Cobalt/Nitrogen Co-Doped Carbon Materials Enhance the Reaction Rate of Sodium-Potassium Alloy Electrodes.

Sodium-potassium (NaK) alloy electrodes are ideal for next-generation dendrite-free alkali metal electrodes due to their dendrite-free nature. However, issues such as slow diffusion kinetics due to the large K+ radius and the loss of active potassium during the reaction severely limit its application. Here a novel cobalt/nitrogen-doped carbon material is designed and it is applied to the construction of a NaK alloy electrode. The experimental and theoretical results indicate that the confining effect of the nitrogen-doped graphitic carbon layer can protect the cobalt nanoparticles from corrosion leaching, while the presence of Co─Nx bonds and cobalt nanoparticles provides more active sites for the reaction, realizing the synergistic effect of adsorption-catalytic modulation, lowering the K+ diffusion energy barrier and promoting charge transfer and ion diffusion. The application of this electrode to a symmetrical battery can achieve more than 1800 stable cycles under a current density of 0.4 mA cm-2 and a charge/discharge specific capacity of 122.64 mAh g-1 under a current of 0.5C in a full battery. This finding provides a new idea to realize a fast, stable, and efficient application of NaK alloy electrodes.

A triple-synergistic small-molecule sulfur cathode promises energetic Cu-S electrochemistry.

Metal-sulfur batteries have received great attention for electrochemical energy storage due to high theoretical capacity and low cost, but their further development is impeded by low sulfur utilization, poor electrochemical kinetics, and serious shuttle effect of the sulfur cathode. To avoid these problems, herein, a triple-synergistic small-molecule sulfur cathode is designed by employing N, S co-doped hierarchical porous bamboo charcoal as a sulfur host in an aqueous Cu-S battery. Expect the enhanced conductivity and chemisorption induced by N, S synergistic co-doping, the intrinsic synergy of macro-/meso-/microporous triple structure also ensures space-confined small-molecule sulfur as high utilization reactant and effectively alleviates the volume expansion during conversion reaction. Under a further joint synergy between hierarchical structure and heteroatom doping, the resulting sulfur cathode endows the Cu-S battery with outstanding electrochemical performance. Cycled at 5 A g-1, it can deliver a high reversible capacity of 2,509.8 mAh g-1 with a good capacity retention of 97.9% after 800 cycles. In addition, a flexible hybrid pouch cell built by a small-molecule sulfur cathode, Zn anode, and gel electrolytes can firmly deliver high average operating voltage of about 1.3 V with a reversible capacity of over 2,500 mAh g-1 under various destructive conditions, suggesting that the triple-synergistic small-molecule sulfur cathode promises energetic metal-sulfur batteries.

Tailoring short-chain sulfur molecules to drive redox dynamics for sulfur-based aqueous battery.

Solid-solid reactions stand out in rechargeable sulfur-based batteries due to the robust redox couples and high sulfur utilization in theory. However, conventional solid-solid reactions in sulfur cathode always present slow reaction kinetics and huge redox polarization due to the low electronic conductivity of sulfur and the generation of various electrochemical inert intermediates. In view of this, it is crucial to improve the electrochemical activity of sulfur cathode and tailor the redox direction. Guided by thermodynamics analysis, short-chain sulfur molecules (S2-4) are successfully synthesized by space-limited domain principle. Unlike conventional cyclic S8 molecules with complex routes in solid-solid reaction, short-chain sulfur molecules not only shorten the length of the redox chain but also inhibit the formation of irreversible intermediates, which brings excellent redox dynamics and reversibility. As a result, the Cu-S battery built by short-chain sulfur molecules can deliver a high reversible capacity of 3,133 mAh g-1. To put this into practice, quasi-solid-state aqueous flexible battery based on short-chain sulfur molecules is also designed and evaluated, showing superior mechanical flexibility and electrochemical property. It indicates that the introduction of short-chain sulfur molecules in rechargeable battery can promote the development and application of high-performance sulfur-based aqueous energy storage systems.

Toward Sustainable Metal-Iodine Batteries: Materials, Electrochemistry and Design Strategies.

Due to the natural abundance of iodine, cost-effective, and sustainability, metal-iodine batteries are competitive for the next-generation energy storage systems with high energy density, and large power density. However, the inherent properties of iodine such as electronic insulation and shuttle behavior of soluble iodine species affect negatively rate performance, cyclability, and self-discharge behavior of metal-iodine batteries, while the dendrite growth and metal corrosion on the anode side brings potential safety hazards and inferior durability. These problems of metal-iodine system still exist and need to be solved urgently. Herein, we summarize the research progress of metal-iodine batteries in the past decades. Firstly, the classification, design strategy and reaction mechanism of iodine electrode are briefly outlined. Secondly, the current development and protection strategy of conventional metal anodes in metal-iodine batteries are highlighted, and some potential anode materials and their design strategies are proposed. Thirdly, the key electrochemical parameters of state-of-art metal-iodine batteries are compared and analyzed to solve critical issues for realizing next-generation iodine-based energy storage systems. Therefore, the aim of this review is to promote the development of metal-iodine batteries and provide guidelines for their design.

Ammonium Ion Batteries: Material, Electrochemistry and Strategy.

Ammonium-ion batteries (AIBs) have recently attracted increasing attention in the field of aqueous batteries owing to their high safety and fast diffusion kinetics. The NH4 + storage mechanism is quite different from that of spherical metal ions (e.g. Li+ , Na+ , K+ , Mg2+ , and Zn2+ ) because of the formation of hydrogen bonds between NH4 + and host materials. Although many materials have been proposed as electrode materials for AIBs, their performances hardly meet the requirement of future electrochemical energy storage devices. It is thus urgent to design and exploit advanced materials for AIBs. This review highlights the state-of-the-art research on AIBs. The insights into the basic configuration, operating mechanism and recent progress of electrode materials and corresponding electrolytes for AIBs have been comprehensively outlined. The electrode materials are classified and compared according to different NH4 + storage behaviour in the structure. The challenges, design strategies and perspectives are also discussed for the future development of AIBs.

Dual synergistic effects assisting Cu-SeS2 electrochemistry for energy storage.

Selenium sulfide (SeS2) features higher electronic conductivity than sulfur and higher theoretical capacity and lower cost than selenium, attracting considerable interest in energy storage field. Although nonaqueous Li/Na/K-SeS2 batteries are attractive for their high energy density, the notorious shuttle effect of polysulfides/polyselenides and the intrinsic limitations of organic electrolyte have hindered the deployment of this technology. To circumvent these issues, here we design an aqueous Cu-SeS2 battery by encapsulating SeS2 in a defect-enriched nitrogen-doped porous carbon monolith. Except the intrinsic synergistic effect between Se and S in SeS2, the porous structure of carbon matrix has sufficient internal voids to buffer the volume change of SeS2 and provides abundant pathways for both electrons and ions. In addition, the synergistic effect of nitrogen doping and topological defect not only enhances the chemical affinity between reactants and carbon matrix but also offers catalytic active sites for electrochemical reactions. Benefiting from these merits, the Cu-SeS2 battery delivers superior initial reversible capacity of 1,905.1 mAh g-1 at 0.2 A g-1 and outstanding long-span cycling performance over 1,000 cycles at 5 A g-1. This work applies variable valence charge carriers to aqueous metal-SeS2 batteries, providing valuable inspiration for the construction of metal-chalcogen batteries.

Synergistic dual conversion reactions assisting Pb-S electrochemistry for energy storage.

SignificanceBased on the analysis of three thermodynamic parameters of various M-S systems (solubility of metal sulfides [MxSy] in aqueous solution, volume change of the metal-sulfur [M-S] battery system, and the potential of S/MxSy cathode redox couple), an aqueous Pb-S battery operated by synergistic dual conversion reactions (cathode: S⇄PbS, anode: Pb2+⇄PbO2) has been officially reported. Benefitting from the inherent insolubility of PbS and a conversion-type counter electrode, the aqueous Pb-S battery exhibited two advantages: it is shuttle effect free and has a dendrite-free nature. Moreover, the practical value of the Pb-S battery was further certified by the prototype S|Pb(NO3)2ǁZn(NO3)2|Zn hybrid cell, which afforded an energy density of 930.9 Wh kg-1sulfur.

Prussian Blue Analogues in Aqueous Batteries and Desalination Batteries.

In the applications of large-scale energy storage, aqueous batteries are considered as rivals for organic batteries due to their environmentally friendly and low-cost nature. However, carrier ions always exhibit huge hydrated radius in aqueous electrolyte, which brings difficulty to find suitable host materials that can achieve highly reversible insertion and extraction of cations. Owing to open three-dimensional rigid framework and facile synthesis, Prussian blue analogues (PBAs) receive the most extensive attention among various host candidates in aqueous system. Herein, a comprehensive review on recent progresses of PBAs in aqueous batteries is presented. Based on the application in different aqueous systems, the relationship between electrochemical behaviors (redox potential, capacity, cycling stability and rate performance) and structural characteristics (preparation method, structure type, particle size, morphology, crystallinity, defect, metal atom in high-spin state and chemical composition) is analyzed and summarized thoroughly. It can be concluded that the required type of PBAs is different for various carrier ions. In particular, the desalination batteries worked with the same mechanism as aqueous batteries are also discussed in detail to introduce the application of PBAs in aqueous systems comprehensively. This report can help the readers to understand the relationship between physical/chemical characteristics and electrochemical properties for PBAs and find a way to fabricate high-performance PBAs in aqueous batteries and desalination batteries.

Copper niobate nanowires boosted by a N, S co-doped carbon coating for superior lithium storage.

With the development of electric vehicles, more and more attention has been paid to the kinetic performance of batteries, which is related to rapid charge/discharge and safety issues. To improve this aspect, Cu2Nb34O87 nanowires covered by nitrogen and sulfur co-doped carbon (Cu2Nb34O87/NSC nanowires) are prepared by electrospinning combined with surface coating. As-prepared Cu2Nb34O87/NSC nanowires present a high ion diffusion coefficient and electronic conductivity, showing good a kinetic performance. Specifically, they deliver a splendid capacity of 311.2 mA h g-1 at 1 C and a superior cycling stability with a capacity fading of 0.031% per cycle upon 1000 cycles. At the same time, the electrochemical and structural reversibility is fully discussed and demonstrated by ex situ XRD, ex situ SEM and ex situ XPS based on the redox couples of Cu2+/Cu+, Nb5+/Nb4+, and Nb4+/Nb3+. Contributing to peculiar physico-chemical properties, Cu2Nb34O87/NSC nanowires are expected to be a candidate material for the anode in lithium-ion batteries.

Hydrogen Bond-Assisted Ultra-Stable and Fast Aqueous NH4+ Storage.

Aqueous ammonium ion batteries are regarded as eco-friendly and sustainable energy storage systems. And applicable host for NH4+ in aqueous solution is always in the process of development. On the basis of density functional theory calculations, the excellent performance of NH4+ insertion in Prussian blue analogues (PBAs) is proposed, especially for copper hexacyanoferrate (CuHCF). In this work, we prove the outstanding cycling and rate performance of CuHCF via electrochemical analyses, delivering no capacity fading during ultra-long cycles of 3000 times and high capacity retention of 93.6% at 50 C. One of main contributions to superior performance from highly reversible redox reaction and structural change is verified during the ammoniation/de-ammoniation progresses. More importantly, we propose the NH4+ diffusion mechanism in CuHCF based on continuous formation and fracture of hydrogen bonds from a joint theoretical and experimental study, which is another essential reason for rapid charge transfer and superior NH4+ storage. Lastly, a full cell by coupling CuHCF cathode and polyaniline anode is constructed to explore the practical application of CuHCF. In brief, the outstanding aqueous NH4+ storage in cubic PBAs creates a blueprint for fast and sustainable energy storage.

A TiSe2 -Graphite Dual Ion Battery: Fast Na-Ion Insertion and Excellent Stability.

The sodium dual ion battery (Na-DIB) technology is proposed as highly promising alternative over lithium-ion batteries for the stationary electrochemical energy-storage devices. However, the sluggish reaction kinetics of anode materials seriously impedes their practical implementation. Herein, a Na-DIB based on TiSe2 -graphite is reported. The high diffusion coefficient of Na-ions (3.21×10-11 -1.20×10-9  cm2 s-1 ) and the very low Na-ion diffusion barrier (0.50 eV) lead to very fast electrode kinetics, alike in conventional surface capacitive storage systems. In-situ investigations reveal that the fast Na-ion diffusion involves four insertion stage compositions. A prototype cell shows a reversible capacity of 81.8 mAh g-1 at current density of 100 mA g-1 , excellent stability with 83.52 % capacity retention over 200 cycles and excellent rate performance, suggesting its potential for next-generation large scale high-performance stationary energy storage systems.

Common ion effect enhanced Prussian blue analogues for aqueous ammonium ion storage.

In order to meet the growing demand of energy storage for the power grid, aqueous NH4+ batteries are attracting increasing attention as a promising alternative due to their environmental significance, abundant resources, and fast diffusion ability. In this work, FeFe(CN)6 (FeHCF) is synthesized as a cathode material for aqueous NH4+ batteries and Fe2(SO4)3 is utilized as a kind of functional additive in the electrolyte based on the "common ion effect" to enhance its electrochemical performance. The results indicate that the initial capacity of FeHCF is about 80 mA h g-1 with a coulombic efficiency of 97.8%. The retention rate can attain 96.3% within nearly 1000 cycles. Multivariate analysis methods are carried out to characterize the mechanism of FeHCF in aqueous NH4+ batteries. From the practical standpoint, FeHCF has outstanding cycling stability and rate capability, making it feasible to be applied in the power grid.

Observation of ZrNb14O37 Nanowires as a Lithium Container via In Situ and Ex Situ Techniques for High-Performance Lithium-Ion Batteries.

Based on the high theoretical capacity and relatively high safety voltage, niobium-based oxides are regarded as promising intercalation-type electrode materials for advanced lithium-ion batteries (LIBs). Here, ZrNb14O37 nanowires are fabricated via a facile electrospinning method, presenting a nanoparticle-in-nanowire architecture. As an anode for LIBs, the as-fabricated ZrNb14O37 nanowires maintain a capacity of 244.9 mA h g-1 at 100 mA g-1 and present excellent cycling capability (0.026% of capacity fading per cycle during 1000 cycles) as well as outstanding rate performance. In situ X-ray diffraction measurement is conducted to understand the fundamental reaction mechanism during the lithiation/delithiation process. The ex situ observations, including X-ray photoelectron spectroscopy and transmission electron microscopy, are further performed to provide more lines of evidence of the reaction mechanism. Moreover, the excellent electrochemical performance of the full cell constructed using ZrNb14O37 nanowires and LiCoO2 suggests that ZrNb14O37 nanowires are a promising anode material. This work sheds new light on understanding the lithium storage mechanism and may open new opportunities to develop new anode materials for LIBs.

H0.92K0.08TiNbO5 Nanowires Enabling High-Performance Lithium-Ion Uptake.

HTiNbO5 has been widely investigated in many fields because of its distinctive properties such as good redox activity, high photocatalytic activity, and environmental benignancy. Here, this work reports the synthesis of one-dimensional H0.92K0.08TiNbO5 nanowires via simple electrospinning followed by an ion-exchange reaction. The H0.92K0.08TiNbO5 nanowires consist of many small "lumps" with a uniform diameter distribution of around 150 nm. Used as an anode for lithium-ion batteries, H0.92K0.08TiNbO5 nanowires exhibit high capacity, fast electrochemical kinetics, and high performance of lithium-ion uptake. A capacity of 144.1 mA h g-1 can be carried by H0.92K0.08TiNbO5 nanowires at 0.5 C in the initial charge, and even after 150 cycles, the reversible capacity can remain at 123.7 mA h g-1 with an excellent capacity retention of 85.84%. For H0.92K0.08TiNbO5 nanowires, the diffusion coefficient of lithium ions is 1.97 × 10-11 cm2 s-1, which promotes the lithium-ion uptake effectively. The outstanding electrochemical performance is ascribed to its morphology and the formation of a stable phase during cycling. In addition, the in situ X-ray diffraction and ex situ transmission electron microscopy techniques are applied to reveal its lithium storage mechanism, which proves the structure stability and electrochemical reversibility, thus achieving high-performance lithium-ion uptake. All these advantages demonstrate that H0.92K0.08TiNbO5 nanowires can be a possible alternative anode material for rechargeable batteries.

Sol-Gel Synthesis and in Situ X-ray Diffraction Study of Li3Nd3W2O12 as a Lithium Container.

In this work, garnet-framework Li3Nd3W2O12 as a novel insertion-type anode material has been prepared via a facile sol-gel method and examined as a lithium container for lithium ion batteries (LIBs). Li3Nd3W2O12 shows a charge capacity of 225 mA h g-1 at 50 mA g-1, and with the current density increasing up to 500 mA g-1, the charge capacity can still be maintained at 186 mA h g-1. After cycling at 500 mA g-1 for 500 cycles, Li3Nd3W2O12 retains about 85% of its first charge capacity changed from 190.2 to 161 mA h g-1. Furthermore, in situ X-ray diffraction technique is adopted for the understanding of the insertion/extraction mechanism of Li3Nd3W2O12. The full-cell configuration LiFePO4/Li3Nd3W2O12 is also assembled to evaluate the potential of Li3Nd3W2O12 for practical application. These results show that Li3Nd3W2O12 is such a promising anode material for LIBs with excellent electrochemical performance and stable structure.

High-Rate Long-Life Pored Nanoribbon VNb9O25 Built by Interconnected Ultrafine Nanoparticles as Anode for Lithium-Ion Batteries.

VNb9O25 is a novel lithium storage material, which has not been systematically investigated so far. Via electrospinning technology, VNb9O25 samples with two different morphologies, pored nanoribbon and rodlike nanoparticles, are prepared in relatively low temperature and time-saving calcination conditions. It is found that the formation process of different morphologies depends on the control of self-aggregation of the precursor by using different sample collectors. Compared with rodlike VNb9O25 (RL-VNb9O25), pored nanoribbon VNb9O25 (PR-VNb9O25) can deliver a higher specific capacity, lower capacity loss, and better cyclability. Even cycled at 1000 mA g-1, the reversible capacity of 132.3 mAh g-1 is maintained by PR-VNb9O25 after 500 cycles, whereas RL-VNb9O25 only exhibits a capacity of 102.7 mAh g-1. The enhancement should be attributed to the pored nanoribbon structure with large specific surface area and shorter pathway for lithium ions transport. Furthermore, the lithium ions insertion/extraction process is verified from refinement results of in situ X-ray diffraction data, which is associated with a lithium occupation process in type III and VI cavities through tunnels I, II, and III. In addition, high structural stability and electrochemical reversibility are also demonstrated. All of these advantages suggest that PR-VNb9O25 is a promising anode material for lithium-ion batteries.

Effect of Sodium-Site Doping on Enhancing the Lithium Storage Performance of Sodium Lithium Titanate.

Via Li(+), Cu(2+), Y(3+), Ce(4+), and Nb(5+) dopings, a series of Na-site-substituted Na1.9M0.1Li2Ti6O14 are prepared and evaluated as lithium storage host materials. Structural and electrochemical analyses suggest that Na-site substitution by high-valent metal ions can effectively enhance the ionic and electronic conductivities of Na2Li2Ti6O14. As a result, Cu(2+)-, Y(3+)-, Ce(4+)-, and Nb(5+)-doped samples reveal better electrochemical performance than bare Na2Li2Ti6O14, especially for Na1.9Nb0.1Li2Ti6O14, which can deliver the highest reversible charge capacity of 259.4 mAh g(-1) at 100 mA g(-1) among all samples. Even when cycled at higher rates, Na1.9Nb0.1Li2Ti6O14 still can maintain excellent lithium storage capability with the reversible charge capacities of 242.9 mAh g(-1) at 700 mA g(-1), 216.4 mAh g(-1) at 900 mA g(-1), and 190.5 mAh g(-1) at 1100 mA g(-1). In addition, ex situ and in situ observations demonstrate that the zero-strain characteristic should also be responsible for the outstanding lithium storage capability of Na1.9Nb0.1Li2Ti6O14. All of this evidence indicates that Na1.9Nb0.1Li2Ti6O14 is a high-performance anode material for rechargeable lithium ion batteries.