Ultra-expanded interlayer spacing of vanadium oxide nanowires intercalated with poly(3,4-ethylene dioxythiophene) in organic ammonium ion batteries.

Rechargeable batteries employing ammonium (NH4+) ions have attracted widespread interest owing to the abundant resources, eco-friendliness, and sustainability of NH4+ ions. Herein, an organic-inorganic hybrid is applied to organic NH4+ ion batteries. A poly (3,4-ethylene dioxythiophene) (PEDOT)-intercalated vanadium oxide nanowire (noted as VO-P-x) is applied for organic NH4+ ion storage. VO-P-x with the optimal content of PEDOT showed an interlayer spacing (d-spacing) expanded to 1.82 nm, exhibiting an ultrahigh initial coulombic efficiency of 91% and a reversible capacity of 163 mA h g-1. A significant improvement in NH4+ ion storage was achieved due to the large interlayer spacing and conductive polymer PEDOT. Combining ex situ X-ray photoelectron spectroscopy (XPS) and multi-sweep cyclic voltammetry tests, the NH4+ ion storage mechanism of VO-P-x was clearly revealed. This study provides a new strategy for designing high-performance organic ammonium batteries.

Control of Gradient Concentration Prussian White Cathodes for High-Performance Potassium-Ion Batteries.

Owing to their abundant resources and low cost, potassium-ion batteries (PIBs) have become a promising alternative to lithium-ion batteries (LIBs). However, the larger ionic radius and higher mass of K+ propose a challenging issue for finding suitable cathode materials. Prussian whites (PWs) have a rigid open framework and affordable synthesis method, but they suffer quick capacity fade due to lattice volume change and structural instability during K+ insertion/extraction. Here, we prepared controllable gradient concentration KxFeaNibMn1-a-b[Fe(CN)6]y·zH2O particles via a facile coprecipitation process, demonstrating high-performance potassium-ion storage. The high-Mn content in the interior can minimize capacity loss caused by electrochemically inert Ni and achieve a high reversible capacity; meanwhile, the high-FeNi content in the exterior can alleviate the volume change of the core material upon cycling, thus enhancing structural stability. Taking the above synergistic effect, the controllable gradient concentration PWs deliver a high reversible capacity of 109.8 mAh g-1 at 100 mA g-1 and good capacity retention of 77.8% after 200 cycles. The gradient concentration PWs can retain structural integrity and stability during long-term cycling. This work provides a prospective strategy to fabricate PWs with stable structure and excellent electrochemical performance for developing high-performance PIBs.

Fe-N-C single-atom nanozyme for ultrasensitive, on-site and multiplex detection of mycotoxins using lateral flow immunoassay.

Sensitive, on-site and multiple detection of mycotoxins is a vital early-warning tool to minimize food losses and protect human health and the environment. Although paper-based lateral flow immunoassay (LFIA) has been extensively applied in mycotoxins monitoring, low-cost, portable, ultrasensitive and quantitative detection is still a formidable challenge. Herein, a series of Fe-N-C single-atom nanozymes (SAzymes) were synthesized and systematic characterized. The optimal Fe-N-C SAzyme with highly efficient catalytic performance was successfully used as both label and catalyst in lateral flow immunoassays for mycotoxin detection. By taking advantage of the catalytic amplified system, the qualitative and quantitative detection can be easily and flexibly done via observing the test lines by naked eyes or a smartphone, with the limit of detections (LODs) of 2.8 and 13.9 pg mL-1 for AFB1 and FB1, which were respectively over 700- and 71,000-fold lower than the maximum limit set by the European Union. Besides, underlying catalytic mechanisms and the active sites of the Fe-N-C SAzyme are also investigated by DFT simulation. This work not only provides a promising detection strategy for the application of advanced SAzymes but also offers experimental and theoretical guidelines to understand the active centers of Fe-N-C SAzymes and the catalytic process.

Preferential Extraction of Lithium from Spent Cathodes and the Regeneration of Layered Oxides for Li/Na-Ion Batteries.

The preferentially selective extraction of Li+ from spent layered transition metal oxide (LiMO2, M = Ni, Co, Mn, etc.) cathodes has attracted extensive interest based on economic and recycling efficiency requirements. Presently, the efficient recycling of spent LiMO2 is still challenging due to the element loss in multistep processes. Here, we developed a facile strategy to selectively extract Li+ from LiMO2 scraps with stoichiometric H2SO4. The proton exchange reaction could be driven using temperature, accompanied by the generation of soluble Li2SO4 and MOOH precipitates. The extraction mechanism includes a two-stage evolution, including dissolution and ion exchange. As a result, the extraction rate of Li+ is over 98.5% and that of M ions is less than 0.1% for S-NCM. For S-LCO, the selective extraction result is even better. Finally, Li2CO3 products with a purity of 99.68% can be prepared from the Li+-rich leachate, demonstrating lithium recovery efficiencies as high as 95 and 96.3% from NCM scraps and S-LCO scraps, respectively. In the available cases, this work also represents the highest recycling efficiency of lithium, which can be attributed to the high leaching rate and selectivity of Li+, and even demonstrates the lowest reagent cost. The regenerated LiNi0.5Co0.24Mn0.26O2 and Na1.01Li0.001Ni0.38Co0.18Mn0.44O2 cathodes also deliver a decent electrochemical performance for Li-ion batteries (LIBs) and Na-ion batteries (NIBs), respectively. Our current work offers a facile, closed-loop, and scalable strategy for recycling spent LIB cathodes based on the preferentially selective extraction of Li+, which is superior to the other leaching technology in terms of its cost and recycling yield.

Organic Ammonium Ion Battery: A New Strategy for a Nonmetallic Ion Energy Storage System.

Nonmetallic ammonium (NH4 + ) ion batteries are promising candidates for large-scale energy storage systems, which have the merit of low molar mass, sustainability, non-toxicity and non-dendrite. Herein, for the first time, we introduce the novel organic ammonium ion batteries (OAIBs). Significantly, a manganese-based Prussian white analogue (noted as MnHCF) as cathode exhibits a reversible capacity of 104 mAh g-1 with 98 % retention over 100 cycles. We further demonstrate the electrochemical performance of the NH4 + ion full cell, which delivers a reversible capacity of 45 mAh g-1 with a broad electrochemical window. Combining ex situ XPS, ex situ XRD results and electrochemical properties, the NH4 + ion storage mechanism of MnHCF in a non-aqueous electrolyte is clearly revealed. This work verifies the feasibility of employing NH4 + ions as charge carriers in organic energy storage systems and provides new insights for designing organic nonmetallic ion batteries with broad electrochemical windows and high energy density.

Novel High-Performance and Low-Cost Electrochromic Prussian White Film.

Prussian white (PW), due to its low cost, easy synthesis, open structure, and fast ion extraction/interaction, is introduced to the electrochromic field. The PW films were successfully grown on indium tin oxide (ITO) glass by a facial hydrothermal method. Impressively, the PW film exhibits excellent electrochemical cycling stability without obvious decay over 10 000 cycles and a high coloration efficiency of 149.3 cm2 C-1. The film also provides the large optical transmittance contrast (over 70%) in a wide wavelength range of 650-800 nm. Furthermore, the PW film shows the rapid coloration and bleaching response. These results suggest that PW is a promising practical candidate of high-performance electrochromic material.

The Quest for Stable Potassium-Ion Battery Chemistry.

Potassium-ion batteries (KIBs) have attracted wide interest for energy storage because of the abundance of the electrode materials involved; however, their electrochemical performances are far behind what can be achieved from lithium-ion batteries (LIBs) or sodium-ion batteries (SIBs). Herein, key promising electrode and electrolyte materials for potassium-ion batteries are identified, the coupled electrochemical reactions in the cell are investigated, and the compatibility between different materials is demonstrated to play the most important role. K2 Mn[Fe(CN)6 ] cathode can deliver a high capacity of ≈125 mAh g-1 and exceptional cycling stability over 61 000 cycles (≈9 months) if the side reactions from the anode can be prevented. Graphite is a good anode material but is subjected to degradation in traditional carbonate electrolytes. New concentrated electrolytes are developed and evaluated. A stable KIB system is demonstrated by coupling a stable K2 Mn[Fe(CN)6 ] cathode, a prepotassiated graphite anode with a concentrated electrolyte to achieve a high energy density of ≈260 Wh kg-1 (based on the active mass of cathode and anode) and good cycling of over 1000 cycles.

Boosting the Electrochemical Performance of Li1.2Ni0.13Co0.13Mn0.54O2 by Rough Coating with the Superionic Conductor Li7La3Zr2O12.

Li-rich Mn-based layered compounds have progressed as promising cathode materials for lithium-ion batteries (LIBs) due to their relatively low cost, considerable energy storage capacity, and high operating voltage. However, they suffer critical drawbacks, such as capacity decay and inferior rate performance, which restrain their real applications. We carried out surface modification via rough coating of superionic conductor Li7La3Zr2O12 (LLZO) on the Li-rich Mn-based layered cathode. The cathode with a LLZO coating exhibits significantly improved electrochemical performance, which mainly benefits from the enhanced Li-ion diffusion and reduced side reactions at electrode/electrolyte interfaces via effective coating of LLZO layer. This work provides a facile and efficient way to design Li-rich Mn-based cathodes for high-energy and stable LIBs.

Hierarchical Copper Sulfide Porous Nanocages for Rechargeable Multivalent-Ion Batteries.

Copper sulfide (CuS) has been identified as a promising positive electrode material for some multivalent-ion batteries (such as the magnesium-ion battery) because of its high theoretical capacity, environmental friendliness, and wide availability. However, the clumsy multivalent-ion with high polarity inclines toward sluggish ion insertion/de-insertion, leading to inadequate electrochemical performance. In this work, the hierarchical CuS porous nanocages are successfully fabricated via a facile one-step room-temperature liquid-phase process and evaluated as positive electrode materials for rechargeable magnesium batteries. Owing to the structural advantages, a high reversible magnesium storage capacity of 228 mA h g-1 is attained, which is superior to the previously reported results under similar conditions. Besides, the application of CuS as positive electrode materials for calcium-ion, zinc-ion, iron-ion, and aluminum-ion batteries is investigated. The hierarchical CuS porous nanocages display promising electrochemical performance in those multivalent-ion battery systems. Our work proves the superiority of the nanostructure design in improving the electrochemical performance of positive electrode materials for multivalent-ion batteries.

N-Doped carbon coated bismuth nanorods with a hollow structure as an anode for superior-performance potassium-ion batteries.

Bismuth (Bi) is a promising anode material for potassium-ion batteries due to its high energy density. However, the large volume change limits its applications. Herein, N-doped carbon coated Bi nanorods with a hollow structure are fabricated and they exhibit excellent long-term cycling performance (88% capacity retention over 1000 cycles) and high-rate ability (297 mA h g-1 at 20C, 94% capacity of that at 1C). Furthermore, the mechanism was expounded by in situ XRD, indicating a multi-phase reaction for the initial discharge process and three two-phase reactions for the subsequent charge/discharge processes.

NASICON-Structured Materials for Energy Storage.

The demand for electrical energy storage (EES) is ever increasing, which calls for better batteries. NASICON-structured materials represent a family of important electrodes due to its superior ionic conductivity and stable structures. A wide range of materials have been considered, where both vanadium-based and titanium-based materials are recommended as being of great interest. NASICON-structured materials are suitable for both the cathode and the anode, where the operation potential can be easily tuned by the choice of transition metal and/or polyanion group in the structure. NASICON-structured materials also represent a class of solid electrolytes, which are widely employed in all-solid-state ion batteries, all-solid-state air batteries, and hybrid batteries. NASICON-structured materials are reviewed with a focus on both electrode materials and solid-state electrolytes.

Hard carbon anodes of sodium-ion batteries: undervalued rate capability.

The rate capability of hard carbon has long been underestimated in prior studies that used carbon/Na two-electrode half-cells. Through a three-electrode cell setup, we discover that it is the overpotential of the sodium counter electrode that drives the half-cells to the lower cutoff potential prematurely during hard carbon sodiation, particularly at high current rates, which prevents the hard carbon anode from being fully sodiated.

Hydronium-Ion Batteries with Perylenetetracarboxylic Dianhydride Crystals as an Electrode.

We demonstrate for the first time that hydronium ions can be reversibly stored in an electrode of crystalline 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). PTCDA exhibits a capacity of 85 mAh g-1 at 1 A g-1 after an initial conditioning process. Ex situ X-ray diffraction revealed reversible and significant structure dilation upon reduction of PTCDA in an acidic electrolyte, which can only be ascribed to hydronium-ion intercalation. The lattice expansion upon hydronium storage was theoretically explored by first-principles density functional theory (DFT) calculations, which confirmed the hydronium storage in PTCDA.

Potassium Secondary Batteries.

Potassium may exhibit advantages over lithium or sodium as a charge carrier in rechargeable batteries. Analogues of Prussian blue can provide millions of cyclic voltammetric cycles in aqueous electrolyte. Potassium intercalation chemistry has recently been demonstrated compatible with both graphite and nongraphitic carbons. In addition to potassium-ion batteries, potassium-O2 (or -air) and potassium-sulfur batteries are emerging. Additionally, aqueous potassium-ion batteries also exhibit high reversibility and long cycling life. Because of potentially low cost, availability of basic materials, and intriguing electrochemical behaviors, this new class of secondary batteries is attracting much attention. This mini-review summarizes the current status, opportunities, and future challenges of potassium secondary batteries.

Polynanocrystalline Graphite: A New Carbon Anode with Superior Cycling Performance for K-Ion Batteries.

We synthesized a new type of carbon-polynanocrystalline graphite-by chemical vapor deposition on a nanoporous graphenic carbon as an epitaxial template. This carbon is composed of nanodomains being highly graphitic along c-axis and very graphenic along ab plane directions, where the nanodomains are randomly packed to form micron-sized particles, thus forming a polynanocrystalline structure. The polynanocrystalline graphite is very unique, structurally different from low-dimensional nanocrystalline carbon materials, e.g., fullerenes, carbon nanotubes, and graphene, nanoporous carbon, amorphous carbon and graphite, where it has a relatively low specific surface area of 91 m2/g as well as a low Archimedes density of 0.92 g/cm3. The structure is essentially hollow to a certain extent with randomly arranged nanosized graphite building blocks. This novel structure with disorder at nanometric scales but strict order at atomic scales enables substantially superior long-term cycling life for K-ion storage as an anode, where it exhibits 50% capacity retention over 240 cycles, whereas for graphite, it is only 6% retention over 140 cycles.

Hierarchical nanoporosity enhanced reversible capacity of bicontinuous nanoporous metal based Li-O2 battery.

High-energy-density rechargeable Li-O2 batteries are one of few candidates that can meet the demands of electric drive vehicles and other high-energy applications because of the ultra-high theoretical specific energy. However, the practical realization of the high rechargeable capacity is usually limited by the conflicted requirements for porous cathodes in high porosity to store the solid reaction products Li2O2 and large accessible surface area for easy formation and decomposition of Li2O2. Here we designed a hierarchical and bicontinuous nanoporous structure by introducing secondary nanopores into the ligaments of coarsened nanoporous gold by two-step dealloying. The hierarchical and bicontinuous nanoporous gold cathode provides high porosity, large accessible surface area and sufficient mass transport path for high capacity and long cycling lifetime of Li-O2 batteries.

Carbon Electrodes for K-Ion Batteries.

We for the first time report electrochemical potassium insertion in graphite in a nonaqueous electrolyte, which can exhibit a high reversible capacity of 273 mAh/g. Ex situ XRD studies confirm that KC36, KC24, and KC8 sequentially form upon potassiation, whereas depotassiation recovers graphite through phase transformations in an opposite sequence. Graphite shows moderate rate capability and relatively fast capacity fading. To improve the performance of carbon K-ion anodes, we synthesized a nongraphitic soft carbon that exhibits cyclability and rate capability much superior to that of graphite. This work may open up a new paradigm toward rechargeable K-ion batteries.

High Energy Density Aqueous Electrochemical Capacitors with a KI-KOH Electrolyte.

We report a new electrochemical capacitor with an aqueous KI-KOH electrolyte that exhibits a higher specific energy and power than the state-of-the-art nonaqueous electrochemical capacitors. In addition to electrical double layer capacitance, redox reactions in this device contribute to charge storage at both positive and negative electrodes via a catholyte of IOx-/I- couple and a redox couple of H2O/Had, respectively. Here, we, for the first time, report utilizing IOx-/I- redox couple for the positive electrode, which pins the positive electrode potential to be 0.4-0.5 V vs Ag/AgCl. With the positive electrode potential pinned, we can polarize the cell to 1.6 V without breaking down the aqueous electrolyte so that the negative electrode potential could reach -1.1 V vs Ag/AgCl in the basic electrolyte, greatly enhancing energy storage. Both mass spectroscopy and Raman spectrometry confirm the formation of IO3- ions (+5) from I- (-1) after charging. Based on the total mass of electrodes and electrolyte in a practically relevant cell configuration, the device exhibits a maximum specific energy of 7.1 Wh/kg, operates between -20 and 50 °C, provides a maximum specific power of 6222 W/kg, and has a stable cycling life with 93% retention of the peak specific energy after 14,000 cycles.

Nanoporous Ru as a carbon- and binder-free cathode for Li-O2 batteries.

Porous carbon-free cathodes are critical to achieve a high discharge capacity and efficient cycling for rechargeable Li-O2 battery. Herein, we present a very simple method to directly grow nanoporous Ru (composed of polycrystalline particles of ∼5 nm) on one side of a current collector of Ni foam via a galvanic replacement reaction. The resulting Ru@Ni can be employed as a carbon- and binder-free cathode for Li-O2 batteries and delivers a specific capacity of 3720 mAh gRu (-1) at a current density of 200 mA gRu (-1) . 100 cycles of continuous discharge and charge are obtained at a very narrow terminal voltage window of 2.75∼3.75 V with a limited capacity of 1000 mAh gRu (-1) . The good performance of the nanoporous Ru@Ni cathode can be mainly attributed to the effective suppression of the by-products related to carbon or binder, the good adhesion of the catalyst to the current collector, and the good permeation of O2 and electrolyte into the active sites of the nanoporous Ru with the open pore system. This new type electrode provides a snapshot toward developing high-performance carbon- and binder-free Li-O2 batteries.