High-performance Rechargeable Batteries Research Articles

Sandwich-Structured Ordered Mesoporous Polydopamine/MXene Hybrids as High-Performance Anodes for Lithium-Ion Batteries.

Organic polymers have attracted significant interest as electrodes for energy storage devices because of their advantages, including molecular flexibility, cost-effectiveness, and environmentally friendly nature. Nevertheless, the real implementation of polymer-based electrodes is restricted by their poor stability, low capacity, and slow electron-transfer/ion diffusion kinetics. In this work, a sandwich-structured composite of ordered mesoporous polydopamine (OMPDA)/Ti3C2Tx has been fabricated by in situ polymerization of dopamine on the surface of Ti3C2Tx via employing the PS-b-PEO block polymer as a soft template. The OMPDA layers with vertically oriented, accessible nanopores (∼20 nm) provide a continuous pore channel for ion diffusion, while the Ti3C2Tx layers guarantee a fast electron-transfer path. The OMPDA/Ti3C2Tx composite anode exhibits high reversible capacity, good rate performance, and excellent cyclability for lithium-ion batteries. The in situ transmission electron microscopy analysis reveals that the OMPDA in the composite only shows a small volume expansion and almost preserves the initial morphology during lithiation. Moreover, these in situ experiments also demonstrate the generation of a stable and ultrathin solid electrolyte interphase layer surrounding the active material, which acts as an electrode protective film during cycling. This study demonstrates the method to develop polymer-based electrodes for high-performance rechargeable batteries.

A high-power aqueous rechargeable Fe-I2 battery

Aqueous Fe-I2 rechargeable batteries are highly desirable for large-scale energy storage because of their intrinsic safety, cost effective, and wide abundance of iron and iodine. However, their development suffers from Fe dendrite growth and severe shuttle effect during cycling. Herein, we demonstrate a high-performance Fe-I2 rechargeable battery using metal iron as anode, iodine/hierarchically porous carbon composite as cathode and an eco-friendly aqueous electrolyte. The anode modified with ascorbic acid effectively suppresses the formation of iron dendrite, while the cathode doped with nitrogen greatly reduces the shuttle of iodine species. The battery operates a reversible redox reaction of FeI2/I2 pair with fast kinetics. A capacity ~190 ​mAh g-1 at current densities up to 5000 ​mA ​g-1 and excellent cycle stability of 100% after 550 cycles at 2000 ​mA ​g-1 are obtained. The battery achieves superior power density of ~1300 ​W ​kg-1 at 120 ​Wh kg-1 and high energy density of 130 ​Wh kg-1 at 356 ​W ​kg-1. Our study shows great promise for high-performance rechargeable batteries with low-cost, eco-friendliness and high safety.

Chemically sodiated ammonium vanadium oxide as a new generation high-performance cathode

Sodium-ion battery technologies must have low cost, safe, and high energy density cathode with prolonging cycle life propositions for any commercial utilizations. Herein, we present for the first time an extremely high energy density (770 W h kg−1) and excellent electrochemical performance of a sodiated and doped ammonium vanadium oxide (Zr-SNVO) cathode. The cathode delivers a high discharge capacity of 255 mAh g−1 with 95% capacity retention after 100 cycles at a current rate of 200 mA g−1. Furthermore, the present report demonstrates the full-cell performance with our cathode against a hydrogenated doped sodium titanium oxide (Zr-HNTO) anode, capable of delivering a high energy density of 220 W h kg−1 (both active mass of cathode and anode are considered). The present study shows a way to produce a high-performance rechargeable sodium-ion battery full-cell using alternative cathode and anode with a comparable energy density of current lithium-ion technology. The present study gives us a direction to make such cells for future renewable energy storage systems.

Reversible AlCl4−/Al2Cl7− conversion in a hybrid Na–Al battery

Owing to the larger radius of sodium ion as compared to that of lithium ion, the kinetics of transport and electrochemical reactions of Na+ ions in the cathode is more sluggish. This results in poor rate performance and inferior long-term cycling stability of sodium-ion batteries. Herein, an Al cathode coordinated with ionic liquid catholyte consisting of 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl3) is designed to pair with Na metal anode to produce a high-performance rechargeable sodium battery. The obtained batteries reach a high voltage of 2.1 V and show excellent long-term cycling stability with 92% capacity retention over 1000 cycles at 100 mA g−1 at 60 °C. Furthermore, the electrochemical processes on Al cathode are revealed dependent on the conversion mechanism of AlCl4−-Al2Cl7− redox couple. This Na–Al hybrid battery offers an idea for addressing affordable and reliable large-scale energy storage.

Dual-confined SeS2 cathode based on polyaniline-assisted double-layered micro/mesoporous carbon spheres for advanced Li–SeS2 battery

Selenium-sulfur solid solutions (SexSy) attracts soaring attention owing to its improved electrical conductivity over sulfur and higher theoretical specific capacity than selenium. Herein, high-performance lithium-selenium/sulfur batteries with a dual-confined cathode configuration by encapsulating SeS2 in double-layered hollow micro/mesoporous carbon spheres (DSMCs) with a conductive polyaniline (PANI) protection sheath are proposed. Polysulfides/polyselenides are efficiently restricted in the cathode via physical and chemical entrapment from DSMCs and PANI as well as chemical binding between selenium and sulfur. Benefiting from the distinct advantages of SeS2 and the well-constructed host framework, the cathode achieves high capacity utilization of 1018 mAh g−1 at 0.2 A g−1, together with outstanding rate capability of 619 mAh g−1 at 2 A g−1 and excellent cycle life over 500 cycles with almost 100% Coulombic efficiency. The novel SexSy-based cathode demonstrates a promising route to surmount some bottlenecks of current lithium-sulfur systems for high-performance rechargeable batteries.

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

Abstractp‐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.

Application Progress of Polyaniline, Polypyrrole and Polythiophene in Lithium-Sulfur Batteries.

With the urgent requirement for high-performance rechargeable Li-S batteries, besides various carbon materials and metal compounds, lots of conducting polymers have been developed and used as components in Li-S batteries. In this review, the synthesis of polyaniline (PANI), polypyrrole (PPy) and polythiophene (PTh) is introduced briefly. Then, the application progress of the three conducting polymers is summarized according to the function in Li-S batteries, including coating layers, conductive hosts, sulfur-containing compounds, separator modifier/functional interlayer, binder and current collector. Finally, according to the current problems of conducting polymers, some practical strategies and potential research directions are put forward. We expect that this review will provide novel design ideas to develop conducting polymer-containing high-performance Li-S batteries.

Fast Zn2+ kinetics of vanadium oxide nanotubes in high-performance rechargeable zinc-ion batteries

Mild aqueous rechargeable Zn-ion batteries emerge as potential grid energy storage devices due to excellent cycling stability, high Coulombic efficiency and low cost. However, reliable cathodes with high rate capability still need to be optimized. Previous vanadium oxide cathodes generally show the mechanism of Zn2+ intercalation into crystal layers, during which the lattice structure of active materials keeps stable. Different from this intercalation mechanism, here, we report a special conversion mechanism of Zn2+ storage. Vanadium oxide nanotubes with interlaminar dodecylamine are employed as the cathode. During the initial activation process, the cathode is fully converted to layered zinc pyrovanadate with amorphous zones induced by protonated dodecylamine, while the discharge process results in reversible formation of an amorphous-phase product during cycling. Layered zinc pyrovanadate can be electrochemically recovered from the amorphous phase after the Zn2+ de-intercalation. Despite an armorphous phase as the discharge product, this active material shows high cycling stability and fast Zn2+ kinetics. In addition, this cathode displays a specific energy density of ~242.5 Wh kg−1 and shows capacity retention of 80.5% after 950 cycles at 2.4 A g−1. Even at a high current density of 9.6 A g−1, the cathode delivers a specific energy of ~50 Wh kg−1 (5460 W kg−1) in 33 s. Although vanadium oxide nanotubes with interlaminar dodecylamine ions show little success in Li/Na-ion batteries with non-aqueous electrolytes, a mild aqueous Zn-ion system rejuvenates this material.

A Composite Bifunctional Oxygen Electrocatalyst for High-Performance Rechargeable Zinc-Air Batteries.

Rechargeable zinc-air batteries are considered as next-generation energy storage devices because of their ultrahigh theoretical energy density of 1086 Wh kg-1 (including oxygen) and inherent safety originating from the use of aqueous electrolyte. However, the cathode processes regarding oxygen reduction and evolution are sluggish in terms of kinetics, which severely limit the practical battery performances. Developing high-performance bifunctional oxygen electrocatalysts is of great significance, yet to achieve better bifunctional electrocatalytic reactivity beyond the state-of-the-art noble-metal-based electrocatalysts remains a great challenge. Herein, a composite Co3 O4 @POF (POF=framework porphyrin) bifunctional oxygen electrocatalyst is proposed to construct advanced air cathodes for high-performance rechargeable zinc-air batteries. The as-obtained composite Co3 O4 @POF electrocatalyst exhibits a bifunctional electrocatalytic reactivity of ΔE=0.74 V, which is better than the noble-metal-based Pt/C+Ir/C electrocatalyst and most of the reported bifunctional ORR/OER electrocatalysts. When applied in rechargeable zinc-air batteries, the Co3 O4 @POF cathode exhibits a reduced discharge-charge voltage gap of 1.0 V at 5.0 mA cm-2 , high power density of 222.2 mW cm-2 , and impressive cycling stability for more than 2000 cycles at 5.0 mA cm-2 .

Halide-Based Materials and Chemistry for Rechargeable Batteries.

Rechargeable batteries are considered one of the most effective energy storage technologies to bridge the production and consumption of renewable energy. The further development of rechargeable batteries with characteristics such as high energy density, low cost, safety, and a long cycle life is required to meet the ever-increasing energy-storage demands. This Review highlights the progress achieved with halide-based materials in rechargeable batteries, including the use of halide electrodes, bulk and/or surface halogen-doping of electrodes, electrolyte design, and additives that enable fast ion shuttling and stable electrode/electrolyte interfaces, as well as realization of new battery chemistry. Battery chemistry based on monovalent cation, multivalent cation, anion, and dual-ion transfer is covered. This Review aims to promote the understanding of halide-based materials to stimulate further research and development in the area of high-performance rechargeable batteries. It also offers a perspective on the exploration of new materials and systems for electrochemical energy storage.

Dendrite-free Zn anodes enabled by functional nitrogen-doped carbon protective layers for aqueous zinc-ion batteries.

Rechargeable aqueous zinc-ion batteries possess the merits of good environmental benignity, high operational safety and high energy density. Nevertheless, the practical application of zinc-ion batteries is severely obstructed by the inhomogeneous deposition of metallic Zn on the anode, which results in serious capacity fading, poor coulombic efficiency, and electrolyte consumption. Herein, we propose a simple strategy of constructing a functional nitrogen-doped carbon network coating layer on zinc foil for dendrite-free Zn stripping/plating. On one hand, the good conductivity of the artificial Zn/electrolyte interface can quickly balance the electric field and lower the nucleation overpotential. On the other hand, the porosity feature and functional groups of the protective layer can provide a fast Zn2+ transportation pathway and generate well-dispersed nucleation seeds. Therefore, the protective layer can effectively hamper the growth of metallic Zn dendrites and resist side reactions. The as-prepared N-C/Zn anode displays superior cycling stability (800 h at 2 mA cm-2 with the capacity of 2 mA h cm-2) and a satisfactory coulombic efficiency of 98.76% during the Zn stripping/plating process. A long cycle life and high specific capacity (162.10 mA h g-1 after 500 cycles at 2.0 A g-1) are also obtained for N-C/Zn||ZnSO4||V2O5 full cells. The strategy provides a facile and effective opportunity for constructing high-performance rechargeable aqueous zinc-ion batteries.

High-performance rechargeable zinc-based dual-ion batteries

All the reported two kinds of nonaqueous zinc-based battery systems present good electrochemical performance and have good potential for large-scale energy storage with good safety and environmental friendliness.

In situ grown 2D hydrated ammonium vanadate nanosheets on carbon cloth as a free-standing cathode for high-performance rechargeable Zn-ion batteries

Ultrathin 2D ammonium vanadate nanosheets were grown on alkali-treated carbon cloth via a facile hydrothermal method. This free-standing cathode enables fast ion/electronic transport and reduces the aggregation of ultrathin ammonium vanadate nanosheets.

Highly crystalline nickel hexacyanoferrate as a long-life cathode material for sodium-ion batteries.

Prussian blue analogs (PBAs) are attractive cathode candidates for high energy density, including long life-cycle rechargeable batteries, due to their non-toxicity, facile synthesis techniques and low cost. Nevertheless, traditionally synthesized PBAs tend to have a flawed crystal structure with a large amount of [Fe(CN)6]4− openings and the presence of crystal water in the framework; therefore the specific capacity achieved has continuously been low with poor cycling stability. Herein, we demonstrate low-defect and sodium-enriched nickel hexacyanoferrate nanocrystals synthesized by a facile low-speed co-precipitation technique assisted by a chelating agent to overcome these problems. As a consequence, the prepared high-quality nickel hexacyanoferrate (HQ-NiHCF) exhibited a high specific capacity of 80 mA h g−1 at 15 mA g−1 (with a theoretical capacity of ∼85 mA h g−1), maintaining a notable cycling stability (78 mA h g−1 at 170 mA g−1 current density) without noticeable fading in capacity retention after 1200 cycles. This low-speed synthesis strategy for PBA-based electrode materials could be also extended to other energy storage materials to fabricate high-performance rechargeable batteries.

Self-catalytic approach to construct graphitized carbon shell for metal oxide: In-situ triggering mechanism and high-performance lithium-ion batteries applications

Carbon modification is one of the most important strategies to boost the performance of the material in many applications, where the carbon modified metal (oxide) anode gains great attention in metal-ion batteries due to their high capacity and improved stability. However, a close-knit carbon coating through an efficient and cost-effective approach remains challenging for satisfying the demand in practical application. Herein, a new in-situ self-catalytic approach by acetylene treatment is presented, in which a tunable graphitized carbon layer can be knitted on the metal (oxide) directly to produce many kinds of core-shell structured metal (oxide)@C hybrid materials. The in-situ triggering mechanism of forming graphitized carbon is discussed in detail using the model of MnO. Then, we find that the as-prepared MnO@C exhibits an extremely high lithium storage capacity of 1077 mAh g−1 and good rate capacities at 10 A g−1 over 500 cycles. In addition, a new full battery of MnO@C || LiNi0.8Co0.1Mn0.1O2 is constructed, where the high capacity retention of 73.1% at 0.5C over 250 cycles is well confirmed. This study not only opens a new avenue to prepare more carbon decorated functional materials but also explores the potential applications of metal (oxide)-based materials for high-performance rechargeable batteries.

A Stable Solid Electrolyte Interphase for Magnesium Metal Anode Evolved from a Bulky Anion Lithium Salt.

Rechargeable magnesium (Mg) metal batteries are a promising candidate for "post-Li-ion batteries" due to their high capacity, high abundance, and most importantly, highly reversible and dendrite-free Mg metal anode. However, the formation of passivating surface film rather than Mg2+ -conducting solid electrolyte interphase (SEI) on Mg anode surface has always restricted the development of rechargeable Mg batteries. A stable SEI is constructed on the surface of Mg metal anode by the partial decomposition of a pristine Li electrolyte in the electrochemical process. This Li electrolyte is easily prepared by dissolving lithium tetrakis(hexafluoroisopropyloxy)borate (Li[B(hfip)4 ]) in dimethoxyethane. It is noteworthy that Mg2+ can be directly introduced into this Li electrolyte during the initial electrochemical cycles for in situ forming a hybrid Mg2+ /Li+ electrolyte, and then the cycled electrolyte can conduct Mg-ion smoothly. The existence of this as-formed SEI blocks the further parasitic reaction of Mg metal anode with electrolyte and enables this electrolyte enduring long-term electrochemical cycles stably. This approach of constructing superior SEI on Mg anode surface and exploiting novel Mg electrolyte provides a new avenue for practical application of high-performance rechargeable Mg batteries.

The preparation of Si/SiC composites by magnesium heat reduction of SiO2 aerogel and study on electrochemistry properties

Silicon, an anode material for lithium ion batteries, has the highest theoretical specific capacity ([Formula: see text] mAh/g). The actual lithium storage capacity of [Formula: see text] mAh/g is about 10 times that of the graphite anode materials class. This study involves magnesium heat reduction of the SiO2 preparation of silicon carbon composites. The Si/SiC composite shows a high initial specific capacity of 1406.7 mAh/g with a current density of 0.1 A/g. The morphology and pore size inherited from the SiO2 aerogel counteracts the volume expansion during the lithiation/delithiation process. This paper provides an articulate methodology for designing silicon anode material for high-performance rechargeable lithium-ion batteries.

Lithium Ion Battery Performance for Different Size of Electrode Particles and Porosity

Nowadays, the interest of high proficiency of Lithium ion batteries is increasing as they provide high volumetric energy densities and to meet the demand of exponentially growth of electronic devices. Furthermore, LIB has shown their potential to offer high performance rechargeable battery in the research of electric vehicles. Electrochemical process of Lithium ion batteries encompasses a complex ion transport between the anode and cathode within an electrolyte. The multiscale LIB model consists of charge transport within electrode particle and in electrolyte and the reaction rate at the electrolyte-electrode particle interface which directly relating the geometry of microstructure (the size of particles, about 1nm) to the behaviour in macroscopic model (within the thickness of electrode, about 1 μm). Thus, the geometry of cell and the interfacial behaviour are significantly control the rate of reaction rate. This study concerns about the effect of geometry variations of cell upon the discharge curve of LiFePO4 cathode material. The electrochemical model is solved using Method of Lines technique by discretising the spatial variable using Finite Difference Method. The simulation result is verified with experimental data of LiFePO4 cell by Yu et. al. [14]. The effect of different sizes of particles and volume fractions upon the cell performance are examined. It has been shown that decreasing the size of electrode particles produce high cell potential but slightly low capacity. On the other hand, the optimal volume fraction is shown to be provided that all the particles are spherical and of the same size. Smaller volume fractions resulted in low capacity.

NiFe nanoparticles embedded N-doped carbon nanotubes as high-efficient electrocatalysts for wearable solid-state Zn-air batteries

Wearable and rechargeable Zn-air batteries (ZABs) hold great potential application in flexible electronic devices, and light-weight power sources for their high energy density and good safety. However, the practical application of ZABs is hindered by their low power density and poor rechargeability, which arises from the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on air cathode. Herein, a high-power, wearable ZAB with impressive electrochemical performances is achieved based on a new NiFe nanoparticles embedded N-doped carbon nanotubes (NiFe/N-CNT) as bifunctional electrocatalyst. The in-situ Raman and oxygen adsorption and DFT calculations reveal that our designed NiFe/N-CNT catalyst can remarkably promote the oxygen adsorption in ORR and OH− adsorption in OER, which enable this NiFe/N-CNT to own superior electrocatalytic activity toward both OER and ORR. The as-fabricated wearable ZAB with the NiFe/N-CNT as air cathode exhibits an ultrahigh open-circuit potential (Voc) of 1.41 V and a remarkable high peak power density of 105.4 mW cm−2, Furthermore, it also obtains a small charge-discharge voltage gap of 0.61 V and superior durability for 800 min. This research provides a new design pathway for the electrocatalysts for high-performance rechargeable and wearable metal-air batteries.

Optimization of Molecular Structure and Electrode Architecture of Anthraquinone-Containing Polymer Cathode for High-Performance Lithium-Ion Batteries.

Molecular structure and electrode architecture play very important roles in electrochemical performance of polymer electrode materials for lithium-ion batteries. Here, a series of anthraquinone-containing polymers with linear (with different molecular weights (MWs)) or cross-linked polymer structures were synthesized by (living) ring-opening metatheses (co)polymerization method. The influences of the molecular structures and electrode preparation process on the architectures and electrochemical performance of polymer electrodes were systematically investigated. It was found that the low MW linear polymers suffer from severe dissolution and thus result in low initial capacity and poor cycling stability. Under optimized electrode preparation process, high MW linear polymers can be uniformly composited with conductive additives and binders and deliver stable cycling performance. Cross-linked polymer shows significantly reduced solubility but a severe aggregation problem, leading to very poor electrochemical performance. Our findings shed light on the molecular structure design and electrode preparation process of polymer electrode materials for high-performance rechargeable batteries.