sodium storage capacities with potentially low cost. However, the precise reaction mechanisms and the interplay between surface properties and electrochemical performance are still not elucidated. Using multimethod analyses, it is herein demonstrated that the TiO₂ electrode undergoes amorphization during the first sodiation and the amorphous phase exhibits pseudocapacitive sodium storage behaviors in subsequent cycles. It is also shown that the pseudocapacitive sodium storage performance is sensitive to the nature of solid electrolyte interphase (SEI) layers. For the first time, it is found that ether‐based electrolytes enable the formation of thin (≈2.5 nm) and robust SEI layers, in contrast to the thick (≈10 nm) and growing SEI from conventional carbonate‐based electrolytes. First principle calculations suggest that the higher lowest unoccupied molecular orbital energies of ether solvents/ion complexes are responsible for the difference. TiO₂ electrodes in ether‐based electrolyte present an impressive capacity of 192 mAh g^?1 at 0.1 A g^?1 after 500 cycles, much higher than that in carbonate‐based electrolyte. This work offers the clarified picture of electrochemical sodiation mechanisms of anatase TiO₂ and guides on strategies about interfacial control for high performance anodes.     

Extending Cycle Life of Mg/S Battery by Activation of Mg Anode/Electrolyte Interface through an LiCl‐Assisted MgCl2 Solubilization Mechanism

Non‐nucleophilic electrolytes that can reversibly plate/strip Mg are essential for realizing high‐performance rechargeable Mg/S batteries. In contrast to organometallic electrolytes, all‐inorganic electrolytes based on MgCl₂‐AlCl₃ complexes are more cost‐effective and hold better stability to air and moisture. A recently developed electrolyte that contains tetrahydrofuran solvated divalent Mg cation, [Mg·6THF][AlCl₄]₂, has exhibited decent compatibility with the sulfur cathode. However, it suffers a large overpotential and short cycle life, which hinders its applications in Mg/S batteries. Here, an efficient plating/stripping of Mg is realized successfully by using LiCl to dissolve MgCl₂ from the electrolyte/electrode interface. As a result, the overpotential of Mg plating/stripping is remarkably reduced to 140/140 mV at a current density of 500 µA cm^?2. Both experiments and density functional theory (DFT) calculations reveal that the LiCl‐assisted solubilization of MgCl₂ facilitates the exposure of fresh surface on the Mg anode. Utilizing such an LiCl‐activation strategy, Mg/S full batteries with a significantly extended cycle life of over 500 cycles, as well as coulombic efficiency close to 100%, are achieved successfully. This work demonstrates the role of LiCl‐assisted interface activation on extending the cycle‐life Mg/S batteries with all‐inorganic electrolytes.     

Catalytically Induced Robust Inorganic-Rich Cathode Electrolyte Interphase for 4.5 V Li||NCM622 Batteries

Tailoring inorganic components of cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) is critical to improving the cycling performance of lithium metal batteries. However, it is challenging due to complicated electrolyte reactions on cathode/anode surfaces. Herein, the species and inorganic component content of the CEI/SEI is enriched with an objectively gradient distribution through employing pentafluorophenyl 4-nitrobenzenesulfonate (PFBNBS) as electrolyte additive guided by engineering bond order with functional groups. In addition, a catalytic effect of LiNi_0.6Mn_0.2Co_0.2O₂ (NCM622) cathode is proposed on the decomposition of PFBNBS. PFBNBS with lower highest occupied molecular orbital can be preferentially oxidized on the NCM622 surface with the help of the catalytic effect to induce an inorganic-rich CEI for superior electrochemical performance at high voltage. Moreover, PFBNBS can be reduced on the Li surface due to its lower lowest unoccupied molecular orbital , increasing inorganic moieties in SEI for inhibiting Li dendrite generation. Thus, 4.5 V Li||NCM622 batteries with such electrolyte can retain 70.4% of initial capacity after 500 cycles at 0.2 C, which is attributed to the protective effect of the excellent CEI on NCM622 and the inhibitory effect of its derived CEI/SEI on continuous electrolyte decomposition.     

Recent Advances in Electrolytes for Potassium-Ion Batteries

Potassium-ion batteries (KIBs) are considered as the potential energy storage devices due to the abundant reserves and low cost of potassium. In the past decade, research on KIBs has generally focused on electrode materials. However, since electrolytes also play a key role in determining the cell performance, this review summarizes recent advances in KIB electrolytes and design strategies. Specifically, the review includes five parts. First, the organic liquid electrolyte is the most widely used type for KIBs. Its two major components, salts and solvents, have a huge impact on the formation of the solid electrolyte interphase and the performance of KIBs. Changes in salts/solvents, the introduction of additives, and the concentration increase all have a positive effect on organic liquid electrolytes. Second, the design of water-in-salt electrolytes can effectively widen the narrow electrochemical stability window of aqueous electrolytes. Third, despite the appealing properties, the ionic liquid electrolytes have not been widely applied due to its high cost. Fourth, the solid-state electrolytes have drawn much attention due to high safety, and current research has been working on improving their ionic conductivity at room temperature. Lastly, perspectives are provided to support the future development of suitable electrolytes for high-performance KIBs.     

Armoring LiNi1/3Co1/3Mn1/3O2 Cathode with Reliable Fluorinated Organic–Inorganic Hybrid Interphase Layer toward Durable High Rate Battery

Ternary layered oxide materials have attracted extensive attention as a promising cathode candidate for high‐energy‐density lithium‐ion batteries. However, the undesirable electrochemical degradation at the electrode–electrolyte interface definitively shortens the battery service life. An effective and viable approach is proposed for improving the cycling stability of the LiNi_1/3Co_1/3Mn_1/3O₂ cathode using lithium difluorophosphate (LiPO₂F₂) paired with fuoroethylene carbonate (FEC) as co‐additives into conventional electrolytes. It is found that the co‐additives can greatly reduce the interface charge transfer impedance and significantly extend the life span of LiNi_1/3Co_1/3Mn_1/3O₂//Li (NMC//Li) batteries. The developed cathode demonstrates exceptional capacity retention of 88.7% and remains structural integrity at a high current of 5C after 500 cycles. Fundamental mechanism study indicates a dense, stable fluorinated organic–inorganic hybrid cathode‐electrolyte interphase (CEI) film derived from LiPO₂F₂ in conjunction with FEC additives on the surface of NMC cathode material, which significantly suppresses the decomposition of electrolyte and mitigates the dissolution of transition metal ions. The interfacial engineering of the electrode materials stabilized by the additives manipulation provides valuable guidance for the development of advanced cathode materials.     

Layered P2‐Type K0.44Ni0.22Mn0.78O2 as a High‐Performance Cathode for Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) are emerging as one of the most promising candidates for large‐scale energy storage owing to the natural abundance of the materials required for their fabrication and the fact that their intercalation mechanism is identical to that of lithium‐ion batteries. However, the larger ionic radius of K⁺ is likely to induce larger volume expansion and sluggish kinetics, resulting in low specific capacity and unsatisfactory cycle stability. A new Ni/Mn‐based layered oxide, P2‐type K_0.44Ni_0.22Mn_0.78O₂, is designed and synthesized. A cathode designed using this material delivers a high specific capacity of 125.5 mAh g^?1 at 10 mA g^?1, good cycle stability with capacity retention of 67% over 500 cycles and fast kinetic properties. In situ X‐ray diffraction recorded for the initial two cycles reveals single solid‐solution processes under P2‐type framework with small volume change of 1.5%. Moreover, a cathode electrolyte interphase layer is observed on the surface of the electrode after cycling with possible components of K₂CO₃, RCO₂K, KOR, KF, etc. A full cell using K_0.44Ni_0.22Mn_0.78O₂ as the cathode and soft carbon as the anode also exhibits exceptional performance, with capacity retention of 90% over 500 cycles as well as superior rate performance. These findings suggest P2‐K_0.44Ni_0.22Mn_0.78O₂ is a promising candidate as a high‐performance cathode for KIBs.     

Reversible Conversion Reactions and Small First Cycle Irreversible Capacity Loss in Metal Sulfide‐Based Electrodes Enabled by Solid Electrolytes

Solid‐state batteries can potentially enable new classes of electrode materials which are unstable against liquid electrolytes. Here, SnS nanocrystals, synthesized by a wet chemical method, are used to fabricate a Li‐ion electrode, and the electrochemical properties of this electrode are examined in both solid and liquid electrolyte designs. The SnS‐based solid‐state cell delivers a capacity of 629 mAh g^?1 after 100 cycles and exhibits an unprecedentedly small irreversible capacity in the first cycle (8.2%), while the SnS‐based liquid cell shows a rapid capacity decay and large first cycle irreversible capacity (44.6%). Cyclic voltammetry (CV) experiments show significant solid electrolyte interphase (SEI) formation in the liquid cell during the first discharge while SEI formation by electrolyte reduction in the solid‐state cell appears negligible. Along with CV, X‐ray photoelectron spectroscopy and energy dispersive spectroscopy are used to investigate the differences between the solid‐state and liquid cells. The reaction chemistry of SnS in solid‐state cells is also studied in detail by ex situ X‐ray diffraction and X‐ray absorption spectroscopy. The overarching findings are that use of a solid electrolyte suppresses materials degradation and electrolyte reduction which leads to a small first cycle irreversible capacity and stable cycling.     

A LiF Nanoparticle‐Modified Graphene Electrode for High‐Power and High‐Energy Lithium Ion Batteries

Surface modification of carbon materials plays an important role in tailoring carbon surface chemistry to specify their electrochemical performance. Here, a surface modification strategy for graphene is proposed to produce LiF‐nanoparticle‐modified graphene as a high‐rate, large‐capacity pre‐lithiated electrode for high‐power and high‐energy lithium ion batteries. The LiF nanoparticles covering the active sites of the graphene surface provide an extra Li source and act as an effective solid electrolyte interphase (SEI) inhibiter to suppress LiFP₆ electrolyte decomposition reactions, affect SEI components, and reduce their thickness. Consequently, the Li‐ion diffusion is greatly sped up and the thermodynamic stability of the electrode is significantly improved. This modified graphene electrode shows excellent rate capability and improved first‐cycle coulombic efficiency, cycling stability, and ultrahigh power and energy densities accessible during fast charge/discharge processes.     

Biocompatible and Biodegradable Organic Transistors Using a Solid‐State Electrolyte Incorporated with Choline‐Based Ionic Liquid and Polysaccharide

Biocompatible, biodegradable, and solid‐state electrolyte‐based organic transistors are demonstrated. As the electrolyte is composed of all edible materials, which are levan polysaccharide and choline‐based ionic liquid, the organic transistor fabricated on the electrolyte can be biocompatible and biodegrable. Compared to the other ion gel based electrolytes, it has superior electrical and mechanical properties, large specific capacitance (≈40 µF cm^?2), non‐volatility, flexibility, and high transparency. Thus, it shows mechanical reliability by maintaining electrical performances under up to 1.11% of effective bending strain, 5% of stretching, and have low operation voltage range when it is utilized in organic transistors. Moreover, the biodegradable electrolyte‐based organic transistors can be applied to bio‐integrated devices, such as electrocardiogram (ECG) recordings on human skin and the heart of a rat. The measured ECG signals from the transistors, compared to signals from electrode‐based sensors, has a superior signal‐to‐noise ratio. The biocompatible and biodegradable materials and devices can contribute to the development of many bioelectronics.     

Tailored Redox Kinetics,Electronic Structures and Electrode/Electrolyte Interfaces for Fast and High Energy‐Density Potassium‐Organic Battery

Potassium‐organic batteries have a great potential for applications in large‐scale electricity grids and electric vehicles because of their low cost and sustainability. However, their inferior cycle stability and more importantly low energy density under fast discharge/charge process of organic cathodes limit their applications. This work introduces a simple polymerization processing which enables comprehensive tuning of redox kinetics, electronic structures, and electrode/electrolyte interfaces of the polymer cathodes. With this approach, a potassium‐organic battery with an impressive energy density of 113 Wh kg^?1 at a high power of 35.2 kW kg^?1 is shown which corresponds to a high current density of 147 C and a fully discharge within 10 s. The battery also has impressive cycling stability that a 100% Columbic efficiency is maintained and shows negligible capacity degradation after 1000 cycle at a high current density of 7.35 C. Using the polymer cathode and a dipotassium terephthalate anode, a full battery with superior energy density and cycling stability is demonstrated among all reported all‐organic full potassium ion batteries.     

Confined Sulfur in Microporous Carbon Renders Superior Cycling Stability in Li/S Batteries

The use of sulfur in the next generation Li‐ion batteries is currently precluded by its poor cycling stability caused by irreversible Li₂S formation and the dissolution of soluble polysulfides in organic electrolytes that leads to parasitic cell reactions. Here, a new C/S cathode material comprising short‐chain sulfur species (predominately S₂) confined in carbonaceous subnanometer and the unique charge mechanism for the subnano‐entrapped S₂ cathodes are reported. The first charge–discharge cycle of the C/S cathode in the carbonate electrolyte forms a new type of thiocarbonate‐like solid electrolyte interphase (SEI). The SEI coated C/S cathode stably delivers ≈600 mAh g^?1 capacity over 4020 cycles (0.0014% loss cycle^?1) at ≈100% Coulombic efficiency. Extensive X‐ray photoelectron spectroscopy analysis of the discharged cathodes shows a new type of S₂ species and a new carbide‐like species simultaneously, and both peaks disappear upon charging. These data suggest a new sulfur redox mechanism involving a separated Li⁺/S^2? ion couple that precludes Li₂S compound formation and prevents the dissolution of soluble sulfur anions. This new charge/discharge process leads to remarkable cycling stability and reversibility.     

Carbonized Polyacrylonitrile‐Stabilized SeSx Cathodes for Long Cycle Life and High Power Density Lithium Ion Batteries

A facile synthesis of selenium sulfide (SeS_x)/carbonized polyacrylonitrile (CPAN) composites is achieved by annealing the mixture of SeS₂ and polyacrylonitrile (PAN) at 600 °C under vacuum. The SeS_x molecules are confined by N‐containing carbon (ring) structures in the carbonized PAN to mitigate the dissolution of polysulfide and polyselenide intermediates in carbonate‐based electrolyte. In addition, formation of solid electrolyte interphase (SEI) on the surface of SeS_x/CPAN electrode in the first cycle further prevents polysulfide and polyselenide intermediates from dissolution. The synergic restriction of SeS_x by both CPAN matrix and SEI layer allows SeS_x/CPAN composites to be charged and discharged in a low‐cost carbonate‐based electrolyte (LiPF₆ in EC/DEC) with long cycling stability and high rate capability. At a current density of 600 mA g^?1, it maintains a reversible capacity of 780 mAh g^?1 for 1200 cycles. Moreover, it retains 50% of the capacity at 60 mA g^?1 even when the current density increases to 6 A g^?1. The superior electrochemical performance of SeS_x/CPAN composite demonstrates that it is a promising cathode material for long cycle life and high power density lithium ion batteries. This is the first report on long cycling stability and high rate capability of selenium sulfide‐based cathode material.     

Designing Dendrite‐Free Zinc Anodes for Advanced Aqueous Zinc Batteries

Zn metal has been regarded as the most promising anode for aqueous batteries due to its high capacity, low cost, and environmental benignity. Zn anode still suffers, however, from low Coulombic efficiency due to the side reactions and dendrite growth in slightly acidic electrolytes. Here, the Zn plating/stripping mechanism is thoroughly investigated in 1 m ZnSO₄ electrolyte, demonstrating that the poor performance of Zn metal in mild electrolyte should be ascribed to the formation of a porous by‐product (Zn₄SO₄(OH)₆·xH₂O) layer and serious dendrite growth. To suppress the side reactions and dendrite growth, a highly viscoelastic polyvinyl butyral film, functioning as an artificial solid/electrolyte interphase (SEI), is homogeneously deposited on the Zn surface via a simple spin‐coating strategy. This dense artificial SEI film not only effectively blocks water from the Zn surface but also guides the uniform stripping/plating of Zn ions underneath the film due to its good adhesion, hydrophilicity, ionic conductivity, and mechanical strength. Consequently, this side‐reaction‐free and dendrite‐free Zn electrode exhibits high cycling stability and enhanced Coulombic efficiency, which also contributes to enhancement of the full‐cell performance when it is coupled with MnO₂ and LiFePO₄ cathodes.     

Engineering Wavy‐Nanostructured Anode Interphases with Fast Ion Transfer Kinetics: Toward Practical Li‐Metal Full Batteries

Fast Li‐metal depletion and severe anode pulverization are the most critical obstacles for the energy‐dense Li‐metal full batteries using thin Li‐metal anodes (<50 µm). Here, a wavy‐nanostructured solid electrolyte interphase (SEI) with fast ion transfer kinetics is reported, which can promote high‐efficiency Li‐metal plating/stripping (>98% at 4 mAh cm^?2) in conventional carbonate electrolyte. Cryogenic transmission electron microscopy (cryo‐TEM) further reveals the fundamental relationship between wavy‐nanostructured SEI, function, and the electrochemical performance. The wavy SEI with greatly decreased surface diffusion resistance can realize grain coarsening of Li‐metal deposition and exhaustive dissolution of active Li‐metal during the stripping process, which can effectively alleviate “dead Li” accumulation and anode pulverization problems in practical full cells. Under highly challenging conditions (45 µm Li‐metal anodes, 4.3 mAh cm^?2 high capacity LiNi_0.8Mn_0.1Co_0.1O₂ cathodes), full cells exhibit significantly improved cycling lifespan (170 cycles; 20 cycles for control cells) via the application of wavy SEI.     

Rational Molecular Design of Benzoquinone‐Derived Cathode Materials for High‐Performance Lithium‐Ion Batteries

p‐Benzoquinone (BQ) is a promising cathode material for lithium‐ion batteries (LIBs) due to its high theoretical specific capacity and voltage. However, it suffers from a serious dissolution problem in organic electrolytes, leading to poor electrochemical performance. Herein, two BQ‐derived molecules with a near‐plane structure and relative large skeleton: 1,4‐bis(p‐benzoquinonyl)benzene (BBQB) and 1,3,5‐tris(p‐benzoquinonyl)benzene (TBQB) are designed and synthesized. They show greatly decreased solubility as a result of strong intermolecular interactions. As cathode materials for LIBs, they exhibit high carbonyl utilizations of 100% with high initial capacities of 367 and 397 mAh g^?1, respectively. Especially, BBQB with better planarity presents remarkably improved cyclability, retaining a high capacity of 306 mAh g^?1 after 100 cycles. The cycling stability of BBQB surpasses all reported BQ‐derived small molecules and most polymers. This work provides a new molecular structure design strategy to suppress the dissolution of organic electrode materials for achieving high performance rechargeable batteries.     

Effects of using multi‐component electrolytes on the stability and properties of solar cells sensitized with simple organic dyes

In this paper we present experimental results for electrochemical (dye‐sensitized) solar cells that were prepared in our laboratory in order to examine some of the major factors affecting the efficiency and the stability of such cells. Nanostructured TiO₂ thin films were prepared and sensitized using an organic dye. For the purpose of this study three different types of electrolytes were developed: a standard‐type electrolyte containing potassium iodide and iodine in propylene carbonate (PC) and two novel, multi‐component electrolytes containing potassium iodide and iodine dissolved in varying mixtures of PC and EG (ethylene glycol). It was demonstrated that the combined properties of the two solvents in the multi‐component electrolytes enhance the efficiency and improve considerably the stability of the cells. Copyright © 2010 John Wiley & Sons, Ltd.     

Solvent-Free Electrolyte for High-Temperature Rechargeable Lithium Metal Batteries

The formation of lithiophobic inorganic solid electrolyte interphase (SEI) on Li anode and cathode electrolyte interphase (CEI) on the cathode is beneficial for high-voltage Li metal batteries. However, in most liquid electrolytes, the decomposition of organic solvents inevitably forms organic components in the SEI and CEI. In addition, organic solvents often pose substantial safety risks due to their high volatility and flammability. Herein, an organic-solvent-free eutectic electrolyte based on low-melting alkali perfluorinated-sulfonimide salts is reported. The exclusive anion reduction on Li anode surface results in an inorganic, LiF-rich SEI with high capability to suppress Li dendrite, as evidenced by the high Li plating/stripping CE of 99.4% at 0.5  mA cm⁻² and 1.0 mAh cm⁻², and 200-cycle lifespan of full LiNi_0.8Co_0.15Al_0.05O₂ (2.0 mAh cm⁻²) || Li (20 µm) cells at 80 °C. The proposed eutectic electrolyte is promising for ultrasafe and high-energy Li metal batteries.